TY - JOUR
A1 - Leiterer, Jork
A1 - Leitenberger, W.
A1 - Emmerling, Franziska
A1 - Thünemann, Andreas
A1 - Panne, Ulrich
T1 - The use of an acoustic levitator to follow crystallization in small droplets by energy-dispersive X-ray diffraction
N2 - For the investigation of small sample volumes, the use of an acoustic levitator was tested as a `sample holder' for hovering droplets in a synchrotron beam. It might be advantageous to use levitated droplets instead of samples confined in solid holders, especially for the study of crystallization processes where the influence of containing walls has to be minimized. In a first experiment, the crystallization of sodium chloride in a small droplet of aqueous solution has been followed with a time resolution of 30 s. The collected diffraction peaks are compared with data in the ICSD database.
KW - EDXD
KW - Noncontact measurement technique
KW - X-ray-scattering
KW - Synchrotron-radiation
KW - Acoustic levitation
PY - 2006
U6 - https://doi.org/10.1107/S0021889806024915
SN - 0021-8898
SN - 1600-5767
VL - 39
IS - 5
SP - 771
EP - 773
PB - Blackwell
CY - Oxford
AN - OPUS4-13516
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Emmerling, Franziska
A1 - Orgzall, I.
A1 - Reck, Günter
A1 - Schulz, Burkhard
A1 - Stockhause, S.
A1 - Schulz, B.
T1 - Structures of substituted di-aryl-1,3,4-oxadiazole derivatives: 2,5-bis(pyridyl)- and 2,5-bis(aminophenyl)-substitution
N2 - Crystal structures of four different di-aryl-1,3,4-oxadiazole compounds (aryl = 2-pyridyl-, 3-pyridyl-, 2-aminophenyl-, 3-aminophenyl-) are determined. Crystallization of di(2-pyridyl)-1,3,4-oxadiazole yielded monoclinic and triclinic polymorphs. The structures are characterized by the occurrence of ππ interactions. Additionally, in case of the aminophenyl compounds intra- as well as intermolecular hydrogen bonds are found that influence the packing motif as well. Since these molecules are often used as ligands in metalorganic complexes similarities and differences of the molecular conformation between the molecules in the pure crystals and that of the ligands in the complexes are discussed.
KW - Crystal structure
KW - 1,3,4-Oxadiazole
KW - Molecular conformation
KW - Hydrogen bonds
PY - 2006
U6 - https://doi.org/10.1016/j.molstruc.2006.03.076
SN - 0022-2860
SN - 1872-8014
SN - 0377-046X
VL - 800
IS - 1-3
SP - 74
EP - 84
PB - Elsevier
CY - Amsterdam
AN - OPUS4-13799
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Tuchalski, G.
A1 - Emmerling, Franziska
A1 - Gröger, K.
A1 - Hänsicke, A.
A1 - Nagel, T.
A1 - Reck, Günter
T1 - X-ray investigations of nebivolol and its isomers
N2 - The molecular and crystal structures of the hydrochlorides of d-nebivolol, dl-nebivolol, and seven nebivolol isomers have been determined by X-ray structure analysis. The absolute configuration of all the compounds could be determined unambiguously using anomal dispersion effects. Two compounds, dl-nebivolol (NEB-1d,l) and the (S,R,S,R) nebivolol isomer (NEB-6), crystallize as racemic mixtures in the centrosymmetric space group P-1. d-Nebivolol and six nebivolol isomers crystallize in space group P212121. The d- and l-nebivolol molecules in NEB-1d and NEB-1d,l adopt a conformation which is significantly different compared with that of all nebivolol isomers. With the exception of dl-nebivolol (NEB-1d,l) numerous intermolecular hydrogen bonds connect the molecules forming molecular layers.
KW - X-ray crystal structure
KW - Nebivolol
PY - 2006
U6 - https://doi.org/10.1016/j.molstruc.2006.03.086
SN - 0022-2860
SN - 1872-8014
SN - 0377-046X
VL - 800
IS - 1-3
SP - 28
EP - 44
PB - Elsevier
CY - Amsterdam
AN - OPUS4-13800
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Kraus, Werner
A1 - Walther, M.
A1 - Jung, C. M.
A1 - Emmerling, Franziska
A1 - Pietzsch, H.-J.
T1 - Bromotricarbonyl{15-[2-(methylsulfanyl)ethylsulfanyl]pentadecanoic acid-kappa2S,S'}rhenium(I)
N2 - The title compound, [ReBr(C18H36O2S2)(CO)3], was synthesized and characterized as a non-radioactive surrogate of a novel Tc-containing fatty acid derivative prepared according to the tricarbonyl/dithioether design with the objective of developing new Tc-based radiopharmaceuticals for the non-invasive diagnosis of myocardial metabolism. The Re chelate contains the metal in the oxidation state +1 and is attached to the terminal position of a fatty acid. The complex formation was accomplished by a ligand exchange reaction using [NBu4]2[Re(CO)3Br3] as starting material.
KW - Fatty acid
KW - Tc-compound
KW - Radio-pharmaceutical
PY - 2006
U6 - https://doi.org/10.1107/S1600536806024081
SN - 1600-5368
VL - 62
IS - 7
SP - m1660
EP - m1662
PB - Munksgaard
CY - Copenhagen
AN - OPUS4-12529
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Meißner, T.
A1 - Bergmann, R.
A1 - Oswald, J.
A1 - Rode, K.
A1 - Stephan, H.
A1 - Richter, W.
A1 - Zänker, H.
A1 - Kraus, Werner
A1 - Emmerling, Franziska
A1 - Reck, Günter
T1 - Chitosan-encapsulated Keggin anion [Ti2W10PO40]7-.Synthesis, characterization and cellular uptake studies
N2 - The Keggin type polyoxotungstate [Ti2W10PO40]7- forms stable associates with the biopolymer chitosan in the nanometer size range. The cluster compound crystallizes from aqueous solution as K4H3[Ti2W10PO40] · 15H2O having a tetragonal structure. Both, the cluster compound and the chitosan/[Ti2W10PO40] associates show a high hydrolytic stability at pH 7.4. The associates formed between the cluster anion [Ti2W10PO40]7- with the polyaminosaccharide chitosan have been characterized by photon correlation spectroscopy, scanning electron microscopy, filtration, centrifugation and zeta potential measurements. The size of the associates formed is in the range of ca. 5×101 to 5×102 nm. These particles have a defined stoichiometry with 56 cluster anions bound per molecule chitosan. The isoelectric point determined by zeta potential measurements was found for a cluster anion to chitosan molar ratio of 5.5, indicating the charge neutralization between protonated chitosan and [Ti2W10PO40]7- anions. Cellular uptake studies with [Ti2W10PO40]7- using tumor cell lines FaDu (human squamous carcinoma) and HT-29 (human adenocarcinoma) showed that the tungsten amount inside the cells is remarkably enhanced in the presence of chitosan.
KW - Cluster compound
KW - Keggin structure
KW - Bipolymer
KW - Chitosan
PY - 2006
U6 - https://doi.org/10.1007/s11243-006-0035-z
SN - 0340-4285
SN - 1572-901X
VL - 31
IS - 5
SP - 603
EP - 610
PB - Springer
CY - Dordrecht
AN - OPUS4-12568
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Kuhlich, Paul
A1 - Emmerling, Franziska
A1 - Kraus, Werner
A1 - Nehls, Irene
A1 - Piechotta, Christian
T1 - 1-(4-bromo-3,5,5,6,8,8-hexamethyl-5,6,7,8-tetrahydronaphthalen-2-yl)ethan-1-one: a precursor for phase-I metabolite of AHTN
N2 - The title compound, C18H25BrO, crystallized as a racemate with four independent molecules in the asymmetric unit. In the crystal, three of these four molecules are linked via C-Br...Br-C halogen bonds [Br...Br = 3.662 (2) and 3.652 (2) Å], forming dimers.
PY - 2013
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-279935
SN - 1600-5368
VL - 69
IS - 4
SP - o545, sup-1
EP - sup-17
PB - Munksgaard
CY - Copenhagen
AN - OPUS4-27993
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Comba, P.
A1 - Emmerling, Franziska
A1 - Jakob, M.
A1 - Kraus, Werner
A1 - Kubeil, M.
A1 - Morgen, M.
A1 - Pietzsch, J.
A1 - Stephan, H.
T1 - Copper(II) chemistry of the functionalized macrocycle cyclam tetrapropionic acid
N2 - The CuII complex of H4TETP (H4TETP = 1,4,8,11-tetraazatetradecane-1,4,8,11-tetrapropionic acid) is five-coordinate with a distorted square-pyramidal structure (τ = 0.45; i.e. the geometry is nearly half-way between square-pyramidal and trigonal-bipyramidal) and a relatively long Cu–N and a short Cu–O bond; the comparison between powder and solution electronic spectroscopy, the frozen solution EPR spectrum and ligand-field-based calculations (angular overlap model, AOM) indicate that the solution and solid state structures are very similar, i.e. the complex has a relatively low 'in-plane' and a significant axial ligand field with a dx²-y² ground state. The ligand-enforced structure is therefore shown to lead to a partially quenched Jahn–Teller distortion and to a relatively low complex stability, lower than with the corresponding acetate-derived ligand H4TETA. This is confirmed by potentiometric titration and by the biodistribution with 64Cu-labeled ligands which show that the uptake in the liver is significantly increased with the H4TETP-based system.
KW - Copper(II)
KW - Chemistry
PY - 2013
U6 - https://doi.org/10.1039/c2dt32356g
SN - 1477-9226
SN - 1477-9234
SN - 1364-5447
VL - 42
IS - 17
SP - 6142
EP - 6148
PB - RSC
CY - Cambridge
AN - OPUS4-28075
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Stephan, H.
A1 - Kubeil, M.
A1 - Emmerling, Franziska
A1 - Müller, C.E.
T1 - Polyoxometalates as versatile enzyme inhibitors
N2 - Polyoxometalates (POMs) are inorganic cluster compounds that have been shown to possess a number of pharmacological properties, including antidiabetic, antibacterial, antiprotozoal, antiviral and anticancer activities. Their molecular mechanism of action is largely unknown. However, several studies indicate that many of their activities may be due to the inhibition of enzymes, in particular, of those enzymes that are accessible from the extracellular space and do not require the penetration of cell membranes. In this review, we describe the recent progress in the preparation and optimization of POMs, and an evaluation of their use as inhibitors of different families of enzymes. The next important steps in this area of research will be to gain a better understanding of the interactions of POMs with enzymes on a structural level through an X-ray crystallographic study of enzyme–POM complexes and the analysis of structure–activity relationships. Furthermore, POMs with increased stability and in vivo half-lives have to be prepared. Surface modification may allow the targeting of POM drugs at their sites of action.
KW - Cluster compounds
KW - Polyoxometalates
KW - Metalloprotein mimics
KW - Enzymes
KW - Inhibitors
KW - Bioinorganic chemistry
PY - 2013
U6 - https://doi.org/10.1002/ejic.201201224
SN - 1434-1948
SN - 1099-0682
VL - 2013
IS - 10-11
SP - 1585
EP - 1594
PB - Wiley-VCH Verl.
CY - Weinheim
AN - OPUS4-28076
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Gnutzmann, Tanja
A1 - Kahlau, R.
A1 - Scheifler, S.
A1 - Friedrichs, Ferdinand
A1 - Rössler, A.
A1 - Rademann, Klaus
A1 - Emmerling, Franziska
T1 - Crystal growth rates and molecular dynamics of nifedipine
N2 - The unusually fast crystallization of the organic compound nifedipine has been investigated in detail using different solutions as precursors for the formation of the initial glassy nifedipine films. Starting from these amorphous films the crystallization process was investigated by time-resolved light microscopy at different temperatures around Tg of nifedipine. In all studied cases (acetone, acetonitrile, ethyl acetate, dichloromethane, tetrahydrofuran) the measured mean crystallization rates are, on average, 10000 times higher than rates reported in previous studies. Such high rates cannot be explained by a classical diffusional crystal growth mechanism of nifedipine. Instead, nifedipine shows a strong propensity for diffusionless growth. Solvent assisted or solvent induced preordering of the glassy modification is suggested to be the most probable driving force behind these fast crystallization processes. The nifedipine crystallization rates can be controlled not only by specific solvent–molecule interactions but also by temperature. Below 40 °C, the temperature dependence of the rates is generally small. Above 40 °C, a slowing down of the crystallization rates with increasing temperatures indicates a kinetic competition between different polymorphs. The molecular dynamics of nifedipine molecules in the amorphous phase as well as the relaxation times are studied by dielectric measurements. The dielectric data corroborate the inherently strong propensity of nifedipine to crystallize diffusionlessly under all conditions.
KW - Fast crystallization
KW - Diffusionless growth
KW - Polymorphism
KW - Nifedipine
KW - Preordering
KW - Raman spectroscopy
KW - Dielectric spectroscopy
PY - 2013
U6 - https://doi.org/10.1039/c2ce26911b
SN - 1466-8033
VL - 15
IS - 20
SP - 4017
EP - 4202
CY - London, UK
AN - OPUS4-28307
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Hennig, C.
A1 - Takao, S.
A1 - Takao, K.
A1 - Weiss, s.
A1 - Kraus, Werner
A1 - Emmerling, Franziska
A1 - Meyer, M.
A1 - Scheinost, A.C.
T1 - Identification of hexanuclear actinide(IV) carboxylates with thorium, uranium and neptunium by EXAFS spectroscopy
N2 - Hydrated actinide(IV) ions undergo hydrolysis and further polymerization and precipitation with increasing pH. The resulting amorphous and partly crystalline oxydydroxides AnOn(OH)4-2n·xH2O can usually be observed as colloids above the An(IV) solubility limit. The aging process of such colloids results in crystalline AnO2. The presence of carboxylates in the solution prevents the occurrence of such colloids by formation of polynuclear complexes through a competing reaction between hydrolysis and ligation. The majority of recently described carboxylates reveals a hexanuclear core of [An6(µ3-O)4(µ3-OH)4]12+ terminated by 12 carboxylate ligands. We found that the An(IV) carboxylate solution species remain often preserved in crystalline state. The An(IV) carboxylates show An–An distances which are ~ 0.03 Å shorter than the An–An distances in AnO2 like colloids. The difference in the distances could be used to identify such species in solution.
T2 - XAFS15 - 15th International conference on X-ray absorption fine structure
CY - Beijing, China
DA - 22.07.2012
KW - Carboxylates
KW - EXAFS
KW - Actinide
PY - 2013
U6 - https://doi.org/10.1088/1742-6596/430/1/012116
SN - 1742-6588
SN - 1742-6596
VL - 430
SP - 012116-1
EP - 012116-5
PB - IOP Publ.
CY - Bristol, UK
AN - OPUS4-28525
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Klimakow, Maria
A1 - Klobes, Peter
A1 - Rademann, K.
A1 - Emmerling, Franziska
T1 - Characterization of mechanochemically synthesized MOFs
N2 - The compound MOF-14 (Cu3(BTB)2, BTB = 4,4',4''-benzenetribenzoate) was synthesized by ball milling and characterized by powder X-ray diffraction (XRD). The raw material was activated using an efficient single washing step to ensure a free pore access. Nitrogen adsorption measurements were carried out to determine the specific areas of the samples before and after activation. To interpret the activation process in terms of blocking effects in the micropore channels, NLDFT evaluations (Nonlocal Density Functional Theory) of the MOF-14 nitrogen isotherms were carried out. In connection with the appearance of additional hysteresis loops in the nitrogen isotherms, calculations of the mesopore size distribution were performed using the method of Barret, Joyner, and Halenda (BJH). The results are compared to those of a structurally analogue MOF, namely HKUST-1 (Cu3(BTC)2, BTC = 1,3,5-benzenetricarboxylate). This comparison showed notable differences regarding the impact of the activation step on the formation of mesopores and their size distribution.
KW - Metal-organic frameworks
KW - Mechanochemistry
KW - Gas adsorption
KW - Specific surface area
KW - MOF-14
PY - 2012
U6 - https://doi.org/10.1016/j.micromeso.2011.11.039
SN - 1387-1811
SN - 1873-3093
VL - 154
SP - 113
EP - 118
PB - Elsevier
CY - Amsterdam
AN - OPUS4-25597
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Schenk, Jonas
A1 - Batzdorf, Lisa
A1 - Emmerling, Franziska
A1 - Kneipp, Janina
A1 - Panne, Ulrich
A1 - Buurman, Merwe
T1 - Simultaneous UV/Vis spectroscopy and surface enhanced raman scattering of nanoparticle formation and aggregation in levitated droplets
N2 - The formation and growth of hydroxylamine reduced silver nanoparticles were investigated by simultaneous Raman and UV/Vis spectroscopy coupled to an acoustic levitator as a sample holder. Based on the UV/Vis spectra, a two step particle formation mechanism with fast initial formation and adjacent coalescence can be proposed for the reduction of silver nitrate with hydroxylamine. The presence of the analyte adenine during particle formation resulted in differences in the adenine SERS signature compared to experiments, where adenine was added after particle synthesis. It was possible to monitor the adenine and sodium chloride induced aggregation of the nanoparticles and its dynamics based on both the extinction spectra and the SERS data. Correlating the information from the extinction spectra with the SERS intensity, the maximum SERS signals were observed at maximum extinction of the aggregated nanoparticle solution at the Raman excitation wavelength.
PY - 2012
U6 - https://doi.org/10.1039/c2ay05744a
SN - 1759-9660
SN - 1759-9679
N1 - Geburtsname von Batzdorf, Lisa: Tröbs, L. - Birth name of Batzdorf, Lisa: Tröbs, L.
N1 - Geburtsname von Buurman, Merwe: Albrecht, M. - Birth name of Buurman, Merwe: Albrecht, M.
VL - 4
IS - 5
SP - 1252
EP - 1258
PB - RSC Publ.
CY - Cambridge
AN - OPUS4-25742
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Mönch, Bettina
A1 - Gebert, Antje
A1 - Emmerling, Franziska
A1 - Becker, Roland
A1 - Nehls, Irene
T1 - Koenigs-Knorr reaction of fusel alcohols with methyl (1-bromo-2,3,4-tri-O-acetyl-alpha-D-glucopyranosid)uronate leading to the protected alkyl glucuronides-crystal structures and high resolution 1H and 13C NMR data
N2 - Crystal structures and high resolution 1H and 13C NMR spectral data for methyl (alkyl 2,3,4-tri-O-acetyl-β-D-glucopyranosid)uronates (alkyl = methyl, ethyl, n-propyl, i-propyl, n-butyl, sec-butyl, i-butyl, n-pentyl, 2-methyl-1-butyl and 3-methyl-1-butyl) are presented.
KW - D-Glucuronic acid derivates
KW - X-ray analysis
KW - High resolution NMR
KW - Anomeric configuration
KW - Synthesis
PY - 2012
U6 - https://doi.org/10.1016/j.carres.2012.01.002
SN - 0008-6215
SN - 1873-426X
VL - 352
SP - 186
EP - 190
PB - Elsevier
CY - Amsterdam
AN - OPUS4-25759
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Noack, J.
A1 - Emmerling, Franziska
A1 - Kirmse, H.
A1 - Kemnitz, E.
T1 - Sols of nanosized magnesium fluoride: formation and stabilisation of nanoparticles
N2 - The formation of magnesium fluoride sols and xerogels according to the fluorolytic sol–gel synthesis based on the reaction of Mg(OMe)2 with non-aqueous HF has been thoroughly investigated by X-ray scattering (WAXS/XRD), TEM, SAXS, DLS and 19F MAS NMR spectroscopy. Mechanistic insights were gained by following the reaction progress and formation of intermediate phases of the fluorination of magnesium alkoxides. For F:Mg ratios of 0.3 and 0.4 the formation of two crystalline phases was observed containing the recently obtained compound [Mg6F2(OCH3)10(CH3OH)14] hexanuclear dicubane units. The stoichiometric reaction yields magnesium fluoride nanoparticles with crystallite sizes below 5 nm, which show broad reflections in the X-ray diffraction pattern. Metal fluoride sols prepared by this way undergo tremendous changes over the first several weeks after synthesis. Immediately after the fluorination, particles of about 120 nm—probably agglomerates—are formed, which break apart in the course of about one month of ageing and low-viscous, transparent sols with particles of about 12 nm are obtained. At the same time structural re-organisation processes within the magnesium fluoride particles are observed by an increase of the (110) reflection in WAXS.
KW - Surface modification
KW - Colloidal particles
KW - Gold nanoparticles
KW - Gel synthesis
KW - Small-angle scattering
KW - Oxide
KW - Polyelectrolytes
KW - Aggregation
KW - Dispersion
PY - 2011
U6 - https://doi.org/10.1039/c1jm11943e
SN - 0959-9428
SN - 1364-5501
VL - 21
IS - 38
SP - 15015
EP - 15021
PB - Royal Society of Chemistry
CY - Cambridge
AN - OPUS4-26183
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Kahlau, R.
A1 - Gnutzmann, Tanja
A1 - Emmerling, Franziska
A1 - Rademann, K.
A1 - Rössler, E.A.
T1 - Quinaldine: Accessing two crystalline polymorphs via the supercooled liquid
N2 - Quinaldine (2-methyl quinoline) is a liquid at room temperature, which can be supercooled to reach finally the glassy state. By heating the glass above the glass transition temperature Tg = 180 K the sample performs two subsequent transitions into, likewise, dielectrically active phases. Thus, the reorientational relaxations of these phases as well as the kinetics of the phase transitions can be tracked in a highly resolved way by dielectric spectroscopy. X-ray diffraction analysis clearly shows two structurally different crystalline phases in addition to the supercooled liquid. Calorimetric measurements support the notion of first order phase transitions, occurring irreversibly in the supercooled regime, and suggest that the intermediate crystalline phase is metastable, too. Analyzing the quite distinct dielectric relaxation strengths, we discuss the possible nature of the two crystalline phases. Additionally, a very similar behavior to quinaldine is observed for 3-methyl quinoline, indicating a broad field of polymorphism among the quinoline derivatives.
KW - Calorimetry
KW - Dielectric liquids
KW - Dielectric relaxation
KW - Glass transition
KW - Liquid structure
KW - Organic compounds
KW - Polymorphism
KW - Supercooling
KW - X-ray diffraction
PY - 2012
U6 - https://doi.org/10.1063/1.4738583
SN - 0021-9606
SN - 1089-7690
VL - 137
IS - 5
SP - 054505-1 - 054505-10
PB - American Institute of Physics
CY - Melville, NY
AN - OPUS4-26347
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Emmerling, Franziska
A1 - Rademann, K.
A1 - Gericke, E.
A1 - Weidemann, S.
A1 - Bansen, R.
A1 - Boeck, T.
T1 - Selective Growth of Trigonal and Hexagonal Shaped Silver Micro-Nano-Platelets at the Water/Oil Interface
T2 - JungChemikerForum
CY - Berlin, Germany
DA - 2013-03-06
PY - 2013
AN - OPUS4-28285
LA - deu
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Schlegel, Moritz-Caspar
A1 - Müller, Urs
A1 - Panne, Ulrich
A1 - Emmerling, Franziska
A1 - Meng, Birgit
ED - Rogge, A.
ED - Meng, B.
T1 - Neue Wege in der Zementanalytik - Hochaufgelöste in-situ Sy-XRD
T2 - 52. DAfStb-Forschungskolloquium
CY - Berlin, Deutschland
DA - 2011-11-07
PY - 2011
SN - 978-3-9814281-0-0
SP - 18
EP - 24
PB - BAM Bundesanstalt für Materialforschung und -prüfung
CY - Berlin
AN - OPUS4-25197
LA - deu
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Sarfraz, Adnan
A1 - Schlegel, Moritz-Caspar
A1 - Wright, J.
A1 - Emmerling, Franziska
T1 - Advanced gas hydrate studies at ambient conditions using suspended droplets
N2 - We report the spontaneous formation of a clathrate hydrate in a suspended droplet at ambient conditions. A novel method for producing and stabilizing clathrates for analytical studies is described.
KW - Clathrates
KW - Thermography
KW - Acoustic levitator
KW - Dichloromethane
PY - 2011
U6 - https://doi.org/10.1039/c1cc13049h
SN - 0022-4936
SN - 1359-7345
VL - 47
IS - 33
SP - 9369
EP - 9371
PB - Royal Society of Chemistry
CY - Cambridge
AN - OPUS4-24480
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Joseph, Viginia
A1 - Matschulat, Andrea
A1 - Polte, Jörg
A1 - Rolf, Simone
A1 - Emmerling, Franziska
A1 - Kneipp, Janina
T1 - SERS enhancement of gold nanospheres of defined size
N2 - Monodisperse, citrate-stabilized gold nanoparticles of sizes ranging from 15 to 40 nm were synthesized and characterized by small angle X-ray scattering and UV-vis experiments. Identical surface properties of nanoparticles of different sizes to avoid variation in the chemical surface-enhanced Raman scattering (SERS) enhancement, as well as selection of experimental conditions so that no aggregation took place, enabled the investigation of enhancement of individual nanospheres. Enhancement factors (EFs) for SERS were determined using the dye crystal violet (CV). EFs for individual gold nanospheres ranged from 102 to 103, in agreement with theoretical predictions. An increase of the EFs of individual spheres with size can be correlated to changes in the extinction spectra of nanoparticle solutions. This confirms that the increase in enhancement with increasing size results from an increase in electromagnetic enhancement. Beyond this dependence of EFs of isolated gold spheres on their size, EFs were shown to vary with analyte concentration as a result of analyte-induced aggregation. This has implications for the application of nanoparticle solutions as SERS substrates in quantitative analytical tasks.
KW - Surface-enhanced Raman scattering
KW - Electromagnetic enhancement factor
KW - Crystal violet
KW - Citrate reduction
KW - Gold nanoparticles
PY - 2011
U6 - https://doi.org/10.1002/jrs.2939
SN - 0377-0486
SN - 1097-4555
VL - 42
IS - 9
SP - 1736
EP - 1742
PB - Wiley
CY - Chichester
AN - OPUS4-24483
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Trowitzsch-Kienast, W.
A1 - Rühl, M.
A1 - Kim, K.Y.
A1 - Emmerling, Franziska
A1 - Erben, U.
A1 - Somasundaram, R.
A1 - Freise, C.
T1 - Absolute configuration of antifibrotic (+)-episesamin isolated from Lindera obtusiloba BLUME
N2 - Fractionation of a 70% ethanolic extract from twigs of Lindera obtusiloba BLUME (Japanese spicebush, Tohaku) yielded fi ve fractions of different polarity. The antifi brotic activity within the chloroform phase was best assessed by an in vitro bioassay using rat hepatic stellate cell (HSC) proliferation and their autocrine transforming growth factor beta (TGF-β) expression as sensitive fibrosis-associated read out. Chromatography of the chloroform extract on Sephadex LH-20 or liquid-liquid extractions yielded a crystalline compound as an active principle, which was identifi ed from NMR and ESI-MS analyses, its melting point, and its optical rotation as (7S,7'S,8S,8'S)-3,4:3',4'-bis(methylenedioxy) -7,9':7',9-diepoxy-lignane [(+)-episesamin]. X-Ray diffraction confirmed the structure and provided, for the fi rst time, directly its absolute confi guration. (+)-Episesamin blocked proliferation and the profi brotic autocrine TGF-β expression HSC without signifi cant cytotoxicity.
KW - TGF-beta
KW - Liver Fibrosis
KW - X-Ray Structure
PY - 2011
SN - 0939-5075
SN - 0341-0382
SN - 0341-0471
VL - 66c
IS - 9/10
SP - 460
EP - 464
PB - Verl. d. Zeitschrift für Naturforschung
CY - Tübingen
AN - OPUS4-24716
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Wolf, S. E.
A1 - Leiterer, Jork
A1 - Pipich, V.
A1 - Barrea, R.
A1 - Emmerling, Franziska
A1 - Tremel, W.
T1 - Strong stabilization of amorphous calcium carbonate emulsion by ovalbumin: gaining insight into the mechanism of "polymer-induced liquid precursor" processes
N2 - The impact of the ovo proteins ovalbumin and lysozyme—present in the first stage of egg shell formation—on the homogeneous formation of the liquid amorphous calcium carbonate (LACC) precursor, was studied by a combination of complementing methods: in situ WAXS, SANS, XANES, TEM, and immunogold labeling. Lysozyme (pI = 9.3) destabilizes the LACC emulsion whereas the glycoprotein ovalbumin (pI = 4.7) extends the lifespan of the emulsified state remarkably. In the light of the presented data: (a) Ovalbumin is shown to behave commensurable to the 'polymer-induced liquid precursor' (PILP) process proposed by Gower et al. Ovalbumin can be assumed to take a key role during eggshell formation where it serves as an effective stabilization agent for transient precursors and prevents undirected mineralization of the eggshell. (b) It is further shown that the emulsified LACC carries a negative surface charge and is electrostatically stabilized. (c) We propose that the liquid amorphous calcium carbonate is affected by polymers by depletion stabilization and de-emulsification rather than 'induced' by acidic proteins and polymers during a so-called polymer-induced liquid-precursor process. The original PILP coating effect, first reported by Gower et al., appears to be a result of a de-emulsification process of a stabilized LACC phase. The behavior of the liquid amorphous carbonate phase and the polymer-induced liquid-precursor phase itself can be well described by colloid chemical terms: electrostatic and depletion stabilization and de-emulsification by depletion destabilization.
KW - Biomineralisation
KW - Calcium carbonate
KW - PILP
KW - LACC
PY - 2011
U6 - https://doi.org/10.1021/ja202622g
SN - 0002-7863
SN - 1520-5126
VL - 133
IS - 32
SP - 12642
EP - 12649
PB - American Chemical Society
CY - Washington, DC
AN - OPUS4-24628
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Kreft, B.
A1 - Bednarczyk, M.
A1 - Emmerling, Franziska
A1 - Marsch, W.C.
T1 - Cutaneous-subcutaneous pseudolymphoma after specific immunotherapy with grass-rye pollen-allergen extract containing aluminium hydroxide
N2 - Allergen-specific immunotherapy is an important treatment procedure in IgE-mediated allergic diseases such as allergic rhinitis or insect toxin allergies. A reduction in the clinical reaction to the allergens to which the patient is known to be sensitized is intended by means of antigen-specific influence on the immune system. The allergenspecific immunotherapy can be applied by subcutaneous injections, and for selected allergens by means of sublingual application of the appropriate allergen. Occasionally, the injection of aluminium hydroxide-adsorbed sera induces a usually transient formation of granulomas. We are reporting on a rare case of cutaneous-subcutaneous pseudolymphoma in the injection area of both upper arms, probably induced by subcutaneous allergen-specific immunotherapy.
KW - Allergen-specific immunotherapy
KW - Pseudolymphoma
KW - Aluminium hydroxide
PY - 2011
SN - 1642-395X
VL - XXVIII
IS - 2
SP - 134
EP - 137
PB - Termedia Wydawnictwa Med.
CY - Pozna´n
AN - OPUS4-24629
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Belombe, M.M.
A1 - Nenwa, J.
A1 - Emmerling, Franziska
T1 - Stacking structure of quinolinium hydrogensquarate
N2 - A new proton-transfer organic salt, quinolinium hydrogensquarate (C13H9NO4), has been synthesized and fully characterized by single crystal x-ray diffraction. The salt crystallizes in the monoclinic space group P21/n with the parameters:
a = 3.8290(12) Å, b = 20.960(6) Å, c = 13.802(4) Å, β = 95.452(5)°, V = 1102.7(6) Å3, Z = 4 formula units. The structure consists of uncommon supramolecular neutral dimers which pile up parallel to [100] forming infinite sheets. These centrosymmetric dimers are held together by lateral hydrogen-bonds whereby two neighboring coplanar hydrogensquarate anions act as a bridge between two terminal quinolinium cations and C-H...O bridgings interlink next neighboring sheets. The bulk structure of this salt is consolidated by weak ππ interactions within the sheets which are neatly ordered side-by-side relative to one another.
KW - Quinolinium squarate
KW - Supramolecular dimer
KW - Crystal structure
KW - Proton-transfer salt
PY - 2011
SN - 0973-4945
VL - 8
IS - 2
SP - 603
EP - 608
CY - Tamil Nadu
AN - OPUS4-24627
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Müller, Urs
A1 - Schlegel, Moritz-Caspar
A1 - Emmerling, Franziska
T1 - Advanced techniques for studying damage mechanisms of cementitious matrices affected by sulfate attack
N2 - Cementitious materials, in particular concrete, are durable materials if prepared appropriately and the Service life of concrete structures is now often required to last 120 years or more. Concrete durability depends strongly on intrinsic (e.g. composition, porosity) and exterior factors (e.g. moisture condition and composition, frost cycles, load pattem). Deleterious actions leading to concrete degradation are often created by the environment. Extemal sulfate attack is one of the more spectacular damage scenarios for concrete structures caused by the ingress of sulfate ions into the pore System of the material and successive formation of expanding phases. Though in recent years well studied there are still many questions remaining conceming the mechanisms of sulfate attack. In particular over the last ten years, with the increased utilization of blended cements, new questions arose concerning the sulfate resistance of those binder Systems. In the presented study therefore a method was developed to analyze the changes of the phase composition within the micro structure due to sulfate attack. The analytical method was based on pX-Ray diffraction (pXRD) using Synchrotron radiation in Debye-Scherrer (transmission) geometry. The spatial resolution of the method is ca. 10 pm and allows the characterization of phase transformations in the wake of damaging processes in more detail compared to other techniques. Furthermore, the experimental setup provides the possibility for analyzing the phase assemblage of a given sample without destroying the micro structure. This is possible because the specimens for phase analysis consists of thick sections, which can be used for further microscopic analysis of the micro structure and micro chemistry (e.g. by SEM-EDX). Samples containing supplementary cementitious materials were measured in comparison and to reconstruct the influence of the degradation process in detail. Additionally, reaction ffonts within the samples were localized by micro x-ray fluorescence analysis (MXRF).
T2 - EMABM 2011 - 13th Euroseminar on microscopy applied to building materials
CY - Ljubljana, Slovenia
DA - 14.06.2011
KW - Sulfate attack
KW - Concrete
KW - Synchrotron
KW - XRD
KW - Phase analysis
PY - 2011
SN - 978-961-90366-7-9
SP - 1
EP - 9
AN - OPUS4-24878
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Mönch, Bettina
A1 - Emmerling, Franziska
A1 - Kraus, Werner
A1 - Becker, Roland
A1 - Nehls, Irene
T1 - Isopropyl 2,3,4,6-tetra-O-acetyl-beta-D-glucopyranoside
N2 - The title compound, C17H26O10, was formed by a Koenigs-Knorr reaction of 2,3,4,6-tetra-O-acetyl-α-D-glucopyranosyl bromide and propan-2-ol. The central ring adopts a chair conformation. The crystal does not contain any significant intermolecular interactions.
PY - 2013
U6 - https://doi.org/10.1107/S1600536812051483
SN - 1600-5368
VL - 69
IS - Part 2
SP - o157, sup-1 - sup-7
PB - Munksgaard
CY - Copenhagen
AN - OPUS4-27572
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Nehls, Irene
A1 - Hanebeck, Olaf
A1 - Becker, Roland
A1 - Emmerling, Franziska
T1 - N-(beta-carboxyethyl)-alpha-isoleucine
N2 - The title compound, {2-[(2-carbamoylethyl)amino]-3-methylpentanoic acid}, C9H18N2O3, is of interest with respect to its biological activity. It was formed during an addition reaction between acrylamide and the amino acid isoleucine. The crystal structure is a three-dimensional network built up by intermolecular N–H···O and O–H···N hydrogen bonds.
KW - Acrylamid
KW - Isoleucin
KW - Derivatisierung
PY - 2013
U6 - https://doi.org/10.1107/S160053681205146X
SN - 1600-5368
VL - 69
IS - Part 2
SP - o172-o173, sup-1 - sup-7
PB - Munksgaard
CY - Copenhagen
AN - OPUS4-27573
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Köppen, Robert
A1 - Emmerling, Franziska
A1 - Koch, Matthias
T1 - rac-2,3-Dibromopropionamide
N2 - The racemic title compound, C3H5Br2NO, was crystallized from methanol. In the crystal, adjacent molecules are linked through N–H···O hydrogen bonds, forming chains along the c-axis direction. These chains are linked through N–H···O hydrogen bonds, forming an undulating two-dimensional network lying parallel to the bc plane. There are also short Br···Br contacts present [3.514 (3) Å].
PY - 2013
U6 - https://doi.org/10.1107/S160053681205132X
SN - 1600-5368
VL - 69
IS - Part 2
SP - o151, sup-1
EP - sup-5
PB - Munksgaard
CY - Copenhagen
AN - OPUS4-27574
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Mönch, Bettina
A1 - Emmerling, Franziska
A1 - Kraus, Werner
A1 - Becker, Roland
A1 - Nehls, Irene
T1 - n-Propyl 2,3,4,6-tetra-O-acetyl-beta-D-glucopyranoside
N2 - The title compound [systematic name: (2R,3R,4S,5R,6R) 2-(acetoxymethyl)-6-propoxytetrahydro-2H-pyran-3,4,5-triyl triacetate], C17H26O10, was formed by a Koenigs-Knorr reaction of 2,3,4,6-tetra-O-acetyl-α-D-glucopyranosyl bromide and n-propanol. The central ring adopts a chair conformation. The crystal does not contain any significant interactions such as hydrogen bonds.
PY - 2013
U6 - https://doi.org/10.1107/S1600536812051495
SN - 1600-5368
VL - 69
IS - Part 2
SP - o158, sup-1 - sup-7
PB - Munksgaard
CY - Copenhagen
AN - OPUS4-27439
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Simo, A.
A1 - Polte, Jörg
A1 - Pfänder, N.
A1 - Vainio, U.
A1 - Emmerling, Franziska
A1 - Rademann, K.
T1 - Formation mechanism of silver nanoparticles stabilized in glassy matrices
N2 - In any given matrix control over the final particle size distribution requires a constitutive understanding of the mechanisms and kinetics of the particle evolution. In this contribution we report on the formation mechanism of silver nanoparticles embedded in a soda-lime silicate glass matrix. For the silver ion-exchanged glass it is shown that at temperatures below 410 °C only molecular clusters (diameter <1 nm) are forming which are most likely silver dimers. These clusters grow to nanoparticles (diameter >1 nm) by annealing above this threshold temperature of 410 °C. It is evidenced that the growth and thus the final silver nanoparticle size are determined by matrix-assisted reduction mechanisms. As a consequence, particle growth proceeds after the initial formation of stable clusters by addition of silver monomers which diffuse from the glass matrix. This is in contrast to the widely accepted concept of particle growth in metal–glass systems, in which it is assumed that the nanoparticle formation is predominantly governed by Ostwald ripening processes.
PY - 2012
U6 - https://doi.org/10.1021/ja309034n
SN - 0002-7863
SN - 1520-5126
VL - 134
IS - 45
SP - 18824
EP - 18833
PB - American Chemical Society
CY - Washington, DC
AN - OPUS4-27539
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Zink, N.
A1 - Emmerling, Franziska
A1 - Häger, T.
A1 - Panthöfer, M.
A1 - Tahir, M.N.
A1 - Kolb, U.
A1 - Tremel, W.
T1 - Low temperature synthesis of monodisperse nanoscaled ZrO2 with a large specific surface area
N2 - Thermal decomposition of Zr(C2O4)2·4H2O within an autoclave or in a conventional tube furnace at temperatures below 380 °C resulted in nano- and micron-sized ZrO2, respectively. Reactions under autogenic pressure yielded monodisperse monoclinic (m) and tetragonal (t) ZrO2 nanoparticles with an average diameter of ~8 nm and interconnected t-ZrO2 nanoparticles with diameters of ~4 nm, depending on the synthesis temperature. Samples were characterised by X-ray diffraction (XRD), small angle X-ray scattering (SAXS), scanning electron microscopy (SEM), transmission electron microscopy (TEM) associated with energy dispersive X-ray spectroscopy (EDS), Raman microspectroscopy and photoluminescence spectroscopy (PL). Nanostructured zirconia materials exhibited high specific areas of 276–385 m2 g-1 which make them promising candidates as catalysts and catalyst supports. Co-existence of m- and t-ZrO2 nanoparticles with diameters of 6–9 nm, i.e. above the critical particle size of 6 nm for the formation of t-ZrO2, demonstrated that the particle size is not the only factor for stabilisation of the t-ZrO2 modification at room temperature.
PY - 2013
U6 - https://doi.org/10.1039/c2dt12496c
SN - 1477-9226
SN - 1477-9234
SN - 1364-5447
VL - 42
SP - 432
EP - 440
PB - RSC
CY - Cambridge
AN - OPUS4-27733
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Gnutzmann, Tanja
A1 - Rademann, K.
A1 - Emmerling, Franziska
T1 - Fast crystallization of organic glass formers
N2 - An unusually fast crystallization of the organic glass former nifedipine has been observed. The crystallization process, starting from an amorphous film to crystalline material, was investigated by time resolved Raman microspectroscopy. The crystallization rates of the initially crystallizing metastable β-form are four orders of magnitude higher than those of previous studies.
KW - Polymorphism
KW - Raman spectroscopy
KW - Crystallization
KW - Nifedipine
PY - 2012
U6 - https://doi.org/10.1039/c1cc16301a
SN - 0022-4936
SN - 0009-241x
SN - 1359-7345
SN - 1364-548x
VL - 48
SP - 1638
EP - 1640
PB - Royal Society of Chemistry
CY - Cambridge
AN - OPUS4-27735
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Merkel, Stefan
A1 - Köppen, Robert
A1 - Koch, Matthias
A1 - Emmerling, Franziska
A1 - Nehls, Irene
T1 - Ergotaminine
N2 - The title compound {systematic name: (6aR,9S)-N-[(2R,5S,10aS,10bS)-5-benzyl-10b-hydroxy-2-methyl-3,6-dioxooctahydro-8H-oxazolo[3,2-a]pyrrolo[2,1-c]pyrazin-2-yl]-7-methyl-4,6,6a,7,8,9-hexahydroindolo[4,3-fg]quinoline-9-carboxamide}, C33H35N5O5, was formed by an epimerization reaction of ergotamine. The non-aromatic ring (ring C of the ergoline skeleton) directly fused to the aromatic rings is nearly planar [maximum deviation = 0.317 (4) Å] and shows an envelope conformation, whereas ring D, involved in an intramolecular N–H···N hydrogen bond exhibits a slightly distorted chair conformation. The structure displays chains running approximately parallel to the diagonal of bc plane that are formed through N–H···O hydrogen bonds.
PY - 2012
U6 - https://doi.org/10.1107/S1600536812003674
SN - 1600-5368
VL - 68
IS - 3
SP - o610-o611, sup1-sup11
PB - Munksgaard
CY - Copenhagen
AN - OPUS4-25452
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Sarfraz, Adnan
A1 - Simo, A.
A1 - Fenger, R.
A1 - Christen, W.
A1 - Rademann, K.
A1 - Panne, Ulrich
A1 - Emmerling, Franziska
T1 - Morphological diversity of caffeine on surfaces: needles and hexagons
N2 - A systematic crystal morphology study on the pharmaceutical model compound caffeine has been conducted on different surfaces: silicon, silver, soda lime glass, and silver subsurface ion-exchanged soda-lime silicate (SIMO) glasses. The morphology of the solid caffeine deposits has been investigated using environmental scanning electron microscopy (ESEM), atomic force microscopy (AFM), and X-ray diffraction (XRD). Needle-shaped caffeine crystals have been observed by drop-casting and also by applying the rapid expansion of supercritical solutions (RESS) technique using supercritical carbon dioxide. The aspect ratio of the crystalline needles typically vary between 10 and 100, but have been observed as large as 500. The XRD data of the RESS products indicate unambiguously the presence of the thermodynamically most stable polymorph of caffeine known as the β-form. Under defined conditions we observe a unique, surface-mediated morphology for caffeine crystals with nearly perfect hexagonal shape. The relative fraction of the hexagons was seen to strongly increase especially when SIMO glasses were used. These hexagons have a distinct upper size limit depending on the solvent and substrate being used. The size distribution analysis of the hexagons yielded an average perimeter of typically 10 µm. The mechanism of the formation process of this new hexagonal motif is explained in terms of the spinodal dewetting of the thin film of caffeine solution on the surface.
KW - Caffeine
KW - Silicon
KW - Silver
KW - Ion exchanged soda lime silicate glass
KW - ESEM
KW - AFM
KW - X-ray diffraction
KW - RESS
KW - Carbon dioxide
KW - Supercritical fluids
PY - 2012
U6 - https://doi.org/10.1021/cg101358q
SN - 1528-7483
VL - 12
IS - 2
SP - 583
EP - 588
PB - American Chemical Society
CY - Washington, DC, USA
AN - OPUS4-25457
LA - deu
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Köppen, Robert
A1 - Riedel, Juliane
A1 - Emmerling, Franziska
A1 - Koch, Matthias
T1 - (3S,11Z)-14,16-dihydroxy-3-methyl-3,4,5,6,9,10-hexahydro-1H-2-benz-oxacyclotetradecine-1,7(8H)-dione (cis-zearalenone): a redetermination
N2 - The title compound, also known as cis-zearalenone (cis-ZEN), C18H22O5, has already been reported elsewhere [Griffin et al. (1981). ACA Ser. 29, 35], but no atomic coordinates are publicly available. The molecule is of interest with respect to its toxicity. In the crystal, intramolecular O—H···O hydrogen bonds stabilize the molecular conformation, while intermolecular O—H···O hydrogen bonds link the molecules to form infinite chains along the [110] and [1¯10] directions. The absolute configuration has been assigned by reference to an unchanging chiral centre in the synthetic procedure.
PY - 2012
U6 - https://doi.org/10.1107/S1600536812002735
SN - 1600-5368
VL - 68
IS - 3
SP - o832, sup1
EP - sup8
PB - Munksgaard
CY - Copenhagen
AN - OPUS4-25546
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Köppen, Robert
A1 - Emmerling, Franziska
A1 - Koch, Matthias
T1 - rac-1-(2-aminocarbonyl-2-bromoethyl)-pyridinium bromide
N2 - In the crystal structure of the title compound, C8H10BrN2O+·-Br–, intermolecular N—H···Br hydrogen bonds link the molecules into infinite chains along [001]. The inclined angle between the pyridine ring plane and the plane defined by the acid amide group is 63.97 (4)°.
PY - 2012
U6 - https://doi.org/10.1107/S1600536812019721
SN - 1600-5368
VL - 68
IS - 6
SP - o1666, sup1
EP - sup5
PB - Munksgaard
CY - Copenhagen
AN - OPUS4-25894
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Schlegel, Moritz-Caspar
A1 - Wenzel, Klaus-Jürgen
A1 - Sarfraz, Adnan
A1 - Panne, Ulrich
A1 - Emmerling, Franziska
T1 - A wall-free climate unit for acoustic levitators
N2 - Acoustic levitation represents the physical background of trapping a sample in a standing acoustic wave with no contact to the wave generating device. For the last three decades, sample holders based on this effect have been commonly used for contact free handling of samples coupled with a number of analytical techniques. In this study, a wall-free climate unit is presented, which allows the control of the environmental conditions of suspended samples. The insulation is based on a continuous cold/hot gas flow around the sample and thus does not require any additional isolation material. This provides a direct access to the levitated sample and circumvents any influence of the climate unit material to the running analyses.
KW - Acoustic levition
PY - 2012
U6 - https://doi.org/10.1063/1.4705968
SN - 0034-6748
SN - 1089-7623
VL - 83
IS - 5
SP - 055101-1 - 055101-3
PB - American Institute of Physics
CY - Melville, NY
AN - OPUS4-25881
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Schlegel, Moritz-Caspar
A1 - Sarfraz, Adnan
A1 - Müller, Urs
A1 - Panne, Ulrich
A1 - Emmerling, Franziska
T1 - Erste Sekunden im Leben eines Bauwerks - In-situ-Synchrotron-Röntgenbeugungsuntersuchungen der Zementhydratation mit Millisekunden-Auflösung
N2 - Höchst dynamische Hydratationsprozesse in den ersten Sekunden bei der Entstehung eines Bauwerkes lassen sich mithilfe von Synchrotron-Röntgenbeugung mit einer sehr hohen Zeitauflösung nachverfolgen. Der Schwerpunkt lag dabei auf der Beeinflussung der Bildung erster kristalliner Hydratationsprodukte während des Frühstadiums der Zementhydratation.
KW - SyXRD
KW - High resolution
KW - In-situ
KW - Colloidal suspension
KW - Cement hydration
KW - In-situ-Analyse
KW - Kolloidale Suspensionen
KW - Röntgenbeugung
KW - Zementhydratation
PY - 2012
U6 - https://doi.org/10.1002/ange.201200993
SN - 0044-8249
SN - 0932-2140
SN - 1521-3757
VL - 124
IS - 20
SP - 5078
EP - 5081
PB - Wiley-VCH
CY - Weinheim
AN - OPUS4-26284
LA - deu
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Gorelik, T.E.
A1 - Sarfraz, Adnan
A1 - Kolb, U.
A1 - Emmerling, Franziska
A1 - Rademann, Klaus
T1 - Detecting crystalline nonequilibrium phases on the nanometer scale
N2 - The use of Automated electron Diffraction Tomography (ADT) is presented as a novel approach for crystallization studies at the nanometer scale for nonequilibrium phases. Here, ADT was applied to elucidate the structural identity of the recently reported hexagonal morphology of caffeine crystals, which grow only on specific surfaces. Caffeine was crystallized from solution on a specially treated TEM carbon grid. The analysis of ADT data revealed that the lattice parameters of these hexagons match those of the high temperature α-form of caffeine. Furthermore, it was observed that in this hexagonal morphology, the α-form remained stable for a prolonged period of time. The stabilization of hexagons can be interpreted in terms of enhanced interactions with the supporting surfaces.
KW - Electron diffraction
KW - Polymorphism caffeine
KW - ADT
PY - 2012
U6 - https://doi.org/10.1021/cg300377j
SN - 1528-7483
VL - 12
IS - 6
SP - 3239
EP - 3242
PB - American Chemical Society
CY - Washington, DC, USA
AN - OPUS4-26285
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Heiden, Sebastian
A1 - Batzdorf, Lisa
A1 - Wenzel, Klaus-Jürgen
A1 - Emmerling, Franziska
T1 - Mechanochemical synthesis and structural characterisation of a theophylline-benzoic acid cocrystal (1:1)
N2 - The structure of a mechanochemically synthesised cocrystal containing theophylline (TP) and benzoic acid (BA) has been determined from powder X-ray diffraction data.
PY - 2012
U6 - https://doi.org/10.1039/c2ce25236h
SN - 1466-8033
N1 - Geburtsname von Batzdorf, Lisa: Tröbs, L. - Birth name of Batzdorf, Lisa: Tröbs, L.
VL - 14
IS - 16
SP - 5128
EP - 5129
CY - London, UK
AN - OPUS4-26286
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Schlegel, Moritz-Caspar
A1 - Sarfraz, Adnan
A1 - Müller, Urs
A1 - Panne, Ulrich
A1 - Emmerling, Franziska
T1 - First seconds in a building's life - In situ synchrotron X-ray diffraction study of cement hydration on the millisecond timescale
N2 - Setting cement: Highly dynamic hydration processes that occur during the first seconds of cement hydration were studied by time-resolved synchrotron X-ray diffraction. Polycarboxylate ether additives were found to influence the formation of the initial crystalline hydration products on a molecular level.
KW - Cement hydration
KW - Colloidal suspensions
KW - In situ analysis
KW - X-ray diffraction
KW - SyXRD
KW - High resolution
KW - In-situ
PY - 2012
U6 - https://doi.org/10.1002/anie.201200993
SN - 1433-7851
SN - 1521-3773
SN - 0570-0833
VL - 51
IS - 20
SP - 4993
EP - 4996
PB - Wiley-VCH
CY - Weinheim
AN - OPUS4-26287
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Ortel, Erik
A1 - Fischer, A.
A1 - Chuenchom, L.
A1 - Polte, Jörg
A1 - Emmerling, Franziska
A1 - Smarsly, B.M.
A1 - Kraehnert, R.
T1 - New triblock copolymer templates, PEO-PB-PEO, for the synthesis of titania films with controlles mesopore size, wall thickness, and bimodal porosity
N2 - The synthesis and properties of a series of new structure-directing triblock copolymers with PEO-PB-PEO structure (PEO = poly(ethylene oxide) and PB = polybutadiene) and their application as superior pore-templates for the preparation of mesoporous titania coatings are reported. Starting from either TiCl4 or from preformed TiO2 nanocrystalline building blocks, mesoporous crystalline titanium oxide films with a significant degree of mesoscopic ordered pores are derived, and the pore size can be controlled by the molecular mass of the template polymer. Moreover, the triblock copolymers form stable micelles already at very low concentration, i.e., prior to solvent evaporation during the evaporation-induced self-assembly process (EISA). Consequently, the thickness of pore walls can be controlled independently of pore size by changing the polymer-to-precursor ratio. Thus, unprecedented control of wall thickness in the structure of mesoporous oxide coatings is achieved. In addition, the micelle formation of the new template polymers is sufficiently distinct from that of typical commercial PPO-PEO-PPO polymers (Pluronics; PPO = poly(propylene oxide)), so that a combination of both polymers facilitates bimodal porosity via dual micelle templating.
KW - Mesoporous materials
KW - Titanium oxide films
KW - Anatase nanoparticles
KW - PEO-PB-PEO
KW - Dual templating
PY - 2012
U6 - https://doi.org/10.1002/smll.201101520
SN - 1613-6810
SN - 1613-6829
VL - 8
IS - 2
SP - 298
EP - 309
PB - Wiley-VCH Verl.
CY - Weinheim
AN - OPUS4-26277
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Som, T.
A1 - Simo, A.
A1 - Fenger, R.
A1 - Troppenz, G.V.
A1 - Bansen, R.
A1 - Pfänder, N.
A1 - Emmerling, Franziska
A1 - Rappich, J.
A1 - Boeck, T.
A1 - Rademann, K.
T1 - Bismuth hexagons: facile mass synthesis, stability and applications
N2 - A unique direct electrodeposition technique involving very high current densities, high voltages and high electrolyte concentrations is applied for highly selective mass synthesis of stable, isolable, surfactant-free, single-crystalline Bi hexagons on a Cu wire at room temperature. A formation mechanism of the hexagons is proposed. The morphology, phase purity, and crystallinity of the material are well characterized by FESEM, AFM, TEM, SAED, EDX, XRD, and Raman spectroscopy. The thermal stability of the material under intense electron beam and intense laser light irradiation is studied. The chemical stability of elemental Bi in nitric acid shows different dissolution rates for different morphologies. This effect enables a second way for the selective fabrication of Bi hexagons. Bi hexagons can be oxidized exclusively to α-Bi2O3 hexagons. The Bi hexagons are found to be promising for thermoelectric applications. They are also catalytically active, inducing the reduction of 4-nitrophenol to 4-aminophenol. This electrodeposition methodology has also been demonstrated to be applicable for synthesis of bismuth-based bimetallic hybrid composites for advanced applications.
KW - Bismuth
KW - Hexagons
KW - Dendrites
KW - Single-crystal
KW - Thermoelectric applications
KW - Catalytic applications
PY - 2012
U6 - https://doi.org/10.1002/cphc.201101009
SN - 1439-4235
VL - 13
IS - 8
SP - 2162
EP - 2169
PB - Wiley-VCH
CY - Weinheim
AN - OPUS4-26278
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Emmerling, Franziska
A1 - Kraus, Werner
A1 - Noll, B.
A1 - Noll, S.
A1 - Pietzsch, H.-J.
T1 - Two mononuclear Tc complexes: [2,2'-(3-phenylpropylimino)- and [2,2'-(propylimino)bis(ethanethiolato)](4-methoxybenzenethiolato)-oxidotechnate(V)
PY - 2007
U6 - https://doi.org/10.1107/S0108270107052870
SN - 0108-2701
SN - 1600-5759
VL - 63
IS - 12
SP - m579
EP - m582
PB - Blackwell Publ.
CY - Oxford
AN - OPUS4-16283
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Peplinski, Burkhard
A1 - Adamczyk, Burkart
A1 - Kley, Gerd
A1 - Adam, Karin
A1 - Emmerling, Franziska
A1 - Simon, Franz-Georg
T1 - New horizons of the structural characterization of stainless steel slags by X-ray powder diffraction
KW - AOD slag
KW - Metal recovery
KW - Metallurgy
KW - Rietveld method
KW - Slags
KW - Stainless steel slags
KW - Quantitative phase analysis (QPA)
PY - 2007
SN - 0930-486X
VL - 26
SP - 61
EP - 66
PB - Oldenbourg
CY - München
AN - OPUS4-16666
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Emmerling, Franziska
A1 - Wolf, S. E.
A1 - Leiterer, Jork
A1 - Kappl, M.
A1 - Tremel, W.
T1 - New insight into the crystallization process of calcium carbonate by a contact-free in situ scattering technique using a levitating drop method
T2 - 14. Vortragstagung Gesellschaft Deutscher Chemiker
CY - Bayreuth, Germany
DA - 2008-09-24
PY - 2008
AN - OPUS4-17954
LA - deu
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Orgzall, I.
A1 - Emmerling, Franziska
A1 - Schulz, B.
A1 - Franco, O.
T1 - High-pressure studies on molecular crystals - relations between structure and high-pressure behavior
N2 - This paper summarizes attempts to understand structureproperty relationships for a large class of aromatic diphenyl-1,3,4-oxadiazole molecules. Starting from the investigation of the crystal structure several common packing motifs as well as characteristic differences are derived. Many different molecules show a rather planar conformation in the solid state. A stronger intermolecular twist is only observed for compounds with substituents occupying the ortho-positions of the phenyl rings. Most crystal structures are characterized by the formation of stacks leading to intense ππ acceptordonor interactions between oxadiazole and phenyl rings. High-pressure investigations result in a soft compression behavior typical for organic molecular crystals. The bulk behavior may be described by the Murnaghan equation of state with similar coefficients (bulk modulus and its pressure derivative) for nearly all investigated compounds but also for related substances. The compression shows a strong anisotropy resulting from the specific features and packing motifs of the crystal structure. This is clearly indicated by a corresponding strain analysis. Additionally to the crystal structure the Raman spectrum was also investigated under increasing pressure. The different pressure behavior of external and internal modes reflects the difference between intra- and intermolecular interactions.
KW - Diphenyl-1,3,4-oxadiazole
KW - Crystal structure
KW - High pressure investigations
KW - Equation of state
KW - Strain analysis
KW - Raman investigations
PY - 2008
U6 - https://doi.org/10.1088/0953-8984/20/29/295206
SN - 0953-8984
SN - 1361-648X
VL - 20
SP - 295206-1 - 295206-15
PB - IOP Publ. Ltd.
CY - Bristol
AN - OPUS4-17784
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Köppen, Robert
A1 - Emmerling, Franziska
A1 - Kohl, Anka
A1 - Becker, Roland
T1 - Delta-Hexabromocyclododecane
N2 - (1R,2S,5R,6S,9S,10R)-Hexabromocyclododecane (C12H18Br6, d-HBCD) was crystallized from acetonitrile. The CBr distances range from 1.962 (8) to 1.982 (8) Å and intermolecular Br...Br contacts contribute to the formation of layers.
PY - 2007
U6 - https://doi.org/10.1107/S1600536807026396
SN - 1600-5368
VL - 63
IS - 7
SP - o3105
PB - Munksgaard
CY - Copenhagen
AN - OPUS4-15048
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Paris, O.
A1 - Li, C.
A1 - Siegel, S.
A1 - Weseloh, G.
A1 - Emmerling, Franziska
A1 - Riesemeier, Heinrich
A1 - Erko, A.
A1 - Fratzl, P.
T1 - A new experimental station for simultaneous X-ray microbeam scanning for small- and wide-angle scattering and fluorescence at BESSY II
N2 - A new instrument for simultaneous microbeam small- and wide-angle X-ray scattering and X-ray fluorescence (SAXS/WAXS/XRF) is presented. The instrument is installed at the microfocus beamline at BESSY II and provides a beam of 10 µm size with a flux of about 109 photons s-1. A SAXS resolution up to 500 Å d-spacing and a range of scattering vectors of almost three orders of magnitude are reached by using a large-area high-resolution CCD-based detector for simultaneous SAXS/WAXS. The instrument is particularly suited for scanning SAXS/WAXS/XRF experiments on hierarchically structured biological tissues. The necessary infrastructure, such as a cryo-stream facility and an on-site preparation laboratory for biological specimens, are available.
KW - Scanning SAXS
KW - Scanning WAXS
KW - Microbeam
KW - Synchrotron radiation
PY - 2007
SN - 0021-8898
SN - 1600-5767
VL - 40
IS - Supplement
SP - s466
EP - s470
PB - Blackwell
CY - Oxford
AN - OPUS4-15049
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Carvalho, José Joao
A1 - Emmerling, Franziska
A1 - Schneider, Rudolf
T1 - 7-(5-Carboxypentyl)-1,3-dimethylxanthine monohydrate
N2 - The title compound [systematic name: 6-(1,3-dimethyl-2,6-dioxo-2,3,6,7-tetrahydro-1H-purin-7-yl)hexanoic acid monohydrate, CAS 61444-23-3], C13H18N4O4·H2O, was synthesized and crystallized from ethyl acetate. Hydrogen bonds between xanthine and water molecules contribute to the formation of layers parallel to (10).
KW - Kristallstruktur
KW - Koffein
KW - Antikörperentwicklung
KW - Biokonjugate
PY - 2007
U6 - https://doi.org/10.1107/S1600536807037257
SN - 1600-5368
VL - 63
IS - 9
SP - o3718
PB - Munksgaard
CY - Copenhagen
AN - OPUS4-15731
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Kraus, Werner
A1 - Emmerling, Franziska
A1 - Noll, B.
A1 - Noll, S.
A1 - Pietzsch, H.-J.
T1 - (4-Methoxybenzenethiolato-kS)oxido[2,2'-(propylimino)bis-(ethanethiolato)-k3S,N,S']rhenium(V)
N2 - The central Re atom of the mononuclear title complex, [Re(C8H18NS2)(C6H4OS)O], is five-coordinate (ReNOS3) with a square-pyramidal geometry comprising a tridentate 2,2'-(propylimino)diethanethiolate ligand, a 4-methoxybenzenethiolate ligand and a doubly-bonded O atom.
PY - 2007
U6 - https://doi.org/10.1107/S1600536807056814
SN - 1600-5368
VL - 63
IS - 12
SP - m3018
PB - Munksgaard
CY - Copenhagen
AN - OPUS4-16196
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Emmerling, Franziska
A1 - Reck, Günter
A1 - Kraus, Werner
A1 - Orgzall, I.
A1 - Schulz, B.
T1 - Structure determination of two asymmetrically substituted oxadiazoles from powder diffraction data
N2 - The crystal structures of the 1,3,4 oxadiazole compounds N,N-dimethyl-N-[4-(1,3,4-oxadiazol-2-yl)phenyl]amine (1) and 2-methyl-5-phenyl-1,3,4-oxadiazole (2) have been determined. In case of 1 no adequate crystals were available; therefore the structure was solved at room temperature from X-ray powder diffraction data using the method of simulated annealing. This solution is compared to a second one obtained by applying the molecular replacement method. Subsequent Rietveld refinements combined with the so called two stage method based on the data collected to 1.6 Å resolution yielded an Rwp value of 7.27% for 1. Compound 1 crystallizes in the orthorhombic space group P212121 with lattice parameters of a = 7.599(4) Å, b = 6.004(2) Å, c = 21.736(3) Å. The crystal structure of 2 was solved by means of single crystal structure analysis (monoclinic space group P21/c, a = 8.010(3) Å, b = 10.783(4) Å, c = 19.234(7) Å, β = 90.794(9)°).
KW - Crystal structure
KW - Oxadiazoles
KW - Powder diffraction X-ray investigations
KW - Structure determination
PY - 2008
U6 - https://doi.org/10.1002/crat.200711053
SN - 0023-4753
SN - 1521-4079
SN - 0232-1300
VL - 43
IS - 1
SP - 99
EP - 107
PB - Wiley-VCH Verlag GmbH & Co. KGaA
CY - Weinheim
AN - OPUS4-16582
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Emmerling, Franziska
A1 - Bricks, J. L.
A1 - Resch-Genger, Ute
A1 - Kraus, Werner
A1 - Schulz, Burkhard
A1 - Li, Yanqin
A1 - Reck, Günter
T1 - Influence of the donor substituent and acceptor alkylation on the structure-analytical properties of mono- and bifunctional biphenyl-type fluorescent reporters
N2 - A systematic structural investigation of R-phenyl-substituted 2,2':6',2"-terpyridines, a family of mono- and bifunctional charge transfer (CT)-operated fluorescent reporters for protons and metal ions, is presented. These molecules are equipped with non-binding and analyte coordinating donor substituents R (R = CF3, H, OMe, OH, DMA, A15C5 equaling monoaza-15-crown-5) of various donor strength and display CT-controlled spectroscopic properties and communication of analytereceptor interactions. The crystal structures of the neutral fluorescent probes are compared to the structures of their terpyridine-alkylated or -protonated counterparts that represent model systems for acceptor protonation or cation coordination. The aim is here a better understanding of the complexation-induced structural and spectroscopic changes and the identification of common packing motifs of bpb-R thereby taking into account the importance of terpyridine building blocks for the construction of supramolecular systems and coordination arrays revealing ππ interactions.
KW - Biphenyl
KW - Terpyridine
KW - Crystal structure
KW - Fluorescent probe
KW - Charge transfer
KW - Bifunctional
PY - 2008
U6 - https://doi.org/10.1016/j.molstruc.2007.03.025
SN - 0022-2860
SN - 1872-8014
SN - 0377-046X
VL - 874
IS - 1-3
SP - 14
EP - 27
PB - Elsevier
CY - Amsterdam
AN - OPUS4-17087
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Emmerling, Franziska
A1 - Bélombé, Michel M.
A1 - Nenwa, Justin
A1 - Bebga, Gouet
T1 - Kristallstruktur von Tris(oxamiddioxim-k2N,N')nickel(II) L(+)-Tartrat, [Ni(H2oxado)3][L(+)-(C4H406)]
T2 - DGK- Jahrestagung in Bremen 2007
CY - Bremen, Germany
DA - 2007-03-05
PY - 2007
AN - OPUS4-14280
LA - deu
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Köppen, Robert
A1 - Emmerling, Franziska
A1 - Becker, Roland
T1 - Decabromodiphenylethane
N2 - Decabromodiphenylethane [systematic name: 1,1'-ethane-1,2-diylbis(pentabromobenzene)], C14H4Br10 (DBDPE), was crystallized from toluene. The molecule shows crystallographic inversion symmetry. The CBr distances are in the range 1.873 (7)1.891 (6) Å; intermolecular BrBr contacts contribute to the formation of ribbons.
KW - Single-crystal X-ray study
KW - T = 273 K
KW - R factor = 0.043
KW - wR factor = 0.121
KW - Data-to-parameter ratio = 20.4
PY - 2007
U6 - https://doi.org/10.1107/S1600536807000219
SN - 1600-5368
VL - 63
IS - 2
SP - o585
EP - o586
PB - Munksgaard
CY - Copenhagen
AN - OPUS4-14565
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Köppen, Robert
A1 - Becker, Roland
A1 - Emmerling, Franziska
A1 - Jung, Christian
A1 - Nehls, Irene
T1 - HBCD enantiomers: absolute configurations and thermal rearrangement
T2 - Organohalogen Compounds
PY - 2006
UR - http://www.dioxin20xx.org/pdfs/2006/06-466.pdf
VL - 68
SP - 1991
EP - 1994
PB - Norwegian Institute of Public Health
AN - OPUS4-14540
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Emmerling, Franziska
A1 - Orgzall, I.
A1 - Dietzel, B.
A1 - Schulz, Burkhard
A1 - Reck, Günter
A1 - Schulz, B.
T1 - Structural studies on trifluoromethyl substituted 2,5-diphenyl-1,3,4-oxadiazoles
N2 - Three new compounds have been synthesized based on the molecular motif 2-[2,6-bis(trifluoromethyl)phenyl]-5-phenyl-1,3,4-oxadiazole, with subsequent CF3-substitution in the ortho-positions of the phenylene ring. The crystal structures of the compounds have been determined by single crystal X-ray diffraction. All compounds have a monoclinic structure. The solid state structure of the compounds is influenced by the electronic properties of the fluorine atoms, leading to the occurrence of CH...F, and CF...ϖ interactions, partly replacing ϖϖ interactions usually observed in the crystal structures of 2,5-diphenyl-1,3,4-oxadiazole derivatives. Other significant interactions than those involving fluorine appear only in rare cases. The strong impact of the fluorine atoms on the intra- and intermolecular interactions, and the molecular conformation lead to novel inputs for the understanding of molecular recognition, supramolecular assembly, and crystal packing of fluorine containing compounds.
KW - Crystal structure
KW - 1,3,4-oxadiazole
KW - Molecular conformation
KW - Weak interactions
PY - 2007
SN - 0022-2860
SN - 1872-8014
SN - 0377-046X
VL - 832
IS - 1-3
SP - 124
EP - 131
PB - Elsevier
CY - Amsterdam
AN - OPUS4-14644
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Emmerling, Franziska
A1 - Engelhardt, S. C.
A1 - Frisch, G.
A1 - Röhr, C.
T1 - Alkalimetalloxoferrate AFeO2 Strukturchemie und Mößbauerspektroskopie
T2 - DGK Jahrestagung
CY - Berlin, Germany
DA - 2007-03-05
PY - 2007
AN - OPUS4-14656
LA - deu
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Köppen, Robert
A1 - Becker, Roland
A1 - Emmerling, Franziska
A1 - Jung, Christian
A1 - Nehls, Irene
T1 - Enantioselective Preparative HPLC Separation of the HBCD-Stereoisomers from the Technical Product and Their Absolute Structure Elucidation Using X-Ray Crystallography
N2 - 1,2,5,6,9,10-Hexabromocyclododecane (HBCD) is a widely used flame retardant, which tends to persist in the environment and accumulates in biota. The six stereoisomers (three racemates named α-, β-, and γ-HBCD) of the technical mixture were isolated with high-performance liquid chromatography (HPLC). Direct separations were performed on a chiral stationary phase containing permethylated -cyclodextrin (NUCLEODEX -PM column) and the pure enantiomers of α-, β-, and γ-HBCD were physically characterized for the first time. The absolute configurations of all six isomers were determined by anomalous dispersion using single crystal X-ray crystallography. Optical rotations αD in tetrahydrofuran were +4.2/-4.0 (α-HBCD), +26.1/-27.5 (β-HBCD), and +68.0/-66.3 (γ-HBCD). The sense of rotation could be correlated with the absolute configurations of α-, β-, and γ-HBCD enantiomers and their order of elution on a chiral permethylated β-cyclodextrin-bonded stationary phase. The diastereomers α-, β-, and γ-HBCD displayed distinctly different melting points as well as 1H-, 13C NMR, and IR spectra.
KW - Brominated flame retardant
KW - Chiral separation
KW - Anomalous dispersion
KW - Crystal structures
KW - Optical rotation
KW - Absolute configuration
PY - 2007
U6 - https://doi.org/10.1002/chir.20366
SN - 0899-0042
SN - 1520-636X
VL - 19
IS - 3
SP - 214
EP - 222
PB - Wiley-Liss
CY - New York, NY
AN - OPUS4-14718
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Wu, D.
A1 - Descalzo López, Ana Belén
A1 - Weik, F.
A1 - Emmerling, Franziska
A1 - Shen, Z.
A1 - You, X.-Z.
A1 - Rurack, Knut
T1 - Ein kernmodifiziertes Rubyrin mit meso-Aryl-Subsituenten und Phenanthren-anellierten Pyrrolringen als hoch konjugierter NIR-Farbstoff und Hg2+-Sonde
KW - Fluoreszenz
KW - NIR-Farbstoffe
KW - Porphyrinoide
KW - Quecksilber
KW - Sensoren
PY - 2008
U6 - https://doi.org/10.1002/ange.200702854
SN - 0044-8249
SN - 0932-2140
SN - 1521-3757
VL - 120
IS - 1
SP - 199
EP - 203
PB - Wiley-VCH
CY - Weinheim
AN - OPUS4-16447
LA - deu
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Wu, D.
A1 - Descalzo López, Ana Belén
A1 - Weik, F.
A1 - Emmerling, Franziska
A1 - Shen, Z.
A1 - You, X.-Z.
A1 - Rurack, Knut
T1 - A core-modified Rubyrin with meso-aryl substituents and phenanthrene-fused pyrrole rings: a highly conjugated near-infrared dye and Hg2+ probe
KW - Fluorescence
KW - Mercury
KW - NIR dyes
KW - Porphyrinoids
KW - Sensors
PY - 2008
U6 - https://doi.org/10.1002/Anie.200702854
SN - 1433-7851
SN - 1521-3773
SN - 0570-0833
VL - 47
IS - 1
SP - 193
EP - 197
PB - Wiley-VCH
CY - Weinheim
AN - OPUS4-16448
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Hennig, C.
A1 - Kraus, Werner
A1 - Emmerling, Franziska
A1 - Ikeda, A.
A1 - Scheinost, A.C.
T1 - Coordination of a Uranium(IV) Sulfate Monomer in an Aqueous Solution and in the Solid State
N2 - Uranium(IV) sulfate in an aqueous solution and the solid state has been investigated with extended X-ray absorption fine structure (EXAFS) and X-ray diffraction (XRD). The coordination polyhedron comprises monodentate sulfate, bidentate sulfate, and water molecules. The coordination modes of sulfate in solution have been determined from the U-S distances with EXAFS. The U-S distance of 3.67 ± 0.02 Å indicates monodentate sulfate, and the U-S distance of 3.08 ± 0.02 Å indicates bidentate coordination. The obtained sulfur coordination numbers of a solution with a [SO42-]/[U4+] ratio of 40 suggest species with compositions of [U(SO4,bid)2(SO4,mon)2·nH2O]4- and [U(SO4,bid)3 (SO4,mon)2·mH2O]6-. Charge-compensating countercations or ion pairing with Na+ and NH4+ could not be detected with EXAFS. One of the solution species, [U(SO4)5H2O]6-, has been conserved in a crystal. The corresponding crystal structure of Na1.5(NH4)4.5[U(SO4)5·H2O]·H2O [space group P1, a = 9.4995(16) Å, b = 9.8903(16) Å, c = 12.744(2) Å, α = 93.669(2)°, β = 103.846(2)°, γ = 109.339(2)°] has been determined by single-crystal XRD. Two monomeric uranium(IV) sulfate complexes and three sodium units are linked in alternating rows and form a one-dimensoinal ribbon structure parallel to the a axis.
PY - 2008
U6 - https://doi.org/10.1021/ic701880h
SN - 0020-1669
SN - 1520-510X
VL - 47
IS - 5
SP - 1634
EP - 1638
PB - American Chemical Society
CY - Washington, DC
AN - OPUS4-17714
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Thünemann, Andreas
A1 - Kegel, Jenny
A1 - Polte, Jörg
A1 - Emmerling, Franziska
T1 - Superparamagnetic Maghemite Nanorods: Analysis by Coupling Field-Flow Fractionation and Small-Angle X-ray Scattering
N2 - We report on the online coupling of asymmetrical flow field-flow fractionation (A4F) with small-angle X-ray scattering (SAXS) for the detection of nanoparticles. The A4F was used to fractionate superparamagnetic maghemite nanoparticles, which were prepared continuously with a micromixer. The outlet of the A4F was directly coupled to a flow capillary of a SAXSess instrument (Kratky type of camera). SAXS curves were recorded in a 1 s time interval. This was possible by using intense synchrotron radiation. The radii of gyration of the nanoparticles, as determined from Guinier plots, increased from 2 to 6 nm with increasing fractionation time of the A4F. A more detailed analysis of the scattering curves revealed that the particles were cylindrical in shape (nanorods), which we attributed to the micromixing preparation technique. The radii of the nanorods increased only slightly from 1.2 to 1.7 nm with increasing fractionation time, while the lengths increased strongly from 7.0 to 30.0 nm. The volume distribution of the nanorods was determined and described by Schultz-Zimm and log-normal distributions. Nanorod volumes increased from 45 to 263 nm³, corresponding to molar masses of 140 × 10³ to 820 × 10³ g mol-1. We propose A4F-SAXS coupling as a new method for analysis of nanoparticles of complex composition in solution. It allows precise online determination of the particles shape and size distributions. This method can be applied to mixtures of nanoparticles of arbitrary shapes and sizes (1-100 nm). Moreover, the total time needed for fractionation and online SAXS data recording is usually only 20 min.
PY - 2008
U6 - https://doi.org/10.1021/ac8004814
SN - 0003-2700
SN - 1520-6882
VL - 80
IS - 15
SP - 5905
EP - 5911
PB - American Chemical Society
CY - Washington, DC
AN - OPUS4-17813
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Leiterer, Jork
A1 - Emmerling, Franziska
A1 - Panne, Ulrich
A1 - Christen, W.
A1 - Rademann, K.
T1 - Tracing Coffee Tabletop Traces
N2 - Crystallization processes under different conditions are of fundamental interest in chemistry, pharmacy, and medicine. Therefore, we have studied the formation of micro- and nanosized crystals using water-caffeine (1,3,7-trimethyl-1H-purine-2,6(3H,7H)-dione) solutions under ambient conditions as a relevant model system. When droplets of an aqueous caffeine solution evaporate and eventually dry on surfaces (glass, polystyrene, and polyester), stable coffee tabletop rings with a perimeter of typically 3 mm are formed after 20 to 50 min. Using a micro focus X-ray beam available at the BESSY µSpot-beamline, the fine structure of different caffeine needles can be distinguished. Unexpectedly, both crystal modifications (α- and β-caffeine) are present, but locally separated in these rings. Furthermore, AFM studies reveal the presence of even smaller particles on a nanometer length scale. To eliminate influences of surface irregularities from the crystallization process, acoustic levitation of liquid samples was employed. Such levitated droplets are trapped in a stable position and only surrounded by air. The solvent in an ultrasonically levitated drop evaporates completely, and the resulting crystallization of caffeine was followed in situ by synchrotron X-ray diffraction. In this case, the diffraction pattern is in accordance with pure α-caffeine and does not indicate the formation of the room temperature polymorph β-caffeine. Hence, our investigations open new vistas that may lead to a controlled formation of cocrystals and novel polymorphs of micro- and nanocrystalline materials, which are of relevance for fundamental studies as well as for pharmaceutical and medical applications.
KW - Polymorphism
KW - Crystallization
KW - Acoustic levitation
KW - Evaporation of droplets
KW - µSpot
KW - Micro spot
KW - Synchrotron radiation
PY - 2008
U6 - https://doi.org/10.1021/la800768v
SN - 0743-7463
SN - 1520-5827
VL - 24
IS - 15
SP - 7970
EP - 7978
PB - American Chemical Society
CY - Washington, DC
AN - OPUS4-17818
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Emmerling, Franziska
A1 - Bentrup, U.
A1 - Radnik, J.
A1 - Martin, A.
A1 - Brückner, A.
A1 - Leiterer, Jork
A1 - Armbruster, U.
T1 - Monitoring von Katalysatorsynthesen mittels simultaner WAXS/SAXS/Raman- und ATR/UV-vis/Raman-Spektroskopie
T2 - ProcessNet-Jahrestagung 2008
CY - Karlsruhe, Germany
DA - 2008-10-07
PY - 2008
AN - OPUS4-17835
LA - deu
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Emmerling, Franziska
A1 - Leiterer, Jork
A1 - Wolf, S. E.
A1 - Tremel, W.
T1 - Contact-free formation of calcium carbonate in a levitated drop: a WAXS / TEM study.
T2 - Jahrestagung der Deutschen Gesellschaft für Kristallographie
CY - Erlangen, Germany
DA - 2008-03-03
PY - 2008
AN - OPUS4-17837
LA - deu
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Díez, I.
A1 - Emmerling, Franziska
A1 - Malz, Frank
A1 - Jäger, Christian
A1 - Schulz, B.
A1 - Orgzall, I.
T1 - Origin of templating processes in polypyrrole synthesis
N2 - The supermolecular mechanism of the template-mediated oxidative polymerization of pyrrole is investigated in detail. It is shown for the first time that 2,5-bis(pyrrol-2-yl)pyrrolidyl complexes with aromatic sulfonic acids such as %#946;-naphtalenesulfonic acid or para-toluenesulfonic acid are formed in the early polymerization step. The crystalline acidbase complexes are isolated and their crystal structures are analyzed. A 2,5-bis(pyrrol-2-yl)pyrrolidyl cation is common to both complexes and forms an inner salt with the sulfonic acid anion. As concluded from NMR investigations the synthesis using sulfonic acids results in a high stereo selectivity with respect to the trans conformation of the pyrrolidyl ring compared with the classical synthesis routine of this compound using hydrochloric acid. The needle-like crystals of the complexes act as hard templates during the next step of the polymerization and result in tubular morphologies of the polypyrrole.
KW - Polypyrrole
KW - Pyrrole complex
PY - 2008
U6 - https://doi.org/10.1016/j.matchemphys.2008.05.057
SN - 0254-0584
VL - 112
IS - 1
SP - 154
EP - 161
PB - Elsevier
CY - Amsterdam
AN - OPUS4-17859
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Emmerling, Franziska
A1 - Becker, Roland
A1 - Reck, Günter
T1 - Mixed crystal of bis(µ2-N,N-di-n-butyldithiocarbamato-S,S,S')-bis(N,N-di-n-butyldithiocarbamato-S,S')-di-zinc(II) and bis(µ2-N,N-di-n-butyldithiopercarbamato-S,O,O')-bis(N,N-di-n-butyldithiocarbamato-S,S')-di-zinc(II)
N2 - The title compounds Zn2[S2CN(n-C4H9)2]4 1 and Zn2[(S(SO)CN(n-C4H9)2)(S2CN(n-C4H9)2)]2 3 build mixed crystals in the ratio 0.42: 0.58. Each compound forms dimers, in which the monomer moieties are related via a two-fold axis, coinciding with that of the monoclinic space group C2/c. The lattice parameters are a = 23.581(9), b = 17.112(5), c = 16.372(9) Å, and β = 128.33(3)°.
KW - Crystal structure
KW - Zinc
KW - Dithiocarbamate
KW - Dithiopercarbamate
PY - 2007
U6 - https://doi.org/10.1002/crat.200710956
SN - 0023-4753
SN - 1521-4079
SN - 0232-1300
VL - 42
IS - 10
SP - 1018
EP - 1023
PB - Wiley-VCH Verlag GmbH & Co. KGaA
CY - Weinheim
AN - OPUS4-17843
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Emmerling, Franziska
A1 - Radnik, J.
A1 - Schneider, M.
A1 - Bentrup, U.
A1 - Armbruster, U.
A1 - Brückner, A.
A1 - Leiterer, Jork
A1 - Martin, A.
T1 - New experimental setup for on-line monitoring of mixed oxide catalyst synthesis at the µ-Spot Beamline at BESSY II
T2 - 18th Users' Meeting at the ESRF
CY - Grenoble, France
DA - 2008-02-05
PY - 2008
AN - OPUS4-17849
LA - deu
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Gniazdowska, E.
A1 - Kraus, Werner
A1 - Emmerling, Franziska
A1 - Spies, H.
A1 - Stephan, H.
T1 - Tetrabutylammonium bis(2-amidobenzenethiolato-kappa2S,N)oxorhenate(V)
N2 - The structure of the title compound, (C16H36N)[Re(C6H5NS)2O], is isomorphous with the corresponding oxotechnetate(V) complex.
KW - Coordination chemistry
KW - Rhenium
KW - Organometallic
PY - 2006
U6 - https://doi.org/10.1107/S160053680601511X
SN - 1600-5368
VL - 62
IS - 6
SP - m1197
EP - m1199
PB - Munksgaard
CY - Copenhagen
AN - OPUS4-12345
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Emmerling, Franziska
A1 - Kraus, Werner
A1 - Iqbal, I.
A1 - Müller, C.
A1 - Röllich, A.
A1 - Stephan, H.
T1 - Polyoxotungstates as potent inhibitors for ecto-nucleotidases
T2 - 37th International Conference of Coordination Chemistry
CY - Cape Town, South Africa
DA - 2006-08-13
PY - 2006
AN - OPUS4-12401
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Emmerling, Franziska
A1 - Orgzall, I.
A1 - Schulz, B.
T1 - Structures of ligands for the construction of metal-organic compounds: substitudes di-aryl-1,3,4-oxadiazole derivatives with pyridyl- and aminophenyl-substitution
T2 - Tag der Chemie, Technical University Berlin
CY - Berlin, Germany
DA - 2006-06-26
PY - 2006
AN - OPUS4-12402
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Schlegel, Moritz-Caspar
A1 - Müller, Urs
A1 - Malaga, Katarina
A1 - Panne, Ulrich
A1 - Emmerling, Franziska
T1 - Spatially resolved investigation of complex multi-phase systems using muXRF, SEM-EDX and high resolution SyXRD
N2 - Spatially resolved analysis of complex multi-phase systems can be validated through different analytical methods. This study compares investigations by scanning electron microscopy coupled with energy dispersive X-ray fluorescence analysis and high resolution X-ray diffraction. The studied sulfate attacked cement paste containing fly ashes consists of different interacting crystalline and amorphous phases. The complementary methods revealed in detail changes in phase composition due to the chemical attack. The advantages and disadvantages of both methods are discussed and suggestions are given for combining them with additional methods to maximize the information content.
KW - EDX-SEM
KW - SyXRD
KW - Spatial investigations
KW - Comparison
KW - High resolution
KW - Cement paste
KW - Sulfate attack
KW - Damaging mechanism
PY - 2013
U6 - https://doi.org/10.1016/j.cemconcomp.2012.08.018
SN - 0958-9465
SN - 1873-393X
VL - 37
SP - 241
EP - 245
PB - Elsevier Ltd.
CY - Barking, Essex
AN - OPUS4-29111
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Eckhardt, B.
A1 - Ortel, Erik
A1 - Bernsmeier, D.
A1 - Polte, J.
A1 - Strasser, P.
A1 - Vainio, U.
A1 - Emmerling, Franziska
A1 - Kraehnert, R.
T1 - Micelle-templated oxides and carbonates of zinc, cobalt, and aluminium and a generalized strategy for their synthesis
N2 - Catalysis, energy storage, and light harvesting require functional materials with tailored porosity and nanostructure. However, common synthesis methods that employ polymer micelles as structure-directing agents fail for zinc oxide, for cobalt oxide, and for metal carbonates in general. We report the synthesis of the oxides and carbonates of zinc, cobalt, and aluminum with micelle-templated structure. The synthesis relies on poly(ethylene oxide)-block-poly(butadiene)-block-poly(ethylene oxide) triblock copolymers and a new type of precursor formed by chemical complexation of a metal nitrate with citric acid. A general synthesis mechanism is deduced. Mechanistic insights allow for the prediction of optimal processing conditions for different oxides and carbonates based on simple thermogravimetric analysis. Employing this synthesis, films of ZnO and Co3O4 with micelle-controlled mesoporosity become accessible for the first time. It is the only soft-templating method reported so far that also yields mesoporous metal carbonates. The developed synthesis is generic in nature and can be applied to many other metal oxides and carbonates.
KW - EISA
KW - Pore templating
KW - Metal oxide
KW - Metal carbonate
KW - Zinc oxide
KW - Cobalt oxide
PY - 2013
U6 - https://doi.org/10.1021/cm400535d
SN - 0897-4756
SN - 1520-5002
VL - 25
IS - 14
SP - 2749
EP - 2758
PB - American Chemical Society
CY - Washington, DC
AN - OPUS4-29113
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Eißler, A.
A1 - Kläring, P.
A1 - Emmerling, Franziska
A1 - Braun, T.
T1 - Alpha-dialdimine complexes of rhodium(I) and iridium(I): Their reactivity with dioxygen and dihydrogen
N2 - The rhodium(I) and iridium(I) complexes [M(Cl){ArN=C(H)C(H)=NAr}(CNtBu)] (1: M = Rh, Ar = 2,6-iPr2C6H3; 2: M = Rh, Ar = Mes; 3: M = Ir, Ar = Mes; Mes = 2,4,6-Me3C6H2) have been prepared by the reaction of [M(µ-Cl)(coe)2]2 (M = Rh, Ir; coe = cyclooctene) with the α-dialdimines ArN=C(H)C(H)=NAr (Ar = 2,6-iPr2C6H3, Mes) in thf, followed by the addition of CNtBu. XANES spectra and DFT calculations on 2 and 3 suggest an oxidation state +I at the metal centers. Treatment of the complexes 2 and 3 with O2 or 18O2 gave the peroxido complexes [M(Cl)(O2){MesN=C(H)C(H)=NMes}(CNtBu)] (4a: M = Rh; 5a: M = Ir) and [M(Cl)(18O2){MesN=C(H)C(H)=NMes}(CNtBu)] (4b: M = Rh; 5b: M = Ir). The reaction of 3 with dihydrogen resulted in the formation of the iridium dihydrido complex [Ir(Cl)(H)2{MesN=C(H)C(H)=NMes}(CNtBu)] (6a). Two isomeric α-imine-amine complexes [Ir(Cl)(H)2{MesN(H)CH2C(H)=NMe}(CNtBu)] (7/7') were obtained after prolonged reaction under H2. All of the complexes were characterized by NMR and IR spectroscopy. In addition, complexes 2, 3,and 7 were characterized by X-ray crystallography.
KW - Rhodium
KW - Iridium
KW - Aldimines
KW - Peroxido ligands
KW - Hydrido ligands
PY - 2013
U6 - https://doi.org/10.1002/ejic.201300625
SN - 1434-1948
SN - 1099-0682
VL - 2013
IS - 27
SP - 4775
EP - 4788
PB - Wiley-VCH Verl.
CY - Weinheim
AN - OPUS4-29094
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Scholz, G.
A1 - Emmerling, Franziska
A1 - Dreger, M.
A1 - Kemnitz, E.
T1 - Mechanochemical synthesis and characterization of hydrated and dehydrated crystalline strontium terephtalates
N2 - A successful mechanochemical synthesis of strontium terephthalate trihydrate is described for the first time. The dehydration of Sr(C8H4O4)·3H2O occurs at about 100 °C and results in a well-defined strontium terephtalate, Sr(C8H4O4), thermally stable up to 550 °C. Both compounds are not described so far in the literature. Their structures were solved by ab initio structure determination and subsequent Rietveld refinement of the powder diffraction data. Further methods like DTA-TG, MAS NMR and FT-IR spectroscopy, and BET measurements were used to characterize these compounds.
KW - Mechanochemical synthesis
KW - Ab initio structure determination
KW - MAS NMR spectroscopy
KW - Strontium
PY - 2013
U6 - https://doi.org/10.1002/zaac.201200550
SN - 0044-2313
SN - 1521-3749
SN - 0372-7874
SN - 0863-1786
SN - 0863-1778
VL - 639
IS - 5
SP - 689
EP - 693
PB - Wiley-VCH
CY - Weinheim
AN - OPUS4-29117
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Stößer, R.
A1 - Feist, M.
A1 - Willgeroth, Carola
A1 - Emmerling, Franziska
A1 - Menzel, Michael
A1 - Reuther, H.
T1 - The 'quiet Goldschmidt' - a mechanochemical, thermoanalytical, and spectroscopic study of selected steps of the aluminothermic reaction
N2 - The Goldschmidt reaction (2Al+α-Fe2O3) was investigated both under mechanical and thermal activation by employing a combination of analytical methods such as ESR and Mössbauer spectroscopy, magnetic susceptibility, X-ray powder diffraction, and thermal analysis (TA). Both the mechanical treatment and the TA runs under air caused the reaction conditions of 'quiet redox reactions' due to a retarding effect and enabled a reaction study in a 'slow motion mode'. This allowed to establish distinct partial steps of the integral reaction process depending on the intensity of the mechanical impact, the educt composition, the gas phase composition, and, finally, the thermal excitation in the TA runs. Particular attention was payed to the role of the gas phase and to the reaction of aluminum with differently activated oxygen species. The phlegmatizing effect was traced back to the formation of Al2O3 coverages of the Al particles.
KW - Thermite reaction
KW - Iron ESR and Mössbauer spectroscopy
KW - Mechanochemical activation
KW - Magnetic moments
KW - DTA-TG
KW - XRD
PY - 2013
U6 - https://doi.org/10.1016/j.jssc.2013.02.032
SN - 0022-4596
SN - 1095-726X
VL - 202
SP - 173
EP - 190
PB - Elsevier
CY - San Diego, Calif.
AN - OPUS4-29528
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Emmerling, Franziska
A1 - Kraus, Werner
A1 - Henning, C.
A1 - Scheinost, A.C.
A1 - Ikeda, A.
T1 - Coordination of U(IV) sulfate in aqueous solution of high ionic strength and in solid state
T2 - Jahrestagung der Deutschen Gesellschaft für Kristallographie
CY - Erlangen, Germany
DA - 2008-03-03
PY - 2008
AN - OPUS4-18726
LA - deu
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Emmerling, Franziska
A1 - Leiterer, Jork
A1 - Tremel, W.
A1 - Wolff, Stephan
T1 - Contact-free Formation of Calcium Carbonate in a Levitated Drop: a WAXS / TEM study
T2 - Jahrestagung der Deutschen Gesellschaft für Kristallographie
CY - Erlangen, Germany
DA - 2008-03-03
PY - 2008
AN - OPUS4-18729
LA - deu
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Bélombé, M.M.
A1 - Nenwa, J.
A1 - Emmerling, Franziska
T1 - Crystal structure of quinolinium trans-diaquabis(oxalato-O,O')-chromate(III), [C9H8N] [Cr(H2O)2(C2O4)2]
PY - 2009
U6 - https://doi.org/10.1524/ncrs.2009.0106
SN - 1433-7266
VL - 224
IS - 2
SP - 239
EP - 240
PB - Oldenbourg
CY - München
AN - OPUS4-19711
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Siegel, David
A1 - Merkel, Stefan
A1 - Koch, Matthias
A1 - Emmerling, Franziska
A1 - Nehls, Irene
T1 - 3-{1-[(2,4-Dinitrophenyl)hydrazino]ethylidene}-5-(1-methylpropyl)pyrrolidine-2,4-dione
KW - Tenuazonic acid 2,4-dinitrophenylhydrazone
KW - X-ray single crystal diffraction
KW - Crystal structure
PY - 2009
U6 - https://doi.org/10.1107/S1600536809012458
SN - 1600-5368
VL - 65
IS - 5
SP - o988
EP - o989
PB - Munksgaard
CY - Copenhagen
AN - OPUS4-19736
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Bentrup, U.
A1 - Radnik, J.
A1 - Armbruster, U.
A1 - Martin, A.
A1 - Leiterer, Jork
A1 - Emmerling, Franziska
A1 - Brückner, A.
T1 - Linking simultaneous in situ WAXS/SAXS/Raman with Raman/ATR/UV-vis spectroscopy: comprehensive insight into the synthesis of molybdate catalyst precursors
N2 - A new setup is presented which enables simultaneous wide- and small-angle X-ray scattering (WAXS/SAXS) and Raman spectroscopic experiments during the synthesis of Mo-based mixed oxide catalyst precursors at the µ-spot beamline at the Berliner Elektronenspeicherring-Gesellschaft für Synchrotronstrahlung (BESSY). Furthermore, we report about the separate monitoring of the same reactions under comparable conditions by simultaneous combined ATR/UVvis/Raman spectroscopic measurements. For testing the performance of both experimental setups two syntheses were described comprising the precipitation of metal molybdates by mixing solutions of metal nitrates and ammonium heptamolybdate. Additionally, the effect of H3PO4 admixture on precipitation was investigated. The combined evaluation of spectroscopic and WAXS/SAXS data allows the discrimination between different molybdate species appearing in solution and precipitate. Furthermore, these molybdate species could be assigned to separate phases of different crystallinity.
KW - In situ
KW - WAXS/SAXS
KW - Raman
KW - ATR
KW - UV-vis
KW - Mixed oxide catalyst
KW - Synthesis
PY - 2009
U6 - https://doi.org/10.1007/s11244-009-9309-y
SN - 1022-5528
VL - 52
IS - 10
SP - 1350
EP - 1359
PB - Springer Science + Business Media
CY - Dordrecht
AN - OPUS4-19794
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Bienert, Ralf
A1 - Emmerling, Franziska
A1 - Thünemann, Andreas
T1 - The size distribution of 'gold standard' nanoparticles
N2 - The spherical gold nanoparticle reference materials RM 8011, RM 8012, and RM 8013, with a nominal radius of 5, 15, and 30 nm, respectively, have been available since 2008 from NIST. These materials are recommended as standards for nanoparticle size measurements and for the study of the biological effects of nanoparticles, e.g., in pre-clinical biomedical research. We report on determination of the size distributions of these gold nanoparticles using different small-angle X-ray scattering (SAXS) instruments. Measurements with a classical Kratky type SAXS instrument are compared with a synchrotron SAXS technique. Samples were investigated in situ, positioned in capillaries and in levitated droplets. The number-weighted size distributions were determined applying model scattering functions based on (a) Gaussian, (b) log-normal, and (c) Schulz distributions. The mean radii are 4.36 ± 0.04 nm (RM 8011), 12.20 ± 0.03 nm (RM 8012), and 25.74 ± 0.27 nm (RM 8013). Low polydispersities, defined as relative width of the distributions, were detected with values of 0.067 ± 0.006 (RM 8011), 0.103 ± 0.003, (RM 8012), and 0.10 ± 0.01 (RM 8013). The results are in agreement with integral values determined from classical evaluation procedures, such as the radius of gyration (Guinier) and particle volume (Kratky). No indications of particle aggregation and particle interactions-repulsive or attractive-were found. We recommend SAXS as a standard method for a fast and precise determination of size distributions of nanoparticles.
KW - Small-angle scattering
KW - Reference materials
KW - Metrology
KW - Nanoparticles
PY - 2009
U6 - https://doi.org/10.1007/s00216-009-3049-5
SN - 1618-2642
SN - 1618-2650
VL - 395
IS - 6
SP - 1651
EP - 1660
PB - Springer
CY - Berlin
AN - OPUS4-20473
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Merkel, Stefan
A1 - Köppen, Robert
A1 - Koch, Matthias
A1 - Emmerling, Franziska
A1 - Nehls, Irene
T1 - Ergometrinine
N2 - The absolute configuration of ergometrinine, C19H23N3O2 {systematic name: (6aR,9S)-N-[(S)-1-hydroxypropan-2-yl]-7-methyl-4,6,6a,7,8,9-hexahydroindolo[4,3-fg]quinoline-9-carboxamide}, was established based on epimerization reaction of ergometrine, which was followed by preparative HPLC. The non-aromatic ring (ring C of the ergoline skeleton) directly fused to the aromatic rings is nearly planar [maximum deviation = 0.271 (3) Å] and shows an envelope conformation, whereas ring D, involved in an intramolecular N-HN hydrogen bond, exibits a slightly distorted chair conformation. The structure displays undulating layers in the ac plane formed by O-H...O and N-H...O hydrogen bonds.
KW - Ergometrinine
KW - Ergometrine
KW - Ergot alkaloids
KW - Indole alkaloids
KW - Crystal structure
KW - Epimerization
PY - 2010
U6 - https://doi.org/10.1107/S1600536810030825
SN - 1600-5368
VL - 66
IS - 9
SP - o2275, sup-1 - sup-9
PB - Munksgaard
CY - Copenhagen
AN - OPUS4-21806
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Polte, Jörg
A1 - Herder, Martin
A1 - Erler, Robert
A1 - Rolf, Simone
A1 - Fischer, A.
A1 - Würth, Christian
A1 - Thünemann, Andreas
A1 - Kraehnert, R.
A1 - Emmerling, Franziska
T1 - Mechanistic insights into seeded growth processes of gold nanoparticles
N2 - A facile approach for the synthesis of monodisperse gold nanoparticles with radii in the range of 7 to 20 nm is presented. Starting from monodisperse seeds with radii of 7 nm, produced in the first step, the addition of a defined amount of additional precursor material permits distinct size regulation and the realization of predicted nanoparticle sizes. These information were derived from ex- and in situ investigations by comprehensive small angle X-ray scattering (SAXS), X-ray absorption near edge structure (XANES) and UV-Vis data to obtain information on the physicochemical mechanisms. The obtained mechanisms can be transferred to other seeded growth processes. Compared to similar approaches, the presented synthesis route circumvents the use of different reducing or stabilizing agents. The size of resulting nanoparticles can be varied over a large size range presented for the first time without a measurable change in the shape, polydispersity or surface chemistry. Thus, the resulting nanoparticles are ideal candidates for size dependence investigations.
KW - Gold nanoparticles
KW - SAXS
KW - XANES
KW - Growth mechanism
PY - 2010
U6 - https://doi.org/10.1039/c0nr00541j
SN - 2040-3364
SN - 2040-3372
VL - 2
IS - 11
SP - 2463
EP - 2469
PB - RSC Publ.
CY - Cambridge
AN - OPUS4-22346
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Siegel, David
A1 - Blaske, Franziska
A1 - Koch, Matthias
A1 - Emmerling, Franziska
A1 - Nehls, Irene
T1 - Deacetyl tenuazonic acid p-toluenesulfonylhydrazone
KW - Deacetyl tenuazonic acid
KW - Toluenesulfonylhydrazine
KW - Hydrazone
KW - Crystal structure
PY - 2009
U6 - https://doi.org/10.1107/S1600536809048958
SN - 1600-5368
VL - E65
IS - 12
SP - o3136 Sup-1 - o3136 Sup-8
PB - Munksgaard
CY - Copenhagen
AN - OPUS4-20608
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Aichmayer, B.
A1 - Wiedemann-Bidlack, F. B.
A1 - Gilow, C.
A1 - Simmer, J.P.
A1 - Yamakoshi, Y.
A1 - Emmerling, Franziska
A1 - Margolis, H.C.
A1 - Fratzl, P.
T1 - Amelogenin nanoparticles in suspension: Deviations from spherical shape and pH-dependent aggregation
N2 - It is well-known that amelogenin self-assembles to form nanoparticles, usually referred to as amelogenin nanospheres, despite the fact that not much is known about their actual shape in solution. In the current paper, we combine SAXS and DLS to study the three-dimensional shape of the recombinant amelogenins rP172 and rM179. Our results show for the first time that amelogenins build oblate nanoparticles in suspension using experimental approaches that do not require the proteins to be in contact with a support material surface. The SAXS studies give evidence for the existence of isolated amelogenin nano-oblates with aspect ratios in the range of 0.45-0.5 at pH values higher than pH 7.2 and show an aggregation of these nano-oblates at lower pH values. The role of the observed oblate shape in the formation of chain-like structures at physiological conditions is discussed as a key factor in the biomineralization of dental enamel.
KW - Enamel
KW - Recombinant amelogenin
KW - rP172
KW - rM179
KW - Self-assembly
KW - SAXS
KW - DLS
KW - Shape
KW - Nanospheres
KW - Oblates
KW - pH dependency
PY - 2010
U6 - https://doi.org/10.1021/bm900983b
SN - 1525-7797
VL - 11
IS - 2
SP - 369
EP - 376
PB - ACS Publ.
CY - Washington, DC, USA
AN - OPUS4-20939
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Polte, Jörg
A1 - Erler, Robert
A1 - Thünemann, Andreas
A1 - Sokolov, S.
A1 - Ahner, T. T.
A1 - Rademann, K.
A1 - Emmerling, Franziska
A1 - Kraehnert, R.
T1 - Nucleation and growth of gold nanoparticles studies via in situ small angle X-ray scattering at millisecond time resolution
N2 - Gold nanoparticles (AuNP) were prepared by the homogeneous mixing of continuous flows of an aqueous tetrachloroauric acid solution and a sodium borohydride solution applying a microstructured static mixer. The online characterization and screening of this fast process (~2 s) was enabled by coupling a micromixer operating in continuous-flow mode with a conventional in-house small angle X-ray scattering (SAXS) setup. This online characterization technique enables the time-resolved investigation of the growth process of the nanoparticles from an average radius of ca. 0.8 nm to about 2 nm. To the best of our knowledge, this is the first demonstration of a continuous-flow SAXS setup for time-resolved studies of nanoparticle formation mechanisms that does not require the use of synchrotron facilities. In combination with X-ray absorption near edge structure microscopy, scanning electron microscopy, and UV-vis spectroscopy the obtained data allow the deduction of a two-step mechanism of gold nanoparticle formation. The first step is a rapid conversion of the ionic gold precursor into metallic gold nuclei, followed by particle growth via coalescence of smaller entities. Consequently it could be shown that the studied synthesis serves as a model system for growth driven only by coalescence processes.
KW - Nanoparticle formation mechanism
KW - SAXS
KW - Microstructured static mixer
KW - Continuous flow
PY - 2010
U6 - https://doi.org/10.1021/nn901499c
SN - 1936-0851
VL - 4
IS - 2
SP - 1076
EP - 1082
PB - ACS Publ.
CY - Washington, DC, USA
AN - OPUS4-20940
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Polte, Jörg
A1 - Emmerling, Franziska
A1 - Radtke, Martin
A1 - Reinholz, Uwe
A1 - Riesemeier, Heinrich
A1 - Thünemann, Andreas
T1 - Real-time monitoring of copolymer stabilized growing gold nanoparticles
N2 - A great challenge in the production of nanoparticles with defined sizes and properties is to control their growth in situ. We developed a dedicated combined small-angle X-ray scattering (SAXS) and X-ray absorption spectroscopy (XAS) setup to monitor nanoparticle formation in solution. The capabilities of simultaneously deriving particle sizes and oxidation states of atoms/ions are illustrated for the formation of spherical gold nanoparticles by the reduction of hydrogen tetrachloroaureate (HAuCl4). Particles with initial radii of 4.60 ± 0.10 nm and final radii of 5.67 ± 0.10 nm were produced in a levitated droplet with a volume of 4 µL. An ethylene oxide/propylene oxide triblock copolymer PEO-PPO-PEO (Pluronic F-127) functions as reducing agent and colloidal stabilizer. XANES shows in situ how the gold was reduced in the droplet from Au(III) to Au(0), and simultaneously SAXS recorded the size distribution of the formed nanoparticles. It is shown that the final particle number is reached quickly. Thereafter, only the particles sizes increase. Comparison of XANES and SAXS shows that the quantity of Au(0) is higher than the quantity of gold located in the nanoparticles while the particles are growing. Finally, all the Au(0) is found in the nanoparticles. We tentatively attribute this finding to the pseudo crown ether effect of the polymer surfactant that kinetically stabilizes gold atoms when formed from gold ions within their protecting cavity. A simple burst mechanism for the gold nanoparticle formation is the consequence. The possibility of an inhomogeneous particles structure with an enhanced density near the particle surface is discussed.
PY - 2010
U6 - https://doi.org/10.1021/la903829q
SN - 0743-7463
SN - 1520-5827
VL - 26
IS - 8
SP - 5889
EP - 5894
PB - American Chemical Society
CY - Washington, DC
AN - OPUS4-21223
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Emmerling, Franziska
T1 - In-situ Untersuchungen von Nukleations-, Kristallisations- und Wachstumsprozessen mit Synchrotronstrahlung
T2 - ANAKON 2011
CY - Zurich, Switzerland
DA - 2011-03-22
PY - 2011
AN - OPUS4-22564
LA - deu
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Emmerling, Franziska
A1 - Klimakow, Maria
A1 - Klobes, Peter
T1 - Gas Adsorption and SAXS Studies of Mechanochemically Prepared MOFs
T2 - XV. POROTEC-Workshop über die Charakterisierung von feinteiligen und porösen Festkörpern
CY - Bad Soden, Germany
DA - 2010-11-16
PY - 2010
AN - OPUS4-22834
LA - deu
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CHAP
A1 - Carvalho, José Joao
A1 - Emmerling, Franziska
A1 - Schneider, Rudolf
ED - Preedy, V.R.
T1 - The chemistry of caffeine
KW - Koffein
KW - Chemie
KW - Kristallstrukturen
KW - Geschichte
PY - 2012
SN - 978-1-84973-367-0
U6 - https://doi.org/10.1039/9781849734752-00041
SN - 2045-1695
N1 - Serientitel: Food and nutritional components in focus – Series title: Food and nutritional components in focus
VL - 2
IS - Chapter 3
SP - 41
EP - 52
PB - RSC Publ.
AN - OPUS4-26531
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Drzymala, Sarah
A1 - Kraus, Werner
A1 - Emmerling, Franziska
A1 - Koch, Matthias
T1 - (3S,7R)-7,14,16-trihydroxy-3-methyl-3,4,5,6,7,8,9,10,11,12-decahydro-1H-2-benzoxacyclotetradecin-1-one
N2 - The asymmetric unit of the title compound, C18H26O5, which is known as α-zearalanol, contains two molecules having the same conformation, with a r.m.s. deviation of less than 0.03 Å for all non-H atoms. In each independent molecule, an intramolecular O—H···O hydrogen bond stabilizes the molecular conformation. In the crystal, O—H···O hydrogen bonds link the molecules, forming infinite chains along [110] and [1¯10].
KW - Alpha-zearalanol
KW - Zearalenon
KW - Estrogen
KW - Growth promoter
KW - Ralgro
PY - 2012
U6 - https://doi.org/10.1107/S1600536812041141
SN - 1600-5368
VL - 68
IS - 11
SP - o3071, sup-1 - sup-11
PB - Munksgaard
CY - Copenhagen
AN - OPUS4-26771
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Krause, Christina
A1 - Yin, Huajie
A1 - Cerclier, C.
A1 - Morineau, D.
A1 - Wurm, Andreas
A1 - Schick, C.
A1 - Emmerling, Franziska
A1 - Schönhals, Andreas
T1 - Molecular dynamics of a discotic liquid crystal investigated by a combination of dielectric relaxation and specific heat spectroscopy
N2 - The molecular dynamics of the discotic liquid crystal pyrene-1,3,6,8-tetracarboxylic tetra(2-ethylhexyl)ester is studied by dielectric relaxation and specific heat spectroscopy. Dielectric spectroscopy shows 3 processes: a β-relaxation at low temperatures and an α-relaxation in the temperature range of the mesophases followed by conductivity. The dielectric α-relaxation is assigned to a restricted glassy dynamics in the plastic crystal as well as in the liquid crystalline phase. The obtained different Vogel–Fulcher–Tammann laws (different Vogel temperatures and fragility) are related to the different restrictions of the dipolar fluctuations in the corresponding phases. By means of specific heat spectroscopy glassy dynamics is also detected in the plastic crystalline phase but with quite a different temperature dependence of the relaxation times. This is discussed considering the different probes involved and how they are influenced by the structure. In the frame of the fluctuation approach a correlation length of glassy dynamics is calculated to 0.78 nm which corresponds to the core–core distance estimated by X-ray scattering.
PY - 2012
U6 - https://doi.org/10.1039/c2sm25610j
SN - 1744-683X
VL - 8
IS - 43
SP - 11115
EP - 11122
PB - RSC Publ.
CY - Cambridge
AN - OPUS4-26826
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Wolf, S. E.
A1 - Lieberwirth, I.
A1 - Natalio, F.
A1 - Bardeau, J.-F.
A1 - Delorme, N.
A1 - Emmerling, Franziska
A1 - Barrea, R.
A1 - Kappl, M.
A1 - Marin, F.
T1 - Merging models of biomineralisation with concepts of nonclassical crystallisation: is a liquid amorphous precursor involved in the formation of the prismatic layer of the Mediterranean Fan Mussel Pinna nobilis?
N2 - The calcitic prisms of Pinna nobilis (Pinnidae, Linnaeus 1758) are shown to be perfect examples of a mesocrystalline material. Based on their ultrastructure and on the occurrence of an amorphous transient precursor during the early stages of prism formation, we provide evidence for the pathway of mesocrystallisation proposed by Seto et al. (2012), which proceeds not by self-organized oriented attachment of crystalline nano-bricks but by aggregation of initially amorphous nanogranules which later transform by epitaxial nucleation to a three-dimensional array of well aligned nanocrystals. We further fathom the role of a liquid amorphous calcium carbonate in biomineralisation processes and provide strong evidence for the occurrence of PILP-like intermediates during prism formation. We develop a new scenario of prism formation based on the presented findings presented findings and discuss the implications of a speculative liquid amorphous calcium carbonate (LACC) intermediate in vivo.
PY - 2012
U6 - https://doi.org/10.1039/c2fd20045g
SN - 1359-6640
SN - 1364-5498
VL - 159
IS - 0
SP - 433
EP - 448
PB - Soc.
CY - Cambridge [u.a.]
AN - OPUS4-27122
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Brandenburg, E.
A1 - von Berlepsch, H.
A1 - Leiterer, Jork
A1 - Emmerling, Franziska
A1 - Koksch, B.
T1 - Formation of alpha-helical nanofibers by mixing beta-structured and alpha-helical coiled coil peptides
N2 - The helical coiled coil is a well-studied folding motif that can be used for the design of nanometer-sized bioinspired fibrous structures with potential applications as functional materials. A two-component system of coiled coil based model peptides is investigated, which forms, under acidic conditions, uniform, hundreds of nanometers long, and ~2.6 nm thick trimeric α-helical fibers. In the absence of the other component and under the same solvent conditions, one model peptide forms β-sheet-rich amyloid fibrils and the other forms stable trimeric α-helical coiled coils, respectively. These observations reveal that the complementary interactions driving helical folding are much stronger here than those promoting the intermolecular β-sheet formation. The results of this study are important in the context of amyloid inhibition but also open up new avenues for the design of novel fibrous peptidic materials.
PY - 2012
U6 - https://doi.org/10.1021/bm300882d
SN - 1525-7797
VL - 13
IS - 11
SP - 3542
EP - 3551
PB - ACS Publ.
CY - Washington, DC, USA
AN - OPUS4-27126
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Emmerling, Franziska
A1 - Eckhardt, B.
A1 - Ortel, Erik
A1 - Bernsmeier, D.
A1 - Strasser, P.
A1 - Polte, J.
A1 - Kraehnert, R.
A1 - Vainio, U.
T1 - A general strategy for the synthesis of micelle-templated mesoporous metal carbonates and metal oxides
T2 - 25. Deutsches Zeolith-Tagung
CY - Hamburg, Germany
DA - 2013-03-06
PY - 2013
AN - OPUS4-27254
LA - deu
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Emmerling, Franziska
A1 - Orgzall, I.
A1 - Dietzel, B.
A1 - Schulz, B.
A1 - Larrucea, J.
T1 - Ordering the amorphous - Structures in PBD LED materials
N2 - The class of 2,5 disubstituted-1,3,4-oxadiazoles containing a biphenyl unit on one side is intensively used as electron transport materials to enhance the performance of organic light emitting diodes (OLEDs). In contrast to the ongoing research on these materials insights in their structure-property relationships are still incomplete. To overcome the structural tentativeness and ambiguities the crystal structures of 2-(4-biphenylyl)-5-(4-tert-butylphenyl)-1,3,4-oxadiazole, that of the related compound 2-(4-biphenylyl)-5-phenyl-1,3,4-oxadiazole and of 2-(4-biphenylyl)-5-(2,6-dimethylphenyl)-1,3,4-oxadiazole are determined. A comparison with the results of GAUSSIAN03 calculations and similar compounds in the Cambridge Structural Database leads to a profound characterization.
KW - OLED
KW - PBD
KW - Diphenyl-1,3,4-oxadiazole
KW - Crystallization
PY - 2012
U6 - https://doi.org/10.1016/j.molstruc.2012.04.040
SN - 0022-2860
SN - 1872-8014
SN - 0377-046X
VL - 1030
SP - 209
EP - 215
PB - Elsevier
CY - Amsterdam
AN - OPUS4-27264
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Hennig, C.
A1 - Takao, S.
A1 - Takao, K.
A1 - Weiss, S.
A1 - Kraus, Werner
A1 - Emmerling, Franziska
A1 - Scheinost, A.C.
T1 - Structure and stability range of a hexanuclear Th(IV)-glycine complex
N2 - A hexanuclear Th(IV)–glycine complex was observed by Th L3-edge EXAFS measurements in an aqueous solution. Within the stability range of this complex the positively charged hexanuclear species [Th6(µ3-O)4(µ3-OH)4(H2O)6(Gly)6(HGly)6]6+ was preserved in a crystal with the composition [Th6(µ3-O)4(µ3-OH)4(H2O)6(Gly)6(HGly)6]·(NO3)3(ClO4)3(H2O)3. This complex appears as a result of a competing reaction between hydrolysis and ligation by glycine. At a pH value below the stability range of the hexanuclear complex, crystals with the composition [Th(H2O)3(HGly)3]·(ClO4)4H2O were obtained from the solution. Three water molecules in the thorium coordination sphere indicate that this complex occurs prior to the onset of Th(IV) hydrolysis.
PY - 2012
U6 - https://doi.org/10.1039/c2dt31367g
SN - 1477-9226
SN - 1477-9234
SN - 1364-5447
VL - 41
SP - 12818
EP - 12823
PB - RSC
CY - Cambridge
AN - OPUS4-27265
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Merkel, Stefan
A1 - Köppen, Robert
A1 - Koch, Matthias
A1 - Emmerling, Franziska
A1 - Nehls, Irene
T1 - Lysergol monohydrate
N2 - In the title compound [systematic name: (7-methyl-4,6,6a,7,8,9-hexahydroindolo[4,3,2-fg]quinoline-9-yl)methanol monohydrate], C16H18N2O·H2O, the non-aromatic ring (ring C of the ergoline skeleton) directly fused to the aromatic rings is nearly planar, with a maximum deviation of 0.659 (3) Å, and shows an envelope conformation. In the crystal, hydrogen bonds between the lysergol and water molecules contribute to the formation of layers parallel to (10-2).
PY - 2012
U6 - https://doi.org/10.1107/S1600536812002632
SN - 1600-5368
VL - 68
IS - 2
SP - o523, sup1
EP - sup8
PB - Munksgaard
CY - Copenhagen
AN - OPUS4-25401
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Merkel, Stefan
A1 - Köppen, Robert
A1 - Koch, Matthias
A1 - Emmerling, Franziska
A1 - Nehls, Irene
T1 - Lumi-ergometrine - structural identification and occurrence in sclerotia
N2 - The fungus Claviceps purpurea grows on grasses
and cereal grains and produces six predominant ergot
alkaloids. These toxic substances undergo different transformation
reactions during storage and cereal processing. One
of these reactions is the addition of water to a double bond in
the ergoline skeleton. Since light is required for this process,
the substances formed were named lumi-ergot alkaloids.
From these, a new asymmetric carbon and consequently two
epimers with different polarities are formed. For investigations
of lumi-ergot alkaloids, ergometrine was used exemplarily
as it represents one of the six ergot alkaloids
predominantly formed by Claviceps purpurea. The main
reaction product, the less polar compound of the two lumiergometrine
epimers, was separated by HPLC and unambiguously
identified as 10-(S)-lumi-ergometrine using X-ray
structural analysis. A HPLC-MS/MS method was developed
for the detection of this substance in sclerotia extracts. Using
this method, the existence of both epimeric forms of lumiergometrine
could be proved in the sclerotia. This is the first
time that the existence of a lumi-transformation product of
ergot alkaloids was proved in naturally grown samples.
KW - Lumi-ergot alkaloids
KW - Sclerotia
KW - Claviceps purpurea
KW - HPLC-MS/MS
PY - 2012
U6 - https://doi.org/10.1007/s12550-011-0116-5
SN - 0178-7888
VL - 28
IS - 1
SP - 59
EP - 66
PB - Springer
CY - Berlin; Heidelberg
AN - OPUS4-25442
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Drzymala, Sarah
A1 - Kraus, Werner
A1 - Emmerling, Franziska
A1 - Koch, Matthias
T1 - (3S)-14,16-Dihydroxy-3-methyl-3,4,5,6,9,10,11,12-octa-hydro-1H-2-benzoxacyclotetradecine-1,7(8H)-dione (zearalanone) monohydrate
N2 - The absolute configuration of the title compound, C18H24O5·H2O, was not been determined by anomalous-dispersion effects, but has been assigned by reference to an unchanging chiral centre in the synthetic procedure. Intramolecular O—H···O hydrogen bonds stabilize the molecular conformation. In the crystal, O—H···O hydrogen bonds link the main molecules and the water molecules, forming an infinite three-dimensional network.
KW - Zearalanone
KW - Crystal structure
PY - 2012
U6 - https://doi.org/10.1107/S1600536812018168
SN - 1600-5368
VL - 68
IS - 5
SP - o1577, sup1
EP - sup7
PB - Munksgaard
CY - Copenhagen
AN - OPUS4-25832
LA - deu
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Purohit, Purv
A1 - Wang, D.-Y.
A1 - Emmerling, Franziska
A1 - Thünemann, Andreas
A1 - Heinrich, G.
A1 - Schönhals, Andreas
T1 - Arrangement of layered double hydroxide in a polyethylene matrix studied by a combination of complementary methods
N2 - Organically modified ZnAl Layered Double Hydroxides (ZnAl-LDH) was synthesized and melt blended with polyethylene to obtain nanocomposites. The resulting morphology was investigated by a combination of Differential Scanning Calorimetry (DSC), Small and Wide-angle X-ray scattering (SAXS and WAXS) and dielectric relaxation spectroscopy (DRS). The arrangement (intercalation) of polyethylene chains between LDH stacks was investigated employing SAXS. The homogeneity of the nanocomposites and average number of stack size (4–6 layers) were determined using scanning microfocus SAXS (BESSY II). DSC and WAXS results show that the degree of crystallinity decreases linearly with the increasing content of LDH. The extrapolation of this dependence to zero estimates a limiting concentration of ca. 45% LDH where the crystallization of PE is completely suppressed by the nanofiller. The dielectric spectra of the nanocomposites show several relaxation processes which are discussed in detail. The intensity of the dynamic glass transition (β-relaxation) increases with the concentration of LDH. This is attributed to the increasing concentration of the exchanged anion sodium dodecylbenzene sulfonate (SDBS) which is adsorbed at the LDH layers. Therefore, a detailed analysis of the β-relaxation provides information about the structure and the molecular dynamics in the interfacial region between the LDH layers and the polyethylene matrix which is otherwise dielectrically invisible (low dipole moment).
KW - Dielectric spectroscopy
KW - Polyethylene nanocomposites
KW - Layered double hydroxides
PY - 2012
U6 - https://doi.org/10.1016/j.polymer.2012.03.041
SN - 0032-3861
SN - 1873-2291
VL - 53
IS - 11
SP - 2245
EP - 2254
PB - Springer
CY - Berlin
AN - OPUS4-25810
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Polte, Jörg
A1 - Tuaev, X.
A1 - Wuithschick, M.
A1 - Fischer, A.
A1 - Thünemann, Andreas
A1 - Rademann, K.
A1 - Kraehnert, R.
A1 - Emmerling, Franziska
T1 - Formation mechanism of colloidal silver nanoparticles: analogies and differences to the growth of gold nanoparticles
N2 - The formation mechanisms of silver nanoparticles using aqueous silver perchlorate solutions as precursors and sodium borohydride as reducing agent were investigated based on time-resolved in situ experiments. This contribution addresses two important issues in colloidal science: (i) differences and analogies between growth processes of different metals such as gold and silver and (ii) the influence of a steric stabilizing agent on the growth process. The results reveal that a growth due to coalescence is a fundamental growth principle if the monomer-supplying chemical reaction is faster than the actual particle formation.
KW - Silver nanoparticle growth
KW - Formation mechanisms
KW - Nucleation
KW - SAXS
PY - 2012
U6 - https://doi.org/10.1021/nn301724z
SN - 1936-0851
VL - 6
IS - 7
SP - 5791
EP - 5802
PB - ACS Publ.
CY - Washington, DC, USA
AN - OPUS4-26427
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Peplinski, Burkhard
A1 - Adam, Christian
A1 - Adamczyk, Burkart
A1 - Müller, Ralf
A1 - Schadrack, Reinhard
A1 - Michaelis, Matthias
A1 - Emmerling, Franziska
A1 - Reuther, H.
A1 - Menzel, Michael
T1 - Evidence of formation of the tridymite form of AlPO4 in some municipal sewage sludge ashes
N2 - Evidence is provided that the tridymite component observed in the X-ray diffraction patterns of some sewage sludge ashes (SSAs) should not be interpreted as the tridymite modification of SiO2 but as the tridymite form of AlPO4. This proof is based on a combined X-ray Powder Diffraction (XRD), X-ray fluorescence (XRF) and Mossbauer spectroscopy investigation of two SSAs produced at two fluidized bed incineration facilities, located in different municipalities and operated differently. The structural and chemical characterization was carried out on the 'as received' SSA samples as well as on the residues of these two SSAs pretreated by leaching in citric acid. In addition, direct proof is presented that the tridymite form of AlPO4 does crystallize from X-ray amorphous precursors under conditions that mimic the huge heating rate and short retention time (just seconds at T ≈ 850 °C) typical for fluidized bed incinerators.
KW - Aluminium phosphate
KW - Ash
KW - Fly ash
KW - Incinerator ash
KW - Sewage sludge ash
KW - Tridymite form
PY - 2013
U6 - https://doi.org/10.1017/S0885715613000869
SN - 0885-7156
VL - 28
IS - S2
SP - S425
EP - S435
PB - JCPDS
CY - Swarthmore, Pa.
AN - OPUS4-29703
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Unterlass, M.M.
A1 - Emmerling, Franziska
A1 - Antonietti, M.
A1 - Weber, J.
T1 - From dense monomer salt crystals to CO2 selective microporous polyimides via solid-state polymerization
N2 - Fully aromatic polyimides are synthesized via solid-state polymerization of the corresponding monomer salts. The crystal structure of salts shows strong hydrogen bonding of the reactive groups and thereby paves the way for solid-state transformations. The polycondensation yields copies of the initial salt crystallite habits, accompanied by the development of a porosity especially suited for CO2.
PY - 2014
U6 - https://doi.org/10.1039/c3cc47674j
SN - 0022-4936
SN - 0009-241x
SN - 1359-7345
SN - 1364-548x
VL - 50
IS - 4
SP - 430
EP - 432
PB - Royal Society of Chemistry
CY - Cambridge
AN - OPUS4-29813
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Bothe, Martin
A1 - Emmerling, Franziska
A1 - Pretsch, Thorsten
T1 - Poly(ester urethane) with varying polyester chain length: Polymorphism and shape-memory behavior
N2 - The swelling, viscoelastic, and mechanical behavior of phase-segregated poly(ester urethane) (PEU) block copolymers, composed of 4,4'-methylenediphenyl diisocyanate, 1,4-butanediol as a chain extender, and crystallizable poly(1,4-butylene adipate) (PBA) with molecular weights between 1330 and 4120 g mol-1, are investigated. Wide-angle X-ray scattering (WAXS) is employed to study the overall PEU crystallinity, which increases from 8.6 to 13.6% at higher PBA contents. The existence of two crystalline, polymorphic PBA phases, a thermodynamically stable α phase and a metastable β phase, is confirmed by further WAXS measurements. Calorimetric and thermomechanical investigations give evidence for controllable PBA polymorphic behavior. The crystallization conditions, like the cooling rate, affect the emerging polymorphic mixture, whereas the storage conditions either promote or inhibit the polymorphic (β to α) transition. The introduced concepts represent a new approach for gaining control over programmable thermoresponsiveness, which may be transferable to other shape-memory polymers with polymorphic switching segments.
KW - Shape-memory polymers
KW - Stimuli-sensitive polymers
KW - Poly(ester urethane)
KW - Polymorphism
PY - 2013
U6 - https://doi.org/10.1002/macp.201300464
SN - 1022-1352
SN - 1521-3935
VL - 214
IS - 23
SP - 2683
EP - 2693
PB - Wiley-VCH Verl.
CY - Weinheim
AN - OPUS4-29892
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Wuithschick, M.
A1 - Paul, B.
A1 - Bienert, Ralf
A1 - Sarfraz, A.
A1 - Vainio, U.
A1 - Sztucki, M.
A1 - Kraehnert, R.
A1 - Strasser, P.
A1 - Rademann, K.
A1 - Emmerling, Franziska
A1 - Polte, J.
T1 - Size-controlled synthesis of colloidal silver nanoparticles based on mechanistic understanding
N2 - Metal nanoparticles have attracted much attention due to their unique properties. Size control provides an effective key to an accurate adjustment of colloidal properties. The common approach to size control is testing different sets of parameters via trial and error. The actual particle growth mechanisms, and in particular the influences of synthesis parameters on the growth process, remain a black box. As a result, precise size control is rarely achieved for most metal nanoparticles. This contribution presents an approach to size control that is based on mechanistic knowledge. It is exemplified for a common silver nanoparticle synthesis, namely, the reduction of AgClO4 with NaBH4. Conducting this approach allowed a well-directed modification of this synthesis that enables, for the first time, the size-controlled production of silver nanoparticles 4–8 nm in radius without addition of any stabilization agent.
KW - Silver nanoparticles
KW - Growth mechanism
KW - SAXS
KW - Size control
KW - Sodium borohydride
PY - 2013
U6 - https://doi.org/10.1021/cm401851g
SN - 0897-4756
SN - 1520-5002
VL - 25
IS - 23
SP - 4679
EP - 4689
PB - American Chemical Society
CY - Washington, DC
AN - OPUS4-30194
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Chinnasamy, R.
A1 - Ravi, J.
A1 - Pradeep, V.V.
A1 - Manoharan, D.
A1 - Emmerling, Franziska
A1 - Bhattacharya, Biswajit
A1 - Ghosh, S.
T1 - Adaptable Optical Microwaveguides From Mechanically Flexible Crystalline Materials
N2 - Flexible organic crystals (elastic and plastic) are important materials for optical waveguides, tunable optoelectronic devices, and photonic integrated circuits. Here, we present highly elastic organic crystals of a Schiff base, 1-((E)-(2,5-dichlorophenylimino)methyl)naphthalen-2-ol (1), and an azine molecule, 2,4-dibromo-6-((E)-((E)-(2,6-dichlorobenzylidene)hydrazono)methyl)phenol (2). These microcrystals are highly flexible under external mechanical force, both in the macroscopic and the microscopic regimes. The mechanical flexibility of these crystals arises as a result of weak and dispersive C−H⋅⋅⋅Cl, Cl⋅⋅⋅Cl, Br⋅⋅⋅Br, and π⋅⋅⋅π stacking interactions. Singly and doubly-bent geometries were achieved from their straight shape by a micromechanical approach using the AFM cantilever tip. Crystals of molecules 1 and 2 display a bright-green and red fluorescence (FL), respectively, and selective reabsorption of a part of their FL band. Crystals 1 and 2 exhibit optical-path-dependent low loss emissions at the termini of crystal in their straight and even in extremely bent geometries. Interestingly, the excitation position-dependent optical modes appear in both linear and bent waveguides of crystals 1 and 2, confirming their light-trapping ability.
KW - Crystal growth
KW - Fluorescence
KW - Mechanophotonics
KW - Micromanipulation
KW - Optical waveguides
PY - 2022
U6 - https://doi.org/10.1002/chem.202200905
SN - 0947-6539
SP - 1
EP - 8
PB - Wiley VHC-Verlag
AN - OPUS4-55018
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Belenguer, A.
A1 - Lampronti, G.
A1 - Michalchuk, Adam
A1 - Emmerling, Franziska
A1 - Sanders, J.
T1 - Quantitative reversible one pot interconversion of three crystalline polymorphs by ball mill grinding
N2 - We demonstrate here using a disulfide system the first example of reversible, selective, and quantitative transformation between three crystalline polymorphs by ball mill grinding. This includes the discovery of a previously unknown polymorph. Each polymorph is reproducibly obtained under well-defined neat or liquid-assisted grinding conditions, revealing subtle control over the apparent thermodynamic stability. We discovered that the presence of a contaminant as low as 1.5% mol mol−1 acting as a template is required to enable all these three polymorph transformations. The relative stabilities of the polymorphs are determined by the sizes of the nanocrystals produced under different conditions and by surface interactions with small amounts of added solvent. For the first time, we show evidence that each of the three polymorphs is obtained with a unique and reproducible crystalline size. This mechanochemical approach gives access to bulk quantities of metastable polymorphs that are inaccessible through recrystallisation.
KW - Mechanochemistry
KW - Polymorph
KW - XRD
PY - 2022
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-549934
SP - 1
EP - 7
PB - Royal Society of Chemistry
AN - OPUS4-54993
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Karafiludis, Stephanos
A1 - de Oliveira Guilherme Buzanich, Ana
A1 - Kochovski, Z.
A1 - Feldmann, Ines
A1 - Emmerling, Franziska
A1 - Stawski, Tomasz
T1 - Ni- and Co-Struvites: Revealing Crystallization Mechanisms and Crystal Engineering toward Applicational Use of Transition Metal Phosphates
N2 - Industrial and agricultural waste streams (waste water, sludges, tailings, etc.) which contain high concentrations of NH4+, PO43–, and transition metals are environmentally harmful and toxic pollutants. At the same time, phosphorous and transition metals constitute highly valuable resources. Typically, separate pathways have been considered to extract hazardous transition metals or phosphate independently from each other. Investigations on the simultaneous removal of multiple components have been carried out only to a limited extent. Here, we report the synthesis routes for Ni- and Co-struvites (NH4MPO4·6H2O, M = Ni2+ and Co2+), which allow for P, ammonia, and metal co-precipitation. By evaluating different reaction parameters, the phase and stability of transition metal struvites as well as their crystal morphologies and sizes could be optimized. Ni-struvite is stable in a wide reactant concentration range and at different metal/phosphorus (M/P) ratios, whereas Co-struvite only forms at low M/P ratios. Detailed investigations of the precipitation process using ex situ and in situ techniques provided insights into the crystallization mechanisms/crystal engineering of these materials. M-struvites crystallize via intermediate colloidal amorphous nanophases, which subsequently aggregate and condense to final crystals after extended reaction times. However, the exact reaction kinetics of the formation of a final crystalline product varies significantly depending on the involved metal cation in the precipitation process: several seconds (Mg) to minutes (Ni) to hours (Co). The achieved level of control over the morphology and size makes precipitation of transition metal struvites a promising method for direct metal recovery and binding them in the form of valuable phosphate raw materials. Under this paradigm, the crystals can be potentially up-cycled as precursor powders for electrochemical or (electro)catalytic applications, which require transition metal phosphates.
KW - Crystallization
KW - Struvite
KW - Nickel
KW - Cobalt
KW - Phosphorous recovery
KW - Up-cycling
KW - Aqueous synthesis
PY - 2022
U6 - https://doi.org/10.1021/acs.cgd.2c00284
VL - 22
IS - 7
SP - 4305
EP - 4315
PB - ACS Publications
CY - Washington D.C.
AN - OPUS4-55286
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - GEN
A1 - Wolf, Jako
A1 - Stawski, Tomasz
A1 - Smales, Glen Jacob
A1 - Thünemann, Andreas
A1 - Emmerling, Franziska
T1 - SI Files for "Towards automation of the polyol process for the synthesis of silver nanoparticles"
N2 - The graphml file: reaction_graph_AgNP.graphml is included. It contains topological information (Fig. 1 in the main text) about the reaction setup and metadata with reaction condtions. It used by the Python API used to control the Chemputer.
SAXS reports. The complete report sheets generated by McSAS are included. They contain extended information characterising the size distributions and the fitting parameters.
NP3_I: saxs_report_NP3_I.pdf
NP3_II: saxs_report_NP3_II.pdf
NP3_III: saxs_report_NP3_III.pdf
NP3_IV: saxs_report_NP3_IV.pdf
NP5_I: saxs_report_NP5_I.pdf
NP5_II: saxs_report_NP5_II.pdf
NP5_III: saxs_report_NP5_III.pdf
KW - Automated synthesis
KW - Silver
KW - Nanoparticles
PY - 2022
U6 - https://doi.org/10.5281/zenodo.5910614
PB - Zenodo
CY - Geneva
AN - OPUS4-55197
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Accorsi, M.
A1 - Tiemann, M.
A1 - Wehrhan, L.
A1 - Finn, Lauren M.
A1 - Cruz, R.
A1 - Rautenberg, Max
A1 - Emmerling, Franziska
A1 - Heberle, J.
A1 - Keller, B. G.
A1 - Rademann, J.
T1 - Pentafluorophosphato-Phenylalanines: Amphiphilic Phosphotyrosine Mimetics Displaying Fluorine-Specific Protein Interactions
N2 - Phosphotyrosine residues are essential functional switches in health and disease. Thus, phosphotyrosine biomimetics are crucial for the development of chemical tools and drug molecules. We report here the discovery and investigation of pentafluorophosphato amino acids as novel phosphotyrosine biomimetics. A mild acidic pentafluorination protocol was developed and two PF5-amino acids were prepared and employed in peptide synthesis. Their structures, reactivities, and fluorine-specific interactions were studied by NMR and IR spectroscopy, X-ray diffraction, and in bioactivity assays. The mono-anionic PF5 motif displayed an amphiphilic character binding to hydrophobic surfaces, to water molecules, and to protein-binding sites, exploiting charge and H−F-bonding interactions. The novel motifs bind 25- to 30-fold stronger to the phosphotyrosine binding site of the protein tyrosine phosphatase PTP1B than the best current biomimetics, as rationalized by computational methods, including molecular dynamics simulations.
KW - Chemical Biology
KW - Drug Development
KW - Pentafluorophosphates
KW - Phosphotyrosine Biomimetics
KW - Protein Tyrosine Phosphatases
PY - 2022
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-549984
SN - 1433-7851
VL - 134
IS - 25
SP - 1
EP - 6
PB - Wiley-VCH GmbH
AN - OPUS4-54998
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Wegner, Karl David
A1 - Häusler, I.
A1 - Knigge, Xenia
A1 - Hodoroaba, Vasile-Dan
A1 - Emmerling, Franziska
A1 - Reiss, P.
A1 - Resch-Genger, Ute
T1 - One-Pot Heat-Up Synthesis of ZnSe Magic-Sized Clusters Using Thiol Ligands
N2 - The synthesis of two new families of ZnSe magic-sized clusters (MSCs) is achieved using the thiol ligand 1-dodecanethiol in a simple one-pot heat-up approach. The sizes of the MSCs are controlled with the thiol ligand concentration and reaction temperature.
KW - ZnSe
KW - Magic-sized cluster
KW - Dodecanethiol
KW - Semiconductor nanocrystals
KW - One-pot synthesis
PY - 2022
U6 - https://doi.org/10.1021/acs.inorgchem.2c00041
VL - 61
IS - 19
SP - 7207
EP - 7211
PB - ACS Publications
CY - Washington, DC (USA)
AN - OPUS4-54880
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Linberg, Kevin
A1 - Röder, Bettina
A1 - Al-Sabbagh, Dominik
A1 - Emmerling, Franziska
A1 - Michalchuk, Adam
T1 - Controlling polymorphism in molecular cocrystals by variable temperature ball milling
N2 - Mechanochemistry offers a unique opportunity to modify and manipulate crystal forms, often providing new products as compared with conventional solution methods. While promising, there is little known about how to control the solid form through mechanochemical means, demanding dedicated investigations. Using a model organic cocrystal system (isonicotinamide:glutaric acid), we here demonstrate that with mechanochemistry, polymorphism can be induced in molecular solids under conditions seemingly different to their conventional thermodynamic (thermal) transition point. Whereas Form II converts to Form I upon heating to 363 K, the same transition can be initiated under ball milling conditions at markedly lower temperatures (348 K). Our results indicate that mechanochemical techniques can help to reduce the energy barriers to solid form transitions, offering new insights into controlling polymorphic forms. Moreover, our results suggest that the nature of mechanochemical transformations could make it difficult to interpret mechanochemical solid form landscapes using conventional equilibrium-based tools.
KW - Mechanochemistry
KW - Polymorphism
KW - TRIS
PY - 2022
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-564728
SP - 1
EP - 16
PB - Royal Society of Chemistry
AN - OPUS4-56472
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Loges, A.
A1 - Scholz, G.
A1 - Amadeu de Sosa, Nader
A1 - Jingjing, S.
A1 - Emmerling, Franziska
A1 - John, T.
A1 - Paulus, B.
A1 - Braun, T.
T1 - Studies on the local structure of the F/OH site in topaz by magic angle spinning nuclear magnetic resonance and Raman spectroscopy
N2 - he mutual influence of F and OH groups in neighboring sites in topaz (Al2SiO4(F,OH)2) was investigated using magic angle spinning nuclear magnetic resonance (MAS NMR) and Raman spectroscopy. The splitting of 19F and 1H NMR signals, as well as the OH Raman band, provides evidence for hydrogen bond formation within the crystal structure. Depending on whether a given OH group has another OH group or fluoride as its neighbor, two different hydrogen bond constellations may form: either OH···O···HO or F···H···O. The proton accepting oxygen was determined to be part of the SiO4 tetrahedron using 29Si MAS NMR. Comparison of the MAS NMR data between an OH-bearing and an OH-free topaz sample confirms that the 19F signal at −130 ppm stems from F− ions that take part in H···F bonds with a distance of ∼ 2.4 Å, whereas the main signal at −135 ppm belongs to fluoride ions with no immediate OH group neighbors. The Raman OH sub-band at 3644 cm−1 stems from OH groups neighboring other OH groups, whereas the sub-band at 3650 cm−1 stems from OH groups with fluoride neighbors, which are affected by H···F bridging. The integrated intensities of these two sub-bands do not conform to the expected ratios based on probabilistic calculations from the total OH concentration. This can be explained by a difference in the polarizability of the OH bond between the different hydrogen bond constellations or partial order or unmixing of F and OH, or a combination of both. This has implications for the quantitative interpretation of Raman data on OH bonds in general and their potential use as a probe for structural (dis-)order. No indication of tetrahedrally coordinated Al was found with 27Al MAS NMR, suggesting that the investigated samples likely have nearly ideal Al/Si ratios, making them potentially useful as high-density electron microprobe reference materials for Al and Si, as well as for F.
KW - Topas
KW - NMR
KW - XRD
PY - 2022
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-561863
SN - 1617-4011
VL - 34
IS - 5
SP - 507
EP - 521
PB - Copernicus Publications
CY - Göttingen
AN - OPUS4-56186
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Emmerling, Franziska
A1 - Hoch, C.
T1 - Laudatio Prof. Dr.-Ing. Caroline Röhr
N2 - It is a laudatio on the ocations of Prof. Dr.-Ing. Caroline Röhrs 60th birthday.
KW - Metal-oxides
PY - 2022
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-561877
SN - 0044-2313
VL - 648
IS - 10
SP - 1
EP - 2
PB - John Wiley & Sons, Ltd
AN - OPUS4-56187
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Zänker, Steffen
A1 - Scholz, G.
A1 - Marquardt, Julien
A1 - Emmerling, Franziska
T1 - Structural changes in Ba-compounds of different hardness induced by high-energy ball milling – evidenced by 137Ba NMR and X-ray powder diffraction
N2 - Changes in the global bulk and local structures, of three different barium compounds (BaZrO3, BaF2, and BaFCl),were induced by mechanical milling and followed using X-ray powder diffraction (PXRD), subsequent microstructure analysis, and 137Ba solid state NMR spectroscopy. Harder materials like BaZrO3 experience significantly higher structural changes upon milling than softer materials like BaF2. Moreover, soft materials with layered structures, like BaFCl, show a pronounced structural change during the milling process. By combining PXRD and solid state NMR, detailed information on the changes to the global and local structures were obtained, which are of interest for mechanochemical synthesis, mechanically treated catalysts or ionic conductors.
KW - Mechanochemistry
KW - X-ray diffraction
KW - Solid state NMR
PY - 2022
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-547397
SN - 0044-2313
VL - 648
IS - 10
SP - 1
EP - 8
PB - Wiley-VCH
CY - Weinheim
AN - OPUS4-54739
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Mazzeo, P. P.
A1 - Prencipe, M.
A1 - Feiler, Torvid
A1 - Emmerling, Franziska
A1 - Bacchi, A.
T1 - On the mechanism of cocrystal mechanochemical reaction via low melting eutectic: A time-resolved in situ monitoring investigation
N2 - Mechanochemistry has become a sustainable and attractive cost-effective synthetic technique, largely used within the frame of crystal engineering. Cocrystals, namely, crystalline compounds made of different chemical entities within the same crystal structure, are typically synthesized in bulk via mechanochemistry; however, whereas the macroscopic aspects of grinding are becoming clear, the fundamental principles that underlie mechanochemical cocrystallization at the microscopic level remain poorly understood. Time-resolved in situ (TRIS) monitoring approaches have opened the door to exceptional detail regarding mechanochemical reactions. We here report a clear example of cocrystallization between two solid coformers that proceeds through the formation of a metastable low melting binary eutectic phase. The overall cocrystallization process has been monitored by time-resolved in situ (TRIS) synchrotron X-ray powder diffraction with a customized ball milling setup, currently available at μ Spot beamline at BESSY-II, Helmholtz-Zentrum Berlin. The binary system and the low melting eutectic phase were further characterized via DSC, HSM, and VT-XRPD.
KW - Mechanochemistry
KW - In situ
KW - Cocrystal
PY - 2022
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-552977
SN - 1528-7505
VL - 22
IS - 7
SP - 4260
EP - 4267
PB - ACS Publ.
CY - Washington, DC
AN - OPUS4-55297
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Kulow, Anicó
A1 - de Oliveira Guilherme Buzanich, Ana
A1 - Reinholz, Uwe
A1 - Emmerling, Franziska
A1 - Hampel, S.
A1 - Fittschen, UEA
A1 - Streli, C.
A1 - Radtke, Martin
T1 - Reconstruction for coded aperture full-field x-ray fluorescence imaging
N2 - X-ray fluorescence imaging is a well-established tool in materials characterization. In this work, we present the adaption of coded aperture imaging to full-field X-ray fluorescence imaging at the synchrotron. Coded aperture imaging has its origins in astrophysics, and has several advantages: Coded apertures are relatively easy to fabricate, achromatic, allow a high photon throughput, and high angular acceptance. Coded aperture imaging is a two-step-process, consisting of the measurement process and a reconstruction step. Different programs have been written, for the raytracing/forward projection and the reconstruction. Experiments with coded aperture in combination with a Color X-ray Camera and an energy-dispersive area detector, have been conducted at the BAMline. Measured samples were successfully reconstructed, and gave a 9.1-fold increase in count rate compared to a polycapillary optic.
KW - Synchrotron
KW - BAMline
KW - Coded Aperture
PY - 2022
SN - 1097-0002
VL - 65
SP - 57
EP - 70
PB - Cambridge University Press
CY - Cambridge
AN - OPUS4-56350
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Lakshmipathi, M.
A1 - Dey, S.
A1 - Emmerling, Franziska
A1 - Bhattacharya, Biswajit
A1 - Michalchuk, Adam
T1 - Designing Dual Mechanical Response in Molecular Crystals through Cocrystallization
N2 - Two isomorphous crystals are reported based on a naphthylvinylpyridine coformer. The crystals are mechanically flexible and exhibit photosalient response to UV irradiation. We therefore show how multiple mechanical phenomena can be simultaneously designed into a single material by cocrystallization.
KW - Cocrystal
KW - Mechanical response
PY - 2022
U6 - https://doi.org/10.1021/acs.cgd.2c00913
SN - 1528-7483
VL - 22
SP - 6838
EP - 6843
PB - ACS Publ.
CY - Washington, DC
AN - OPUS4-56561
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Linberg, Kevin
A1 - Emmerling, Franziska
A1 - Michalchuk, Adam
T1 - Unintended Rate Enhancement in Mechanochemical Kinetics by Using Poly(methyl methacrylate) Jars
N2 - Time-resolved in situ (TRIS) X-ray diffraction has changed how mechanochemical transformations are studied but requires the use of X-ray transparent jars often made from poly(methyl methacrylate) (PMMA). However, using PMMA jars can alter the apparent kinetics of mechanochemical polymorphism by an order of magnitude, questioning the interpretability of established TRIS methods. Our results suggest that rate enhancement in PMMA jars may not be dominated by chemical effects of the polymer, but rather a result of different equilibrium temperatures within the jar. These features must be better understood before control over mechanochemical reactions can be achieved.
KW - Mechanochemistry
KW - Organic compounds
KW - Polymers
KW - Materials
PY - 2022
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-565276
SN - 1528-7483
SP - 1
EP - 5
PB - ACS Publications
AN - OPUS4-56527
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Ravi, J.
A1 - Feiler, Torvid
A1 - Mondal, A.
A1 - Michalchuk, Adam
A1 - Reddy, C. M.
A1 - Bhattacharya, Biswajit
A1 - Emmerling, Franziska
A1 - Chandrasekar, R.
T1 - Plastically bendable organic crystals for monolithic and hybrid micro-optical circuits
N2 - Fluorescent plastically bendable crystals are a promising alternative to silicon-based materials for fabricating photonic integrated circuits, owing to their optical attributes and mechanical compliance. Mechanically bendable plastic organic crystals are rare. Their formation requires anisotropic intermolecular interactions and slip planes in the crystal lattice. This work presents three fluorescent plastically bendable crystalline materials namely, 2-((E)-(6-methylpyridin-2-ylimino)methyl)-4-chlorophenol (SB1), 2-((E)-(6-methylpyridin-2-ylimino)methyl)-4-bromophenol (SB2), and 2-((E)-(6-Bromopyridin-2-ylimino)methyl)-4-bromophenol (SB3) molecules. The crystal plasticity in response to mechanical stress facilitates the fabrication of various monolithic and hybrid (with a tip-to-tip coupling) photonic circuits using mechanical micromanipulation with an atomic force microscope cantilever tip. These plastically bendable crystals act as active (self-guiding of fluorescence) and passive waveguides both in straight and extremely bent (U-, J-, and O-shaped) geometries. These microcircuits use active and passive waveguiding principles and reabsorbance and energy-transfer mechanisms for their operation, allowing input-selective and direction-specific signal transduction.
KW - Flexible crystals
KW - Flexible waveguide
PY - 2022
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-565302
SN - 2195-1071
SP - 1
EP - 10
PB - Wiley-VCH
CY - Weinheim
AN - OPUS4-56530
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Getenet, M.
A1 - Garcia-Ruiz, J. M.
A1 - Otálora, F.
A1 - Emmerling, Franziska
A1 - Al-Sabbagh, Dominik
A1 - Verdugo-Escamilla, E.
T1 - A comprehensive methodology for monitoring evaporitic mineral precipitation and hydrochemical evolution of saline lakes: The case of Lake Magadi soda brine (East African Rift Valley, Kenya)
N2 - Lake Magadi, East African Rift Valley, is a hyperalkaline and saline soda lake highly enriched in Na+, K+, CO32–, Cl–, HCO3–, and SiO2 and depleted in Ca2+ and Mg2+, where thick evaporite deposits and siliceous sediments have been forming for 100 000 years. The hydrogeochemistry and the evaporite deposits of soda lakes are subjects of growing interest in paleoclimatology, astrobiology, and planetary sciences. In Lake Magadi, different hydrates of sodium carbonate/bicarbonate and other saline minerals precipitate. The precipitation sequence of these minerals is a key for understanding the hydrochemical evolution, the paleoenvironmental conditions of ancient evaporite deposits, and industrial crystallization. However, accurate determination of the precipitation sequence of these minerals was challenging due to the dependency of the different hydrates on temperature, water activity, pH and pCO2, which could induce phase transformation and secondary mineral precipitation during sample handling. Here, we report a comprehensive methodology applied for monitoring the evaporitic mineral precipitation and hydrochemical evolution of Lake Magadi. Evaporation and mineral precipitations were monitored by using in situ video microscopy and synchrotron X-ray diffraction of acoustically levitated droplets. The mineral patterns were characterized by ex situ Raman spectroscopy, X-ray diffraction, and scanning electron microscopy. Experiments were coupled with thermodynamic models to understand the evaporation and precipitation-driven hydrochemical evolution of brines. Our results closely reproduced the mineral assemblages, patterns, and textural relations observed in the natural setting. Alkaline earth carbonates and fluorite were predicted to precipitate first followed by siliceous sediments. Among the salts, dendritic and acicular trona precipitate first via fractional crystallization─reminiscent of grasslike trona layers of Lake Magadi. Halite/villiaumite, thermonatrite, and sylvite precipitate sequentially after trona from residual brines depleted in HCO3–. The precipitation of these minerals between trona crystals resembles the precipitation process observed in the interstitial brines of the trona layers. Thermonatrite precipitation began after trona equilibrated with the residual brines due to the absence of excess CO2 input. We have shown that evaporation and mineral precipitation are the major drivers for the formation of hyperalkaline, saline, and SiO2-rich brines. The discrepancy between predicted and actual sulfate and phosphate ion concentrations implies the biological cycling of these ions. The combination of different in situ and ex situ methods and modeling is key to understanding the mineral phases, precipitation sequences, and textural relations of modern and ancient evaporite deposits. The synergy of these methods could be applicable in industrial crystallization and natural brines to reconstruct the hydrogeochemical and hydroclimatic conditions of soda lakes, evaporite settings, and potentially soda oceans of early Earth and extraterrestrial planets.
KW - Crystallization
KW - Precipitation
KW - Crystals
KW - Evaporation
KW - Minerals
PY - 2022
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-546712
SN - 1528-7483
VL - 22
IS - 4
SP - 2307
EP - 2317
PB - ACS Publications
CY - Washington, DC
AN - OPUS4-54671
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Wolf, J.
A1 - Stawski, Tomasz
A1 - Smales, Glen Jacob
A1 - Thünemann, Andreas
A1 - Emmerling, Franziska
T1 - Towards automation of the polyol process for the synthesis of silver nanoparticles
N2 - Metal nanoparticles have a substantial impact across diferent felds of science, such as photochemistry, energy conversion, and medicine. Among the commonly used nanoparticles, silver nanoparticles are of special interest due to their antibacterial properties and applications in sensing and catalysis. However, many of the methods used to synthesize silver nanoparticles often do not result in well-defned products, the main obstacles being high polydispersity or a lack of particle size tunability. We describe an automated approach to on-demand synthesis of adjustable particles with mean radii of 3 and 5 nm using the polyol route. The polyol process is a promising route for silver nanoparticles e.g., to be used as reference materials. We characterised the as-synthesized nanoparticles using small-angle X-ray scattering, dynamic light scattering and further methods, showing that automated synthesis can yield colloids with reproducible and tuneable properties.
KW - Sillver
KW - Nanoparticles
KW - Automated synthesis
KW - Chemputer
KW - Scattering
KW - SAXS
PY - 2022
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-546803
VL - 12
IS - 1
SP - 1
EP - 9
PB - Nature Springer
AN - OPUS4-54680
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Martins, Ines
A1 - Al-Sabbagh, Dominik
A1 - Bentrup, U.
A1 - Marquardt, Julien
A1 - Schmid, Thomas
A1 - Scoppola, E.
A1 - Kraus, Werner
A1 - Stawski, Tomasz
A1 - de Oliveira Guilherme Buzanich, Ana
A1 - Yusenko, Kirill
A1 - Weidner, Steffen
A1 - Emmerling, Franziska
T1 - Formation Mechanism of a Nano-Ring of Bismuth Cations and Mono-Lacunary Keggin-Type Phosphomolybdate
N2 - A new hetero-bimetallic polyoxometalate (POM) nano-ring was synthesized in a one-pot procedure. The structure consists of tetrameric units containing four bismuth-substituted monolacunary Keggin anions including distorted [BiO8] cubes. The nano-ring is formed via self-assembly from metal precursors in aqueous acidic medium. The compound (NH4)16[(BiPMo11O39)4] ⋅ 22 H2O; (P4Bi4Mo44) was characterized by single-crystal X-ray diffraction, extended X-ray absorption fine structure spectroscopy (EXAFS), Raman spectroscopy, matrix-assisted laser desorption/ionisation-time of flight mass spectrometry (MALDI-TOF), and thermogravimetry/differential scanning calorimetry mass spectrometry (TG-DSC-MS). The formation of the nano-ring in solution was studied by time-resolved in situ small- and wide-angle X-ray scattering (SAXS/WAXS) and in situ EXAFS measurements at the Mo−K and the Bi−L3 edge indicating a two-step process consisting of condensation of Mo-anions and formation of Bi−Mo-units followed by a rapid self-assembly to yield the final tetrameric ring structure.
KW - Bismuth
KW - In situ EXAFS
KW - In situ SAXS/WAXS
KW - Lacunary Keggin ion
KW - Polyoxometalates
KW - Self-assembly
PY - 2022
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-546823
SN - 0947-6539
VL - 28
IS - 27
SP - 1
EP - 7
PB - Wiley-VCH
CY - Weinheim
AN - OPUS4-54682
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Rautenberg, Max
A1 - Gernhard, M.
A1 - Radnik, Jörg
A1 - Witt, Julia
A1 - Roth, C.
A1 - Emmerling, Franziska
T1 - Mechanochemical synthesis of fluorine-containing Co-doped zeolitic imidazolate frameworks for producing electrocatalysts
N2 - Catalysts derived from pyrolysis of metal organic frameworks (MOFs) are promising candidates to replace expensive and scarce platinum-based electrocatalysts commonly used in polymer electrolyte membrane fuel cells. MOFs contain ordered connections between metal centers and organic ligands. They can be pyrolyzed into metal- and nitrogen-doped carbons, which show electrocatalytic activity toward the oxygen reduction reaction (ORR). Furthermore, metal-free heteroatom-doped carbons, such as N-F-Cs, are known for being active as well. Thus, a carbon material with Co-N-F doping could possibly be even more promising as ORR electrocatalyst. Herein, we report the mechanochemical synthesis of two polymorphs of a zeolitic imidazole framework, Co-doped zinc 2-trifluoromethyl-1H-imidazolate (Zn0.9Co0.1(CF3-Im)2). Time-resolved in situ X-ray diffraction studies of the mechanochemical formation revealed a direct conversion of starting materials to the products. Both polymorphs of Zn0.9Co0.1(CF3-Im)2 were pyrolyzed, yielding Co-N-F containing carbons, which are active toward electrochemical ORR.
KW - Mechanochemistry
KW - Metal-organic-frameworks
KW - Nobel-metal free electrocatalysis
PY - 2022
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-546833
SN - 2296-2646
VL - 10
IS - 840758
SP - 1
EP - 13
PB - Frontiers Media
CY - Lausanne
AN - OPUS4-54683
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Gugin, Nikita
A1 - Villajos Collado, José Antonio
A1 - Feldmann, Ines
A1 - Emmerling, Franziska
T1 - Mix and wait – a relaxed way for synthesizing ZIF-8
N2 - Herein we report the synthesis of a zeolitic imidazolate framework (ZIF-8) by an easy “mix and wait” procedure. In a closed vial, without any interference, the mixture of 2-methylimidazole and basic zinc carbonate assembles into the crystalline product with approx. 90% conversion after 70 h. The reaction exhibits sigmoidal kinetics due to the self-generated water which accelerates the reaction.
KW - In-situ analysis
KW - Mechanochemistry
KW - MOF
KW - Synthesis
KW - ZIF-8
PY - 2022
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-546841
VL - 12
SP - 8940
EP - 8944
PB - Royal Society of Chemistry
AN - OPUS4-54684
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Emmerling, Franziska
A1 - Martins, Ines
T1 - Carbamazepine Dihydroxybenzoic Acid Cocrystals: Exploring Packing Interactions and Reaction Kinetics
N2 - Herein, we present the mechanochemical formation of three new cocrystals containing the active pharmaceutical ingredient carbamazepine and dihydroxybenzoic acids as coformers (CBZ:2,4-DHBA 1:1, CBZ:2,5-DHBA 1:1, and CBZ:2,6-DHBA 1:1). Rietveld methods were used for three different purposes: (i) refining all structures solved using powder X-ray diffraction, (ii) performing a quantitative phase analysis of the diffraction data collected from ex situ mechanochemical reactions at different milling times, and (iii) determining the cocrystallization kinetic profiles. The rate of cocrystallization was found to be higher for the formation of CBZ:2,4-DHBA and CBZ:2,6-DHBA, reaching an equilibrium after 600 s of milling. In the case of CBZ:2,5-DHBA a short induction period of 20 s was detected prior to the start of the reaction and an equilibrium was reached after 1200 s. An empirical trend between the rate of cocrystallization and the structural complexity of the cocrystal product was found. The slowest cocrystallization rate observed for CBZ:2,5-DHBA corresponds to the crystal structure deviating substantially from the hydrogen-bonding motif found in the reactants.
KW - Mechanochemistry
KW - In situ real-time monitoring
KW - Kinetics
PY - 2021
U6 - https://doi.org/10.1021/acs.cgd.1c00902
VL - 21
IS - 12
SP - 6961
EP - 6970
PB - ACS Publications
AN - OPUS4-54407
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Stawski, Tomasz
A1 - Smales, Glen Jacob
A1 - Scoppola, E.
A1 - Jha, D.
A1 - Morales, L. F. G.
A1 - Moya, A.
A1 - Wirth, R.
A1 - Pauw, Brian Richard
A1 - Emmerling, Franziska
A1 - Van Driessche, A. E. S.
T1 - Seeds of imperfection rule the mesocrystalline disorder in natural anhydrite single crystals
N2 - In recent years, we have come to appreciate the astounding intricacies associated with the formation of minerals from ions in aqueous solutions. In this context, a number of studies have revealed that the nucleation of calcium sulfate systems occurs nonclassically, involving the aggregation and reorganization of nanosized prenucleation species. In recent work, we have shown that this particle-mediated nucleation pathway is actually imprinted in the resultant micrometer-sized CaSO4 crystals. This property of CaSO4 minerals provides us with the unique opportunity to search for evidence of nonclassical nucleation pathways in geological environments.
In particular, we focused on large anhydrite Crystals extracted from the Naica Mine in Mexico. We were able to shed light on this mineral's growth history by mapping defects at different length scales. Based on this, we argue that the nanoscale misalignment of the structural subunits, observed in the initial calcium sulfate crystal seeds, propagates through different length scales both in morphological, as well as in strictly crystallographic aspects, eventually causing the formation of large mesostructured single crystals of anhydrite. Hence, the nonclassical nucleation mechanism introduces a “seed of imperfection,” which leads to a macroscopic “single” crystal whose fragments do not fit together at different length scales in a self-similar manner. Consequently, anisotropic voids of various sizes are formed with very welldefined walls/edges. However, at the same time, the material retains in part its single crystal nature.
KW - Calcium sulfate
KW - Anhydrite
KW - Mesocrystal
KW - Nucleation
KW - Naica
PY - 2021
U6 - https://doi.org/10.1073/pnas.2111213118
SN - 0027-8424
VL - 118
IS - 48
SP - 1
EP - 11
PB - National Academy of Sciences (USA)
CY - Washington
AN - OPUS4-53820
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Yusenko, Kirill
A1 - Kabelitz, Anke
A1 - Schokel, Alexander
A1 - Wagner, Ralf
A1 - Prinz, Carsten
A1 - Kemnitz, E
A1 - Emmerling, Franziska
A1 - Krahl, Thoralf
A1 - de Oliveira Guilherme Buzanich, Ana
T1 - Local Structure of Europium-Doped Luminescent Strontium Fluoride Nanoparticles: Comparative X-ray Absorption Spectroscopy and Diffraction Study
N2 - Rare-earth based luminescent materials are key functional components for the rational design of light-conversion smart devices. Stable Eu3+-doped strontium fluoride (SrF2) nanoparticles were prepared at room temperature in ethylene glycol. Their luminescence depends on the Eu content and changes after heat treatment. The crystallinity of heat-treated material increases in comparison with as-synthesized samples. Particles were investigated in solution using X-ray diffraction, small-angle X-ray scattering, and X-ray spectroscopy. After heat treatment, the size of the disordered nanoparticles increases together with a change of their local structure. Interstitial fluoride ions can be localized near Eu3+ ions. Therefore, non-radiative relaxation from other mechanisms is decreased. Knowledge about the cation distribution is key information for understanding the luminescence properties of any material.
KW - SrF2
KW - EXAFS
KW - Eu
PY - 2021
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-540094
VL - 7
IS - 11
SP - 1221
EP - 1229
PB - Wiley Online Library
AN - OPUS4-54009
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Michalchuk, Adam
A1 - Emmerling, Franziska
T1 - Time-Resolved InSitu Monitoring of Mechanochemical Reactions
N2 - Mechanochemical transformations offer environmentally benign synthesis routes, whilst enhancing both the speed and selec-tivity of reactions. In this light, mechanochemistry promises to trans-form the way in which chemistry is done in both academia and indus-try but is greatly hindered by a current lack in mechanistic understand-ing. The continued development and use of time-resolved in situ(TRIS) approaches to monitor mechanochemical reactions provides a new dimension to elucidatethese fascinating transformations. We here discuss recent trends in method development that have pushed the boundaries of mechanochemical research. New features of mech-anochemical reactions obtained by TRIS techniques are subse-quently discussed, shedding light on how different TRISapproaches have beenused. Emphasis is placed on the strength of combining complementary techniques. Finally, we outline our views for the po-tential of TRIS methods in mechanochemical research, towards es-tablishing a new, environmentally benign paradigm in the chemical sciences
KW - Mechanochemistry
KW - Material synthesis
KW - Green chemistry
PY - 2022
U6 - https://doi.org/10.1002/anie.202117270
SN - 1433-7851
SP - 1
EP - 15
PB - Wiley-VCH
CY - Weinheim
AN - OPUS4-54321
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Casali, C.
A1 - Feiler, Torvid
A1 - Heilmann, Maria
A1 - Braga, D.
A1 - Emmerling, Franziska
A1 - Grepioni, F.
T1 - Too much water? Not enough? In situ monitoring of the mechanochemical reaction of copper salts with dicyandiamide
N2 - n situ monitoring of mechanochemical reactions between dicyandiamide (DCD) and CuX2 salts (X = Cl−, NO3−), for the preparation of compounds of agrochemical interest, showed the appearance of a number of phases. It is demonstrated that milling conditions, such as the amount of water added in wet grinding and/or the milling frequency, may affect the course of the mechanochemical reactions, and drive the reaction towards the formation of different products. It has been possible to discover by in situ monitored experiments two novel crystalline forms, namely the neutral complexes [Cu(DCD)2(OH2)2(NO3)2] (2) and [Cu(DCD)2(OH2)Cl2]·H2O (4), in addition to the previously known molecular salt [Cu(DCD)2(OH2)2][NO3]2·2H2O (1, DIVWAG) and neutral complex [Cu(DCD)2(OH2)Cl2] (3, AQCYCU), for which no synthesis conditions were available. Compounds 2 and 4 were fully characterized via a combination of solid-state techniques, including X-ray diffraction, Raman spectroscopy and TGA.
KW - Mechanochemistry
KW - In situ
PY - 2022
U6 - https://doi.org/10.1039/d1ce01670a
VL - 24
IS - 6
SP - 1292
EP - 1298
PB - RSC
AN - OPUS4-54344
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Heilmann, Maria
A1 - Prinz, Carsten
A1 - Bienert, Ralf
A1 - Wendt, R.
A1 - Kunkel, B.
A1 - Radnik, Jörg
A1 - Hoell, A.
A1 - Wohlrab, S.
A1 - de Oliveira Guilherme Buzanich, Ana
A1 - Emmerling, Franziska
T1 - Size-Tunable Ni–Cu Core–Shell Nanoparticles—Structure, Composition, and Catalytic Activity for the Reverse Water–Gas Shift Reaction
N2 - A facile and efficient methodology is described for the solvothermal synthesis of size-tunable, stable, and uniform NiCu core–shell nanoparticles (NPs) for application in catalysis. The diameter of the NPs is tuned in a range from 6 nm to 30 nm and to adjust the Ni:Cu ratio from 30:1 to 1:1. Furthermore, the influence of different reaction parameters on the final NPs is studied. The NPs are structurally characterized by a method combination of transmission electron microscopy, anomalous small-angle X-ray scattering, X-ray absorption fine structure, and X-ray photoelectron spectroscopy. Using these analytical methods, it is possible to elucidate a core–shell–shell structure of all particles and their chemical composition. In all cases, a depletion from the core to the shell is observed, with the core consisting of NiCu alloy, surrounded by an inner Ni-rich shell and an outer NiO shell. The SiO2-supported NiCu core–shell NPs show pronounced selectivity of >99% for CO in the catalytic reduction of CO2 to CO using hydrogen as reactant (reverse water–gas shift reaction) independent of size and Ni:Cu ratio.
KW - Nanoparticles
KW - Core-shell
KW - Catalysis
PY - 2022
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-543606
SN - 1438-1656
SP - 1
EP - 13
PB - Wiley VCH
AN - OPUS4-54360
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Lakshmipathi, M.
A1 - Tothadi, S.
A1 - Emmerling, Franziska
A1 - Bhattacharya, Biswajit
A1 - Ghosh, S.
T1 - Different mechanical responses of dimorphic forms of Anthracene Schiffbase crystal
N2 - We obtained concomitant dimorphic forms of Anthracene Schiffbase (N-(anthracen-9-yl methylene)-2,5- dichloroaniline) from hexane solvent. Two polymorphs can be differentiated by their morphology and mechanical properties. One form is long acicular type and elastically bendable while another form is block shaped and brittle in nature. Mechanical property is attributed to underlying crystal packing. Hirsh- feld analysis and energy framework calculations were done to corroborate structure-property correlation of two forms.
KW - Elasticity
KW - Mechanical properties
KW - Anthracene schiff base
KW - Dimorphs
PY - 2021
U6 - https://doi.org/10.1016/j.molstruc.2021.132182
VL - 1252
SP - 1
EP - 8
PB - Elsevier B.V.
AN - OPUS4-54356
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Emmerling, Franziska
T1 - In situ investigations of mechanochemical processes
N2 - Overview of the present BAM activities in the field of in situ analytics of mechanochemical processes. Recent results for the synthesis of metal organic frameworks and cocrystals are presented.
T2 - HZB Seminar
CY - Online meeting
DA - 21.01.2022
KW - Mechanochemistry
KW - In situ real-time monitoring
PY - 2022
AN - OPUS4-54296
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Yusenko, Kirill
A1 - Emmerling, Franziska
A1 - de Oliveira Guilherme Buzanich, Ana
T1 - X-Ray absorption spectroscopy to study multicomponent materials
N2 - Detailed study of multicomponent systems in solid-state as well as in solution using X-ray diffraction and X-ray spectroscopy is one of the most common topics in modern materials chemistry. 5-6 component high-entropy alloys such as fcc- and bcc-structured AlxCoCrFeNi and fluorescent nanoparticles based on fluorite-structured SrF2 doped by rare-earth metals in organic solutions have high complexity and their local structure cannot be resolved using only diffraction. X-ray absorption spectroscopy should be applied to understand peculiarities in their local structure and make a link between structure on short and long ranges and their macroscopic properties. Here, based on two representativee examples, we discuss how a combination of several X-ray absorption edges might give new insights into complex materials.
T2 - Virtual meeting of the African Light Source
CY - Online meeting
DA - 15.11.2021
KW - EXAFS
KW - Synchrotron studies
PY - 2021
AN - OPUS4-54014
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Casali, L.
A1 - Broll, V.
A1 - Ciurili, S.
A1 - Braga, D.
A1 - Emmerling, Franziska
A1 - Gepioni, F.
T1 - Facilitating Nitrification Inhibition through Green, Mechanochemical Synthesis of a Novel Nitrapyrin Complex
N2 - Nitrapyrin (NP) is applied to cultivated soils to inhibit the enzymatic activity of ammonia monooxygenase (AMO), but its poor aqueous solubility and high volatility severely limit its application. β-Cyclodextrin (β-CD) is commonly used to form inclusion complexes with hydrophobic molecules, improving water solubility and stability upon complexation. Here we report on the mechanochemical synthesis of the inclusion complex β-CD·NP, characterized via a combination of solid-state techniques, including exsitu and in situ X-ray diffraction, Raman and NMR spectroscopies, transmission electron microscopy, and energy dispersive X-ray spectroscopy. The pure inhibitor NP was also structurally characterized. The β-CD·NP complex presents improved solubility and thermal stability, and still inhibits the enzymatic activity of AMO with high efficacy. All results indicate that the inclusion of NP into β-CD represents a viable route for the preparation of a novel class of inhibitors, with improved properties related to stability, water solubility, and good inhibition activity.
KW - Mechanochemistry
KW - Nitrification
PY - 2021
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-537154
VL - 21
IS - 10
SP - 5792
EP - 5799
PB - ACS Publications
AN - OPUS4-53715
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Emmerling, Franziska
T1 - Shaken not stirred: enhancing the flavor of mechanochemistry
N2 - Mechanochemistry is increasingly used for synthesizing soft matter materials including metal organic compounds and cocrystals.1 The ever-increasing interest in this method is contrasted by a limited mechanistic understanding of the mechanochemical reactivity and selectivity. Time-resolved in situ investigations of milling reactions provide direct insights in the underlying mechanisms.2-4 We recently introduced different setups enabling in situ investigation of mechanochemical reactions using synchrotron XRD combined with Raman spectroscopy and thermography. The presented setup allows the detection of crystalline, amorphous, eutectic, and liquid intermediates. Furthermore, the chemical composition of the reaction mixture was found to be directly correlated with changes in the temperature profile of the reaction. The resulting deeper kinetic and thermodynamic understanding of milling processes is the key for future optimization of mechanochemical syntheses. In this contribution, we will discuss our recent results investigating the formation of (polymorphic) cocrystals and coordination polymers.2,3,5 Our results indicate that in situ investigation of milling reactions offer a new approach to tune and optimize mechanochemical syntheses.
T2 - BCA/BACG joint spring meeting
CY - Online meeting
DA - 29.03.2021
KW - Mechanochemistry
KW - Cocrystals
KW - Crystal Engineering
PY - 2021
AN - OPUS4-53995
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Emmerling, Franziska
T1 - Shaken not stirred: in situ investigations of mechanochemical processes
N2 - Mechanochemistry has emerged as one of the most interesting synthetic protocols to produce new materials. The development of mechanochemistry as a synthetic method is supported by excellent research by many groups worldwide in a wide range of applications. The potential of mechanochemistry is also reflected in the inclusion in IUPAC’s 10 chemical innovations that will change our world’.[1] Solvent-free methodologies lead to unique chemical processes during synthesis with the consequent formation of martials with new properties.2 In this contribution, we will discuss our recent results investigating the formation of (polymorphic) cocrystals, coordination polymers, metal oxides and metal nanoparticles.[3-8] We introduced different setups enabling in situ investigation of mechanochemical reactions using synchrotron XRD combined with Raman spectroscopy and thermography.
T2 - Deutsche Kristallzüchtertagung
CY - Berlin, Germany
DA - 06.10.2021
KW - Mechanochemistry
KW - In situ real-time monitoring
KW - Crystal
PY - 2021
AN - OPUS4-53996
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Emmerling, Franziska
T1 - Scientific Writing - best practice tools
N2 - Personal view of an experienced writer on how to write a paper.
T2 - MatchingCamp 2021
CY - Bad Belzig, Germany
DA - 08.11.2021
KW - Writing
PY - 2021
AN - OPUS4-53999
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Lee, P.-W.
A1 - Kaynak, T.
A1 - Al-Sabbagh, Dominik
A1 - Emmerling, Franziska
A1 - Schalley, C.
T1 - Effect of Perfluorinated Side-Chain Length on the Morphology, Hydrophobicity, and Stability of Xerogel Coatings
N2 - Superhydrophobic surfaces can be quickly formed with supramolecular materials. Incorporating low-molecular-weight gelators (LMWGs) with perfluorinated chains generates xerogel coatings with low surface energies and high roughness. Here, we examine and compare the properties of the xerogel coatings formed with eight different LMWGs. These LMWGs all have a trans-1,2-diamidocyclohexane core and two perfluorinated ponytails, whose lengths vary from three to ten carbon atoms (CF3 to CF10). Investigation of the xerogels aims to provide in-depth information on the chain length effect. LMWGs with a higher degree of fluorination (CF7 to CF10) form superhydrophobic xerogel coatings with very low surface energies. Scanning electron microscopy images of the coatings show that the aggregates of CF5 and CF7 are fibrous, while the others are crystal-like. Aggregates of CF10 are particularly small and further assemble into a porous structure on the micrometer scale. To test their stabilities, the xerogel coatings were flushed multiple times with a standardized water flush test. The removal of material from the surface in these flushes was monitored by a combination of the water contact angle, contact angle hysteresis, and coating thickness measurements. A new method based on image processing techniques was developed to reliably determine the change of the coating thickness. The CF7, CF9, and CF10 surfaces show consistent hydrophobicity and coating durability after repetitive flushing tests. The length of the perfluorinated side chains thus has a significant effect on the morphology of the deposited xerogel coatings, their roughness, and, in consequence, their hydrophobicity and mechanical durability.
KW - Coating materials
KW - Amorphous materials
KW - Hydrophobicity
KW - Materials Stability
PY - 2021
U6 - https://doi.org/10.1021/acs.langmuir.1c02341
SN - 1520-5827
VL - 37
IS - 49
SP - 14390
EP - 14397
PB - ACS Publications
AN - OPUS4-54071
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Feiler, Torvid
A1 - Michalchuk, Adam
A1 - Schröder, V.
A1 - List-Kratochvil, E.
A1 - Emmerling, Franziska
A1 - Bhattacharya, Biswajit
T1 - Elastic Flexibility in an Optically Active Naphthalidenimine-Based Single Crystal
N2 - Organic single crystals that combine mechanical flexibility and optical properties are important for developing flexible optical devices, but examples of such crystals remain scarce. Both mechanical flexibility and optical activity depend on the underlying crystal packing and the nature of the intermolecular interactions present in the solid state. Hence, both properties can be expected to be tunable by small chemical modifications to the organic molecule. By incorporating a chlorine atom, a reportedly mechanically flexible crystal of (E)-1-(4-bromo-phenyl)iminomethyl-2-hydroxylnaphthalene (BPIN) produces (E)-1-(4-bromo-2-chloro-phenyl)iminomethyl-2-hydroxyl-naphthalene (BCPIN). BCPIN crystals show elastic bending similar to BPIN upon mechanical stress, but exhibit a remarkable difference in their optical properties as a result of the chemical modification to the backbone of the organic molecule. This work thus demonstrates that the optical properties and mechanical flexibility of molecular materials can, in principle, be tuned independently.
KW - Elastic Crystal
PY - 2021
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-539040
VL - 11
IS - 11
SP - 1397
PB - MDPI
AN - OPUS4-53904
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - GEN
A1 - Stawski, Tomasz
A1 - Smales, Glen Jacob
A1 - Scoppola, E.
A1 - Jha, D.
A1 - Morales, L. F. G.
A1 - Moya, A.
A1 - Wirth, R.
A1 - Pauw, Brian Richard
A1 - Emmerling, Franziska
A1 - Van Driessche, A. E. S.
T1 - Supplementary data set for "Seeds of imperfection rule the mesocrystalline disorder in natural anhydrite single crystals"
N2 - In recent years, we have come to appreciate the astounding intricacy of the formation process of minerals from ions in aqueous solutions. In this context, a number of studies have revealed that nucleation in the calcium sulfate system is non-classical, involving the aggregation and reorganization of nanosized prenucleation particles. In a recent work we have shown that this particle-mediated nucleation pathway is actually imprinted in the resultant single micron-sized CaSO4 crystals. This property of CaSO4 minerals provides us with an unique opportunity to search for evidence of non-classical nucleation pathways in geological environments. In particular, we focused on the quintessential single crystals of anhydrite extracted from the Naica mine in Mexico. We elucidated the growth history from this mineral sample by mapping growth defects at different length scales. Based on these data we argue that the nano-scale misalignment of the structural sub-units observed in the initial calcium sulfate crystal seed propagate through different length-scales both in morphological, as well as strictly crystallographic aspects, eventually causing the formation of large mesostructured single crystals of anhydrite. Hence, the nanoparticle mediated nucleation mechanism introduces a 'seed of imperfection', which leads to a macroscopic single crystal, in which its fragments do not fit together at different length-scales in a self-similar manner. Consequently, anisotropic voids of various sizes are formed with very well-defined walls/edges. But, at the same time the material retains its essential single crystal nature. These findings shed new light on the longstanding concept of crystal structure.
KW - Calcium sulfate
KW - Mesocrystal
KW - Anhydrite
PY - 2021
U6 - https://doi.org/10.5281/zenodo.4943234
PB - Zenodo
CY - Geneva
AN - OPUS4-53765
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Heilmann, Maria
A1 - Simões, R. G.
A1 - Bernardes, C. E. S.
A1 - Ramisch, Yen
A1 - Bienert, Ralf
A1 - Röllig, Matthias
A1 - Emmerling, Franziska
A1 - Minas da Piedade, M. E.
T1 - Real-Time In situ XRD Study of Simvastatin Crystallization in Levitated Droplets
N2 - Simvastatin (SV) is an important active pharmaceutical ingredient (API) for treatment of hyperlipidemias, which is known to exist in different crystalline and amorphous phases. It is, therefore, an interesting model to investigate how the outcome of evaporative crystallization in the contactless environment of an acoustically levitated droplet may be influenced by key experimental conditions, such as temperature, solvent properties (e.g., polarity and hygroscopicity), and dynamics of the evaporation process. Here, we describe a real-time and in situ study of simvastatin evaporative crystallization from droplets of three solvents that differ in volatility, polarity, and protic character (acetone, ethanol, and ethyl acetate). The droplet monitorization relied on synchrotron X-ray diffraction (XRD), Raman spectroscopy, imaging, and thermographic analysis. A pronounced solvent-dependent behavior was observed. In ethanol, a simvastatin amorphous gel-like material was produced, which showed no tendency for crystallization over time; in ethyl acetate, a glassy material was formed, which crystallized on storage over a two-week period to yield simvastatin form I; and in acetone, form I crystallized upon solvent evaporation without any evident presence of a stable amorphous intermediate. The XRD and Raman results further suggested that the persistent amorphous phase obtained from ethanol and the amorphous precrystallization intermediate formed in ethyl acetate were similar. Thermographic analysis indicated that the evaporation process was accompanied by a considerable temperature decrease of the droplet surface, whose magnitude and rate correlated with the solvent volatility (acetone > ethyl acetate > ethanol). The combined thermographic and XRD results also suggested that, as the cooling effect increased, so did the amount of residual water (most likely captured from the atmosphere) remaining in the droplet after the organic solvent was lost. Finally, the interpretation of the water fingerprint in the XRD time profiles was aided by molecular dynamics simulations, which also provided insights into the possible role of H2O as an antisolvent that facilitates simvastatin crystallization.
KW - Simvastatin
KW - In-situ
KW - API
KW - Crystallization
PY - 2021
U6 - https://doi.org/10.1021/acs.cgd.1c00509
SN - 1528-7483
VL - 21
IS - 8
SP - 4665
EP - 4673
PB - ACS Publications
AN - OPUS4-53663
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Liu, X.
A1 - Michalchuk, Adam
A1 - Bhattacharya, Biswajit
A1 - Emmerling, Franziska
A1 - Pulham, C.
T1 - High-pressure reversibility in a plastically flexible coordination polymer crystal
N2 - Single crystals which exhibit mechanical flexibility are promising materials for advanced technological applications. Before such materials can be used, a detailed understanding of the mechanisms of bending is needed. Using single crystal X-ray diffraction and microfocus Raman spectroscopy, we study in atomic detail the high-pressure response of the plastically flexible coordination polymer [Zn(μ-Cl)2(3,5-dichloropyridine)2]n (1). Contradictory to three-point bending, quasi-hydrostatic compression of (1) is completely reversible, even following compression to over 9 GPa. A structural phase transition is observed at ca. 5 GPa. DFT calculations show this transition to result from the pressure-induced softening of low-frequency vibrations. This phase transition is not observed during three-point-bending. Microfocus synchrotron X-ray diffraction revealed that bending yields significant mosaicity, as opposed to compression. Hence, our studies indicate of overall disparate mechanical responses of bulk flexibility and quasi-hydrostatic compression within the same crystal lattice. We suspect this to be a general feature of plastically bendable materials.
KW - High pressure
KW - Density functional theory
KW - Mechanically flexible crystals
PY - 2021
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-530360
VL - 12
IS - 1
SP - 3871
AN - OPUS4-53036
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Lampronti, G.
A1 - Michalchuk, Adam
A1 - Mazzeo, P.
A1 - Belenguer, Ana
A1 - Sanders, J. K. M.
A1 - Bacchi, A.
A1 - Emmerling, Franziska
T1 - Changing the game of time resolved X-ray diffraction on the mechanochemistry playground by downsizing
N2 - Time resolved in situ (TRIS) monitoring has revolutionised the study of mechanochemical transformations but has been limited by available data quality. Here we report how a combination of miniaturised grinding jars together with innovations in X-ray powder diffraction data collection and state-of-the-art analysis strategies transform the power of TRIS synchrotron mechanochemical experiments. Accurate phase compositions, comparable to those obtained by ex situ measurements, can be obtained with small sample loadings. Moreover, microstructural parameters (crystal size and microstrain) can be also determined with high confidence. This strategy applies to all chemistries, is readily implemented, and yields high-quality diffraction data even using a low energy synchrotron source. This offers a direct avenue towards the mechanochemical investigation of reactions comprising scarce, expensive, or toxic compounds. Our strategy is applied to model systems, including inorganic, metal-organic, and organic mechanosyntheses, resolves previously misinterpreted mechanisms in mechanochemical syntheses, and promises broad, new directions for mechanochemical research.
KW - Mechanochemistry
KW - Synchrotron radiation
KW - Material synthesis
PY - 2021
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-535932
SN - 2041-1723
VL - 12
IS - 1
SP - 1
EP - 9
PB - Nature Publishing Group
CY - London
AN - OPUS4-53593
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Gernhard, M.
A1 - Rautenberg, Max
A1 - Hörner, G.
A1 - Weber, B.
A1 - Emmerling, Franziska
A1 - Roth, C.
T1 - Mechanochemical Synthesis as a Greener Way to ProduceIron-based Oxygen Reduction Catalysts
N2 - Iron-based catalysts have been reported manifold and studied as platinum group metal (PGM) free alternatives for the catalysis of the oxygen reduction reaction (ORR). However, their sustainable preparation by greener synthesis approaches is usually not discussed. In this work, we propose a new method for the sustainable preparation of such catalysts by using a mechanochemical approach, with no solvents and non-toxic chemicals. The materials obtained from low temperature carbonization (700 °C) exhibit considerable and stable catalytic performance for ORR in alkaline medium. A catalyst obtained
from iron hydroxide, tryptophan, dicyandiamide, and ammonium nitrate shows the best electrocatalytic Performance with an overpotential of 921 mV vs. RHE at 0.1 mA/cm2 and an electron transfer number of 3.4.
KW - PGM-free catalyst
KW - Oxygen Reduction Reaction
KW - AEMFC
KW - Mössbauer Spectroscopy
KW - Sustainable Synthesis
PY - 2021
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-535326
VL - 647
IS - 22
SP - 2080
EP - 2087
PB - Weinheim-VCH GmbH
AN - OPUS4-53532
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Martins, I.
A1 - Carta, M.
A1 - Haferkamp, Sebastian
A1 - Feiler, Torvid
A1 - Delogu, F.
A1 - Colacino, E.
A1 - Emmerling, Franziska
T1 - Mechanochemical N‑Chlorination Reaction of Hydantoin: In Situ Real-Time Kinetic Study by Powder X‑ray Diffraction and Raman Spectroscopy
N2 - Mechanochemistry has become a valuable tool for the synthesis of new molecules, especially in the field of organic chemistry. In the present work, we investigate the kinetic profile of the chlorination reaction of N-3-ethyl-5,5-dimethylhydantoin (EDMH) activated and driven by ball milling. The reaction has been carried out using 2 mm, 4 mm, 5 mm, 6 mm, and 8 mm ball sizes in a new small custom-made Perspex milling jar. The Crystal structure of the starting material EDMH and the 1-chloro-3-ethyl5,5′-dimethyl hydantoin (CEDMH) chlorination product was solved by single-crystal X-ray diffraction. The reaction was monitored, in situ and in real time, by both powder X-ray diffraction (PXRD) and Raman spectroscopy. Our kinetic data show that the reaction progress to equilibrium is similar at all milling ball sizes. The induction period is very short (between 10 and 40 s) when using 4 mm, 5 mm, 6 mm, and 8 mm balls. For the reaction performed with a 2 mm ball, a significantly longer induction period of 9 min was observed. This could indicate that an initial energy accumulation and higher mixing efficiency are necessary before the reaction starts. Using different kinetic models, we found that the amount of powder affected by critical loading conditions during individual impacts is significantly dependent on the ball size used. An almost linear correlation between the rate of the chemical transformations and the ball volume is observed.
KW - Mechanochemistry
KW - In situ real-time monitoring
KW - N-Chlorination
KW - Kinetics
KW - Hydantoin
KW - Powder X-ray diffraction
KW - Raman spectroscopy
PY - 2021
U6 - https://doi.org/10.1021/acssuschemeng.1c03812
VL - 9
IS - 37
SP - 12591
EP - 12601
AN - OPUS4-53541
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Souza, B.
A1 - Chauque, S.
A1 - de Oliveira, P.
A1 - Emmerling, Franziska
A1 - Torresi, R.
T1 - Mechanochemical optimization of ZIF-8/Carbon/S8 composites for lithium-sulfur batteries positive electrodes
N2 - The application of lithium-sulfur (Li-S) batteries is still limited by their rapid capacity fading. The pulverization of the sulfur positive electrode after the lithiation and the consequence dissolution of long chain polysulfides in organic solvents lead to the shuttle effect. To address these issues, here we report the mechanochemical preparation of ZIF-8 (Zeolitic Imidazole Framework-8)-based composites as sulfur hosts for positive electrodes in Li-S batteries. We studied different methods for the incorporation of conductive carbon. Also, the replacement of Zn2+ metal centers by other bivalent metals (Cu2+, Co2+ and Ni2+), enabled the preparation of other ZIF-8-based materials. The positive electrode ZIF-8/C/S8 showed initial discharges of 772 mA h g−1 while the pristine one, ZIF-8/S8, displayed 502 mA h g−1. The enhanced performance of 54% for ZIF-8/C/S8 indicates that the direct mechanochemical synthesis of ZIF-8 with conductive carbon is beneficial at initials charge/discharge process in comparison to traditional slurry preparation (ZIF-8/S8). Also, the Li2S6 absorption tests shows 87% of discoloration with ZIF-8/C/S8, confirming the better polysulfides absorption.
KW - Lithium-sulfur battery
KW - Metal organic frameworks
KW - ZIF-8
KW - Mechanochemistry
PY - 2021
U6 - https://doi.org/10.1016/j.jelechem.2021.115459
VL - 896
SP - 115459
PB - Elsevier B.V.
AN - OPUS4-53542
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Fink, Friedrich
A1 - Emmerling, Franziska
A1 - Falkenhagen, Jana
T1 - Identification and Classification of Technical Lignins by means of Principle Component Analysis and k-Nearest Neighbor Algorithm
N2 - The characterization of technical lignins is a key step for the efficient use and processing of this material into valuable chemicals and for quality control. In this study 31 lignin samples were prepared from different biomass sources (hardwood, softwood, straw, grass) and different pulping processes (sulfite, Kraft, organosolv). Each lignin was analysed by attenuated total reflectance Fourier transform infrared (ATR-FT-IR) spectroscopy. Statistical analysis of the ATR-FT-IR spectra by means of principal component analysis (PCA) showed significant differences between the lignins. Hence, the samples can be separated by PCA according to the original biomass. The differences observed in the ATR-FT-IR spectra result primarily from the relative ratios of the p-hydroxyphenyl, guaiacyl and syringyl units. Only limited influence of the pulping process is reflected by the spectral data. The spectra do not differ between samples processed by Kraft or organosolv processes. Lignosulfonates are clearly distinguishable by ATR-FT-IR from the other samples. For the classification a model was created using the k-nearest neighbor (k NN) algorithm. Different data pretreatment steps were compared for k=1…20. For validation purposes, a 5-fold cross-validation was chosen and the different quality criteria Accuracy (Acc), Error Rate (Err), Sensitivity (TPR) and specificity (TNR) were introduced. The optimized model for k=4 gives values for Acc = 98.9 %, Err = 1.1 %, TPR = 99.2 % and TNR = 99.6 %.
KW - Classification
KW - PCA
KW - K-nearest neighbor
KW - FT-IR
KW - Technical lignin
PY - 2021
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-533855
VL - 1
IS - 8
SP - 350
EP - 396
PB - Wiley-VCH GmbH
AN - OPUS4-53385
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Zänker, Steffen
A1 - Scholz, Gudrun
A1 - Krahl, Thoralf
A1 - Prinz, Carsten
A1 - Emmerling, Franziska
A1 - Kemnitz, E.
T1 - Luminescent properties of Eu3+/Tb3+ doped fluorine containing coordination polymers
N2 - Lanthanides doped coordination polymers (CPs) with different binding motifs were synthesized to investigate the influence of the different fluorine positions in the structure on the decay time τ of the excited states. Fluorine can be integrated into the network mechanochemically via a fluorinated organic linker, here barium tetrafluoroterephthalate Ba(p-BDC-F4)2 or directly via a metal-fluorine bond (barium terephthalate fluoride BaF(p-BDC)0.5). The CP with a metal-fluorine bond shows the highest lifetime of the excited states of lanthanides (Eu3+, Tb3+ or Eu3+& Tb3+). The excitation of the lanthanides can be performed directly via the excitation wavelength typical for lanthanides and via the excitation wavelength of the linker. This enabled the simultaneous excitation of Eu3+ and Tb3+ in one CP. In the emission spectra (λem = 393 nm) of the mixed doped CPs (Eu3+ and Tb3+) the bands of both lanthanides can be observed. The integration into the crystal lattice and the homogeneous distribution of the lanthanides in the CPs is shown by X-ray diffraction, TEM, STEM-EDS measurements and the long decay times.
KW - Alkaline earth metal coordination polymers
KW - Fluorine coordination polymers
KW - Lanthanides doped coordination polymers
KW - Luminescence
PY - 2021
U6 - https://doi.org/10.1016/j.solidstatesciences.2021.106614
VL - 117
SP - 106614
PB - Elsevier Masson SAS
AN - OPUS4-52559
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Feiler, Torvid
A1 - Bhattacharya, Biswajit
A1 - Michalchuk, Adam
A1 - Rhim, S.-Y.
A1 - Schöder, V.
A1 - List-Kratochvil, E.
A1 - Emmerling, Franziska
T1 - Tuning the mechanical flexibility of organic molecular crystals by polymorphism for flexible optical waveguides
N2 - The ability to selectively tune the optical and the mechanical properties of organic molecular crystals offers a promising approach towards developing flexible optical devices. These functional properties are sensitive to crystallographic packing features and are hence expected to vary with polymorphic modification. Using as a model system the photoluminescent material 4-bromo-6-[(6-chloropyridin-2-ylimino)methyl]phenol (CPMBP), we herein demonstrate the simultaneous tuning of mechanical flexibility and photoluminescence properties via polymorphism. Two new polymorphic forms of CPMBP were obtained from a solution and fully characterised using a combination of experiments and density functional theory simulations. These polymorphic forms exhibit remarkably distinct mechanical properties and an order of magnitude difference in photoluminescence quantum yield. The mechanically plastic form has a higher quantum yield than the brittle polymorphic form. However, their photoluminescence emission profile is largely unaffected by the observed polymorphism, thereby demonstrating that the optical properties and bulk mechanical properties can in principle be tuned independently. By distinguishing between active (involving absorption and emission) and passive (involving no absorption) light propagation, the waveguiding properties of the plastic form of CPMBP (form II) were explored using the straight and bent crystals to highlight the potential applications of CPMBP in designing flexible optical devices. Our results demonstrated that polymorph engineering would be a promising avenue to achieve concurrent modulation of the optical and mechanical properties of photoluminescent molecular crystals for next-generation flexible optical device applications.
KW - Mechanochemistry
KW - Flexible
PY - 2021
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-532075
VL - 23
IS - 34
SP - 5815
EP - 5825
PB - Royal Society of Chemistry
CY - London
AN - OPUS4-53207
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Quiroz, J.
A1 - de Oliveira, P. F. M.
A1 - Shetty, S.
A1 - Oropeza, F.
A1 - Peña O’Shea, V.
A1 - Rodrigues, L.
A1 - Rodrigues, M.
A1 - Torresi, R.
A1 - Emmerling, Franziska
A1 - Camargo, P.
T1 - Bringing earth-abundant plasmonic catalysis to light: Gram-scale mechanochemical synthesis and tuning of activity by dual excitation of antenna and reactor sites
N2 - The localized surface plasmon resonance (LSPR) excitation in plasmonic nanoparticles (NPs) in the visible and near-infrared ranges is currently at the forefront of improving photocatalytic performances via plasmonic photocatalysis. One bottleneck of this field is that the NPs that often display the best optical properties in the visible and near-infrared ranges are based on expensive noble metals such as silver (Ag) and gold (Au). While earth-abundant plasmonic materials have been proposed together with catalytic metals in antenna–reactor systems, their performances remain limited by their optical properties. Importantly, the synthesis of plasmonic photocatalysts remains challenging in terms of scalability while often requiring several steps, high temperatures, and special conditions. Herein, we address these challenges by developing a one-pot, gram-scale, room-temperature synthesis of earth-abundant plasmonic photocatalysts while improving their activities beyond what has been dictated by the LSPR excitation of the plasmonic component. We describe the mechanochemical synthesis of earth-abundant plasmonic photocatalysts by using MoO3 (antenna) and Au (reactor) NPs as a proof-of-concept example and demonstrate that the dual plasmonic excitation of antenna and reactor sites enables the tuning of plasmonic photocatalytic performances toward the reductive coupling of nitrobenzene to azobenzene as a model reaction. In addition to providing a pathway to the facile and gram-scale synthesis of plasmonic photocatalysts, the results reported herein may open pathways to improved activities in plasmonic catalysis.
KW - MoO3
KW - Au nanoparticles
KW - Localized surface plasmon resonance
KW - Plasmonic photocatalysis
KW - Nitrobenzene reduction
PY - 2021
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-532089
VL - 9
IS - 29
SP - 9750
EP - 9760
PB - American Chemical Society
CY - Washington, DC
AN - OPUS4-53208
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Chapartegui-Arias, Ander
A1 - Raysyan, A.
A1 - Belenguer, A. M.
A1 - Jaeger, Carsten
A1 - Tchipilov, Teodor
A1 - Prinz, Carsten
A1 - Abad Andrade, Carlos Enrique
A1 - Beyer, S.
A1 - Schneider, Rudolf
A1 - Emmerling, Franziska
T1 - Tailored mobility in a zeolite imidazolate framework (ZIF) antibody conjugate
N2 - Zeolitic imidazolate framework (ZIF) hybrid fluorescent nanoparticles and ZIF antibody conjugates have been synthesized, characterized, and employed in lateral-flow immunoassay (LFIA). The bright fluorescence of the conjugates and the possibility to tailor their mobility gives a huge potential for diagnostic assays. An enzyme-linked immunosorbent assay (ELISA) with horseradish peroxidase (HRP) as label, proved the integrity, stability, and dispersibility of the antibody conjugates, LC-MS/MS provided evidence that a covalent link was established between these metal-organic frameworks and lysine residues in IgG antibodies.
KW - ZIF
KW - ELISA
PY - 2021
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-532096
SN - 0947-6539
SN - 1521-3765
VL - 27
IS - 36
SP - 9414
EP - 9421
PB - Wiley-VCH
CY - Weinheim
AN - OPUS4-53209
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Linberg, Kevin
A1 - Röder, Bettina
A1 - Al-Sabbagh, Dominik
A1 - Emmerling, Franziska
A1 - Michalchuk, Adam
T1 - Controlling polymorphism in molecular cocrystals by variable temperature ball milling
N2 - Mechanochemistry offers a unique opportunity to modify and manipulate crystal forms, often providing new products as compared with conventional solution methods. While promising, there is little known about how to control the solid form through mechanochemical means, demanding dedicated investigations. Using a model organic cocrystal system (isonicotinamide:glutaric acid), we here demonstrate that with mechanochemistry, polymorphism can be induced in molecular solids under conditions seemingly different to their conventional thermodynamic (thermal) transition point.
Whereas Form II converts to Form I upon heating to 363 K, the same transition can be initiated under ball milling conditions at markedly lower temperatures (348 K). Our results indicate that mechanochemical techniques can help to reduce the energy barriers to solid form transitions, offering new insights into controlling polymorphic forms. Moreover, our results suggest that the nature of mechanochemical transformations could make it difficult to interpret mechanochemical solid form landscapes using conventional equilibrium-based tools.
KW - Mechanochemistry
KW - Kinetics
KW - In situ
PY - 2022
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-558878
SP - 1
EP - 16
PB - Royal Society of Chemistry
AN - OPUS4-55887
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Mazzeo, P
A1 - Lampronti, G
A1 - Michalchuk, Adam
A1 - Belenguer, A
A1 - Bacchi, A
A1 - Emmerling, Franziska
T1 - Accurate extrinsic and intrinsic peak broadening modelling for time-resolved in situ ball milling reactions via synchrotron powder X-ray diffraction
N2 - The debate on the mechanisms which underpin mechanochemical reactions via ball mill grinding is still open. Our ability to accurately measure the microstructural (crystal size and microstrain) evolution of materials under milling conditions as well as their phase composition as a function of time is key to the in-depth understanding of the kinetics and driving forces of mechanochemical transformations. Furthermore, all ball milling reactions end with a steady state or milling equilibrium – represented by a specific phase composition and relative microstructure – that does not change as long as the milling conditions are maintained. The use of a standard sample is essential to determine the instrumental contribution to the X-ray powder diffraction (XRPD) peak broadening for time-resolved in situ (TRIS) monitoring of mechanochemical reactions under in operando conditions. Using TRIS-XRPD on a ball milling setup, coupled with low-energy synchrotron radiation, we investigated different data acquisition and analysis strategies on a silicon standard powder. The diffraction geometry and the microstructural evolution of the standard itself have been studied to model the instrumental contribution to XRPD peak broadening throughout the grinding activity. Previously proposed functions are here challenged and further developed. Importantly, we show that minor drifts of the jar position do not affect the instrumental resolution function significantly. We here report and discuss the results of such investigations and their application to TRIS-XRPD datasets of inorganic and organic ball mill grinding reactions.
KW - Mechanochemistry
KW - In situ diffraction
KW - Synchrotron radiation
KW - Sustainable chemisry
PY - 2022
U6 - https://doi.org/10.1039/d2fd00104g
SP - 1
EP - 17
PB - Royal Society of Chemistry
AN - OPUS4-55932
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Rautenberg, Max
A1 - Bhattacharya, Biswajit
A1 - Das, Chayanika
A1 - Emmerling, Franziska
T1 - Mechanochemical Synthesis of Phosphonate-Based Proton Conducting Metal-Organic Frameworks
N2 - Water-stable metal−organic frameworks (MOFs) with proton-conducting behavior have attracted great attention as promising materials for proton-exchange membrane fuel cells. Herein, we report the mechanochemical gram-scale synthesis of three new mixed-ligand phosphonate-based MOFs, {Co(H2PhDPA)(4,4′-bipy)H2O)·2H2O}n (BAM-1), {Fe(H2PhDPA)(4,4′-bipy) (H2O)·2H2O}n (BAM-2), and {Cu(H2PhDPA)(dpe)2(H2O)2·2H2O}n (BAM-3) [where H2PhDPA = phenylene diphosphonate, 4,4′-bipy = 4,4′-bipyridine, and dpe = 1,2-di(4-pyridyl)ethylene]. Single-crystal X-ray diffraction measurements revealed that BAM-1 and BAM-2 are isostructural and possess a three-dimensional (3D) network structure comprising one-dimensional (1D) channels filled with guest water molecules. Instead, BAM-3 displays a 1D network structure extended into a 3D supramolecular structure through hydrogenbonding and π−π interactions. In all three structures, guest water molecules are interconnected with the uncoordinated acidic hydroxyl groups of the phosphonate moieties and coordinated water molecules by means of extended hydrogen-bonding interactions. BAM-1 and BAM-2 showed a gradual increase in proton conductivity with increasing temperature and reached 4.9 × 10−5 and 4.4 × 10−5 S cm−1 at 90 °C and 98% relative humidity (RH). The highest proton conductivity recorded for BAM-3 was 1.4 × 10−5 S cm−1 at 50 °C and 98% RH. Upon further heating, BAM-3 undergoes dehydration followed by a phase transition to another crystalline form which largely affects its performance. All compounds exhibited a proton hopping (Grotthuss model) mechanism, as suggested by their low activation energy.
KW - Mechanochemistry
KW - Metal-organic-frameworks
KW - Proton conductivity
PY - 2022
U6 - https://doi.org/10.1021/acs.inorgchem.2c01023
VL - 61
SP - 10801
EP - 10809
PB - ACS Publications
AN - OPUS4-55448
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Ghazanfari, M. R.
A1 - Vittadello, L.
A1 - Al-Sabbagh, Dominik
A1 - Santhosh, A.
A1 - Frankcom, C.
A1 - Fuß, F.
A1 - von Randow, C. A.
A1 - Siemensmeyer, K.
A1 - Vrijmoed, J. C.
A1 - Emmerling, Franziska
A1 - Jerabek, P.
A1 - Irmlau, M.
A1 - Thiele, G.
T1 - Remarkable Infrared Nonlinear Optical, Dielectric, and Strong Diamagnetic Characteristics of Semiconducting K3[BiS3]
N2 - The ternary sulfido bismuthate K3[BiS3] is synthesized in quantitative yields. The material exhibits nonlinear optical properties with strong second harmonic generation properties at arbitrary wavelengths in the infrared spectral range and a notable laser-induced damage threshold of 5.22 GW cm−2 for pulsed laser radiation at a wavelength of 1040 nm, a pulse duration of 180 fs, and a repetition rate of 12.5 kHz. K3[BiS3] indicates semiconductivity with a direct optical band gap of 2.51 eV. Dielectric and impedance characterizations demonstrate κ values in the range of 6−13 at 1 kHz and a high electrical resistivity. A strong diamagnetic behavior with a susceptibility of −2.73 × 10−4 m3 kg−1 at room temperature is observed. These results suggest it is a promising nonlinear optical candidate for the infrared
region. The synergic physical characteristics of K3[BiS3] provide insight into the correlation of optical, electrical, and magnetic properties.
KW - Electrical properties
KW - Insulators
KW - Materials
KW - Nonlinear optics
KW - Quantum mechanics
PY - 2022
U6 - https://doi.org/10.1021/acs.jpclett.2c01689
VL - 13
IS - 30
SP - 6987
EP - 6993
PB - ACS Publications
AN - OPUS4-55456
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Emmerling, Franziska
T1 - Cocrystal polymorphs & Mechanochemistry - Mechanism & Kinetics
N2 - Mechanochemistry is an effective, environmentally benign, and facile method for the synthesis of new crystal forms. Different milling parameters are known to affect the mechanisms and rates of product formation: milling frequency, milling time, filling degree of the milling jar, ball diameter and vessel size, degree of milling ball filling, and material of jars. The increasing interest in mechanochemistry is contrasted by a limited mechanistic understanding of mechanochemical reactivity and selectivity. Control over ball milling transformations is needed before the transformative potential of mechanochemical processing can be realized. Different analytical methods and their combinations have been developed for the time-resolved in situ monitoring of mechanochemical transformations, including powder X-ray diffraction, X-ray absorption spectroscopy, NMR, Raman spectroscopy, and thermography. Here we will discuss our recent results investigating the formation of polymorphic cocrystals thereby elucidating the influence of milling parameters (solvent, temperature, time) and reaction sequences on the formation mechanism and kinetics. For the mechanochemical chlorination reaction of hydantoin normalizing the kinetic profiles to the volume of the milling ball showed clearly that milling reaction kinetics are conserved. Here physical kinetics dominate reaction rates in a ball-milling transformation. Attempting to interpret such kinetics in purely chemical terms risk misinterpreting the results. Our results indicate that time-resolved in situ investigations of milling reactions offer a new approach to tune and optimize mechanochemical processes.
T2 - 33th European Crrystallography Meeting
CY - Versailles, France
DA - 23.08.2022
KW - Mechanochemistry
KW - Cocrystals
KW - Kinetics
KW - Polymorphs
PY - 2022
AN - OPUS4-55586
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Lakshmipathi, M.
A1 - Emmerling, Franziska
A1 - Bhattacharya, Biswajit
A1 - Ghosh, S.
T1 - Structure-mechanical property correlation of a series of 4-(1-Napthylvinyl) pyridine based cocrystals
N2 - We obtained three 4-(1-Napthylvinyl) pyridine based cocrystals ( 1–3 ) and studied its structure mechan- ical property correlation which aimed towards various applications for photo switches, mechanical ac- tuators etc. Selection of coformer molecules is important in fine tuning mechanical property outcome of synthesized cocrystals. Amongst three cocrystals, cocrystal 1 is mechanically flexible and its mechani- cal property is attributed to underlying crystal packing features which is in line with existing elastically bendable crystals while other two cocrystals ( 2, 3 ) are brittle in nature. Hirshfeld analysis was carried out to illustrate structure-property correlation particularly in terms of number as well as types of non- covalent interactions in the lattice and further to corroborate the space of the molecules in the lattice.
KW - Cocrystals
KW - Mechanical properties
KW - Halogen bond interaction
KW - Structure-mechanical property correlation
PY - 2022
U6 - https://doi.org/10.1016/j.molstruc.2022.133670
SN - 0022-2860
VL - 1268
SP - 1
EP - 16
PB - Elsevier
CY - Amsterdam
AN - OPUS4-55547
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Emmerling, Franziska
T1 - Cocrystal polymorphs & Mechanochemistry - Mechanism & Kinetics
N2 - Mechanochemistry is an effective, environmentally benign, and facile method for the synthesis of new crystal forms. Different milling parameters are known to affect the mechanisms and rates of product formation: milling frequency, milling time, filling degree of the milling jar, ball diameter and vessel size, degree of milling ball filling, and material of jars. The increasing interest in mechanochemistry is contrasted by a limited mechanistic understanding of mechanochemical reactivity and selectivity. Control over ball milling transformations is needed before the transformative potential of mechanochemical processing can be realized. Different analytical methods and their combinations have been developed for the time-resolved in situ monitoring of mechanochemical transformations, including powder X-ray diffraction, X-ray absorption spectroscopy, NMR, Raman spectroscopy, and thermography. Here we will discuss our recent results investigating the formation of polymorphic cocrystals thereby elucidating the influence of milling parameters (solvent, temperature, time) and reaction sequences on the formation mechanism and kinetics. For the mechanochemical chlorination reaction of hydantoin normalizing the kinetic profiles to the volume of the milling ball showed clearly that milling reaction kinetics are conserved. Here physical kinetics dominate reaction rates in a ball-milling transformation. Attempting to interpret such kinetics in purely chemical terms risk misinterpreting the results. Our results indicate that time-resolved in situ investigations of milling reactions offer a new approach to tune and optimize mechanochemical processes.
T2 - 3rd CEFMC meeting
CY - Kashmir, India
DA - 31.08.2022
KW - Mechanochemistry
KW - Crystal Engeneering
PY - 2022
AN - OPUS4-55641
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Pütz, E.
A1 - Smales, Glen Jacob
A1 - Jegel, O.
A1 - Emmerling, Franziska
A1 - Tremel, W.
T1 - Tuning ceria catalysts in aqueous media at the nanoscale: how do surface charge and surface defects determine peroxidase- and haloperoxidase-like reactivity
N2 - Designing the shape and size of catalyst particles, and their interfacial charge, at the nanometer scale can radically change their performance. We demonstrate this with ceria nanoparticles. In aqueous media, nanoceria is a functional mimic of haloperoxidases, a group of enzymes that oxidize organic substrates, or of peroxidases that can degrade reactive oxygen species (ROS) such as H2O2 by oxidizing an organic substrate. We show that the chemical activity of CeO2−x nanoparticles in haloperoxidase- and peroxidaselike reactions scales with their active surface area, their surface charge, given by the ζ-potential, and their surface defects (via the Ce3+/Ce4+ ratio). Haloperoxidase-like reactions are controlled through the ζ-potential as they involve the adsorption of charged halide anions to the CeO2 surface, whereas peroxidase-like reactions without charged substrates are controlled through the specific surface area SBET. Mesoporous CeO2−x particles, with large surface areas, were prepared via template-free hydrothermal reactions and characterized by small-angle X-ray scattering. Surface area, ζ-potential and the Ce3+/Ce4+ ratio are controlled in a simple and predictable manner by the synthesis time of the hydrothermal reaction as demonstrated by X-ray photoelectron spectroscopy, sorption and ζ-potential measurements. The surface area increased with synthesis time, whilst the Ce3+/Ce4+ ratio scales inversely with decreasing ζ-potential. In this way the catalytic activity of mesoporous CeO2−x particles could be tailored selectively for haloperoxidase- and peroxidase-like reactions. The ease of tuning the surface properties of mesoporous CeO2x particles by varying the synthesis time makes the synthesis a powerful general tool for the preparation of nanocatalysts according to individual needs.
KW - SAXS
KW - Ceria
KW - Zeta potential
PY - 2022
U6 - https://doi.org/10.1039/D2NR03172H
SP - 1
EP - 12
PB - Royal Society of Chemistry
AN - OPUS4-55649
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Emmerling, Franziska
T1 - Mechanochemical formation of multicomponent crystal systems: Mechanism & Kinetics
N2 - Mechanochemistry is an effective, environmentally benign, and facile method for the synthesis of new multicomponent crystal systems. Different milling parameters are known to affect the mechanisms and rates of product formation: milling frequency, milling time, filling degree of the milling jar, ball diameter and vessel size, degree of milling ball filling, and material of jars. The increasing interest in mechanochemistry is contrasted by a limited mechanistic understanding of the mechanochemical reactivity and selectivity.
Different analytical methods and their combinations have been developed for the time resolved in situ monitoring of mechanochemical transformations, including powder X-ray diffraction, X-ray adsorption spectroscopy, NMR, Raman spectroscopy, and thermography.
Here we will discuss our recent results investigating the formation of (poly-morphic) cocrystals, metal-organic compounds, and salts, thereby elucidating the influence of milling parameters and reaction sequences on the formation mechanism and kinetics. For the mechanochemical chlorination reaction of hydantoin normalizing the kinetic profiles to the volume of the milling ball showed clearly that milling reaction kinetics are conserved. Here physical kinetics dominate reaction rates in a ball-milling transformation. Attempting to interpret such kinetics in purely chemical terms risk misinterpreting the results.
Our results indicate that time-resolved in situ investigation of milling reactions offer a new approach to tune and optimize mechanochemical processes.
T2 - 25th International Conference on the Chemistry of the Organic Solid State (ICCOSS XXV)
CY - Ohrid, Macedonia
DA - 03.07.2022
KW - Mechanochemistry
KW - In situ real-time monitoring
KW - Crystal Engineering
PY - 2022
AN - OPUS4-55413
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Emmerling, Franziska
T1 - Mechanochemical formation of multicomponent crystals systems
N2 - Mechanochemistry is an effective, environmentally benign, and facile method for the synthesis of new multicomponent crystal systems. Different milling parameters are known to affect the mechanisms and rates of product formation: milling frequency, milling time, filling degree of the milling jar, ball diameter and vessel size, degree of milling ball filling, and material of jars. The increasing interest in mechanochemistry is contrasted by a limited mechanistic understanding of mechanochemical reactivity and selectivity.
Different analytical methods and their combinations have been developed for the time-resolved in situ monitoring of mechanochemical transformations, including powder X-ray diffraction, X-ray absorption spectroscopy, NMR, Raman spectroscopy, and thermography.
Here we will discuss our recent results investigating the formation of (polymorphic) cocrystals, metal-organic compounds, and salts, thereby elucidating the influence of milling parameters and reaction sequences on the formation mechanism and kinetics. Our results indicate that time-resolved in situ investigations of milling reactions offer a new approach to tune and optimize mechanochemical processes.
T2 - 5ECQUL Forging Bonds
CY - Lisbon, Portugal
DA - 12.07.2022
KW - Mechanochemistry
KW - In situ real-time monitoring
KW - N-Chlorination
PY - 2022
AN - OPUS4-55414
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Emmerling, Franziska
T1 - Shaken not stirred: enhancing the flavor of mechanochemistry
N2 - compounds and cocrystals. The ever-increasing interest in this method is contrasted by a limited mechanistic understanding of the mechanochemical reactivity and selectivity. Different milling parameters are known to affect the mechanisms and rates of product formation: milling frequency, milling time, filling degree of the milling jar, ball diameter and vessel size, degree of milling ball filling, and material of jars. Time-resolved in situ investigations of milling reactions (Figure 1) provide direct insights into the underlying mechanisms. We recently introduced different setups enabling in situ investigation of mechanochemical reactions using synchrotron XRD and XAS combined with Raman spectroscopy and thermography. The presented setup allows the detection of crystalline, amorphous, eutectic, and liquid intermediates. Furthermore, the chemical composition of the reaction mixture was found to be directly correlated with changes in the temperature profile of the reaction. The resulting deeper kinetic and thermodynamic understanding of milling processes is the key to future optimization of mechanochemical syntheses. In this contribution, we will discuss our recent results investigating the formation of (polymorphic) cocrystals and coordination polymers. Our results indicate that time-resolved in situ investigations of mechanochemical processes are key for tuning and optimizing mechanochemical syntheses allowing to unleash the potential of mechanochemistry for a green materials design.
T2 - 2nd National Crystallographic Meeting Lisbon, Portugal
CY - Lisbon, Portugal
DA - 15.07.2022
KW - Mechanochemistry
KW - In situ real-time monitoring
KW - Crystal
PY - 2022
AN - OPUS4-55415
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Emmerling, Franziska
T1 - Mechanochemical formation of multicomponent crystal systems: Mechanism & Kinetics
N2 - Mechanochemistry is an effective, environmentally benign, and facile method for the synthesis of new multicomponent crystal systems. Different milling parameters are known to affect the mechanisms and rates of product formation: milling frequency, milling time, filling degree of the milling jar, ball diameter and vessel size, degree of milling ball filling, and material of jars. The increasing interest in mechanochemistry is contrasted by a limited mechanistic understanding of the mechanochemical reactivity and selectivity. Different analytical methods and their combinations have been developed for the time resolved in situ monitoring of mechanochemical transformations, including powder X-ray diffraction, X-ray adsorption spectroscopy, NMR, Raman spectroscopy, and thermography.1 Here we will discuss our recent results investigating the formation of (polymorphic) cocrystals2–3 and metal-organic frameworks,4 thereby elucidating the influence of milling parameters and reaction sequences on the formation mechanism and kinetics. For the mechanochemical chlorination reaction of hydantoin normalizing the kinetic profiles to the volume of the milling ball showed clearly that milling reaction kinetics are conserved.6 Here physical kinetics dominate reaction rates in a ball-milling transformation. Attempting to interpret such kinetics in purely chemical terms risk misinterpreting the results. Our results indicate that time-resolved in situ investigation of milling reactions offer a new approach to tune and optimize mechanochemical processes.
T2 - 10th International conference on Mechanochemistry and Mechanical Alloying
CY - Cagliari, Italy
DA - 06.06.2022
KW - Mechanochemistry
KW - In situ real-time monitoring
KW - Cocrystal
PY - 2022
AN - OPUS4-55421
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Rautenberg, Max
A1 - Bhattacharya, Biswajit
A1 - Witt, Julia
A1 - Jain, Mohit
A1 - Emmerling, Franziska
T1 - In situ time-resolved monitoring of mixed-ligand metal–organic framework mechanosynthesis
N2 - The mechanism of mixed-ligand metal–organic framework (MOF) formation, and the possible role of intermediate single-ligand metal complexes during mechanosynthesis, have not been explored yet. For the first time, we report here in situ real-time monitoring of the mechanochemical formation mechanism of mixed-ligand MOFs. Our results show that binary phases can act as intermediates or competing products in one-pot and stepwise synthesis.
KW - Mechanochemistry
KW - Metal-organic-frameworks
KW - In situ X-ray diffraction
KW - Mixed-ligand MOFs
PY - 2022
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-558167
SP - 1
EP - 4
PB - Royal Society of Chemistry
AN - OPUS4-55816
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Pakrashy, S.
A1 - Mandal, P. K.
A1 - Goswami, J. N.
A1 - Dey, S. K.
A1 - Choudhury, S. M.
A1 - Bhattacharya, Biswajit
A1 - Emmerling, Franziska
A1 - Alasmary, F. A.
A1 - Dolai, M.
T1 - Bioinformatics and Network Pharmacology of the First Crystal Structured Clerodin: Anticancer and Antioxidant Potential against Human Breast Carcinoma Cell
N2 - Clerodin was isolated from the medicinal plant Clerodendrum infortunatum, and CSD search showed the first crystal structure of clerodin by a single-crystal X-ray diffraction study. We checked its binding potential with target proteins by docking and conducted network pharmacology analysis, ADMET analysis, in silico pathway analysis, normal mode analysis (NMA), and cytotoxic activity studies to evaluate clerodin as a potential anticancer agent. The cell viability studies of clerodin on the human breast carcinoma cell line (MCF-7) showed toxicity on MCF-7 cells but no toxicity toward normal human lymphocyte cells (HLCs). The anticancer mechanism of clerodin was validated by its enhanced capacity to produce intracellular reactive oxygen species (ROS) and to lower the reduced glutathione content in MCF-7 cells.
KW - Anticancer
KW - Clerodin
PY - 2022
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-567600
SN - 2470-1343
VL - 7
IS - 51
SP - 48572
EP - 48582
PB - ACS Publ.
CY - Washington, DC
AN - OPUS4-56760
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Kulla, Hannes
A1 - Greiser, Sebastian
A1 - Benemann, Sigrid
A1 - Rademann, K.
A1 - Emmerling, Franziska
T1 - In Situ Investigation of a Self-Accelerated Cocrystal Formation by Grinding Pyrazinamide with Oxalic Acid
N2 - A new cocrystal of pyrazinamide with oxalic acid was prepared mechanochemically and characterized by PXRD, Raman spectroscopy, solid-state NMR spectroscopy, DTA-TG, and SEM. Based on powder X-ray diffraction data the structure was solved. The formation pathway of the reaction was studied in situ using combined synchrotron PXRD and Raman spectroscopy. Using oxalic acid dihydrate the initially neat grinding turned into a rapid self-accelerated liquid-assisted grinding process by the release of crystallization water. Under these conditions, the cocrystal was formed directly within two minutes.
KW - in situ
KW - cocrystal
KW - mechanochemistry
KW - pyrazinamide
KW - hydrate
PY - 2016
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-372357
SN - 1420-3049
VL - 21
IS - 7
SP - Article 917, 1
EP - 9
AN - OPUS4-37235
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - de Oliveira Guilherme Buzanich, Ana
A1 - Radtke, Martin
A1 - Reinholz, Uwe
A1 - Riesemeier, Heinrich
A1 - Emmerling, Franziska
T1 - Time- & spatial-resolved X-ray absorption fine structure (XAFS) spectroscopy in a single-shot – new analytical possibilities for in situ material characterization
N2 - A new concept that comprises both time- and lateral-resolved X-ray absorption fine-structure information simultaneously in a single shot is presented. This uncomplicated set-up was tested at the BAMline at BESSY-II (Berlin, Germany). The primary broadband beam was generated by a double multilayer monochromator. The transmitted beam through the sample is diffracted by a convexly bent Si (111) crystal, producing a divergent beam. This, in turn, is collected by either an energy-sensitive area detector, the so-called color X-ray camera, or by an area-sensitive detector based on a CCD camera, in θ-2θ geometry. The first tests were performed with thin metal foils and some iron oxide mixtures. A time resolution of lower than 1 s together with a spatial resolution in one dimension of at least 50 µm is achieved.
KW - Time resolution
KW - Single-shot XAFS
PY - 2016
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-370892
SN - 1600-5775
IS - 23
SP - 769
EP - 776
PB - International Union of Crystallography
CY - Chester, UK
AN - OPUS4-37089
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Hoffmann, Holger
A1 - Baldofski, Stefanie
A1 - Hoffmann, Kristin
A1 - Flemig, Sabine
A1 - Silva, C. P.
A1 - Esteves, V. I.
A1 - Emmerling, Franziska
A1 - Panne, Ulrich
A1 - Schneider, Rudolf
T1 - Structural considerations on the selectivity of an immunoassay for sulfamethoxazole
N2 - Sulfamethoxazol (SMX),a sulfonamide, is a widely used bacteriostatic antibiotic and therefore a promising marker for the entry of anthropogenic Pollution in the environment. SMX is frequently found in wastewater and surface water. This study presents the production of high affinity and selective polyclonal antibodies for SMX and the development and Evaluation of a direct competitive enzyme-linked immunosorbent assay(ELISA)for the quantification of SMX in environmental watersamples. The crystal structures of the cross-reacting compounds sulfamethizole, N4-acetyl-SMX andsuccinimidyl-SMX were determined by x-ray diffraction aiming to explain their high cross-reactivity. These crystal structures are described for the first time. The quantification range of the ELISA is 0.82–63 µg/L. To verify our results, the SMX concentration in 20 environmental samples,including wastewater and surfacewater,was determined by ELISA and tandem mass spectrometry(MS/MS).A good Agreement of the measured SMX concentrations was found with average recoveries of 97–113%for the results of ELISA compared to LC-MS/MS.
KW - X-Ray diffraction
KW - Sulfamethoxazole
KW - ELISA
KW - LC-MS/MS
PY - 2016
U6 - https://doi.org/10.1016/j.talanta.2016.05.049
SN - 0039-9140
SN - 1873-3573
IS - 158
SP - 198
EP - 207
PB - Elsevier B.V.
CY - Amsterdam, Netherlands
AN - OPUS4-36676
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - de Oliveira Guilherme Buzanich, Ana
A1 - Radtke, Martin
A1 - Reinholz, Uwe
A1 - Riesemeier, Heinrich
A1 - Emmerling, Franziska
ED - de Oliveira Guilherme Buzanich, Ana
ED - Strange, R. W.
T1 - Time- and spatial-resolved XAFS spectroscopy in a
single shot: new analytical possibilities for in situ
material characterization
N2 - A new concept that comprises both time- and lateral-resolved X-ray absorption fine-structure information simultaneously in a single shot is presented. This uncomplicated set-up was tested at the BAMline at BESSY-II (Berlin, Germany). The primary broadband beam was generated by a double multilayer monochromator. The transmitted beam through the sample is diffracted by a convexly bent Si (111) crystal, producing a divergent beam. This, in turn, is collected by either an energy-sensitive area detector, the so-called color X-ray camera, or by an area-sensitive detector based on a CCD camera, in θ–2θ geometry. The first tests were performed with thin metal foils and some iron oxide mixtures. A time resolution of lower than 1 s together with a spatial resolution in one dimension of at least 50 mm is achieved.
KW - Single-shot XAFS
KW - Time resolution
PY - 2016
UR - http://scripts.iucr.org/cgi-bin/paper?S1600577516003969
U6 - https://doi.org/10.1107/S1600577516003969
SN - 1600-5775
VL - 23
SP - 769
EP - 776
PB - International Union of Crystallography
CY - Liverpool, UK
AN - OPUS4-35903
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Wilke, Manuel
A1 - Batzdorf, Lisa
A1 - Fischer, Franziska
A1 - Rademann, Klaus
A1 - Emmerling, Franziska
T1 - Cadmium phenylphosphonates: preparation, characterisation and in situ investigation
N2 - The successful mechanochemical syntheses of three cadmium phenylphosphonates indicates that mechanochemistry is ideally suited for synthesizing metal phosphonates. With this powerful synthesis tool it is possible to synthesize rapidly and efficiently both known and novel phosphonates. The Crystal structures of the two new compounds, and, were solved from PXRD data. They contain monodeprotonated phenylphosphonate and neutral phenylphosphonic acid ligands. The synthesis pathways of all three compounds were investigated in situ. A diffusion mechanism is corroborated by our findings.
Intermediates could be detected and identified. The kinetically favored product (3) could always be detected during the syntheses. The thermodynamic stability of the compounds and the stoichiometric ratio of the starting materials are the two directing factors for the synthesis of the final products.
KW - Mechanochemistry
KW - Metal phosphonate
KW - In situ
KW - MOF
KW - XRD
PY - 2016
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-363322
SN - 2046-2069
VL - 6
IS - 42
SP - 36011
EP - 36019
PB - Royal Soc Chemistry
CY - Cambridge, UK
AN - OPUS4-36332
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Bach, S.
A1 - Visnow, E.
A1 - Panthöfer, M.
A1 - Gorelik, T.
A1 - de Oliveira Guilherme Buzanich, Ana
A1 - Gulo, A.
A1 - Kolb, U.
A1 - Emmerling, Franziska
A1 - Lind, C.
A1 - Tremel, W.
T1 - Hydrate networks under mechanical stress – A case study for Co3(PO4)2·8H2O
N2 - The nature of the bound water in solids with hydrogen-bonded networks depends not only on temperature and pressure but also on the nature of the constituents. The collapse and reorientation of these network structures determines the stability of hydrated solids and transitions to other crystalline or amorphous phases. Here, we study the mechanochemically induced loss of bound water in Co₃(PO₄)₂·8H₂O and compare this process to the behavior under hydrostatic pressure.
The associated phase transition and its kinetics were monitored by X-ray powder diffraction with Synchrotron radiation and quantitative IR spectroscopy. High shearing forces are responsible for the degradation of the hydrogen-bonded network and the concomitant crystalline–amorphous transformation. UV/Vis spectroscopy, extended X-ray absorption spectroscopy (EXAFS), and X-ray absorption near-edge spectroscopy (XANES) provided information about the short-range order in the amorphous solid, and thermal analysis revealed its composition and showed that the moderate charge densities of the Co²⁺ and PO₄³⁻ ions, which make the hydration enthalpy comparable to the binding energy of the counteranions, and the Formation of hydrogen-bonded networks favor multistage crystallization processes associated with the release and uptake of coordinated water. The changes of the Co²⁺ coordination induce a color change from pink to blue; therefore, Co₃(PO₄)₂·8H₂O can be used as an overheat temperature indicator.
KW - Mechanochemistry
KW - Amorphous materials
KW - Hydrates
KW - Cobalt
KW - Phosphates
PY - 2016
U6 - https://doi.org/10.1002/ejic.201501481
SN - 1434-1948
SN - 1099-0682
VL - 2016
IS - 13-14
SP - 2072
EP - 2081
PB - Wiley-VCH Verlag GmbH & Co. KGaA
CY - Weinheim, Germany
AN - OPUS4-36434
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Wilke, Manuel
A1 - de Oliveira Guilherme Buzanich, Ana
A1 - Reinholz, Uwe
A1 - Rademann, Klaus
A1 - Emmerling, Franziska
T1 - The structure and in situ synthesis investigation of isomorphic mononuclear molecular metal phenylphosphonates
N2 - We describe a fast and effective synthesis for molecular metal phosphonates. Isomorphic compounds [M(II)(HO₃PPh)₂(H₂O₃PPh)₂(H₂O)₂] (M = Mn (1), Co (2), Ni (3); Ph = C₆H₅) were obtained by grinding. The complexes are mononuclear compounds containing neutral and monodeprotonated phenylphosphonic acid and water as ligands. The crystal structures were determined using powder X-ray diffraction (PXRD) data and validated by extended X-ray absorption fine structure (EXAFS) data. Combined synchrotron XRD measurements and Raman spectroscopy were conducted for investigating the reactions in situ. Based on these data, the intermediates were characterized and the formation mechanism was derived.
KW - Mechanochemistry
KW - Metal phosphonate
KW - In situ
KW - XRD
PY - 2016
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-363944
SN - 1477-9226
SN - 1477-9234
SN - 1364-5447
VL - 45
IS - 23
SP - 9460
EP - 9467
AN - OPUS4-36394
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Sobisch, T.
A1 - Emmerling, Franziska
A1 - Girod, Matthias
A1 - Menzel, Michael
A1 - Lerche, D.
T1 - Advantages of dual wavelength detection for size determination of nanoparticles with analytical centrifugation
KW - Particle size distributions
KW - Dual wavelength detection
KW - Analytical centrifugation
KW - Nanoparticle separation
PY - 2013
SN - 978-3-944261-28-7
SN - 978-3-944261-36-2
SN - 978-3-944261-52-2
VL - 4
SP - 9
EP - 11
AN - OPUS4-30802
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Fischer, Franziska
A1 - Scholz, G.
A1 - Benemann, Sigrid
A1 - Rademann, K.
A1 - Emmerling, Franziska
T1 - Evaluation of the formation pathways of cocrystal polymorphs in liquid-assisted syntheses
N2 - The synthesis of the polymorphic cocrystal caffeine:anthranilic acid was investigated to obtain a better understanding of the processes leading to the formation of different polymorphic forms. In the case of these cocrystal polymorphs synthesized by liquid-assisted grinding a distinct influence of the dipole moment of the solvent was found. A pre-coordination between the solvent molecules and the caffeine:anthranilic acid cocrystal could be identified in the formation of form II. In the case of form II the solvent can be regarded as a catalyst. The formation pathway of each polymorph was evaluated using synchrotron X-ray diffraction.
KW - cocrystal
KW - synchrotron X-ray diffraction
KW - caffeine
PY - 2014
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-313222
SN - 1466-8033
VL - 16
IS - 35
SP - 8272
EP - 8278
CY - London, UK
AN - OPUS4-31322
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Krause, Christina
A1 - Zorn, R.
A1 - Emmerling, Franziska
A1 - Falkenhagen, Jana
A1 - Frick, B.
A1 - Huber, P.
A1 - Schönhals, Andreas
T1 - Vibrational density of states of triphenylene based discotic liquid crystals: dependence on the length of the alkyl chain
N2 - The vibrational density of states of a series of homologous triphenylene-based discotic liquid crystals HATn (n = 5, 6, 8, 10, 12) depending on the length of the aliphatic side chain is investigated by means of inelastic neutron scattering. All studied materials have a plastic crystalline phase at low temperatures, followed by a hexagonally ordered liquid crystalline phase at higher temperatures and a quasi isotropic phase at the highest temperatures. The X-ray scattering pattern for the plastic crystalline phase of all materials shows a sharp Bragg reflection corresponding to the intercolumnar distance in the lower q-range and a peak at circa 17 nm-1 related to intracolumnar distances between the cores perpendicular to the columns as well as a broad amorphous halo related to the disordered structure of the methylene groups in the side chains in the higher q-range. The intercolumnar distance increases linearly with increasing chain length for the hexagonal columnar ordered liquid crystalline phase. A similar behaviour is assumed for the plastic crystalline phase. Besides n = 8 all materials under study exhibit a Boson peak. With increasing chain length, the frequency of the Boson peak decreases and its intensity increases. This can be explained by a self-organized confinement model. The peaks for n = 10, 12 are much narrower than for n = 5, 6 which might imply the transformation from a rigid system to a softer one with increasing chain length. Moreover the results can also be discussed in the framework of a transition from an uncorrelated to a correlated disorder with increasing n where n = 8 might be speculatively considered as a transitional state.
KW - X-ray scattering
KW - Neutron scattering
KW - Differential scanning calorimetry
PY - 2014
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-304789
SN - 1463-9076
SN - 1463-9084
VL - 16
IS - 16
SP - 7324
EP - 7333
PB - The Royal Soc. of Chemistry
CY - Cambridge
AN - OPUS4-30478
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Stroh, Julia
A1 - Schlegel, Moritz-Caspar
A1 - Irassar, E.F.
A1 - Meng, Birgit
A1 - Emmerling, Franziska
T1 - Applying high resolution SyXRD analysis on sulfate attacked concrete field samples
N2 - High resolution synchrotron X-ray diffraction (SyXRD) was applied for a microstructural profile analysis of concrete deterioration after sulfate attack. The cement matrices consist of ordinary Portland cement and different amounts of supplementary cementitious materials, such as fly ash, natural pozzolana and granulated blast furnace slag. The changes of the phase composition were determined along the direction of sulfate ingress. This approach allows the identification of reaction fronts and zones of different phase compositions and conclusions about the mechanisms of sulfate attack. Two reaction fronts were localized in the initial 4 mm from the sample surface. The mechanism of deterioration caused by the exposition in the sulfate-bearing soil is discussed. SyXRD is shown to be a reliable method for investigation of cementitious materials with aggregates embedded in natural environments.
KW - X-ray diffraction (B)
KW - High resolution
KW - Degradation (C)
KW - Sulfate attack (C)
KW - Concrete (E)
PY - 2014
U6 - https://doi.org/10.1016/j.cemconres.2014.07.015
SN - 0008-8846
SN - 1873-3948
VL - 66
SP - 19
EP - 26
PB - Pergamon Press
CY - New York, NY
AN - OPUS4-31253
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Gärtner, Stefanie
A1 - Carvalho, J.J.
A1 - Emmerling, Franziska
A1 - Garbe, L.-A.
A1 - Schneider, Rudolf
T1 - Polyclonal murine and rabbit antibodies for the bile acid isolithocholic acid
N2 - Bile acids are relevant markers for clinical research. This study reports the production of antibodies for isolithocholic acid, the isomer of the extensively studied lithocholic acid. The IgG titer and affinity maturation were monitored during the immunizations of three mice and two rabbits. In both animal models, polyclonal antibodies with a high selectivity and affinity were produced. The development of a direct competitive ELISA with a test midpoint of 0.69 ± 0.05 µg/L and a measurement range from 0.09–15 µg/L is reported. Additionally, the crystal structure of isolithocholic acid is described for the first time.
KW - ELISA
KW - Crystal structure
KW - Competitive assay
KW - Immunization monitoring
KW - 3ß-hydroxy-5ß-cholanic acid
PY - 2015
U6 - https://doi.org/10.1080/15321819.2014.924419
SN - 1532-1819
SN - 1532-4230
VL - 36
IS - 3
SP - 233
EP - 252
PB - Taylor & Francis
CY - Philadelphia, Pa.
AN - OPUS4-31836
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Balski, Matthias
A1 - Emmerling, Franziska
A1 - Kipphardt, Heinrich
A1 - Panne, Ulrich
T1 - Determination of boron in silicon without use of additional complexing agents
N2 - Methods for the determination of boron in various matrices described in the literature usually employ complexing agents like mannitol to retain the volatile boron species during matrix evaporation steps. However, also relatively high boron recoveries from silicon containing samples have been reported when no complexing agents were added to the digestion acids. The mechanism behind this matrix-dependant recovery has been investigated by studying the boron recovery in the analysis of solar grade silicon. It was found that the NH4+ ion formed by the reduction of nitric acid during sample digestion is responsible for the higher recovery of boron, which leads to a possible analysis method without the use of complexing agents if the sample preparation procedure is carefully optimized.
KW - Boron
KW - Complexing agents
KW - Matrix evaporation
KW - Sample enrichment
PY - 2014
U6 - https://doi.org/10.1039/c4ay00410h
SN - 1759-9660
SN - 1759-9679
VL - 6
IS - 12
SP - 4003
EP - 4008
PB - RSC Publ.
CY - Cambridge
AN - OPUS4-30956
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Batzdorf, Lisa
A1 - Nguyen, Thi Yen
A1 - Rump, Doreen
A1 - Emmerling, Franziska
T1 - Crystallization behavior of carbamazepine
N2 - Carbamazepine (CBZ) is known for its variety of anhydrous and hydrous polymorphs. Herein, a thorough analysis of the crystallization behavior of CBZ is presented. The influence of the solvent and the concentration on the crystallization behavior under different environmental conditions is investigated by combined in situ XRD and Raman spectroscopy measurements. Crystallization studies conducted via conventional crystallization in glass tubes and in levitated droplets using an acoustic levitator indicate a dependence of the crystallization process from solvent and surface.
KW - Carbamazepine
KW - Polymorphism
KW - Acoustic levitation
KW - XRD
KW - Raman spectroscopy
PY - 2014
U6 - https://doi.org/10.1515/zpch-2013-0452
SN - 0942-9352
SN - 2196-7156
SN - 0044-3336
SN - 0044-3328
SN - 0942-9352
N1 - Geburtsname von Batzdorf, Lisa: Tröbs, L. - Birth name of Batzdorf, Lisa: Tröbs, L.
VL - 228
IS - 4-5
SP - 493
EP - 501
PB - Oldenbourg
CY - München
AN - OPUS4-30627
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Batzdorf, Lisa
A1 - Zimathies, Annett
A1 - Panne, Ulrich
A1 - Emmerling, Franziska
T1 - Mechanochemical synthesis of [Zn3(C2O4)3(4,4'-bipy)4] and its reorganization at high temperatures
N2 - The metal organic layered structure catena-(bis(µ2-4,4'-bipyridine)-tris(µ2-oxalato)-bis(4,4'-bipyridine)-tri-zinc(ii)) ([Zn3(C2O4)3(4,4'-bipy)4]) was synthesized mechanochemically applying three different routes. The synthesis succeeded by i) simultaneously neat grinding the three starting materials zinc acetate dihydrate, oxalic acid dihydrate and 4,4'bipyridine, ii) grinding two compounds and adding the third afterwards, independent of the sequence. The products were characterized using powder X-ray diffraction, Raman spectroscopy, gas adsorption measurements, and scanning electron microscopy. Temperature-dependent synchrotron XRD measurements revealed that the monoclinic structure of [Zn3(C2O4)3(4,4'-bipy)4] rearranges reversibly to a higher ordered orthorhombic structure [Zn(C2O4)(4,4'-bipy)] at high temperatures.
KW - Mechanochemistry
KW - Metal organic compounds
KW - Synchrotron radiation
KW - Reorganization
PY - 2014
U6 - https://doi.org/10.1515/zpch-2014-0445
SN - 0942-9352
SN - 2196-7156
SN - 0044-3336
SN - 0044-3328
SN - 0942-9352
N1 - Geburtsname von Batzdorf, Lisa: Tröbs, L. - Birth name of Batzdorf, Lisa: Tröbs, L.
VL - 228
IS - 4-5
SP - 575
EP - 585
PB - Oldenbourg
CY - München
AN - OPUS4-30628
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Batzdorf, Lisa
A1 - Wilke, Manuel
A1 - Szczerba, Wojciech
A1 - Reinholz, Uwe
A1 - Emmerling, Franziska
T1 - Mechanochemical synthesis and characterisation of two new bismuth metal organic frameworks
N2 - Two metal organic structures composed of the ligands benzene-1,4-dicarboxylate and pyridine-
2,5-dicarboxylate and bismuth cations are presented: (H2Im)[Bi(1,4-bdc)2] (1) and
[Bi(pydc)(NO3)2(H2O)2]*H2O (2) (bdc = benzenedicarboxylate, H2Im = imidazole cation, pydc
= pyridinedicarboxylate). Both compounds were synthesised via grinding and the crystal
structure of compound (2) was solved based on its powder diffraction pattern. Compound 1
crystallises isostructurally to the dimethyl ammonium containing compound (dma)[(Bi(1,4-
bdc)2]. Raman spectroscopy and Extended X-ray absorption fine structure (EXAFS)
measurements provided additional information about the two mechanochemically
synthesised metal organic compounds.
KW - crystal structure
KW - mechanochemically synthesis
KW - powder diffraction measurements
PY - 2014
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-306296
UR - http://pubs.rsc.org/en/content/articlepdf/2014/ce/c3ce42633e
SN - 1466-8033
N1 - Geburtsname von Batzdorf, Lisa: Tröbs, L. - Birth name of Batzdorf, Lisa: Tröbs, L.
VL - 16
IS - 25
SP - 5560
EP - 5565
CY - London, UK
AN - OPUS4-30629
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Batzdorf, Lisa
A1 - Emmerling, Franziska
T1 - Mechanochemical synthesis and characterisation of cocrystals and metal-organic compounds
N2 - The mechanochemical synthesis of two model compounds, a metal organic framework ([Bi(1,4-bdc)2]*(Im) (bdc = benzene dicarboxylate, Im = imidazole cation)) and a cocrystal (Carbamazepine:Indometacin 1:1) were followed ex situ by combined analytical methods. Powder X-ray diffraction (XRD) and Raman spectroscopy data were evaluated for the synthesis of the metal organic framework. XRD measurements and REM images were analysed for the synthesis of the cocrystal. The measurements revealed that both model compounds were synthesised within minutes. The metal organic framework [Bi(1,4-bdc)2]*(Im) is synthesised via an intermediate structure. The cocrystal Carbamazepine:Indometacin 1:1 is formed within few seconds and afterwards the crystallite size decreases extremely.
KW - Powder X-ray diffraction (XRD)
KW - Raman spectroscopy
KW - mechanochemical synthesis
PY - 2014
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-306305
UR - http://pubs.rsc.org/en/content/articlepdf/2014/fd/c3fd00163f
SN - 1359-6640
SN - 1364-5498
N1 - Geburtsname von Batzdorf, Lisa: Tröbs, L. - Birth name of Batzdorf, Lisa: Tröbs, L.
SP - 109
EP - 119
PB - RSC
CY - Cambridge [u.a.]
AN - OPUS4-30630
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Klobes, Peter
A1 - Klimakow, Maria
A1 - Emmerling, Franziska
T1 - Gas adsorption and SAXS studies of mechanochemically prepared Cu3 (BTC)2
T2 - CPM-5 - 5th - International Workshop "Characterization of Porous Materials: from Angstroms to Millimeters", New Brunswick, NJ, USA
CY - New Brunswick, NJ, USA
DA - 2009-06-24
PY - 2009
AN - OPUS4-18713
LA - deu
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Emmerling, Franziska
A1 - Hennig, C.
A1 - Kraus, Werner
A1 - Ikeda, A.
A1 - Scheinost, A.C.
T1 - Coordination of the limiting U (IV) carbonate species in aqueous solution - a comparative EXAFS and XRD investigation
T2 - DGK Tagung (Deutsche Gesellschaft für Kristallographie)
CY - Hanover, Germany
DA - 2009-03-09
PY - 2009
AN - OPUS4-18718
LA - deu
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Juran, S.
A1 - Walther, M.
A1 - Stephan, H.
A1 - Bergmann, R.
A1 - Steinbach, J.
A1 - Kraus, Werner
A1 - Emmerling, Franziska
A1 - Comba, P.
T1 - Hexadentate Bispidine derivatives as versatile bifunctional chelate agents for Copper(II) radioisotopes
PY - 2009
U6 - https://doi.org/10.1021/bc800461e
SN - 1043-1802
SN - 1520-4812
VL - 20
IS - 2
SP - 347
EP - 359
CY - Washington, DC
AN - OPUS4-19068
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Winterlik, J.
A1 - Fecher, G.H.
A1 - Jenkins, C.A.
A1 - Medvedev, S.
A1 - Felser, C.
A1 - Kübler, J.
A1 - Mühle, C.
A1 - Doll, K.
A1 - Jansen, M.
A1 - Palasyuk, T.
A1 - Trojan, I.
A1 - Eremets, M.I.
A1 - Emmerling, Franziska
T1 - Exotic magnetism in the alkali sesquioxides Rb4O6 and Cs4O6
KW - Caesium compounds
KW - Crystal structure
KW - Density functional theory
KW - Electronic structure
KW - Ferromagnetic materials
KW - Frustration
KW - Magnetic transitions
KW - Magnetisation
KW - Raman spectra
KW - Rubidium compounds
KW - Spin glasses
KW - X-ray diffraction
PY - 2009
U6 - https://doi.org/10.1103/PhysRevB.79.214410
SN - 1098-0121
SN - 0163-1829
SN - 0556-2805
SN - 1095-3795
SN - 1550-235X
VL - 79
IS - 21
SP - 214410-1 - 214410-6
PB - American Institute of Physics
CY - Melville, NY
AN - OPUS4-19796
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Leiterer, Jork
A1 - Emmerling, Franziska
A1 - radnik, J.
A1 - Bentrup, U.
A1 - Brückner, A.
T1 - Flying droplets as model system for spray drying - An in situ synchrotron X-ray scattering study on complex oxides catalyst precursors
N2 - As a model for spray drying the early stages of crystallization of complex molybdate catalyst precursors were monitored online in droplets levitated acoustically. Synchron X-ray scattering techniques were applied to study the drying process of a typical molybdate catalysts precursor prepared from Ni-,Fe-,Bi-nitrate, ammonium heptamolybdate and H3PO4. Comparison with diffraction patterns obtained from sessile droplets shows significant differences in the crystal growth, whereas the final crystal structure – including a Keggin-type anion – is identical in both cases. The levitated samples exhibit a decelerated growth with a large number of small crystallites at the beginning of the crystallization, whereas in case of the sessile droplets a small number of large crystallites were observed after a few minutes. The acoustic levitation using an ultrasonic trap proves to be an elegant tool to mimic spray drying and offers new possibilities in relation to the understanding of the drying process.
KW - Acoustic levitation
KW - Spray drying
KW - Molybdate catalysts
KW - X-ray scattering
PY - 2010
U6 - https://doi.org/10.1016/j.cattod.2009.11.001
SN - 0920-5861
VL - 155
IS - 3-4
SP - 326
EP - 330
PB - Elsevier
CY - Amsterdam
AN - OPUS4-21998
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Klimakow, Maria
A1 - Klobes, Peter
A1 - Thünemann, Andreas
A1 - Rademann, K.
A1 - Emmerling, Franziska
T1 - Mechanochemical synthesis of metal-organic frameworks: A fast and facile approach toward quantitative yields and high specific surface areas
N2 - The strategy of utilizing mechanochemical synthesis to obtain metal–organic frameworks (MOFs) with high surface areas is demonstrated for two model systems. The compounds HKUST-1 (Cu3(BTC)2, BTC = 1,3,5-benzenetricarboxylate) and MOF-14 (Cu3(BTB)2, BTB = 4,4',4''-benzenetribenzoate) were synthesized by ball milling and characterized by powder X-ray diffraction (XRD), Raman spectroscopy, scanning electron microscopy (SEM) and thermal analysis (DTA/DTG/MS). The specific surface area (SSA) of both compounds was characterized by nitrogen adsorption. To verify these results and to understand how the synthetic conditions influence the pore structure and the surface area, additional small-angle X-ray scattering (SAXS) experiments were carried out. Our investigations confirm that this synthesis approach is a promising alternative method for distinct MOFs. This facile method leads to materials with surface areas of 1713 m²/g, which is comparable to the highest given values in the literature for the respective compounds.
KW - Metal-organic frameworks
KW - Mechanochemistry
KW - Green-chemistry synthesis
KW - Gas adsorption
KW - SAXS
KW - Specific surface area
PY - 2010
U6 - https://doi.org/10.1021/cm1012119
SN - 0897-4756
SN - 1520-5002
VL - 22
IS - 18
SP - 5216
EP - 5221
PB - American Chemical Society
CY - Washington, DC
AN - OPUS4-21999
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Siegel, David
A1 - Koch, Matthias
A1 - Emmerling, Franziska
A1 - Nehls, Irene
T1 - Deacetyl tenuazonic acid
KW - Deacetyl tenuazonic acid
KW - X-ray single crystal diffraction
KW - Crystal structure
PY - 2009
U6 - https://doi.org/10.1107/S1600536809015372
SN - 1600-5368
VL - 65
IS - 6
SP - o1201
PB - Munksgaard
CY - Copenhagen
AN - OPUS4-19429
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Emmerling, Franziska
A1 - Polte, Jörg
A1 - Riesemeier, Heinrich
A1 - Thünemann, Andreas
A1 - Kraehnert, R.
T1 - In situ structure analysis using acoustic levitated droplets
T2 - In-situ Studies with Photons, Neutrons and Electrons Scattering 1st International Workshop
CY - Berlin, Germany
DA - 2009-09-01
PY - 2009
AN - OPUS4-20150
LA - deu
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Walter, Astrid
A1 - Pfeifer, Dietmar
A1 - Kraus, Werner
A1 - Emmerling, Franziska
A1 - Schneider, Rudolf
A1 - Panne, Ulrich
A1 - Weller, Michael G.
T1 - Triacetone Triperoxide (TATP): Hapten design and development of antibodies
N2 - Triacetone triperoxide (TATP), an improvised explosive, is a potential security threat because of its cost-efficient synthesis and the difficulty in detecting it. A highly selective antibody could provide the necessary specificity to the detection process. To obtain antibodies, a hapten made from acetone, hydrogen peroxide, and 7-oxooctanoic acid has been designed, synthesized, and confirmed by NMR that displays the utmost similarity to the analyte. The single-crystal X-ray structures of the solvated species TATP·methanol (1:1) and the TATP derivate were determined. In both compounds, the molecules exhibit D3 symmetry and adopt a twisted boat-chair conformation. The hapten was coupled to bovine serum albumin, and mice were immunized. An immune response against TATP was elicited, and selective antibodies were detected in the mouse serum, which should be very useful for the development of a TATP biosensor system. An ELISA with a limit of detection for TATP of 65 µg L-1 is shown.
KW - TATP
KW - Triacetone triperoxide
KW - Explosive
KW - Antibody
KW - Hapten immunoassay
KW - Structure
PY - 2010
U6 - https://doi.org/10.1021/la1018339
SN - 0743-7463
SN - 1520-5827
VL - 26
IS - 19
SP - 15418
EP - 15423
PB - American Chemical Society
CY - Washington, DC
AN - OPUS4-22469
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Köppen, Robert
A1 - Koch, Matthias
A1 - Emmerling, Franziska
A1 - Nehls, Irene
T1 - rac-(1R,2R,4S)-1,2-Dibromo-4-[(1R)-1,2-dibromoethyl]cyclohexane
N2 - In the title compound, C8H12Br4, the cyclohexane ring exhibits a chair conformation. The C-Br distances range from 1.964 (6) to 1.985 (5) Å and the C-C distances range from 1.496 (6) to 1.543 (7) Å. Short intermolecular BrBr contacts [3.467 (4) Å] occur in the crystal.
PY - 2010
U6 - https://doi.org/10.1107/S160053681004763X
SN - 1600-5368
VL - 66
IS - 12
SP - o3318,sup-1 - o3318,sup-7
PB - Munksgaard
CY - Copenhagen
AN - OPUS4-22616
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Polte, Jörg
A1 - Kraehnert, R.
A1 - Radtke, Martin
A1 - Reinholz, Uwe
A1 - Riesemeier, Heinrich
A1 - Thünemann, Andreas
A1 - Emmerling, Franziska
T1 - New insights of the nucleation and growth process of gold nanoparticles via in situ coupling of SAXS and XANES
N2 - Although metallic nanoparticles play an important role in the area of nanotechnology, a coherent mechanistic explanation for the evolution of the particles during their chemical synthesis has not yet been provided in many cases. To gain a profound understanding of the growth mechanism of colloidal nanoparticles, new approaches using Small Angle X-Ray Scattering (SAXS) combined with X-ray absorption near-edge structure (XANES) are presented. This combination allows for insights into two prominent syntheses routes of gold nanoparticles (GNP): The 'slow' reaction using sodium citrate (30-90 min) as a reducing agent and the 'fast' reaction employing NaBH4 (within few seconds). In the first case data derived with the coupled XANES and SAXS suggests a four-step particle formation mechanism. For the second system a time resolution in the order of 100-200 ms was achieved by coupling a common laboratory SAXS instrument with a microstructured mixer, which allows data acquisition in a continuous-flow mode. The results indicate a coalescence driven growth process. Based on the capabilities to deduce the size, number and polydispersity of the particles, the results of both methods enable the development of mechanistic schemes explaining the different phases of particle formation and growth, thus providing a basis for improved control over the synthesis processes.
KW - SAXS
KW - XANES
KW - Nanoparticle formation
PY - 2010
U6 - https://doi.org/10.1088/1742-6596/247/1/012051
SN - 1742-6588
SN - 1742-6596
VL - 247
IS - 1
SP - 012051-1 - 012051-10
PB - IOP Publ.
CY - Bristol, UK
AN - OPUS4-22684
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Hennig, C.
A1 - Ikeda-Ohno, A.
A1 - Emmerling, Franziska
A1 - Kraus, Werner
A1 - Bernhard, G.
T1 - Comparative investigation of the solution species [U(CO3)5]6- and the crystal structure of Na6[U(CO3)5].12H2O
PY - 2010
U6 - https://doi.org/10.1039/B922624A
SN - 1477-9226
SN - 1477-9234
SN - 1364-5447
VL - 39
IS - 15
SP - 3744
EP - 3750
PB - RSC
CY - Cambridge
AN - OPUS4-23047
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Polte, Jörg
A1 - Ahner, T. T.
A1 - Delißen, Friedmar
A1 - Sokolov, S.
A1 - Emmerling, Franziska
A1 - Thünemann, Andreas
A1 - Kraehnert, R.
T1 - Mechanism of gold nanoparticle formation in the classical citrate synthesis method derived from coupled in situ XANES and SAXS evaluation
PY - 2010
U6 - https://doi.org/10.1021/ja906506j
SN - 0002-7863
SN - 1520-5126
VL - 132
IS - 4
SP - 1296
EP - 1301
PB - American Chemical Society
CY - Washington, DC
AN - OPUS4-23048
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Polte, Jörg
A1 - Erler, Robert
A1 - Thünemann, Andreas
A1 - Emmerling, Franziska
A1 - Kraehnert, R.
T1 - SAXS in combination with a free liquid jet for improved time-resolved in situ studies of the nucleation and growth of nanoparticles
PY - 2010
U6 - https://doi.org/10.1039/c0cc03238g
SN - 0022-4936
SN - 0009-241x
SN - 1359-7345
SN - 1364-548x
VL - 46
IS - 48
SP - 9209
EP - 9211
PB - Royal Society of Chemistry
CY - Cambridge
AN - OPUS4-23049
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Hoffmann, Katrin
A1 - Dietzel, B.
A1 - Schulz, B.
A1 - Reck, Günter
A1 - Hoffmann, Angelika
A1 - Orgzall, I.
A1 - Resch-Genger, Ute
A1 - Emmerling, Franziska
T1 - Combined structural and fluorescence studies of methyl-substituted 2,5-diphenyl-1,3,4-oxadiazoles - relation between electronic properties and packing motifs
N2 - Prerequisite for the rational design of functional organic materials with tailor-made electronic properties is the knowledge of the structure–property relationship for the specific class of molecules under consideration. This encouraged us to systematically study the influence of the molecular structure and substitution pattern of aromatically substituted 1,3,4-oxadiazoles on the electronic properties and packing motifs of these molecules and on the interplay of these factors. For this purpose, seven diphenyl-oxadiazoles equipped with methyl substituents in the ortho- and meta-position(s) were synthesized and characterized. Absorption and fluorescence spectra in solution served here as tools to monitor substitution-induced changes in the electronic properties of the individual molecules whereas X-ray and optical measurements in the solid state provided information on the interplay of electronic and packing effects. In solution, the spectral position of the absorption maximum, the size of Stokes shift, and the fluorescence quantum yield are considerably affected by ortho-substitution in three or four ortho-positions. This results in blue shifted absorption bands, increased Stokes shifts, and reduced fluorescence quantum yields whereas the spectral position and vibrational structure of the emission bands remain more or less unaffected. In the crystalline state, however, the spectral position and shape of the emission bands display a strong dependence on the molecular structure and/or packing motifs that seem to control the amount of dye–dye-interactions. These observations reveal the limited value of commonly reported absorption and fluorescence measurements in solution for a straightforward comparison of spectroscopic results with single X-ray crystallography. This underlines the importance of solid state spectroscopic studies for a better understanding of the interplay of electronic effects and molecular order.
KW - Diphenyl-oxadiazoles
KW - X-ray structure
KW - Packing motif
KW - Optical properties
KW - Fluorescence quantum yield
PY - 2011
U6 - https://doi.org/10.1016/j.molstruc.2010.11.071
SN - 0022-2860
SN - 1872-8014
SN - 0377-046X
VL - 988
IS - 1-3
SP - 35
EP - 46
PB - Elsevier
CY - Amsterdam
AN - OPUS4-23253
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Kuhlich, Paul
A1 - Emmerling, Franziska
A1 - Piechotta, Christian
A1 - Nehls, Irene
T1 - Methyl 3,5,5,6,8,8-hexamethyl-5,6,7,8-tetrahydronaphthalene-2-carboxylate (AHTN-COOMe)
N2 - Crystals of the title compound, C18H26O2, were grown from ethyl acetate. Due to the racemic precursor, the title compound is also obtained as a racemate. Disorder was observed during structure refinement, originating from two possible half-chair conformations of the non-aromatic ring. The disorder was refined by introducing split positions in the cyclo-hexane ring regarding the two possible R and S-enantiomers at the chiral CH group [ratio 0.744 (3):0.256 (3)]. The crystal structure features pairs of inversion-related molecules connected by pairs of non-classical C–H···O hydrogen bonds.
KW - AHTN
KW - Tonalide
KW - Cyclic musk
KW - AHTN-COOMe
KW - Disinfection by-product
KW - Esterification
PY - 2011
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-232769
SN - 1600-5368
VL - E67
IS - 2
SP - o485, sup-1
EP - sup-11
PB - Munksgaard
CY - Copenhagen
AN - OPUS4-23276
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Purohit, Purv
A1 - Huacuja Sánchez, Jesús
A1 - Wang, D.-Y.
A1 - Emmerling, Franziska
A1 - Thünemann, Andreas
A1 - Heinrich, G.
A1 - Schönhals, Andreas
T1 - Structure - property relationships of nanocomposites based on polypropylene and layered double hydroxides
N2 - Nanocomposites based on polypropylene (PP) and organically modified ZnAl layered double hydroxides (ZnAl-LDH) were prepared by melt blending and investigated by a combination of differential scanning calorimetry (DSC), small- and wide-angle X-ray scattering (SAXS and WAXS), and dielectric relaxation spectroscopy (DRS). An average number of stack size of LDH layers is calculated by analyzing the SAXS data which is close to that of pure organically modified ZnAl-LDH. Scanning microfocus SAXS investigations show that the ZnAl-LDH is homogeneously distributed in the PP matrix as stacks of 4–5 layers with an intercalated morphology. DSC and WAXS results show that the degree of crystallinity decreases linearly with the increasing content of LDH. The extrapolation of this dependence to zero estimates a limiting concentration of ca. 40% LDH where the crystallization of PP is completely suppressed by the nanofiller. The dielectric spectra of the nanocomposites show several relaxation processes which are discussed in detail. The intensity of the dynamic glass transition (β-relaxation) increases with the concentration of LDH. This is attributed to the increasing concentration of the exchanged anion dodecylbenzenesulfonate (SDBS) which is adsorbed at the LDH layers. Therefore, a detailed analysis of the β-relaxation provides information about the structure and the molecular dynamics in the interfacial region between the LDH layers and the polypropylene matrix which is otherwise dielectrically invisible (low dipole moment). As a main result, it is found that the glass transition temperature in this interfacial region is by 30 K lower than that of pure polypropylene. This is accompanied by a drastic change of the fragility parameter deduced from the relaxation map.
KW - Nanocomposites
KW - Layered double hydroxide
KW - Dielectric spectroscopy
KW - X-ray scattering
KW - Polypropylene
PY - 2011
U6 - https://doi.org/10.1021/ma200323k
SN - 0024-9297
SN - 1520-5835
VL - 44
IS - 11
SP - 4342
EP - 4354
PB - American Chemical Society
CY - Washington, DC
AN - OPUS4-23921
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Walther, M.
A1 - Matterna, M.
A1 - Juran, S.
A1 - Fähnemann, S.
A1 - Stephan, H.
A1 - Kraus, Werner
A1 - Emmerling, Franziska
T1 - Imidazole-containing bispidine ligands: synthesis, structure and Cu(II) complexation
N2 - The preparation and characterization of tris-pyridyl bispidine (3,7-diazabicyclo[3.3.1]nonane) derivatives with benzimidazole and imidazole donor groups at the N-3 position of the bispidine Skeleton and their copper(II) complexes are reported. The impact of the hetaryl substituents on the configurational isomerism of piperidones and their corresponding bispidones has been studied by NMR spectroscopy, revealing the exclusive appearance in the enol form for the piperidones in solution and the trans-configuration regarding the two pyridyl substituents, as well as the sole formation of the unsymmetric exo-endo isomers for the corresponding bispidones. Thus, the bispidones are preorganized ligands for building pentacoordinated complexes, confirmed by the preparation and characterization of the corresponding Cu(II) complexes. Of the di-pyridyl piperidones with benzimidazole and imidazole substituents, and of the Cu(II) complex of the benzimidazole-containing bispidone, Crystals have become available for the analysis by X-ray diffraction, showing that the piperidones form the enol tautomers also in the solid state.
KW - Piperidone
KW - Bispidine
KW - Copper(II)
KW - Configuration isomerism
PY - 2011
SN - 0932-0776
SN - 0340-5087
SN - 0044-3174
VL - 66b
SP - 721
EP - 728
PB - Verl. d. Zeitschrift für Naturforschung
CY - Tübingen
AN - OPUS4-24091
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Wolf, S. E.
A1 - Müller, L.
A1 - Barrea, R.
A1 - Kampf, C.J.
A1 - Leiterer, Jork
A1 - Panne, Ulrich
A1 - Hoffmann, T.
A1 - Emmerling, Franziska
A1 - Tremel, W.
T1 - Carbonate-coordinated metal complexes precede the formation of liquid amorphous mineral emulsions of divalent metal carbonates
N2 - During the mineralisation of metal carbonates MCO3 (M = Ca, Sr, Ba, Mn, Cd, Pb) liquid-like amorphous intermediates emerge. These intermediates that form via a liquid/liquid phase separation behave like a classical emulsion and are stabilized electrostatically. The occurrence of these intermediates is attributed to the formation of highly hydrated networks whose stability is mainly based on weak interactions and the variability of the metal-containing pre-critical clusters. Their existence and compositional freedom are evidenced by electrospray ionization mass spectrometry (ESI-MS). Liquid intermediates in non-classical crystallisation pathways seem to be more common than assumed.
PY - 2011
U6 - https://doi.org/10.1039/c0nr00761g
SN - 2040-3364
SN - 2040-3372
IS - 3
SP - 1158
EP - 1165
PB - RSC Publ.
CY - Cambridge
AN - OPUS4-23355
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Schlegel, Moritz-Caspar
A1 - Müller, Urs
A1 - Panne, Ulrich
A1 - Emmerling, Franziska
T1 - Deciphering the sulfate attack of cementitious materials by high-resolution micro-x-ray diffraction
N2 - The durability of cementitious materials depends, among others, on their resistance against chemical attack during the service life of a building. Here, we present an approach to analyze changes in the phase composition due to chemical attack in the form of sulfate ingress within the microstructure. Micro-X-ray (µX-ray) diffraction using synchrotron radiation in Debye–Scherrer (transmission) geometry allowed a spatial resolution of 10 µm. Phase transformations in the wake of damaging processes were observed in a detailed high-resolution imaging study. In comparison, samples containing supplementary cementitious materials were investigated and used to reconstruct the influence of different degeneration processes in detail. Additionally, reaction fronts within the bulk were localized by micro-X-ray fluorescence analysis. The experimental setup provided the possibility for analyzing the phase assemblage of a given sample without destroying the microstructure. The specimens for phase analysis are thick sections of the primary material and can be used for further microscopic analysis of the microstructure and microchemistry, e.g., scanning electron microscopy–energy-dispersive X-ray spectroscopy (SEM–EDX) or Raman spectroscopy.
PY - 2011
U6 - https://doi.org/10.1021/ac200181g
SN - 0003-2700
SN - 1520-6882
VL - 83
IS - 10
SP - 3744
EP - 3749
PB - American Chemical Society
CY - Washington, DC
AN - OPUS4-23669
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Takao, S.
A1 - Takao, K.
A1 - Kraus, Werner
A1 - Emmerling, Franziska
A1 - Scheinost, A.C.
A1 - Bernhard, G.
A1 - Hennig, C.
T1 - First hexanuclear U IV and Th IV formate complexes - Structure and stability range in aqueous solution
KW - Actinides
KW - Polynuclear species
KW - Formic acid
KW - Bridging ligands
PY - 2009
U6 - https://doi.org/10.1002/ejic.200900899
SN - 1434-1948
SN - 1099-0682
VL - 2009
IS - 32
SP - 4771
EP - 4775
PB - Wiley-VCH Verl.
CY - Weinheim
AN - OPUS4-20329
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Peplinski, Burkhard
A1 - Fitch, A.N.
A1 - Evans, A.
A1 - Ibberson, R.M.
A1 - Többens, D.M.
A1 - Cranswick, L.M.D.
A1 - Dörfel, Ilona
A1 - Emmerling, Franziska
A1 - Matschat, Ralf
T1 - Structural characterization of a coarse-grained transparent silicon carbide powder by a combination of powder diffraction techniques
N2 - Diffraction of hard synchrotron radiation as well as constant-wavelength and time-of-flight neutron diffraction were used for the structural characterization of a silicon carbide powder having extremely low levels of chemical impurities, high perfection of the crystalline lattice and a grain size of up to 150 µm. The presence of three polytypes was ascertained and the ratios of their mass fractions were determined to be w15R : w6H = 0.002,3(8) and w4H : w6H = 0.000,6(2).
KW - Silicon carbide
KW - Polytypes
KW - Phase quantification
KW - Reference material
PY - 2009
U6 - https://doi.org/10.1524/zksu.2009.0009
SN - 0930-486X
VL - 30 EPDIC 2008
SP - 61
EP - 66
PB - Oldenbourg
CY - München
AN - OPUS4-20561
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Peplinski, Burkhard
A1 - Adam, Christian
A1 - Michaelis, Matthias
A1 - Kley, Gerd
A1 - Emmerling, Franziska
A1 - Simon, Franz-Georg
T1 - Reaction sequences in the thermochemical treatment of sewage sludge ashes revealed by X-ray powder diffraction - A contribution to the European project SUSAN
N2 - The sequence of reactions accompanying the thermochemical treatment of an iron- and aluminium-bearing sewage sludge ash was ascertained by investigating two systematic series of samples. The ash was thermochemically treated in a lab-scale rotary furnace after mixing it with a chlorine-donor, either CaCl2 or MgCl2. Within each of these two sample series only a single process parameter, the reaction temperature, was varied, namely between 350 and 1050°C. It was found, that among the numerous crystalline phases present in the raw ash only quartz and hematite continue to exist after thermochemical treatments carried out at 1050°C, whereas all other components undergo at least one decomposition-recrystallization cycle. Some of the components re-crystallize even several times. It was proved that the restructuring of the calcium- and phosphorus-bearing mineral phases proceeds via the formation of chlorspodioside, Ca2PO4Cl. The influence of the type of chlorine-donor on the final product was elucidated in detail and - to the best of our knowledge - for the first time crystalline AlPO4 was found in a sewage sludge ash and its decomposition was investigated, too.
KW - XRD
KW - Phosphorus recovery
KW - Sewage sludge ash
KW - Urban mining
KW - Fertilizers
PY - 2009
U6 - https://doi.org/10.1524/zksu.2009.0068
SN - 0930-486X
VL - 30 EPDIC 2008
SP - 459
EP - 464
PB - Oldenbourg
CY - München
AN - OPUS4-20562
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Klimakow, Maria
A1 - Leiterer, Jork
A1 - Kneipp, Janina
A1 - Rössler, E.
A1 - Panne, Ulrich
A1 - Rademann, K.
A1 - Emmerling, Franziska
T1 - Combined synchrotron XRD/Raman measurements: In situ identification of polymorphic transitions during crystallization processes
N2 - A combination of two analytical methods, time-resolved X-ray diffraction (XRD) and Raman spectroscopy, is presented as a novel tool for crystallization studies. An acoustic levitator was employed as sample environment. This setup enables the acquisition of XRD and Raman data in situ simultaneously within a 20 s period and hence permits investigation of polymorphic phase transitions during the crystallization process in different solvents (methanol, ethanol, acetone, dichloromethane, acetonitrile). These real time measurements allow the determination of the phase content from the onset of the first crystalline molecular assemblies to the stable system. To evaluate the capability of this approach, the setup was applied to elucidate the crystallization process of the polymorphic compound nifedipine. The results indicate the existence of solvent-dependent transient phases during the crystallization process. The quality of the data allowed the assignment of the lattice constants of the hitherto unknown crystal structure of the β-polymorph.
KW - Synchrotron radiation
KW - XRD
KW - Raman spectroscopy
KW - Polymorphism
KW - Crystallization
KW - Acoustic levitation
KW - Nifedipine
PY - 2010
U6 - https://doi.org/10.1021/la100540q
SN - 0743-7463
SN - 1520-5827
VL - 26
IS - 13
SP - 11233
EP - 11237
PB - American Chemical Society
CY - Washington, DC
AN - OPUS4-21396
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Klimakow, Maria
A1 - Rademann, K.
A1 - Emmerling, Franziska
T1 - Towards novel pseudo-polymorphs of nifedipine: elucidation of a slow crystallization process
N2 - The crystallization of nifedipine was studied by means of synchrotron-X-ray diffraction, single-crystal X-ray structural analysis, and Raman spectroscopy. The results of slow evaporation (24 h in minimum) using dimethyl sulfoxide (DMSO) are presented. Since fast crystallization processes (typically minutes) in different solvents always led to the final formation of the thermodynamically most stable α-polymorph of nifedipine, we observed a novel pseudo-polymorph due to slow crystallization from DMSO. The single-crystal X-ray structure of the solvated species nifedipine·DMSO (1:1) is reported for the first time. In addition, the crystallization process on surfaces was followed by means of light microscopy and environmental scanning electron microscopy (ESEM) coupled with energy-dispersive X-ray spectroscopy (EDS) analysis. Different diffractions pattern and Raman spectra were observed for crystals grown from stock solution and those obtained by drying the solution on soda lime silicate surfaces.
KW - Synchrotron radiation
KW - Polymorphism
KW - Crystallization
KW - Nifedipine
PY - 2010
U6 - https://doi.org/10.1021/cg100186v
SN - 1528-7483
VL - 10
IS - 6
SP - 2693
EP - 2698
PB - American Chemical Society
CY - Washington, DC, USA
AN - OPUS4-21398
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Siegel, David
A1 - Troyanov, S.
A1 - Noack, J.
A1 - Emmerling, Franziska
A1 - Nehls, Irene
T1 - Alternariol
N2 - In the title compound (systematic name: 3,7,9-trihydroxy-1-methyl-6H-benzo[c]chromen-6-one), C14H10O5, the methyl group is shifted out of the molecular plane due to a steric collision, thus causing a slight twist of the benzene rings. The molecular structure is stabilized by an intramolecular O-H...O hydrogen bond, generating an S(6) ring. In the crystal, molecules are connected by intermolecular O-H...O hydrogen bonds into a three-dimensional network.
KW - Alternariol
KW - Kristallstruktur
PY - 2010
U6 - https://doi.org/10.1107/S1600536810017502
SN - 1600-5368
VL - 66
IS - 6
SP - o1366
PB - Munksgaard
CY - Copenhagen
AN - OPUS4-21400
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Stößer, R.
A1 - Feist, M.
A1 - Patzwaldt, K.
A1 - Menzel, Michael
A1 - Emmerling, Franziska
ED - Brooks, H.
T1 - Redox reactions of K3[Fe(CN)6] during mechanochemically stimulated phase transitions of AlOOH
N2 - Thermally induced redox reactions of K3[Fe(CN)6] (1) were investigated for a broad temperature range by thermal methods and structure analytical methods (ESR and Mößbauer spectroscopy, X-ray Powder diffraction and XANES). Based on the influence of the mechanically activated and transforming matrices 2 and 3, redox processes can be tuned to form doped Al2O3 systems which contain either isolated Fe3+ centres or redox active phases and precursors like (Al1-xFex)2O3 (4), (Al3-xFex)O4 (5), Fe3O4, Fe2O3 and Fe0. The phase Fe3C and the chemically reactive C-species were detected during the reaction of 1. The final composition of the doped products of α-Al2O3 is mainly influenced by the chemical nature of the Fe doping component, the applied temperature and time regime, and the composition of the gas phase (N2, N2/O2 or N2/H2). From the solid state chemistry point of view it is interesting that the transforming matrix (2 and 3) possesses both oxidative and protective properties and that the incorporation of the Fe species can be performed systematically.
KW - A. Inorganic compounds
KW - C. Mössbauer spectroscopy
KW - C. Thermogravimetric analysis
KW - D. Electron paramagnetic resonance
KW - ESR-Spektroskopie
KW - Kaliumhexacyanoferrat(III)
KW - Mechanische Aktivierung
KW - Mößbauer-Spektroskopie
KW - Redoxreaktionen
KW - TA-MS-Messungen
PY - 2011
U6 - https://doi.org/10.1016/j.jpcs.2011.03.016
SN - 0022-3697
VL - 72
IS - 6
SP - 794
EP - 799
PB - Pergamon Press
CY - New York, NY
AN - OPUS4-23685
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Peplinski, Burkhard
A1 - Adam, Christian
A1 - Reuther, H.
A1 - Vogel, Christian
A1 - Adamczyk, Burkart
A1 - Menzel, Michael
A1 - Emmerling, Franziska
A1 - Simon, Franz-Georg
T1 - First identification of the tridymite form of AlPO4 in municipal sewage sludge ash
N2 - Sewage sludge and sewage sludge ashes (SSA) are produced in huge amounts at municipal waste water treatment plants (WWTP) all around the world and have become an issue for many urbanized areas. To deal with this unceasing mass flow in an ecologically and economically responsible way a comprehensive chemical and structural characterization of all types of SSA is needed. X-ray powder diffraction (XRD) is one of the most promising analytical methods for this task. Although, there has been ample chemical evidence showing that many SSA contain aluminium phosphate as a major component up to now no aluminium phosphate or aluminium-rich mixed phosphate phase has been reported to be identified by XRD in a SSA produced at a mono-incineration facility. The outcome of the present com-bined XRD and Mossbauer spectroscopy investigation provides comprehensive evidence closing this gap for the first time.
KW - Aluminium phosphate
KW - AlPO4
KW - Tridymite
KW - Sewage sludge ash
KW - Incinerator
KW - Ash
PY - 2011
U6 - https://doi.org/10.1524/zkpr.2011.0067
SN - 0044-2968
VL - 1
SP - 443
EP - 448
PB - Oldenbourg
CY - München
AN - OPUS4-24297
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Riddell, N.
A1 - Becker, Roland
A1 - Chittim, B.
A1 - Emmerling, Franziska
A1 - Köppen, Robert
A1 - Lough, A.
A1 - McAlees, A.
A1 - McCrindle, R.
T1 - Preparation and X-ray structural characterization of further stereoisomers of 1,2,5,6,9,10-hexabromocyclododecane
N2 - Technical 1,2,5,6,9,10-hexabromocyclododecane (HBCD) consists largely of three diastereomers (α-, β-, and γ-HBCD) produced by the trans addition of bromine to cis,trans,trans-cyclododeca-1,5,9-triene (CDT). However, another seven diastereomers are theoretically possible and may be produced by trans addition of bromine across the double bonds of the other three isomers of 1,5,9-CDT. There are indications that small amounts of the minor HBCD isomers may be present in commercial HBCD mixtures or in products containing this brominated flame retardant (BFR). Such minor components may indeed derive from traces of other 1,5,9-CDTs in the cis, trans, trans starting material, however their formation may also be possible through isomerizations during the processing of this BFR or by bioisomerization subsequent to its release into the environment. Two of the seven additional diastereomers (δ- and ε-HBCD) were synthesized previously from trans,trans,trans-CDT. We now report the preparation of the remaining five diastereomers, ζ-, η-, and θ-HBCD from cis,cis,trans-CDT and ι- and κ-HBCD from cis,cis,cis-CDT, and their characterization by 1H NMR spectroscopy and X-ray crystallography. The availability of these further diastereomers of HBCD should aid in determining if the minor isomers are present in commercial samples of this BFR, in products containing HBCDs, or in environmental samples. We have also carried out an X-ray crystal structure determination on ε-HBCD, so that crystal structures are now available for all 10 HBCD diastereomers.
KW - Brominated flame retardants
KW - HBCDs
KW - Minor isomers
KW - X-ray
PY - 2011
U6 - https://doi.org/10.1016/j.chemosphere.2011.06.014
SN - 0045-6535
SN - 0366-7111
VL - 84
IS - 7
SP - 900
EP - 907
PB - Elsevier Science
CY - Kidlington, Oxford
AN - OPUS4-24298
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Sobina, E.
A1 - Zimathis, Anett
A1 - Prinz, Carsten
A1 - Emmerling, Franziska
A1 - de Santis Neves, R.
A1 - Galhardo, C. E.
A1 - De Robertis, E.
A1 - WANG, H.
A1 - Mizuno, K.
A1 - Kurokawa, A.
A1 - Unger, Wolfgang
T1 - Final report of CCQM-K136 measurement of porosity properties (specific adsorption, BET specific surface area, specific pore volume and pore diameter) of nanoporous Al2O3
N2 - The CCQM-K136 key comparison for determination of the porosity properties of aluminum oxide has been organized jointly by the surface and micro/nano analysis working groups of CCQM to test the abilities of the metrology institutes to measure the porosity properties (specific adsorption, BET specific surface area, specific pore volume and pore diameter) of nanoporous Al2O3.
Ural Scientific Research Institute for Metrology (UNIIM) acted as the coordinating laboratory for this comparison with BAM Federal Institute for Materials Research and Testing (BAM) as co-coordinating laboratory. Five NMIs and one DI participated in this key comparison. All participants used a gas adsorption method, here nitrogen adsorption at 77.3 K, for analysis according to the international standards ISO 15901-2 and 9277.
KW - BET specific surface area
KW - Specific adsorption
KW - Pore diameter
KW - Specific pore volume
KW - Nanoporous Al2O3
PY - 2016
UR - http://iopscience.iop.org/article/10.1088/0026-1394/53/1A/08014
U6 - https://doi.org/10.1088/0026-1394/53/1A/08014
SN - 0026-1394
SN - 1681-7575
VL - 2016
IS - 53 Technical Supplement
SP - Article 08014, 1
EP - 39
PB - IOPscience
AN - OPUS4-38282
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Fischer, Franziska
A1 - Wenzel, Klaus-Jürgen
A1 - Rademann, K.
A1 - Emmerling, Franziska
T1 - Quantitative determination of activation energies in mechanochemical reactions
N2 - Mechanochemical reactions often result in 100% yields of single products, making purifying procedures obsolete. Mechanochemistry is also a sustainable and eco-friendly method. The ever increasing interest in this method is contrasted by a lack in mechanistic understanding of the mechanochemical reactivity and selectivity. Recent in situ investigations provided direct insight into formation pathways. However, the currently available theories do not predict temperature T as an influential factor. Here, we report the first determination of an apparent activation energy for a mechanochemical reaction. In a temperaturedependent in situ study the cocrystallisation of ibuprofen and nicotinamide was investigated as a model system. These experiments provide a pivotal step towards a comprehensive understanding of milling reaction mechanisms.
KW - Mechanochemistry
KW - Cocrystal
KW - Activation energy
KW - Milling
PY - 2016
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-377444
SN - 1463-9076
SN - 1463-9084
VL - 18
IS - 33
SP - 23320
EP - 23325
AN - OPUS4-37744
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Bach, S.
A1 - Panthöfer, M.
A1 - Bienert, Ralf
A1 - de Oliveira Guilherme Buzanich, Ana
A1 - Emmerling, Franziska
A1 - Tremel, W.
T1 - Role of water during crystallization of amorphous cobalt phosphate nanoparticles
N2 - The transformation of amorphous precursors into crystalline solids and the associated mechanisms are still poorly understood. We illuminate the formation and reactivity of an amorphous cobalt phosphate hydrate precursor and the role of water for its crystallization process. Amorphous cobalt phosphate hydrate nanoparticles (ACP) with diameters of ∼20 nm were prepared in the absence of additives from aqueous solutions at low concentrations and with short reaction times. To avoid the kinetically controlled transformation of metastable ACP into crystalline Co₃(PO₄)₂ × 8H₂O (CPO) its separation must be fast. The crystallinity of ACP could be controlled through the temperature during precipitation. A second amorphous phase (HT-ACP) containing less water and anhydrous Co₃(PO₄)₂ was formed at higher temperature by the release of coordinating water. ACP contains approximately five molecules of structural water per formula unit as determined by thermal analysis (TGA) and quantitative IR spectroscopy. The Co²+ coordination in ACP is tetrahedral, as shown by XANES/EXAFS spectroscopy, but octahedral in crystalline CPO. ACP is stable in the absence of water even at 500 °C. In the wet state, the transformation of ACP to CPO is triggered by the diffusion and incorporation of water into the structure. Quantitative in situ IR analysis allowed monitoring the crystallization kinetics of ACP in the presence of water.
KW - Fluorapatite-gelatin nanocomposites
KW - Calcium-carbonate
KW - Zinc phosphate
KW - Crystal-growth
KW - Nucleation
KW - Polymorphism
PY - 2016
U6 - https://doi.org/10.1021/acs.cgd.6b00208
SN - 1528-7483
SN - 1528-7505
VL - 16
IS - 8
SP - 4232
EP - 4239
PB - ACS Publications
AN - OPUS4-37616
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Fischer, Franziska
A1 - Lubjuhn, Dominik
A1 - Greiser, Sebastian
A1 - Rademann, K.
A1 - Emmerling, Franziska
T1 - Supply and demand in the ball mill: competitive cocrystal reactions
N2 - The stability of different theophylline cocrystals under milling conditions was investigated by competitive cocrystal reactions. To determine the most stable cocrystal form under milling conditions, the active pharmaceutical ingredient theophylline was either ground with two similar coformers (benzoic acid, benzamide, or isonicotinamide), or the existing theophylline cocrystals were ground together with a competitive coformer. All competitive reactions were investigated by in situ powder X-ray diffraction disclosing the formation pathway of the milling processes. On the basis of these milling reactions, a stability order (least to most stable) was derived: tp/bs < tp/ba < tp/ina < bs/ina.
KW - Mechanochemistry
KW - Cocrystal
KW - Milling
PY - 2016
U6 - https://doi.org/10.1021/acs.cgd.6b00928
SN - 1528-7483
SN - 1528-7505
VL - 16
IS - 10
SP - 5843
EP - 5851
AN - OPUS4-38097
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Wilke, Manuel
A1 - Kabelitz, Anke
A1 - Gorelik, T. E.
A1 - de Oliveira Guilherme Buzanich, Ana
A1 - Reinholz, Uwe
A1 - Kolb, U.
A1 - Rademann, K.
A1 - Emmerling, Franziska
T1 - The crystallisation of copper(II) phenylphosphonates
N2 - The crystal structures and syntheses of four different copper(II) phenylphosphonates, the monophenylphosphonates α-, β-, and γ-Cu(O3PC6H5)·H2O (α-CuPhPmH (1) β-CuPhPmH (2) and γ-CuPhPmH (3)), and the diphosphonate Cu(HO3PC6H5)2·H2O (CuPhP2mH (4)), are presented. The compounds were synthesized from solution at room temperature, at elevated temperature, under hydrothermal conditions, and mechanochemical conditions. The structures of α-CuPhPmH (1) and CuPhP2mH (4) were solved from powder X-ray diffraction data. The structure of β-CuPhPmH (2) was solved by single crystal X-ray analysis. The structures were validated by extended X-ray absorption fine structure (EXAFS) and DTA analyses. Disorder of the crystal structure was elucidated by electron diffraction. The relationship between the compounds and their reaction pathways were investigated by in situ synchrotron measurements.
KW - Mechanochemistry
KW - Metal phosphonate
KW - In situ
PY - 2016
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-384217
SN - 1477-9226
SN - 1477-9234
VL - 45
IS - 43
SP - 17453
EP - 17463
PB - The Royal Society of Chemistry
AN - OPUS4-38421
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Emmerling, Franziska
A1 - Fischer, Franziska
A1 - Kulla, Hannes
A1 - Wilke, Manuel
T1 - In situ analysis of mechanochemical reactions using combined X-ray diffraction and Raman spectroscopy
N2 - Mechanochemistry is increasingly used for synthesizing various materials including metal organic compounds and cocrystals. Although this synthesis approach offers a fast and pure synthesis in high yields, there is a lack in understanding the mechanisms of milling reactions. The necessary data can only be obtained in in situ experiments, which were only recently established for milling reactions. Herein, we present a novel setup enabling a combined in situ investigation of mechanochemical reactions using synchrotron XRD and Raman spectroscopy.
The specific combination allows to study milling processes comprehensively on the level of the molecular and crystalline structure and thus obtaining reliable data for mechanistic studies. Besides well-known MOFs like ZIF-8, the formation process of new metal phosphonates and model cocrystals could be studied in detail. The syntheses pathway of the different compounds could be revealed. The results prove that the presented method combination is applicable for a wide range of materials and will provide the necessary understanding to tune and optimize mechanochemically synthesized compounds.
T2 - 3oth Meeting of the European Crystallographic Association
CY - Basel, Switzerland
DA - 28.08.2016
KW - Mechanochemistry
KW - In situ
PY - 2016
AN - OPUS4-38363
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - de Oliveira Guilherme Buzanich, Ana
A1 - Radtke, Martin
A1 - Reinholz, Uwe
A1 - Riesemeier, Heinrich
A1 - Emmerling, Franziska
ED - de Oliveira Guilherme Buzanich, Ana
T1 - Time- and spatial-resolved X-ray absorption fine structure (XAFS) spectroscopy in a single-shot: new analytical possibilities for in situ material characterization
N2 - A new concept that comprises both time- and lateral-resolved X-ray absorption fine-structure information simultaneously in a single shot is presented. This uncomplicated set-up was tested at the BAMline at BESSY-II (Berlin, Germany). The primary broadband beam was generated by a double multilayer monochromator. The transmitted beam through the sample is diffracted by a convexly bent Si (111) crystal, producing a divergent beam. This, in turn, is collected by either an energy-sensitive area detector, the so-called color X-ray camera, or by an area-sensitive detector based on a CCD camera, in θ-2θ geometry. The first tests were performed with thin metal foils and some iron oxide mixtures. A time resolution of lower than 1 s together with a spatial resolution in one dimension of at least 50 µm is achieved.
KW - Single-shot XAFS
KW - Time resolution
KW - Spatial resolution
KW - Divergent XAFS
PY - 2016
U6 - https://doi.org/10.1107/S1600577516003969
SN - 1600-5775
VL - 23
SP - 769
EP - 776
PB - International Union of Crystallography
AN - OPUS4-38370
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Stroh, Julia
A1 - Meng, Birgit
A1 - Emmerling, Franziska
T1 - Monitoring of sulphate attack on hardened cement paste studied by synchrotron XRD
N2 - The complex matter of external sulphate attack on cement-based construction materials is still not completely understood. The concentration of sulphate is a crucial factor for the formation of secondary phases and phase transitions of cement hydrates due to sulphate ingress into the microstructure. The sulphate attack on building materials for high and low sulphate concentrations was monitored by laboratory experiments. Hardened cement paste consisting of ordinary Portland cement (CEM I) were exposed to aqueous solutions of sodium sulphate for 18 months. Three sample compositions were used for this research, including different supplementary cementitious materials (SCM). The phase composition was determined for different time spans by high resolution synchrotron X-ray diffraction. Cross sections of exposed cement prisms were investigated as a representation of the microstructural profile. Based on the data, a temporal and spatial determination of the stages of the sulphate attack and the deterioration course was possible. Cement matrices blended with slag showed the highest resistance against sulphate attack.
KW - Cement paste
KW - Sulphate attack
KW - Mineral additions
KW - Concentration
KW - Monitoring
PY - 2015
U6 - https://doi.org/10.1016/j.solidstatesciences.2015.08.006
SN - 1293-2558
SN - 1873-3085
VL - 48
SP - 278
EP - 285
PB - Elsevier Masson SAS
CY - Amsterdam
AN - OPUS4-34281
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Fischer, Franziska
A1 - Joester, Maike
A1 - Rademann, K.
A1 - Emmerling, Franziska
T1 - Survival of the fittest: competitive co-crystal reactions in the ball mill
N2 - The driving forces triggering the formation of co-crystals under milling conditions were investigated by using a set of multicomponent competitive milling reactions. In these reactions, different active pharmaceutical ingredients were ground together with a further compound acting as coformer. The study was based on new co-crystals including the coformer anthranilic acid. The results of the competitive milling reactions indicate that the formation of co-crystals driven by intermolecular recognition are influenced and inhibited by kinetic aspects including the formation of intermediates and the stability of the reactants.
PY - 2015
U6 - https://doi.org/10.1002/chem.201500925
SN - 0947-6539
SN - 1521-3765
VL - 21
IS - 42
SP - 14969
EP - 14974
PB - Wiley-VCH Verl.
CY - Weinheim
AN - OPUS4-34861
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Peplinski, Burkhard
A1 - Adam, Christian
A1 - Adamczyk, Burkart
A1 - Müller, Ralf
A1 - Michaelis, Matthias
A1 - Krahl, T.
A1 - Emmerling, Franziska
T1 - Nanocrystalline and stacking-disordered beta-cristobalite AlPO4: the now deciphered main constituent of a municipal sewage sludge ash from a full-scale incineration facility
N2 - For the first time evidence is provided that a nanocrystalline and stacking-disordered, chemically stabilized β-cristobalite form of AlPO4 occurs in a sewage sludge ash (SSA). This proof is based on a combined X-ray powder diffraction and X-ray fluorescence investigation of an SSA produced at a large-scale fluidized bed incineration facility serving a catching area with a population of 2 million. The structural and chemical characterization was carried out on 'as received' SSA samples as well as on solid residues remaining after leaching this SSA in sodium hydroxide solution. Thus, it was ascertained that the observed nanocrystalline and stacking-disordered cristobalite-like component belongs to the aluminum phosphate component of this SSA, rather than to its silicon dioxide component. In addition, a direct proof is presented that the chemically stabilized β-cristobalite form of AlPO4 does crystallize from X-ray amorphous precursors under conditions that mimic the huge heating rate and short retention time (just seconds at T ≈ 850°C), typical for fluidized bed incinerators.
KW - Aluminum phosphate
KW - Chemical stabilization of high-temperature forms
KW - Cristobalite form
KW - Stacking disorder
KW - Incinerator ash
KW - Sewage sludge ash
PY - 2015
U6 - https://doi.org/10.1017/S0885715614001213
SN - 0885-7156
VL - 30
IS - Supplement S 1
SP - S31
EP - S35
PB - JCPDS
CY - Swarthmore, Pa.
AN - OPUS4-33435
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Batzdorf, Lisa
A1 - Fischer, Franziska
A1 - Wilke, Manuel
A1 - Wenzel, Klaus-Jürgen
A1 - Emmerling, Franziska
T1 - Direct in situ investigation of milling reactions using combined x-ray diffraction and raman spectroscopy
N2 - The combination of two analytical methods including time-resolved in situ X-ray diffraction (XRD) and Raman spectroscopy provides a new opportunity for a detailed analysis of the key mechanisms of milling reactions. To prove the general applicability of our setup, we investigated the mechanochemical synthesis of four archetypical model compounds, ranging from 3D frameworks through layered structures to organic molecular compounds. The reaction mechanism for each model compound could be elucidated. The results clearly show the unique advantage of the combination of XRD and Raman spectroscopy because of the different information content and dynamic range of both individual methods. The specific combination allows to study milling processes comprehensively on the level of the molecular and crystalline structures and thus obtaining reliable data for mechanistic studies.
PY - 2015
U6 - https://doi.org/10.1002/anie.201409834
SN - 1433-7851
SN - 1521-3773
SN - 0570-0833
VL - 54
IS - 6
SP - 1799
EP - 1802
PB - Wiley-VCH
CY - Weinheim
AN - OPUS4-34630
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Schlegel, M.C.
A1 - Stroh, Julia
A1 - Malaga, K.
A1 - Meng, Birgit
A1 - Panne, Ulrich
A1 - Emmerling, Franziska
T1 - Pathway of a damaging mechanism - Analyzing chloride attack by synchrotron based X-ray diffraction
N2 - Typically, the changes of the phase compositions due to the chemical attack are studied in-situ only by chemical analysis or microscopy. In this study, the chloride transport and binding in the cement matrix in different cementitious materials was analyzed by synchrotron based X-ray diffraction (SyXRD) and energy dispersive X-ray spectroscopy (EDX). Sample materials consisting of cement paste were embedded in high concentrated sodium chloride solution over different time spans. Afterwards, the phase and chemical compositions were determined. The high spatial resolution and the information about the chloride distribution offer a detailed view of chloride binding in the cement matrix and allow the conclusions about the degradation mechanisms. The results are discussed related to the influence of different supplementary cementitious materials on the damaging mechanism.
KW - Portland cement
KW - In-situ
KW - X-Ray diffraction
KW - EDX
KW - Durability
KW - Chloride attack
PY - 2015
U6 - https://doi.org/10.1016/j.solidstatesciences.2015.03.021
SN - 1293-2558
SN - 1873-3085
VL - 44
SP - 45
EP - 54
PB - Elsevier Masson SAS
CY - Amsterdam
AN - OPUS4-33171
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Fischer, Franziska
A1 - Scholz, G.
A1 - Batzdorf, Lisa
A1 - Wilke, Manuel
A1 - Emmerling, Franziska
T1 - Synthesis, structure determination, and formation of a theobromine: oxalic acid 2:1 cocrystal
N2 - The structure and the formation pathway of a new theobromine : oxalic acid (2 : 1) cocrystal are presented. The cocrystal was synthesised mechanochemically and its structure was solved based on the powder X-ray data. The mechanochemical synthesis of this model compound was studied in situ using synchrotron XRD. Based on the XRD data details of the formation mechanism were obtained. The formation can be described as a self-accelerated ('liquid like') process from a highly activated species.
KW - ssNMR spectroscopy
KW - Synchrotron measurements
KW - API molecule
PY - 2015
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-331567
SN - 1466-8033
VL - 17
IS - 4
SP - 824
EP - 829
CY - London, UK
AN - OPUS4-33156
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Leng, Jing
A1 - Purohit, Purv
A1 - Kang, N.
A1 - Wang, D.-Y.
A1 - Falkenhagen, Jana
A1 - Emmerling, Franziska
A1 - Thünemann, Andreas
A1 - Schönhals, Andreas
T1 - Structure-property relationships of nanocomposites based on polylactide and MgAl layered double hydroxides
N2 - Nanocomposites based on poly(ʟ-lactide) (PLA) and organically modified MgAl Layered Double Hydroxides (MgAl-LDH) were prepared by melt blending and investigated by a combination of Differential Scanning Calorimetry (DSC), Small- and Wide-Angle X-ray Scattering (SAXS, WAXS), and dielectric spectroscopy (BDS). Scanning microfocus SAXS investigations show that the MgAl-LDH is homogeneously distributed in the matrix as stacks of 6 layers and/or partly exfoliated layers. DSC and WAXS show that the degree of crystallinity decreases linearly with the content of LDH. The extrapolation of the dependencies (DSC and WAXS) to zero estimates a limiting concentration of LDH CCri of ca. 21 wt% where the crystallization of PLA is completely suppressed by the nanofiller. The dielectric behavior of neat PLA show two relaxation regions, a β-relaxation at low temperatures related to localized fluctuations and the α-relaxation at higher temperatures due to the dynamic glass transition. The dielectric spectra of the nanocomposites show several additional relaxation processes compared to neat PLA which are discussed in detail. For the nanocomposites around 260 K (ƒ = 1 kHz) an additional process is observed which intensity increases with increasing concentration of LDH. This process is mainly attributed to the exchanged dodecylbenzene sulfonate (SDBS) molecules which are adsorbed at the LDH layers and form a mixed phase with the polymer close to the layers and stacks. An analysis of this process provides information about the molecular dynamics in the interfacial region between the LDH layers and the PLA matrix which reveal glassy dynamics in this region. In the temperature range around 310 K (ƒ = 1 kHz) a further process is observed. Its relaxation rate has an unusual saddle-like temperature dependence. It was assigned to rotational fluctuations of water molecules in a nanoporous environment provided by the LDH filler. Above the glass transition temperature a further process is observed at temperatures above. It is related to Maxwell/Wagner/Sillars polarization due to the blocking of charges at the nanofiller.
KW - Polymer based nanocomposites
KW - Polylactide
KW - Layered double hydroxides
KW - Dielectric spectroscopy
PY - 2015
U6 - https://doi.org/10.1016/j.eurpolymj.2015.05.008
SN - 0014-3057
SN - 1873-1945
VL - 68
SP - 338
EP - 354
PB - Elsevier
CY - Oxford
AN - OPUS4-33257
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Ortel, Erik
A1 - Polte, J.
A1 - Bernsmeier, D.
A1 - Eckhardt, B.
A1 - Paul, B.
A1 - Bergmann, A.
A1 - Strasser, P.
A1 - Emmerling, Franziska
A1 - Kraehnert, R.
T1 - Pd/TiO2 coatings with template-controlled mesopore structure as highly active hydrogenation catalyst
N2 - Micro-structured reactors offer excellent mass and heat transport capabilities and can therefore sustain very high reaction rates and space–time-yields also for highly exothermic catalytic reactions. However, such high rates cannot be reached when the reactors are coated or filled with conventional catalysts powders. We present a strategy for the direct synthesis of highly active wall-coated supported catalysts via co-deposition of a pore template (here micelles formed from PEO-b-PPO-b-PEO) and a precursors for the metal oxide (TiCl4) along with a compatible precursor for the active metal (PdCl2). The obtained catalytic coatings possess a template-controlled open pore structure and excellent mechanical stability. Moreover, the active metal is highly dispersed and well-distributed across the coating also at high Pd loadings. The corresponding high activity along with rapid mass transfer enabled by the open pore system results in the best space–time-yields in the gas-phase hydrogenation of butadiene reported so far in literature for a supported catalyst.
KW - Titanium oxide films
KW - Palladium nanoparticle
KW - Wall-coated supported catalysts
KW - Template-controlled mesoporous materials
KW - Hydrogenation of 1,3-butadiene
PY - 2015
U6 - https://doi.org/10.1016/j.apcata.2014.12.044
SN - 0926-860X
SN - 1873-3875
VL - 493
SP - 25
EP - 32
PB - Elsevier
CY - Amsterdam
AN - OPUS4-32465
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - RPRT
A1 - Thünemann, Andreas
A1 - Emmerling, Franziska
A1 - Hodoroaba, Vasile-Dan
T1 - Review of existing calibration or reference
N2 - We report on calibration standards of nanoparticles meeting the definition of a nanomaterial given by the European Commission (EU 2011) which are relevant for the characterisation methods applied in the NanoDefine project. We found that the Impact of nanoparticles is outstanding in the scientific literature. A number of 270.000 paper titles on nanoparticles are listed in the Web of Science data base. But surprisingly, the availability of suitable certified standard reference materials is scarce. Only a few sources were found. For example, BAM provides the database Nanoscaled Reference Materials at http://www.nano-refmat.bam.de/en/ in cooperation with the ISO/TC 229 Nanotechnologies. In addition, two publications from 2013 on nanoscale reference materials are available. Candidates of nano-(certified) reference materials from other ongoing or just finished FP6 and FP7 nano-metrology projects have been extracted from the Compendium of Projects in the European NanoSafety Cluster (Compendium NSC, 2013). Recommendations for selection of representative test materials and calibration standards for NanoDefine internal tasks, respectively, are also given.
KW - Nanomaterial
KW - Reference materials
KW - Certified reference materials
PY - 2014
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-389836
UR - http://www.nanodefine.eu/index.php/downloads/nanodefine-technical-reports
SP - 1
EP - 18
CY - Wageningen, The Netherlands
AN - OPUS4-38983
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Hoffmann, Holger
A1 - Baldofski, Stefanie
A1 - Hoffmann, Kristin
A1 - Flemig, Sabine
A1 - Silva, C. P.
A1 - Esteves, V. I.
A1 - Emmerling, Franziska
A1 - Panne, Ulrich
A1 - Schneider, Rudolf
T1 - Structural considerations on the selectivity of an immunoassay for sulfamethoxazole
N2 - Sulfamethoxazol (SMX),a sulfonamide, is a widely used bacteriostatic antibiotic and therefore a promising marker for the entry of anthropogenic Pollution in the environment. SMX is frequently found in wastewater and surface water. This study presents the production of high affinity and selective polyclonal antibodies for SMX and the development and Evaluation of a direct competitive enzyme-linked immunosorbent assay(ELISA)for the quantification of SMX in environmental watersamples. The crystal structures of the cross-reacting compounds sulfamethizole, N4-acetyl-SMX andsuccinimidyl-SMX were determined by x-ray diffraction aiming to explain their high cross-reactivity. These crystal structures are described for the first time. The quantification range of the ELISA is 0.82–63 µg/L. To verify our results, the SMX concentration in 20 environmental samples,including wastewater and surfacewater,was determined by ELISA and tandem mass spectrometry(MS/MS).A good Agreement of the measured SMX concentrations was found with average recoveries of 97–113%for the results of ELISA compared to LC-MS/MS.
KW - X-Ray diffraction
KW - ELISA
KW - LC-MS/MS
KW - Sulfamethoxazole
PY - 2016
U6 - https://doi.org/10.1016/j.talanta.2016.05.049
SN - 0039-9140
SN - 1873-3573
IS - 158
SP - 198
EP - 207
PB - Elsevier B.V.
CY - Amsterdam, Netherlands
AN - OPUS4-38530
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Beyer, Sebastian
A1 - Prinz, Carsten
A1 - Schürmann, Robin
A1 - Feldmann, Ines
A1 - Zimathies, Annett
A1 - Blocki, Anna
A1 - Bald, Ilko
A1 - Schneider, Rudolf
A1 - Emmerling, Franziska
T1 - Ultra-sonication of ZIF-67 crystals results in ZIF-67 nano-flakes
N2 - Zeolitic Imidazolate Frameworks (ZIFs) are crystalline materials
that comprise of metal nodes and Imidazole derivatives as
linkers. ZIF-67 is often used in polymer composite materials
e. g. for gas separation membranes. Post-synthesis treatment of
ZIF-67 crystals with ultrasound leads to unforeseen plasticity
that resulted in sintered ZIF-67 and ZIF-67 nano-flakes.
Consequently, ultrasound increases the external surface area of
ZIF-67 which might improve e.g. blending with polymers in
composite materials. These new morphologies of ZIF-67 were
characterized by transmission electron, scanning electron, and
atomic force microscopy. The ultrasound treatment of ZIF-67
did not result in the formation of an amorphous framework or
a meta-stable crystal structure as indicated by powder x-ray
diffraction. In addition, ultra-sonicated ZIF-67 retained the high
gas adsorption capacity and pore size compared to synthesized
ZIF-67. The morphological changes are hard to detect with
standard analytical methods that are usually utilized for MOF
characterization. These findings also suggest that sonochemical
treatment of ZIFs leads to structural effects beyond increasing
the amount of nucleation clusters during sono-chemical synthesis,
which is currently not addressed in the field.
KW - ZIF
PY - 2016
U6 - https://doi.org/10.1002/slct.201601513
SN - 2365-6549
VL - 1
IS - 18
SP - 5905
EP - 5908
AN - OPUS4-38496
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Fischer, Franziska
A1 - Greiser, Sebastian
A1 - Peifer, Dietmar
A1 - Jäger, Christian
A1 - Rademann, K.
A1 - Emmerling, Franziska
T1 - Mechanochemically Induced Conversion of Crystalline Benzamide Polymorphs by Seeding
N2 - Benzamide has been known for its polymorphism for almost 200 years.Three polymorphic forms are described. To date,itwas only possible to crystallizeametastable form in amixture together with the thermodynamically most stable form I. Acomplete transformation of form Iinto the metastable form III by mechanochemical treatment has been achieved. Catalytic amounts of nicotinamide seeds were used to activate the conversion by mechanochemical seeding. NMR experiments indicated that the nicotinamide molecules were incorporated statistically in the crystal lattice of benzamide form III during the conversion. The transformation pathway was evaluated using in situ powder X-ray diffraction.
KW - Nicotinamide
KW - Benzamide
KW - In situ reactions
KW - Mechanochemistry
KW - Polymorphs
PY - 2016
U6 - https://doi.org/10.1002/anie.201607358
VL - 128
IS - 46
SP - 14493
EP - 14497
PB - WILEY-VCH
CY - Weinheim
AN - OPUS4-38472
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Tumanova, N.
A1 - Tumanov, N.
A1 - Robeyns, K.
A1 - Fischer, Franziska
A1 - Fusaro, L.
A1 - Morelle, F.
A1 - Ban, V.
A1 - Hautier, G.
A1 - Filinchuk, Y.
A1 - Wouters, J.
A1 - Leyssens, T.
A1 - Emmerling, Franziska
T1 - Opening Pandora’s Box: Chirality, Polymorphism, and Stoichiometric Diversity in Flurbiprofen/Proline Cocrystals
N2 - Proline has been widely used for various cocrystallization applications, including pharmaceutical cocrystals. Combining enantiopure and racemic flurbiprofen and proline, we discovered 18 new crystal structures. Liquid-assisted grinding proved highly efficient to explore all the variety of crystal forms. A unique combination of stateof-the-art characterization techniques, comprising variable temperature in situ X-ray diffraction and in situ ball-milling, along with other physicochemical methods and density functional theory calculations, was indispensable for identifying all the phases. Analyzing the results of in situ ball-milling, we established a stepwise mechanism for the formation of several 1:1 cocrystals via an intermediate 2:1 phase. The nature of the solvent in liquidassisted grinding was found to significantly affect the reaction rate and, in some cases, the reaction pathway.
KW - Mechanochemistry
KW - Polymorphs
KW - In situ
PY - 2018
UR - https://pubs.acs.org/doi/abs/10.1021/acs.cgd.7b01436
U6 - https://doi.org/10.1021/acs.cgd.7b01436
VL - 18
IS - 2
SP - 954
EP - 961
PB - American Chemical Society
AN - OPUS4-44365
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Beyer, Sebastian
A1 - Schürmann, Robin
A1 - Feldmann, Ines
A1 - Blocki, A.
A1 - Bald, Ilko
A1 - Schneider, Rudolf
A1 - Emmerling, Franziska
T1 - Maintaining Stable Zeolitic Imidazolate Framework (ZIF) Templates during Polyelectrolyte Multilayer Coating
N2 - Equipping ZIF particles with a polyelectrolyte membrane provides functional groups at their interface, enabling further conjugations necessary for applications such as targeted drug delivery. Previous approaches to coat ZIF particles with polyelectrolytes led to surface corrosion of the template material. This work overcomes previous limitations by performing a Layer-by-Layer (LbL) polyelectrolyte coating onto ZIF-8 and ZIF-67 particles in nonaqueous environment. Using the 2-methylimidazolium salt of polystyrensulfonic acid instead of the acid itself and polyethyleneimine in methanol led to intact ZIF particles after polyelectrolyte coating. This was verified by electron microscopy. Further, zetapotential and atomic force microscopy measurements confirmed a continuous polyelectrolyte multilayer built up. The here reported adaption to the well-studied (LbL) polyelectrolyte selfassembly process provides a facile method to equip ZIF particles with a nanometer thin polyelectrolyte multilayer membrane.
KW - Zeolithe
KW - Molecular Organic Frameworks
KW - MOF
KW - ZIF
KW - Layer-by-Layer
KW - Beschichtung
KW - Polyelektrolyt
PY - 2018
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-447729
SN - 2215-0382
VL - 22
SP - 14
EP - 17
PB - Elsevier B.V.
CY - Amsterdam, NL
AN - OPUS4-44772
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Zauer, M.
A1 - Prinz, Carsten
A1 - Adolphs, J.
A1 - Emmerling, Franziska
A1 - Wagenführ, A.
T1 - Sorption surfaces and energies of untreated and thermally modified wood evaluated by means of excess surface work (ESW)
N2 - Water vapor sorption surface areas and sorption energies of untreated
and thermally modified Norway spruce [Picea abies (L.) Karst.], sycamore maple (Acer pseudoplatanus L.) and European ash (Fraxinus excelcior L.) were investigated by means of dynamic vapor sorption (DVS) measurements and excess surface work (ESW) evaluation method, respectively. Adsorption and desorption experiments in the hygroscopic range and desorption tests from water saturation were conducted.
Thermodynamically, ESW is the sum of the surface free energy and the isothermal isobaric work of sorption. From the amount adsorbed in the first Minimum a specific surface area similar to the BET surface area can be obtained. The results show that untreated spruce has a significantly higher specific water vapor Sorption surface and sorption energy compared to both hardwoods maple and ash. Thermal modification of the woods leads to a significant reduction of water vapor Sorption surface and sorption energy. The determined surface area and energy are higher in desorption direction than in adsorption direction, whereby the highest values in Desorption direction from water saturation, especially for maple and ash, were obtained.
The surface areas calculated by means of the ESW method are similar to the surface areas calculated by means of the BET method, particularly in adsorption direction.
KW - Excess surface work
KW - Dynamic vapor sorption
KW - Wood
KW - BET
PY - 2018
U6 - https://doi.org/10.1007/s00226-018-1021-2
SN - 1432-5225
SN - 0043-7719
VL - 52
IS - 4
SP - 957
EP - 969
PB - Springer
CY - Berlin Heidelberg
AN - OPUS4-44975
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Kulla, Hannes
A1 - Haferkamp, Sebastian
A1 - Akhmetova, Irina
A1 - Röllig, Mathias
A1 - Maierhofer, Christiane
A1 - Rademann, Klaus
A1 - Emmerling, Franziska
T1 - In situ investigations of mechanochemical one-pot syntheses
N2 - We present an in situ triple coupling of synchrotron X-ray diffraction with Raman spectroscopy, and thermography to study milling reactions in real time. This combination of methods allows a correlation of the structural evolution with temperature information. The temperature information is crucial for understanding both the thermodynamics and reaction kinetics. The reaction mechanisms of three prototypical mechanochemical syntheses, a cocrystal formation, a C@C bond formation (Knoevenagel condensation), and the formation
of a manganese-phosphonate, were elucidated. Trends in the temperature development during milling are identified. The heat of reaction and latent heat of crystallization of the product contribute to the overall temperature increase. A decrease in temperature occurs via release of, for example, water as a byproduct.
Solid and liquid intermediates are detected. The influence of the mechanical impact could be separated from temperature effects caused by the reaction.
KW - In situ studies
KW - Mechanochemistry
KW - Raman spectroscopy
KW - Thermography
KW - X-ray diffraction
PY - 2018
U6 - https://doi.org/10.1002/anie.201800147
SN - 1433-7851
SN - 1521-3773
VL - 57
IS - 20
SP - 5930
EP - 5933
PB - Wiley-VCH
CY - Weinheim
AN - OPUS4-44946
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Al-Terkawi, Abdal-Azim
A1 - Scholz, G.
A1 - Prinz, Carsten
A1 - Zimathies, Annett
A1 - Emmerling, Franziska
A1 - Kemnitz, E.
T1 - Hydrated and dehydrated Ca-coordination polymers based on benzene-dicarboxylates: mechanochemical synthesis, structure refinement, and spectroscopic characterization
N2 - A series of Ca-based coordination polymers were prepared mechanochemically by milling Ca(OH)2 with phthalic acid (H2oBDC), isophthalic acid (H2mBDC), and terephthalic acid (H2pBDC). The hydrated compounds [Ca(oBDC)(H2O)], [Ca(mBDC)(H2O)3.4], and [Ca(pBDC)(H2O)3] were prepared for the first time via mechanochemical routes. The refined structures were validated by extended X-ray absorption data. The new dehydrated compound [Ca(oBDC)] (1-H2O), obtained after the thermal post-treatment of 1 in a reversible phase transition process, was determined ab initio based on the powder X-ray diffraction (PXRD) data. The materials were thoroughly characterized using elemental analysis, thermal analysis, and spectroscopic methods: magic-angle spinning NMR and attenuated total reflection-infrared spectroscopy. The specific surface areas and sorption properties of the hydrated and dehydrated samples were determined using the isotherms of gas sorption and dynamic vapor sorption measurements.
KW - Mechanochemistry
KW - XRD
PY - 2018
UR - http://pubs.rsc.org/en/content/articlehtml/2017/ce/c7ce01906h
U6 - https://doi.org/10.1039/C7CE01906H
VL - 20
SP - 946
EP - 961
PB - Royal Society of Chemistry
AN - OPUS4-44440
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Krause, B.
A1 - Meyer, T.
A1 - Sieg, H.
A1 - Kästner, Claudia
A1 - Reichardt, P.
A1 - Tentschert, J.
A1 - Jungnickel, H.
A1 - Estrela-Lopis, I.
A1 - Burel, A.
A1 - Chevance, S.
A1 - Gauffre, F.
A1 - Jalili, P.
A1 - Meijer, J.
A1 - Böhmert, L.
A1 - Braeuning, A.
A1 - Thünemann, Andreas
A1 - Emmerling, Franziska
A1 - Fessard, V.
A1 - Laux, P.
A1 - Lampen, A.
A1 - Luch, A.
T1 - Characterization of aluminum, aluminum oxide and titanium dioxide nanomaterials using a combination of methods for particle surface and size analysis
N2 - The application of appropriate analytical techniques is essential for nanomaterial (NM) characterization. In this study, we compared different analytical techniques for NM analysis. Regarding possible adverse health effects, ionic and particulate NM effects have to be taken into account. As NMs behave quite differently in physiological media, special attention was paid to techniques which are able to determine the biosolubility and complexation behavior of NMs. Representative NMs of similar size were selected: aluminum (Al0) and aluminum oxide (Al2O3), to compare the behavior of metal and metal oxides. In addition, titanium dioxide (TiO2) was investigated. Characterization techniques such as dynamic light scattering (DLS) and nanoparticle tracking analysis (NTA) were evaluated with respect to their suitability for fast characterization of nanoparticle dispersions regarding a particle's hydrodynamic diameter and size distribution. By application of inductively coupled plasma mass spectrometry in the single particle mode (SP-ICP-MS), individual nanoparticles were quantified and characterized regarding their size. SP-ICP-MS measurements were correlated with the information gained using other characterization techniques, i.e. transmission electron microscopy (TEM) and small angle X-ray scattering (SAXS). The particle surface as an important descriptor of NMs was analyzed by X-ray diffraction (XRD). NM impurities and their co-localization with biomolecules were determined by ion beam microscopy (IBM) and confocal Raman microscopy (CRM). We conclude advantages and disadvantages of the different techniques applied and suggest options for their complementation. Thus, this paper may serve as a practical guide to particle characterization techniques.
KW - Small-angle X-ray scattering
KW - SAXS
PY - 2018
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-447057
SN - 2046-2069
VL - 8
IS - 26
SP - 14377
EP - 14388
PB - The Royal Society of Chemistry
AN - OPUS4-44705
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Al-Terkawi, Abdal-Azim
A1 - Scholz, Gudrun
A1 - Emmerling, Franziska
A1 - Kemnitz, Erhard
T1 - Ca-Tetrafluorophthalate and Sr-isophthalate: mechanochemical synthesis and characterization in comparison with other Ca-and Sr-coordination polymers
N2 - New Ca- and Sr-based coordination polymers (CPs) were mechanochemically synthesized by milling metal hydroxide samples (M = Ca, Sr) with tetrafluorophthalic acid (H2oBDC-F4) and isophthalic acid (H2mBDC). [Ca(oBDC-F4)(H2O)2] (1) exhibits a small surface area which is slightly increased after removing the crystal water. On the other hand, the hydrated sample of the nonfluorinated [Sr(mBDC)(H2O)3.4] (2) reveals a small BET surface area which remains unchanged even after the release of crystal water via thermal treatment. The new compounds 1 and 2 are similar to their Sr- and Ca-analogs, respectively. These findings are confirmed by thermal analysis, MAS NMR, and ATR-IR measurements, in addition to the Le Bail refinements for the measured powder X-ray data of 1 and 2. Ca- and Sr-CPs based on perfluorinated dicarboxylic systems and their nonfluorinated analogs diverse in structural and chemical properties depending on the geometries of the organic linkers and the presence of fluorine atoms. The fluorinations of organic ligands lead to the formation of fluorinated CPs with higher dimensionalities compared to their nonfluorinated counterparts. Conversely, the thermal stabilities of the latter are higher than those of the fluorinated CPs.
KW - Mechanochemistry
PY - 2018
U6 - https://doi.org/10.1039/c8dt00695d
SN - 1477-9226
SN - 1477-9234
VL - 47
IS - 16
SP - 5743
EP - 5754
PB - Royal Society of Chemistry
CY - Cambridge
AN - OPUS4-44696
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Al-Terkawi, Abdal-Azim
A1 - Scholz, Gudrun
A1 - Emmerling, Franziska
A1 - Kemnitz, Erhard
T1 - Barium coordination polymers based on fluorinated and fluorine-free benzene-dicarboxylates: Mechanochemical synthesis and spectroscopic characterization
N2 - A series of new Ba-based coordination polymers (CPs) were mechanochemically synthesized by milling Ba-hydroxide samples with perfluorinated and fluorine-free benzene-dicarboxylic acids, including tetrafluoroisophthalic acid (H2mBDC-F4), tetrafluorophthalic acid (H2oBDC-F4), isophthalic acid (H2mBDC) and phthalic acid (H2oBDC). The new fluorinated CPs: [Ba(mBDC-F4)$0.5H2O] (1) and [Ba(oBDC-F4)·1.5H2O] (2) are compared to their nonfluorinated counterparts: [Ba(mBDC)·2.5H2O] (3), and [Ba(oBDC)·1H2O] (4). These materials are thoroughly characterized using powder X-ray diffraction. The products obtained by milling are all hydrated but vary in their water contents. Compositions and local structures are investigated by elemental analysis, thermal analysis, MAS NMR and attenuated total reflectioninfrared spectroscopy. These materials exhibit high thermal stabilities but small surface areas that remain unchanged even after thermal treatments.
KW - Mechanochemical synthesis
KW - Barium
KW - Fluorine
KW - Coordination polymers
KW - PXRD
KW - MAS NMR spectroscopy
PY - 2018
UR - https://www.sciencedirect.com/science/article/pii/S1293255817310798
U6 - https://doi.org/10.1016/j.solidstatesciences.2018.03.013
SN - 1293-2558
SN - 1873-3085
VL - 79
SP - 99
EP - 108
PB - Elsevier
AN - OPUS4-44880
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Breitfeld, Steffen
A1 - Scholz, G.
A1 - Emmerling, Franziska
A1 - Kemnitz, E.
T1 - BaF-benzenedicarboxylate: the first mechanochemical
N2 - Anewbariumcoordination polymer, BaF-benzenedicarboxylate (BaF(p-BDC)0.5), with fluorine directly coordinated to the metal cation, was prepared by mechanochemical synthesis routes. Phase-pure BaF-benzenedicarboxylate was synthesized by milling starting either from barium hydroxide or from Barium acetate as sources for barium cations. In both cases, the second reactant was 1,4-benzenedicarboxylic acid (H2(p-BDC)). Ammonium fluoride was used as fluorinating agent directly at milling. This is the first mechanochemical synthesis of coordination polymers where fluorine is directly coordinated to the metal cation.
Following the second possibility, barium acetate fluoride (Ba(OAc)F) is formed as ntermediate product after milling, and the new coordination polymer is accessible only after washing with water and dimethyl sulfoxide. The new compound BaF(p-BDC)0.5 was characterized by X-ray powder diffraction, FTIR-, and 19F, 1H-13C CP MAS NMR spectroscopies, DTA-TG, and elemental Analysis.
KW - Milling
KW - MOF
PY - 2018
U6 - https://doi.org/10.1007/s10853-018-2331-3
SN - 0022-2461
VL - 53
IS - 19
SP - 13682
EP - 13689
PB - Springer
AN - OPUS4-45677
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Emmerling, Franziska
A1 - Haferkamp, Sebastian
A1 - Kraus, Werner
T1 - Studies on the mechanochemical Knoevenagel condensation of fluorinated benzaldehyde derivates
N2 - The mechanochemical Knoevenagel condensation of three fluorinated benzaldehyde derivates and malononitrile was investigated. The reactions were performed under solvent- and catalyst-free conditions and resulted in highly crystalline products after crystallization from a viscous phase in the milling jar.
The quality of the obtained crystals was sufficient for single-crystal X-ray diffraction circumventing a recrystallization step. To gain more information on the reaction, progress was investigated in situ using time-resolved Raman spectroscopy. The results show a direct conversion of the reactants.
KW - C-C coupling
KW - Knoevenagel condensation
KW - In situ
KW - Mechanochemistry
PY - 2018
U6 - https://doi.org/10.1007/s10853-018-2492-0
SN - 0022-2461
VL - 53
IS - 19
SP - 13713
EP - 13718
PB - Springer Link
AN - OPUS4-45682
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Schiffmann, J.
A1 - Emmerling, Franziska
A1 - Martins, Ines
A1 - Van Wüllen, L.
T1 - In-situ reaction monitoring of a mechanochemical ball mill reaction with solid state NMR
N2 - We present an approach towards the in situ solid state NMR monitoring of mechanochemical reactions in a ball mill. A miniaturized vibration ball mill is integrated into the measuring coil of a home-built solid state NMR probe, allowing for static solid state NMR measurements during the mechanochemical reaction within the vessel. The setup allows to quantitatively follow the product evolution of a prototypical mechanochemical reaction, the formation of zinc phenylphosphonate from zinc acetate and phenylphosphonic acid. MAS NMR investigations on the final reaction mixture confirmed a reaction yield of 89% in a typical example. Thus, NMR spectroscopy may in the future provide complementary information about reaction mechanisms of mechanochemical reactions and team up with other analytical methods which have been employed to follow reactions in situ, such as Raman spectroscopy or X-ray diffraction.
KW - Mechanochemistry
KW - Solid state NMR
KW - NMR probe Development
PY - 2020
U6 - https://doi.org/10.1016/j.ssnmr.2020.101687
VL - 109
SP - 101687
PB - Elsevier Inc.
AN - OPUS4-51283
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Lumpe, H.
A1 - Menke, Annika
A1 - Haisch, C.
A1 - Mayer, P.
A1 - Kabelitz, Anke
A1 - Yusenko, Kirill
A1 - de Oliveira Guilherme Buzanich, Ana
A1 - Block, T.
A1 - Pöttgen, R.
A1 - Emmerling, Franziska
A1 - Daumann, L.
T1 - The Earlier the Better: Structural Analysis and Separation of Lanthanides with Pyrroloquinoline Quinone
N2 - Lanthanides (Ln) are critical raw materials, however, their mining and purification have a considerable negative environmental impact and sustainable recycling and separation strategies for these elements are needed. In this study, the precipitation and solubility behavior of Ln complexes with pyrroloquinoline quinone (PQQ), the cofactor of recently discovered lanthanide (Ln) dependent methanol dehydrogenase (MDH) enzymes, is presented. In this context, the molecular structure of a biorelevant europium PQQ complex was for the first time elucidated outside a protein environment. The complex crystallizes as an inversion symmetric dimer, Eu2PQQ2, with binding of Eu in the biologically relevant pocket of PQQ. LnPQQ and Ln1Ln2PQQ complexes were characterized by using inductively coupled plasma mass spectrometry (ICP‐MS), infrared (IR) spectroscopy, 151Eu‐Mössbauer spectroscopy, X‐ray total scattering, and extended X‐ray absorption fine structure (EXAFS). It is shown that a natural enzymatic cofactor is capable to achieve separation by precipitation of the notoriously similar, and thus difficult to separate, lanthanides to some extent.
KW - PQQ
KW - Lanthanoide
KW - Coordination chemistry
KW - Rare earth elements separations
PY - 2020
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-512707
VL - 26
IS - 44
SP - 10133
EP - 10139
AN - OPUS4-51270
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Emmerling, Franziska
T1 - New insights in cocrystal formations: in situ investigations of mechanochemical syntheses
N2 - Mechanochemistry is increasingly used for synthesizing soft matter materials including metal organic compounds and cocrystals. The ever-increasing interest in this method is contrasted by a limited mechanistic understanding of the mechanochemical reactivity and selectivity. Time-resolved in situ investigations of milling reactions provide direct insights in the underlying mechanisms. We introduced a setup enabling in situ investigation of mechanochemical reactions using synchrotron XRD combined with Raman spectroscopy. The specific combination allows to study milling processes comprehensively on the level of the molecular and crystalline structure and thus obtaining reliable data for mechanistic studies. We discuss our recent results investigating the formation of (polymorphic) cocrystals. First investigations of a mechanochemical synthesis under controlled temperature which allow determining the activation barrier are presented.6 Furthermore, X-ray diffraction and in situ Raman spectroscopy coupled with thermography revealed a low temperature increase during milling reactions due to the mechanical impact and clear temperature increases as a result of the reaction heat. Our results indicate that in situ investigation of milling reactions offer a new approach to tune and optimize mechanochemically synthesized compounds.
T2 - CSEC Seminar University of Edinburgh
CY - Edinburgh, Scotland
DA - 16.05.2019
KW - Mechanochemistry
KW - Acoustic levitation
KW - In situ
PY - 2019
AN - OPUS4-48098
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Haferkamp, Sebastian
A1 - Paul, Andrea
A1 - Michalchuk, Adam
A1 - Emmerling, Franziska
T1 - Unexpected polymorphism during a catalyzed mechanochemical Knoevenagel condensation
N2 - The transformation of a base-catalyzed, mechano-assisted Knoevenagel condensation of mono-fluorinated benzaldehyde derivatives (p-, m-, o-benzaldehyde) with malonodinitrile was investigated in situ and in real time. Upon milling, the para-substituted product was found to crystallize initially into two different polymorphic forms, depending on the quantity of catalyst used. For low catalyst concentrations, a mechanically metastable phase (monoclinic) was initially formed, converting to the mechanically stable phase (triclinic) upon further grinding. Instead, higher catalyst concentrations crystallize directly as the triclinic product. Inclusion of catalyst in the final product, as evidenced by mass spectrometric analysis, suggests this complex polymorphic pathway may be due to seeding effects. Multivariate analysis for the in situ Raman spectra supports this complex formation pathway, and offers a new approach to monitoring multi-phase reactions during ball milling.
KW - Ball milling
KW - C-C coupling
KW - In situ
KW - Mechanochemistry
KW - Multivariate data analysis
PY - 2019
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-481872
SN - 1860-5397
VL - 15
SP - 1141
EP - 1148
PB - Beilstein Insitut
CY - Frankfurt am Main
AN - OPUS4-48187
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Lumpe, H.
A1 - Menke, A.
A1 - Haisch, C.
A1 - Mayer, P.
A1 - Kabelitz, Anke
A1 - Yusenko, Kirill
A1 - de Oliveira Guilherme Buzanich, Ana
A1 - Block, T.
A1 - Pöttgen, R.
A1 - Emmerling, Franziska
A1 - Daumann, L. J.
T1 - The Earlier the Better: Structural Analysis and Separation of Lanthanides with Pyrroloquinoline Quinone
N2 - Lanthanides (Ln) are critical raw materials, however, their mining and purification have a considerable negative environmental impact and sustainable recycling and separation strategies for these elements are needed. In this study, the precipitation and solubility behavior of Ln complexes with pyrroloquinoline quinone (PQQ), the cofactor of recently discovered lanthanide (Ln) dependent methanol Dehydrogenase (MDH) enzymes, is presented. In this context, the molecular structure of a biorelevant europium PQQ complex was for the first time elucidated outside a protein environment.
The complex crystallizes as an inversion symmetric dimer, Eu2PQQ2, with binding of Eu in the biologically relevant pocket of PQQ. LnPQQ and Ln1Ln2PQQ complexes were characterized by using inductively coupled Plasma mass spectrometry (ICP-MS), infrared (IR) spectroscopy, 151Eu-Mössbauer spectroscopy, X-ray total scattering, and Extended X-ray absorption fine structure (EXAFS). It is shown that a natural enzymatic cofactor is capable to achieve Separation by precipitation of the notoriously similar, and thus difficult to separate, lanthanides to some extent.
KW - Lanthanides
KW - Structural Analysis
KW - Separation
PY - 2020
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-510821
SN - 0947-6539
VL - 26
SP - 1
EP - 8
PB - WILEY-VCH Verlag GmbH & co. KGaA
AN - OPUS4-51082
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - de Oliveira, P. F. M.
A1 - Torresi, R.
A1 - Emmerling, Franziska
A1 - Carmago, P.
T1 - Challenges and opportunities in the bottom-up mechanochemical synthesis of noble metal nanoparticles
N2 - Mechanochemistry is a promising alternative to solution-based protocols across the chemical sciences, enabling different types of chemistries in solvent-free and environmentally benign conditions. The use of mechanical energy to promote physical and chemical transformations has reached a high level of refinement, allowing for the design of sophisticated molecules and nanostructured materials. Among them, the synthesis of noble metal nanoparticles deserves special attention due to their catalytic applications. In this review, we discuss the recent progress on the development of mechanochemical strategies for the controlled synthesis of noble metal nanostructures. We start by covering the fundamentals of different preparation routes, namely top-down and bottom-up approaches. Next, we focus on the key examples of the mechanochemical synthesis of non-supported and supported metal nanoparticles as well as hybrid nanomaterials containing noble metals. In these examples, in addition to the principles and synthesis mechanisms, their performances in catalysis are discussed. Finally, a perspective of the field is given, where we discuss the opportunities for future work and the challenges of mechanochemical synthesis to produce well-defined noble metal nanoparticles.
KW - Mechanochemistry
KW - Nanoparticles
PY - 2020
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-512080
VL - 8
IS - 32
SP - 16114
AN - OPUS4-51208
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Rautenberg, Max
A1 - Bhattacharya, Biswajit
A1 - Akhmetova, Irinia
A1 - Emmerling, Franziska
T1 - Mechanochemical and solution syntheses of two novel cocrystals of orcinol with two N,N0-Dipyridines: Structural diversity with varying ligand flexibility
N2 - We studied the influence of coformers flexibility on the supramolecular assembly of 5-substituted resorcinol. Two cocrystals of orcinol (ORL) with two dipyridine molecules, i.e. 1,2-di(4-pyridyl)ethane (ORLeBPE) and 1,2-di(4-pyridyl)ethylene (ORLeBPY), were prepared by mechanochemical synthesis and slow evaporation of solvent. The new crystalline solids were thoroughly characterized by single crystal Xray diffraction (SCXRD), powder X-ray diffraction analysis (PXRD), Fourier-transform infrared spectroscopy (FT-IR), differential thermal analysis (DTA), and thermogravimetric analysis (TGA). Structural determination reveals that in both cocrystals, the phenolepyridine, i.e. OeH/N(py) heterosynthon takes the main role in the formation of cocrystals. In ORLeBPE, the components form infinite 1D zig-zag chains, which are extended to 2D layer structure by inter-chain CeH/O interactions between BPE hydrogen atoms and hydroxyl oxygen atoms of ORL. In ORLeBPY, the components form a 0D fourcomponent complex. Formation of the discrete assemblies is attributed to the comparative rigid nature of BPY, which restricts the formation of an extended network.
KW - Cocrystal
KW - Single crystal
KW - X-ray diffraction
KW - Mechanochemistry
PY - 2020
U6 - https://doi.org/10.1016/j.molstruc.2020.128303
SN - 0022-2860
VL - 1217
SP - 128303
PB - Elsevier B.V.
AN - OPUS4-51023
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Zänker, Steffen
A1 - Scholz, G.
A1 - Heise, M.
A1 - Kemnitz, E.
A1 - Emmerling, Franziska
T1 - New 2D layered structures with direct fluorine-metal bonds: MF(CH3COO) (M: Sr, Ba, Pb)
N2 - New coordination polymers with 2D network structures with fluorine directly coordinated to the metal ion were prepared both via mechanochemical synthesis and fluorolytic sol–gel synthesis. Depending on the synthesis route, the samples show different particle sizes, according to SEM imaging. The crystal structures of barium acetate fluoride, strontium acetate fluoride, and lead acetate fluoride (BaFIJCH3COO), SrFIJCH3COO) and PbFIJCH3COO)) were solved from X-ray powder diffraction data. The structure solution is backed by the results from 19F MAS NMR, FT IR data, and thermal analysis. The calculated chemical shifts of the 19F MAS NMR spectra coincide well with the measured ones. It turns out that the grinding conditions have a remarkable influence on the mechanochemical synthesis and its products. Our systematic study also indicates a strong influence of the atomic radii of Ca, Sr, Ba, and Pb on the success of the syntheses.
KW - Mechanochemistry
KW - Coordination polymers
PY - 2020
U6 - https://doi.org/10.1039/d0ce00287a
VL - 22
IS - 16
SP - 2772
EP - 2780
PB - Royal Society of Chemistry
AN - OPUS4-50789
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Kervarec, M.-C.
A1 - Kemnitz, E.
A1 - Scholz, G.
A1 - Rudic, S.
A1 - Jäger, Christian
A1 - Braun, T.
A1 - Michalchuk, Adam
A1 - Emmerling, Franziska
T1 - A HF Loaded Lewis-Acidic Aluminium Chlorofluoride for Hydrofluorination Reactions
N2 - The very strong Lewis acid aluminium chlorofluo-ride (ACF) was loaded with anhydrous HF. The interactionbetween the surface of the catalyst and HF was investigatedusing a variety of characterization methods, which revealed he formation of polyfluorides. Moreover, the reactivity ofthe HF-loaded ACF towards the hydrofluorination of alkyneswas studied.
KW - Aluminium
KW - HF
KW - Hydrofluorination
KW - Metal fluorides
PY - 2020
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-508360
VL - 26
SP - 1
PB - Wiley Online Libary
AN - OPUS4-50836
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Wilke, Manuel
A1 - Klimakow, Maria
A1 - Rademann, K.
A1 - Emmerling, Franziska
T1 - Fast and efficient synthesis of a host guest system: a mechanochemical approach
N2 - An unusually fast and effective synthesis procedure for a host guest system consisting of a metal organic framework (MOF) and a polyoxometalate (POM) is described. The material was synthesised mechanochemically and the evolution of the structure was monitored ex and in situ using synchrotron X-ray diffraction (XRD).
KW - Mechanochemistry
KW - MOF
KW - in situ
PY - 2016
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-354910
UR - http://pubs.rsc.org/en/Content/ArticleLanding/2016/CE/C5CE01868D#!divAbstract
VL - 18
IS - 7
SP - 1096
EP - 1100
AN - OPUS4-35491
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Stroh, Julia
A1 - Schlegel, Moritz-Caspar
A1 - Schmidt, Wolfram
A1 - Nguyen, Thi Yen
A1 - Meng, Birgit
A1 - Emmerling, Franziska
T1 - Time-resolved in situ investigation of Portland cement hydration influenced by chemical admixtures
N2 - Numerous admixtures are used in the building practice to customize the properties of the cement paste during application. The influences of admixtures on the course of cement hydration and formation of hydrate phases have to be considered. Polycarboxylate ether (PCE) based polymeric superplasticizers (SPs) are known to retard the setting of the cement paste. The extent of the retardation differs depending on the molecular structure of the SP. Additionally, the presence of a stabilizing agent (SA) in the cement paste has a retarding side effect on the setting. The initial cement hydration processes and the detailed mechanisms of the retardation influenced by PCEs, as well as their interactions with particular SAs, are insufficiently understood. Up to now, only the results of phenomenological studies were taken into account to describe this retardation process. A detailed structure analysis monitoring the change of the phase composition during the hydration was never applied. Both SP and SA affect the adsorption of the sulphate ions on the clinker particles, causing changes in the formation of ettringite during the initial hydration, and are therefore a crucial part of the setting process itself. Here, the initial hydration of cement influenced by the interaction of SP and SA was monitored in situ by synchrotron X-ray diffraction. The high time resolution of the measurements allowed a continuous detection of the hydrates formed. The hydration was followed from the starting point of water addition and for couple of hours afterwards. The hydration of the levitated cement pellets containing starch as SA was initialized by adding aqueous solutions of different commercial SPs. Changes in the ettringite formation were detected in comparison to the reference hydration of pure cement.
KW - Synchrotron
KW - Portland cement Initial hydration
KW - Superplasticizer
KW - Stabilizer
KW - XRD
PY - 2016
U6 - https://doi.org/http://dx.doi.org/10.1016/j.conbuildmat.2015.12.097
IS - 106
SP - 18
EP - 26
PB - Elsevier
AN - OPUS4-35467
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Fischer, Franziska
A1 - Heidrich, Adrian
A1 - Greiser, Sebastian
A1 - Benemann, Sigrid
A1 - Rademann, K.
A1 - Emmerling, Franziska
T1 - Polymorphism of mechanochemically synthesized cocrystals: a case study
N2 - The liquid-assisted grinding cocrystallisation of theophylline with benzamide leading to polymorphic compounds was investigated. A solvent screening with seventeen different solvents was performed. The dipole moment of the solvent used in the synthesis determines the structure of the polymorphic product. A detailed investigation leads to the determination of the kinetically and thermodynamically favored product. In situ observations of the formation pathway during the grinding process of both polymorphs show that the thermodynamically favored cocrystal is formed in a two-step mechanism with the kinetic cocrystal as intermediate.
KW - cocrystal
KW - mechanochemistry
KW - theophylline
KW - benzamide
KW - milling
KW - polymorphism
PY - 2016
U6 - https://doi.org/10.1021/acs.cgd.5b01776
SN - 1528-7483
SN - 1528-7505
VL - 16
IS - 3
SP - 1701
EP - 1707
AN - OPUS4-35618
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Fischer, Franziska
A1 - Schmidt, M. U.
A1 - Greiser, Sebastian
A1 - Emmerling, Franziska
T1 - The challenging case of the theophylline–benzamide cocrystal
N2 - Theophylline has been used as an active pharmaceutical ingredient (API) in the treatment of pulmonary diseases, but due to its low water solubility reveals very poor bioavailability. Based on its different hydrogen-bond donor and acceptor groups, theophylline is an ideal candidate for the formation of cocrystals. The crystal structure of the 1:1 benzamide cocrystal of theophylline, C7H8N4O2·-C7H7NO, was determined from synchrotron X-ray powder diffraction data. The compound crystallizes in the tetragonal space group P41 with four Independent molecules in the asymmetric unit. The molecules form a hunter’s fence packing.
The crystal structure was confirmed by dispersion-corrected DFT calculations.
The possibility of salt formation was excluded by the results of Raman and 1H solid-state NMR spectroscopic analyses.
KW - powder diffraction
KW - theophylline
KW - benzamide
KW - cocrystal
KW - crystal structure
KW - active pharmaceutical ingredient
KW - dispersion-corrected density-functional theory
PY - 2016
U6 - https://doi.org/10.1107/S2053229616002643
SN - 2053-2296
VL - 72
IS - 3
SP - 217
EP - 224
AN - OPUS4-35621
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Gnutzmann, Tanja
A1 - Nguyen, Thi Yen
A1 - Rademann, K.
A1 - Emmerling, Franziska
T1 - Solvent-triggered crystallization of polymorphs studied in situ
N2 - The crystallization of a highly polymorphic compound was studied in situ by combined time-resolved X-ray diffraction and Raman spectroscopy. Any influences of solid surfaces, temperature, and humidity on the crystallization were omitted by the use of a specially designed acoustic levitator. Investigations of polymorphic phase transitions during the crystallization process in different solvents allowed a structure assignment from first crystalline assemblies to final crystalline form. For the first time, it was possible to yield pure phases of selected polymorphs of the model compound ROY (5-methyl-2-[(2-nitrophenyl)amino]-3-thiophenecarbonitrile) directly from solution. The influence of the solvent on the final products and transient phases during the crystallization process was elucidated.
KW - Polymorphism
KW - Crystallization
KW - In situ WAXS
KW - In situ Raman spectroscopy
KW - ROY
PY - 2014
U6 - https://doi.org/10.1021/cg501287v
SN - 1528-7483
VL - 14
IS - 12
SP - 6445
EP - 6450
PB - American Chemical Society
CY - Washington, DC, USA
AN - OPUS4-32583
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Abbott, A. P.
A1 - Abolibda, T. Z.
A1 - Davis, S.J.
A1 - Emmerling, Franziska
A1 - Lourdin, D.
A1 - Leroy, E.
A1 - Wise, W. R.
T1 - Glycol based plasticisers for salt modified starch
N2 - Starch is one of the most common and easily obtained natural polymers, making it attractive as a potential bio-based alternative to synthetic polymers. This study shows that a simple quaternary ammonium salt combined with urea or glycols forms effective modifiers that produce flexible plastics with good mechanical properties that are comparable to some polyolefin plastics. The processing conditions are shown to significantly affect the structure of the polymer which has a concomitant effect upon the mechanical and physical properties of the resulting plastic. Using a glycerol based modifier results in a totally sustainable and biodegradable material which can be injection moulded.
KW - biodegradable material
KW - flexible plastics
KW - injection moulded
PY - 2014
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-351426
SN - 2046-2069
VL - 4
IS - 76
SP - 40421
EP - 40427
PB - RSC Publishing
CY - London
AN - OPUS4-35142
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Nguyen, Thi Yen
A1 - Rademann, K.
A1 - Emmerling, Franziska
T1 - Direct evidence of polyamorphism in paracetamol
N2 - While polymorphism is a common phenomenon in the crystallization processes of organic compounds, polyamorphism has gained importance only recently. Using sophisticated sample environments and applying in situ scattering methods and vibrational spectroscopy, the complete crystallization process of organic compounds from solution can be traced and characterized. Diffuse scattering from amorphous intermediates can be investigated by analyzing the atomic pair distribution function (PDF) to gain further insights into molecular pre-orientation. The crystallization behavior of paracetamol was studied exemplarily under defined, surface-free conditions. Based on the choice of the solvent, the formation of different polymorphs is promoted. The thermodynamically stable form I and the metastable orthorhombic form II could be isolated in pure form directly from solution. For both polymorphs, the crystallization from solution proceeds via a distinct amorphous precursor phase. PDF analyses of these different amorphous states indicate a specific pre-orientation of the analyte molecules introduced by the solvent. The resulting crystalline polymorph is already imprinted in these proto-crystalline precursors. Direct experimental evidence for the polyamorphism of paracetamol is provided.
PY - 2015
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-351366
SN - 1466-8033
VL - 17
IS - 47
SP - 9029
EP - 9036
PB - Royal Society of Chemistry
CY - London, UK
AN - OPUS4-35136
LA - deu
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Kabelitz, Anke
A1 - de Oliveira Guilherme Buzanich, Ana
A1 - Joester, Maike
A1 - Reinholz, Uwe
A1 - Radtke, Martin
A1 - Bienert, Ralf
A1 - Schulz, K.
A1 - Schmack, R.
A1 - Kraehnert, R.
A1 - Emmerling, Franziska
T1 - Time-resolved in situ studies on the formation mechanism of iron oxide nanoparticles using combined fast-XANES and SAXS
N2 - The reaction of iron chlorides with an alkaline reagent is one of the most prominent methods for the synthesis of iron oxide nanoparticles. We studied the particle formation mechanism using triethanolamine as reactant and stabilizing agent. In situ fast-X-ray absorption near edge spectroscopy and small-angle X-ray scattering provide information on the oxidation state and the structural information at the same time. In situ data were complemented by ex situ transmission electron microscopy, wide-angle X-ray scattering and Raman analysis of the formed nanoparticles. The formation of maghemite nanoparticles (γ-Fe2O3) from ferric and ferrous chloride was investigated. Prior to the formation of these nanoparticles, the formation and conversion of intermediate phases (akaganeite, iron(II, III) hydroxides) was observed which undergoes a morphological and structural collapse. The thus formed small magnetite nanoparticles (Fe3O4) grow further and convert to maghemite with increasing reaction time.
KW - oxidation state
KW - structural information
KW - maghemite
PY - 2015
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-351376
SN - 1466-8033
VL - 17
IS - 44
SP - 8463
EP - 8470
CY - London, UK
AN - OPUS4-35137
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Emmerling, Franziska
T1 - Steuerung und kontrollierte Bildung polymorpher Molekülkristallphasen
T2 - Berichtskolloquium für die zweite Periode SPP 1415
CY - Bad Soden
DA - 2015-05-05
PY - 2015
AN - OPUS4-33951
LA - deu
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Emmerling, Franziska
A1 - Gnutzmann, Tanja
A1 - Nguyen, Thi Yen
A1 - Rademann, K.
T1 - SOLVENT TRIGGERED CRYSTALLIZATION OF POLYMORPHS STUDIED IN SITU BY XRD AND RAMAN SPECTROSCOPY
T2 - 8th Bologna's Convention on Crystal Forms: Crystals in Food & Pharma 2015
CY - Bologna, Italien
DA - 2015-06-14
PY - 2015
AN - OPUS4-33953
LA - deu
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Emmerling, Franziska
A1 - Fischer, Franziska
A1 - Batzdorf, Lisa
A1 - Wilke, Manuel
A1 - Wenzel, Klaus-Jürgen
T1 - Direct in situ analysis of milling reactions for mechanistic studies using X-ray diffraction combined with Raman spectroscopy
T2 - GDCh Wissenschaftsforum
CY - Dresden
DA - 2015-08-30
PY - 2015
AN - OPUS4-33947
LA - deu
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Emmerling, Franziska
T1 - Direct in situ analysis of milling reactions for mechanistic studies using X-ray diffraction combined with Raman spectroscopy
T2 - Symposium: Mech´cheM 2015
CY - Montpellier, France
DA - 2015-07-15
PY - 2015
AN - OPUS4-33949
LA - deu
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Emmerling, Franziska
T1 - In situ investigation of crystallization processes using levitated droplets
T2 - Cost Meeting
CY - Marseille, France
DA - 2015-06-22
PY - 2015
AN - OPUS4-33950
LA - deu
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Mönch, Bettina
A1 - Kraus, Werner
A1 - Köppen, Robert
A1 - Emmerling, Franziska
T1 - The different conformations and crystal structures of dihydroergocristine
N2 - The identification of different forms of dihydroergocristine (DHEC) was carried out by crystallization from different organic solvents. DHEC was identified as potential template for molecularly imprinted polymers (MIPs) for the epimeric specific analysis of ergot alkaloids (EAs) in food. DHEC was crystallized from different solvents in order to mimic the typical MIP synthesis conditions. Four new solvatomorphs of DHEC were obtained. All solvatomorphs contain a water molecule in the crystal structure, whereas three compounds contain an additional solvent molecule. Based on the conformation of DHEC a comparison with typical EA molecules was possible. The analysis showed that DHEC is a suitable template for MIPs for EAs.
PY - 2016
U6 - https://doi.org/10.1016/j.molstruc.2015.10.008
SN - 0022-2860
SN - 1872-8014
SN - 0377-046X
VL - 1105
SP - 389
EP - 395
PB - Elsevier B.V.
CY - Amsterdam
AN - OPUS4-35009
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Som, Tirtha
A1 - Troppenz, G.V.
A1 - Wendt, R. R.
A1 - Wollgarten, M.
A1 - Rappich, J.
A1 - Emmerling, Franziska
A1 - Rademann, Klaus
T1 - Graphene oxide/alpha-Bi2O3 composites for visible-light photocatalysis, chemical catalysis, and solar energy conversion
N2 - The growing challenges of environmental purification by solar photocatalysis, precious-metal-free catalysis, and photocurrent generation in photovoltaic cells receive the utmost global attention. Here we demonstrate a one-pot, green chemical synthesis of a new stable heterostructured, ecofriendly, multifunctional microcomposite that consists of α-Bi2O3 microneedles intercalated with anchored graphene oxide (GO) microsheets (1.0 wt?%) for the above-mentioned applications on a large economical scale. The bare α-Bi2O3 microneedles display two times better photocatalytic activities than commercial TiO2 (Degussa-P25), whereas the GO-hybridized composite exhibits approximately four to six times enhanced photocatalytic activities than the neat TiO2 photocatalyst in the degradation of colored aromatic organic dyes (crystal violet and rhodamine 6G) under visible-light irradiation (300 W tungsten lamp). The highly efficient activity is associated with the strong surface adsorption ability of GO for aromatic dye molecules, the high carrier acceptability, and the efficient electron–hole pair separation in Bi2O3 by individual adjoining GO sheets. The introduction of Ag nanoparticles (2.0 wt?%) further enhances the photocatalytic performance of the composite over eightfold because of a plasmon-induced electron-transfer process from Ag nanoparticles through the GO sheets into the conduction band of Bi2O3. The new composites are also catalytically active and catalyze the reduction of 4-nitrophenol to 4-aminophenol in the presence of borohydride ions. Photoanodes assembled from GO/α-Bi2O3 and Ag/GO/α-Bi2O3 composites display an improved photocurrent response (power conversion efficiency ~20?% higher) over those prepared without GO in dye-sensitized solar cells.
KW - Bismuth
KW - Dyes/pigments
KW - Environmental chemistry
KW - Graphene
KW - Photochemistry
PY - 2014
U6 - https://doi.org/10.1002/cssc.201300990
SN - 1864-5631
SN - 1864-564X
VL - 7
IS - 3
SP - 854
EP - 865
PB - Wiley-VCH
CY - Weinheim
AN - OPUS4-30390
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Stroh, Julia
A1 - Meng, Birgit
A1 - Emmerling, Franziska
T1 - Deterioration of hardened cement paste under combined sulphatechloride attack investigated by synchrotron XRD
N2 - The exact mechanisms of the phase transitions caused by a combined sulphate-chloride attack are discussed controversially. The main points concern the mutual influences of sulphate and chloride ions during the secondary binding processes of these anions within cement hydrate phases. We simulated combined sulphate-chloride attack under laboratory conditions using solutions containing NaCl and Na2SO4 in different concentrations. Three sample compositions were used for the preparation of the specimens. In two of them, 30% of Portland cement was replaced by supplementary cementitious materials (fly ash, slag). The phase distribution in the samples was determined using synchrotron X-ray diffraction. The analysis with high spatial resolution allows the localisation of the secondary phase formation in the microstructural profile of the sample. A mechanism of the phase developments under combined sulphate-chloride attack is derived.
KW - Cement paste
KW - Sulphate-chloride attack
KW - Portland cement
KW - Mineral additions
PY - 2016
U6 - https://doi.org/10.1016/j.solidstatesciences.2016.04.002
IS - 56
SP - 29
EP - 44
PB - Elsevier Masson SAS
CY - Issy les Moulineaux cedex; France
AN - OPUS4-35936
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Al-Terkawi, Abdal-Azim
A1 - Scholz, G.
A1 - Emmerling, Franziska
A1 - Kemnitz, E.
T1 - Mechanochemical synthesis, characterization, and structure determination of new alkaline earth metal-tetrafluoroterephthalate frameworks: Ca(pBDC‑F4 )·4H2O, Sr(pBDC‑F4 )·4H2O, and Ba(pBDC‑F4 )
N2 - New fluorinated alkaline earth metal−organic frameworks were successfully synthesized by milling of metal hydroxides M(OH)2 with tetrafluoroterephthalic acid H2 pBDC-F4. Both calcium- and strontium-tetrafluoroterephthalates are tetrahydrated, while the barium tetrafluoroterephthalate is free of coordinating water molecules. The two isomorphic structures Ca(pBDC-F4)·4H2O and Sr(pBDC-F4)·4H2O were solved from the powder diffraction data by ab initio structure determination and subsequent Rietveld refinement. The products were thoroughly characterized by elemental analysis, thermal analysis, magicangle spinning NMR, Fourier transform infrared spectroscopy, scanning electron microscopy imaging, and Brunauer−Emmett−Teller measurements. Our findings suggest that the mechanochemical synthesis route is a promising approach for the preparation of new fluorinated alkaline earth metal−organic frameworks.
KW - Mechanochemistry
KW - MOFs
KW - XRD
PY - 2016
UR - http://pubs.acs.org/doi/abs/10.1021/acs.cgd.5b01457
U6 - https://doi.org/10.1021/acs.cgd.5b01457
SN - 1528-7483
VL - 16/4
SP - 1923
EP - 1933
PB - American Chemical Society
CY - Washington, DC, USA
AN - OPUS4-35940
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Radunz, Sebastian
A1 - Kraus, Werner
A1 - Bischoff, F. A.
A1 - Emmerling, Franziska
A1 - Resch-Genger, Ute
A1 - Tschiche, Harald
T1 - Temperature- and Structure-Dependent Optical Properties and Photophysics of BODIPY Dyes
N2 - We report on the temperature- and structural-dependent optical properties and photophysics of a set of boron dipyrromethene (BODIPY) dyes with different substitution patterns of their meso-aryl subunit. Single-crystal Xray diffraction analysis of the compounds enabled a classification of the dyes into a sterically hindered and a unhindered group. The steric hindrance refers to a blocked rotational motion of the aryl subunit around the bond connecting this moiety to the meso-position of the BODIPY core. The energy barriers related to this rotation were simulated by DFT calculations. As follows from the relatively low rotational barrier calculated to about 17 kcal/mol, a free rotation is only possible for sterically unhindered compounds. Rotational barriers of more than 40 kcal/mol determined for the sterically hindered compounds suggest an effective freezing of the rotational motion in These molecules. With the aid of temperature-dependent spectroscopic measurements, we could show that the ability to rotate directly affects the optical properties of our set of BODIPY dyes. This accounts for the strong temperature dependence of the fluorescence of the sterically unhindered compounds which show a drastic decrease in fluorescence quantum yield and a significant shortening in fluorescence lifetime upon heating. The optical properties of the sterically hindered compounds, however, are barely affected by temperature. Our results suggest a nonradiative deactivation of the first excited singlet state of the sterically unhindered compounds caused by a conical intersection of the potential energy surfaces of the Ground and first excited state which is accessible by rotation of the meso-subunit. This is in good agreement with previously reported deactivation mechanisms. In addition, our results suggest the presence of a second nonradiative depopulation pathway of the first excited singlet state which is particularly relevant for the sterically hindered compounds.
KW - Fluorescence
KW - Sensor
KW - Switch
KW - pH
KW - BODIPY
KW - Dye
KW - Probe
KW - Synthesis
KW - Photophysics
KW - Mechanism
PY - 2020
U6 - https://doi.org/10.1021/acs.jpca.9b11859
SN - 1089-5639
VL - 124
IS - 9
SP - 1787
EP - 1797
PB - American Chemical Society
AN - OPUS4-50639
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Haferkamp, Sebastian
A1 - Emmerling, Franziska
A1 - Akhmetova, Irina
A1 - Kulla, Hannes
A1 - Rademann, K.
T1 - Insights into the mechanochemical Knoevenagel condensation
N2 - Mechanochemistry paves the way to simple, fast, and green syntheses, but there is a lack in understanding of the underlying mechanisms. Here, we present a universal strategy for simultaneous real-time in situ analysis, combining X-ray diffraction, Raman spectroscopy, and thermography.
T2 - Bessy User Meeting 2019
CY - Berlin, Germany
DA - 05.12.2019
KW - Mechanochemistry
PY - 2019
AN - OPUS4-50122
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Emmerling, Franziska
T1 - Ein Blick in die Welt der Mechanochemie
N2 - Perhaps due in no small part to its historical mystique, mechanochemistry has been shrowded in relative obscurity for quite some time. The successes of mechanochemistry in organic synthesis have often been curtailed by a fundamentally limited mechanistic understanding. Lately, however, the community has made great strides towards understanding the fundamentals, as well as large steps forward regarding industrially significant scale-up via twin-screw extrusion. A variety of recent work has traded in some of mechanochemistry’s mystique for simple, straight-forward chemical guidelines.
T2 - Seminar Anorganische Chemie Universität Kiel
CY - Kiel, Germany
DA - 22.10.19
KW - Mechanochemistry
KW - XRD
PY - 2019
AN - OPUS4-50134
LA - mul
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Emmerling, Franziska
T1 - Shaken or levitated? A time resolved perspective on unconventional crystallization
N2 - This Outlook provides a brief overview of the recent achievements and opportunities created by acoustic levitation and mechanochemistry, including access to materials, molecular targets, and synthetic strategies that are difficult to access by conventional means.
T2 - Vortragsreihe Analytik Merck
CY - Darmstadt, Germany
DA - 18.11.19
KW - Levitation
KW - Acoustic levitation
KW - X-ray and electron diffraction
PY - 2019
AN - OPUS4-50135
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Emmerling, Franziska
T1 - May the force be with you - in situ investigation of mechanochemical reactions
N2 - The past decade has seen a reawakening of solid-state to chemical synthesis, driven by the search for new, cleaner synthetic methodologies. Mechanochemistry has advanced to a widely applicable technique.
T2 - SALSA's "Make and Measure 2019
CY - Berlin, Germany
DA - 25.10.2019
KW - Mechanochemistry
KW - Metal–organic frameworks
PY - 2019
AN - OPUS4-50138
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Emmerling, Franziska
A1 - Villajos Collado, José Antonio
A1 - Jagorel, Noëmie
A1 - Reinsch, Stefan
T1 - Increasing Exposed Metal Site Accessibility in a Co-MOF-74 Material With Induced Structure-Defects
N2 - Metal-organic frameworks (MOFs) are promising nanoporous materials with many practical applications. This owes largely to their remarkable porosity and the presence of specific chemical functionalities, such as exposed metal sites (EMS). The MOF-74 structure is known for exhibiting one of the highest EMS densities among porous materials. Moreover, the inclusion of structural defects has been proposed to enhance activity further. This was previously achieved by mixing the original linker together with a second one, having lower topology. The presence of structural defects was evidenced by the resulting crystalline properties and thermal stability. In this work, different mixtures of tetratopic 2,5-dihydroxyterephthalic acid with up to 60% of the tritopic hydroxyterephtalic acid were used to synthesize crystalline Co-MOF-74-like materials. Materials synthesized from higher proportions than 30% of hydroxyterephtalic acid in the synthesis media collapse upon partial removal of the solvent molecules. This indicates the presence of structural defects and the importance of the solvent molecules in stabilizing the crystalline structures. Electron microscope images show that crystal size reduces with inclusion of hydroxyterephtalic acid as the second linker. The presence of coordinated solvent molecules at the EMS was evaluated by Fourier-transform infrared spectra (FTIR) spectroscopy, so that a higher degree of solvent-exchange was observed during washing for defective structures. Furthermore, TG analysis suggests defective structures exhibit lower desolvation temperatures than the defect-free structures. Finally, N2 adsorption-desorption analyses at −196°C showed an enhanced accessibility of the gas to the inner porosity of the defective structures and therefore, the EMS of the material. All these finding make this pathway interesting to enhance the potential interest of these materials for an industrial application because of both a facilitated activation and a better access to the active sites.
KW - MOF-74
KW - Structural defects
KW - Mixed-linkers
KW - Exposed metal sites
KW - Facilitated activation
PY - 2019
U6 - https://doi.org/10.3389/fmats.2019.00230
VL - 6
SP - 230
PB - Frontiers Media
CY - Lausanne
AN - OPUS4-49256
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Chapartegui-Arias, Ander
A1 - Villajos Collado, José Antonio
A1 - Myxa, Anett
A1 - Beyer, Sebastian
A1 - Falkenhagen, Jana
A1 - Schneider, Rudolf
A1 - Emmerling, Franziska
T1 - Covalently Fluorophore-Functionalized ZIF‑8 Colloidal Particles as a Sensing Platform for Endocrine-Disrupting Chemicals Such as Phthalates Plasticizers
N2 - We present the optical sensing of phthalate Esters (PAEs), a group of endocrine-disrupting chemicals. The sensing takes place as changes in the fluorescence emission intensity of aminopyrene covalently bound to the organic ligands of the metal−organic framework compound ZIF-8. In the presence of PAEs, a quenching of the fluorescence emission is observed. We evaluated strategies to engineer colloidal size distribution of the sensing particles to optimize the sensory response to PAEs. A thorough characterization of the modified ZIF-8 nanoparticles included powder X-ray diffractometry, transmission electron microscopy, high-performance liquid chromatography, and photophysical characterization. The presented capability of the fluorophore-functionalized ZIF-8 to sense PAEs complements established methods such as chromatography-based procedures, which cannot be used on-site and paves the way for future developments such as hand-held quick sensing devices.
KW - Sensing
KW - MOF
PY - 2019
U6 - https://doi.org/10.1021/acsomega.9b01051
VL - 4
IS - 17
SP - 17090
EP - 17097
PB - ACS
AN - OPUS4-49562
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Emmerling, Franziska
T1 - Mechanochemistrry - a time resolved perspective on unconventional crystallization
N2 - Green chemsistry apporoach for the synthesis of metal organic frameworks.
T2 - IFW BAM Workshop
CY - Berlin, Germany
DA - 25.11.2019
KW - Mechanochemistry
KW - XRD
KW - Metal-organic-frameworks
PY - 2019
AN - OPUS4-50110
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Bhattacharya, Biswajit
A1 - Michalchuk, Adam
A1 - Silbernagl, Dorothee
A1 - Rautenberg, Max
A1 - Schmid, Thomas
A1 - Feiler, Torvid
A1 - Reimann, K.
A1 - Ghalgaoui, A.
A1 - Sturm, Heinz
A1 - Paulus, B.
A1 - Emmerling, Franziska
T1 - A Mechanistic Perspective on Plastically Flexible Coordination Polymers
N2 - Mechanical flexibility in single crystals of covalently bound materials is a fascinating and poorly understood phenomenon. We present here the first example of a plastically flexible one-dimensional (1D) coordination polymer. The compound [Zn(m-Cl)2(3,5-dichloropyridine)2]n is flexible over two crystallographic faces. Remarkably, the single crystal remains intact when bent to 1808. A combination of microscopy, diffraction, and spectroscopic studies have been used to probe the structural response of the crystal lattice to mechanical bending. Deformation of the covalent polymer chains does not appear to be responsible for the observed macroscopic bending. Instead, our results suggest that mechanical bending occurs by displacement of the coordination polymer chains. Based on experimental and theoretical evidence, we propose a new model for mechanical flexibility in 1D coordination polymers. Moreover, our calculations propose a cause of the different mechanical properties of this compound and a structurally similar elastic material
KW - Coordination polymer
KW - Flexible crystals
KW - Mechanical properties
KW - Plastic deformation
PY - 2020
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-504755
VL - 59
IS - 14
SP - 5557
EP - 5561
PB - Wiley-VCH
AN - OPUS4-50475
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Burek, K.
A1 - Dengler, J.
A1 - Emmerling, Franziska
A1 - Feldmann, Ines
A1 - Kumke, M. U.
A1 - Stroh, Julia
T1 - Lanthanide Luminescence Revealing the Phase Composition in Hydrating Cementitious Systems
N2 - The hydration process of Portland cement in a cementitious system is crucial for development of the high-quality cementbased construction material. Complementary experiments of Xray diffraction analysis (XRD), scanning electron microscopy (SEM) and time-resolved laser fluorescence spectroscopy (TRLFS) using europium (Eu(III)) as an optical probe are used to analyse the hydration process of two cement systems in the absence and presence of different organic admixtures.
We Show that different analysed admixtures and the used sulphate carriers in each cement system have a significant influence on the hydration process, namely on the time-dependence in the formation of different hydrate phases of cement. Moreover, the effect of a particular admixture is related to the type of sulphate carrier used.
The quantitative information on the amounts of the crystalline cement paste components is accessible via XRD analysis. Distinctly different morphologies of ettringite and calcium-silicate-hydrates (C-S-H) determined by SEM allow visual conclusions about formation of these phases at particular ageing times. The TRLFS data provides information about the admixture influence on the course of the silicate reaction. The dip in the dependence of the luminescence decay times on the hydration time indicates the change in the structure of C-S-H in the early hydration period. Complementary information from XRD, SEM and TRLFS provides detailed information on distinct periods of the cement hydration process.
KW - Cement admixtures
KW - Cement hydration
KW - Europium
KW - Luminescence
KW - SEM
KW - X-ray diffraction
PY - 2019
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-504842
VL - 8
IS - 12
SP - 1441
EP - 1452
PB - Wiley-VCH
AN - OPUS4-50484
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Sobina, E.
A1 - Zimathies, Annett
A1 - Prinz, Carsten
A1 - Emmerling, Franziska
A1 - de Santis Neves, R.
A1 - Wang, H.
A1 - Mizuno, K.
A1 - Devoille, L.
A1 - Steel, E.
A1 - Ceyhan, A.
A1 - Sadak, E.
ED - Sobina, E.
T1 - Final report of CCQM-K153 Measurement of Specific Adsorption A [mol/kg] of N-2 and Kr on nonporous SiO2 at LN temperature (to enable a traceable determination of the Specific Surface Area (BET) following ISO 9277)
N2 - CCQM key comparison K-153 Measurement of Specific Adsorption A [mol/kg] of N-2 and Kr on nonporous SiO2 at LN temperature (to enable a traceable determination of the Specific Surface Area (BET) following ISO 9277) has been performed by the Surface Analysis Working Group (SAWG) of the Consultative Committee for Amount of Substance (CCQM). The objective of this key comparison is to compare the equivalency of the National Metrology Institutes (NMIs) and Designated Institutes (DIs) for the measurement of specific adsorption, BET specific surface area) of nonporous substances (sorbents, ceramics, catalytic agents, etc) used in advanced technology.
In this key comparison, a commercial nonporous silicon dioxide was supplied as a sample. Eight NMIs participated in this key comparison, but only five NMI's have reported in time. All participants used a gas adsorption method, here nitrogen and (or) krypton adsorption at 77.3 K, for analysis according to the international standards ISO 15901-2 and 9277.
In this key comparison, the degrees of equivalence uncertainties for specific adsorption nitrogen and krypton, BET specific surface area were established.
KW - Nonporous SiO2
KW - Specific Adsorption of N-2 and Kr
KW - BET specific surface area
PY - 2019
U6 - https://doi.org/10.1088/0026-1394/56/1A/08013
VL - 56
IS - 1A
SP - 08013
PB - IOP publishing Ltd
CY - Bristol, UK
AN - OPUS4-50358
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Kulla, Hannes
A1 - Becker, C.
A1 - Michalchuk, Adam
A1 - Linberg, Kevin
A1 - Paulus, B.
A1 - Emmerling, Franziska
T1 - Tuning the Apparent Stability of Polymorphic Cocrystals through Mechanochemistry
N2 - Mechanochemistry has become a valuable method for the synthesis of new materials and molecules, with a particular strength for screening and preparing multicomponent crystals. In this work, two novel cocrystals of pyrazinamide (PZA) with pimelic acid (PA) were prepared mechanochemically. Their formation was monitored in real time by in situ synchrotron powder X-ray diffraction. Control over the polymorphic form was obtained through the selective choice of liquid additive via liquid assisted grinding. Slurry experiments and dispersion-corrected density functional theory calculations suggest that Form I is the thermodynamically stable form under ambient conditions. Upon aging, Form II converts to Form I. The stability of Form II upon aging was found to depend strongly on the milling duration, intensity, and material of the milling vessels. Longer or higher energy milling drastically increased the lifetime of the Form II product. For the first time, this work also demonstrates that the choice of milling jar can have a decisive effect on the aging stability of a bulk polymorphic powder. In contrast to material prepared in steel milling vessels, the preparation of Form II in Perspex (PMMA) vessels increased its lifetime 3-fold. These findings offer a new dimension to garnering control over mechanochemical cocrystallization and demonstrate the critical importance of the careful and timely ex situ screening of ball mill grinding reactions. This will be of importance for potential industrial applications of mechanochemical cocrystallization where understanding polymorph longevity is crucial for the development of a robust preparative protocol.
KW - Physical and chemical processes
KW - Organic compounds
KW - Liquids
KW - Materials
KW - Stability
PY - 2019
U6 - https://doi.org/10.1021/acs.cgd.9b01158
VL - 19
IS - 12
SP - 7271
EP - 7279
PB - ACS Publications
AN - OPUS4-50281
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Herzel, Hannes
A1 - Grevel, K.-D.
A1 - Emmerling, Franziska
A1 - Dachs, E.
A1 - Benisek, A.
A1 - Adam, Christian
A1 - Majzlan, J.
T1 - Thermodynamic properties of calcium alkali phosphates Ca(Na,K)PO4
N2 - Calcium alkali phosphates Ca(Na,K)PO4 are main constituents of bioceramics and thermochemically produced phosphorus fertilizers because of their bioavailability. Sparse thermodynamic data are available for the endmembers CaNaPO4 and CaKPO4. In this work, the missing data were determined for the low-temperature phase modifications of the endmembers CaNaPO4 and CaKPO4 and three intermediate Ca(Na,K)PO4 compositions. Standard enthalpy of formation ranges from - 2018.3 ± 2.2 kJ mol-1 to - 2030.5 ± 2.1 kJ mol-1 and standard entropy from 137.2 ± 1.0 J mol-1 K-1 to 148.6 ± 1.0 J mol-1 K-1 from sodium endmember b-CaNaPO4 to potassium endmember b0-CaKPO4.
Thermodynamic functions are calculated up to 1400 K for endmembers and the sodium-rich intermediate phase b-Ca(Na0.93K0.07)PO4. Functions above 640 K are extrapolated because of the phase transition from low- to high-temperature phase. Impurities in the synthesized intermediate phases c-Ca(Na0.4K0.6)PO4 and c-Ca Na0.35K0.65)PO4 and one additional phase transition around 500 K impeded the determination of high-temperature thermodynamic functions. In general, data for phase transition temperatures agree with the previously reported phase diagrams.
KW - Formation enthalpy
KW - Heat capacity
KW - Phase transformation
KW - Bioceramics
KW - Phosphorus fertilizer
KW - Entropy
PY - 2020
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-507640
VL - 55
SP - 8477
EP - 8490
PB - Springer
AN - OPUS4-50764
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Heilmann, Maria
A1 - Kulla, Hannes
A1 - Prinz, Carsten
A1 - Bienert, Ralf
A1 - Reinholz, Uwe
A1 - de Oliveira Guilherme Buzanich, Ana
A1 - Emmerling, Franziska
T1 - Advances in Nickel Nanoparticle Synthesis via Oleylamine Route
N2 - Nickel nanoparticles are an active research area due to their multiple applications as catalysts in different processes. A variety of preparation techniques have been reported for the synthesis of these nanoparticles, including solvothermal, microwave-assisted, and emulsion techniques. The well-studied solvothermal oleylamine synthesis route comes with the drawback of needing standard air-free techniques and often space-consuming glassware. Here, we present a facile and straightforward synthesis method for size-controlled highly monodisperse nickel nanoparticles avoiding the use of, e.g., Schlenk techniques and space-consuming labware. The nanoparticles produced by this novel synthetic route were investigated using small-angle X-ray scattering, transmission electron microscopy, X-ray diffraction, and X-ray spectroscopy. The nanoparticles were in a size range of 4–16 nm, show high sphericity, no oxidation, and no agglomeration after synthesis.
KW - Nanoparticle synthesis
KW - Nickel nanoparticles
KW - SAXS
KW - TEM
KW - XAS
PY - 2020
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-507531
VL - 10
IS - 4
SP - 713
PB - MDPI
AN - OPUS4-50753
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Linberg, Kevin
A1 - Ali, Naveed Zafar
A1 - Etter, M.
A1 - Michalchuk, Adam
A1 - Rademann, K.
A1 - Emmerling, Franziska
T1 - A Comparative Study of the Ionic Cocrystals NaX (α-d-Glucose)2 (X = Cl, Br, I)
N2 - The mechanochemical formation of the ionic cocrystals of glucose (Glc) and sodium salts Glc2NaCl·H2O (1) and Glc2NaX (X = Br (2), I (3)) is presented. Products are formed by co-milling Glc with three sodium salts (NaCl, NaBr, NaI). The ionic cocrystals were obtained under both neat grinding and liquid-assisted grinding conditions, the later found to accelerate the reaction kinetics. The crystal structures of the ionic cocrystals (2) and (3) were solved from powder X-ray diffraction data. The structure solution contrasts with the structure of Glc2NaCl·H2O (1) where the electron density at three halide crystallographic sites is modeled as of being the intermediate between water molecule and a chloride ion. The reaction pathways of the three ionic cocrystals were investigated in real time using our tandem approach comprising a combination of in situ synchrotron powder X-ray diffraction and Raman spectroscopy. The results indicate the rapid formation of each cocrystal directly from their respective starting materials without any intermediate moiety formation. The products were further characterized by DTA-TG and elemental analysis.
KW - In situ
KW - Co-crystal
KW - Mechanochemistry
KW - Glucose
PY - 2019
U6 - https://doi.org/10.1021/acs.cgd.8b01929
VL - 19
IS - 8
SP - 4293
EP - 4299
PB - ACS Publications
AN - OPUS4-48781
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Emmerling, Franziska
A1 - Stock, Norbert
A1 - Tadei, Marco
A1 - Demel, Jan
A1 - Cabeza, Aurelio
A1 - Viviani, Riccardo
A1 - Demadis, Konstantinos
A1 - Vassaki, Maria
T1 - New directions in metal phosphonate and phosphinate chemistry
N2 - In September 2018, the First European Workshop on Metal Phosphonates Chemistry brought together some prominent researchers in the field of metal phosphonates and phosphinates with the aim of discussing past and current research efforts and identifying future directions. The scope of this perspective article is to provide a critical overview of the topics discussed during the workshop, which are divided into two main areas: synthesis and characterisation, and applications. In terms of synthetic methods, there has been a push towards cleaner and more efficient approaches. This has led to the introduction of high-throughput synthesis and mechanochemical synthesis. The recent success of metal–organic frameworks has also promoted renewed interest in the synthesis of porous metal phosphonates and phosphinates. Regarding characterisation, the main advances are the development of electron diffraction as a tool for crystal structure determination and the deployment of in situ characterisation techniques, which have allowed for a better understanding of reaction pathways. In terms of applications, metal phosphonates have been found to be suitable materials for several purposes: they have been employed as heterogeneous catalysts for the synthesis of fine chemicals, as solid sorbents for gas separation, notably CO2 capture, as materials for electrochemical devices, such as fuel cells and rechargeable batteries, and as matrices for drug delivery.
KW - Metal phosphonates
KW - Metal–organic frameworks
KW - X-ray and electron diffraction
PY - 2019
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-484346
SN - 2073-4352
VL - 9
IS - 5
SP - 270, 1
EP - 36
PB - MDPI
AN - OPUS4-48434
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Stroh, Julia
A1 - Feiler, Torvid
A1 - Ali, N. Z.
A1 - Minas da Piedade, M. E.
A1 - Emmerling, Franziska
T1 - Mechanistic Insights into a Sustainable Mechanochemical Synthesis of Ettringite
N2 - Mechanochemistry offers an environmentally benign and facile synthesis method for a variety of cement paste constituents. In addition, these methods can be used to selectively tune the properties of cement components. The mineral ettringite is an important component of cementitious materials and has additional technological potential due to its ion exchange properties.
Synthesis of ettringite via mechanochemistry is an environmentally friendly alternative to conventional wet-chemical synthesis established in industry. This contribution explores the mechanism of a two-step mechanochemical synthesis of ettringite, which was previously found to greatly improve the reaction conversion as compared with one-pot synthesis. The crystallinity of Al(OH)3 was found to decrease during the first stage of this mechanochemical synthesis. This was correlated to a significant decrease in the particle size of Al(OH)3 in this stage. No other significant changes were found for the other components, suggesting that mechanochemical activation of Al(OH)3 is responsible for the enhanced formation of ettringite by the two-step approach. The environmentally friendly approach developed for ettringite synthesis offers a versatile synthetic strategy, which can be applied to synthesise further cementitious materials.
KW - Ettringite
KW - Mechanochemistry
KW - Sustainability
KW - X-ray diffraction
PY - 2019
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-489172
VL - 8
IS - 7
SP - 1012
EP - 1019
PB - ChemPubSoc
AN - OPUS4-48917
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Kulla, Hannes
A1 - Michalchuk, Adam
A1 - Emmerling, Franziska
T1 - Manipulating the dynamics of mechanochemical ternary cocrystal formation
N2 - The mechanism of ternary cocrystal formation, and the potential role of intermediate binary phases, has been debated for some time. We report here the first in situ real-time monitoring of two prototypic ternary cocrystals. Our results suggest that the question is more complicated than previously considered. The mechanism of mechanochemical ternary cocrystal formation depends on the milling conditions, here the milling frequency and addition of liquid. Binary phases can form under certain conditions, but do not act as intermediates in the formation of the ternary cocrystals. Rather, binary phases are competitive with the ternary phase, and their formation appears to compete with that of the ternary components. The presence of binary phases leads to an increase in the overall reaction time. The results reported here offer the first insights into the true complexities of mechanochemical multi-component synthesis of higher order multi-component crystals and demonstrate a new understanding of the influence of milling condition for the study of mechanisms and kinetics.
KW - Mechanochemistry
KW - In situ
KW - Cocrystal
PY - 2019
UR - https://pubs.rsc.org/en/content/articlepdf/2019/cc/c9cc03034d
U6 - https://doi.org/10.1039/c9cc03034d
SN - 1364-548X
VL - 55
IS - 66
SP - 9793
EP - 9796
PB - RSC
AN - OPUS4-48613
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Emmerling, Franziska
T1 - How to write your thesis
N2 - Useful tips & tricks to overcome procrastination and get you PhD thesis written.
T2 - 13. Interdisziplinäres Doktorandenseminar
CY - Berlin, Germany
DA - 19.03.2019
KW - Outreach
KW - Pomodore
KW - Deep work
PY - 2019
AN - OPUS4-48097
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Al-Terkawi, Abdal-Azim
A1 - Prinz, Carsten
A1 - Scholz, Gudrun
A1 - Kemnitz, Erhard
A1 - Emmerling, Franziska
T1 - Ca-, Sr-, and Ba-Coordination polymers based on anthranilic acid via mechanochemistry
N2 - Ca-, Sr-, and Ba-Based coordination polymers (CPs) were prepared mechanochemically by milling metal-hydroxide samples with anthranilic acid (oABAH). {[Ca(oABA)2(H2O)3]}n consists of one-dimensional polymeric chains that are further connected by a hydrogen-bonding network. {[Sr(oABA)2(H2O)2]·H2O}n is a one-dimensional CP in which water molecules bridge Sr2+ ions and increase the dimensionality by building an extended network. {[Ba(oABA)2(H2O)]}n crystallizes as a two-dimensional CP comprising one bridging water molecule. The cation radii influence the inorganic connectivity and dimensionality of the resulting crystal structures. The crystal structures were refined from powder X-ray diffraction data using the Rietveld method. The local coordination environments were studied via extended X-ray absorption fine structure (EXAFS) measurements. The compounds were further characterized using comprehensive analytical methods such as elemental analysis, thermal analysis, MAS NMR, imaging, and dynamic vapor sorption (DVS) measurements. Compounds 1, 2, and 3 exhibit small surface areas which decrease further after thermal annealing experiments. All compounds exhibit a phase transformation upon heating, which is only reversible in 3.
KW - Mechanochemistry
KW - XRD
PY - 2019
U6 - https://doi.org/10.1039/c9dt00991d
SN - 1477-9226
SN - 1477-9234
VL - 48
IS - 19
SP - 6513
EP - 6521
PB - Royal Society of Chemistry
AN - OPUS4-48014
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Kabelitz, Anke
A1 - Dinh, H. A.
A1 - Emmerling, Franziska
T1 - Early stage in situ detection of polynuclear aluminum phases in aqueous solution
N2 - Polynuclear cationic aluminum hydroxide phases are known intermediates in the formation of aluminum oxides or (oxide) ydroxides upon hydrolysis of aluminum salt solutions. In the presence of sulfate anions, these aluminum polyoxocations (Al13) can form crystalline Al13 sulfates with varying chemical composition.
The formation of these Al13 sulfates in aqueous solution has been poorly understood. Here, we investigate the early stage crystallization of Al13 clusters in a sulfate-containing solution, in situ and in real time. Dynamics associated with Al13 sulfate formation have been obtained for the first time, using Synchrotron X-ray diffraction (XRD) of solutions suspended by acoustic levitation. Time-resolved in situ data show that the cubic phase, Na [(AlO4)Al12(OH)24(H2O)12](SO4)4*10H2O, forms after only minutes. The Formation mechanism of Al13 sulfates was found to depend on the sulfate:aluminum (SO4:Al) ratio. Ex situ XRD of the product Al13 sulfates in solution shows that for SO4:Al ratio ≤ 1.5 two other crystalline phases form, and convert to the cubic phase upon washing and drying. In situ XRD for the same ratio shows transient formation of an intermediate during the crystallization process.
KW - Polyoxocation
KW - In situ
KW - Crystallization
KW - Acoustic levitation
KW - Synchroton x-ray diffraction
PY - 2019
U6 - https://doi.org/10.1016/j.poly.2019.05.049
VL - 170
SP - 639
EP - 648
PB - Elsevier Ltd.
AN - OPUS4-48552
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Emmerling, Franziska
T1 - Foschung an der BAM - Von Termiten bis zum 3D Druck in der Schwerelosigkeit
N2 - Eine Übersicht über die Forschung an der BAM mit Schwerpunkt auf dem Fachbereich Strukturanalytik
T2 - Naturwissenschaftstag in Senftenberg
CY - Senftenberg, Germany
DA - 14.06.19
KW - Mechanochemie
KW - XRD
PY - 2019
AN - OPUS4-48393
LA - deu
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Feiler, Torvid
A1 - Bhattacharya, Biswajit
A1 - Michalchuk, Adam
A1 - Schröder, V.
A1 - List-Kratochvil, E.
A1 - Emmerling, Franziska
T1 - Mechanochemical Syntheses of Isostructural Luminescent Cocrystals of 9-Anthracenecarboxylic Acid with two Dipyridines Coformers
N2 - Tuning and controlling the solid-state photophysical properties of organic luminophore are very important to develop next-generation organic luminescent materials. With the aim of discovering new functional luminescent materials, new cocrystals of 9-anthracene carboxylic acid (ACA) were prepared with two different dipyridine coformers: 1,2-bis(4-pyridyl)ethylene and 1,2-bis(4-pyridyl)ethane. The cocrystals were successfully obtained by both mechanochemical approaches and conventional solvent crystallization. The newly obtained crystalline solids were characterized thoroughly using a combination of single crystal X-ray diffraction, powder X-ray diffraction, Fourier-transform infrared spectroscopy, differential thermal analysis, and thermogravimetric analysis. Structural analysis revealed that the cocrystals are isostructural, exhibiting two-fold interpenetrated hydrogen bonded networks. While the O–H···N hydrogen bonds adopts a primary role in the stabilization of the cocrystal phases, the C–H···O hydrogen bonding interactions appear to play a significant role in guiding the three-dimensional assembly. Both π···π and C–H···π interactions assist in stabilizing the interpenetrated structure. The photoluminescence properties of both the starting materials and cocrystals were examined in their solid states. All the cocrystals display tunable photophysical properties as compared to pure ACA. Density functional theory simulations suggest that the modified optical properties result from charge transfers between the ACA and coformer molecules in each case. This study demonstrates the potential of crystal engineering to design solid-state luminescence switching materials through cocrystallization.
KW - Cocrystal
KW - Mechanochemical synthesis
KW - Luminescence
KW - X-ray diffraction
KW - DFT calculation
PY - 2020
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-518226
VL - 10
IS - 10
SP - 889
PB - MDPI
AN - OPUS4-51822
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Surov, A.
A1 - Vasilev, N.
A1 - Voronin, A.
A1 - Churakov, A.
A1 - Emmerling, Franziska
A1 - Perlovich, G.
T1 - Ciprofloxacin salts with benzoic acid derivatives: structural aspects, solid-state properties and solubility performance
N2 - n this work, three new pharmaceutical hydrated salts of ciprofloxacin with selected derivatives of benzoic acid, namely 4-hydroxybenzoic acid, 4-aminobenzoic acid and gallic acid, were obtained and systematically investigated by several solid-state analytical techniques. In situ Raman spectroscopy was applied to elucidate the alternative pathways of the solid forms' formation under mechanochemical conditions. Crystal structure analysis and a CSD survey allowed us to establish a distinct supramolecular motif formed by infinite columnar stacks of ciprofloxacin dimers arranged in the “head-to-tail” manner. An alternative “head-to-head” packing arrangement was only observed in the crystal of the hydrated ciprofloxacin salt with 4-aminobenzoic acid. In addition, the pH-solubility behavior of the solid forms was thoroughly investigated. Furthermore, a distinct structure–property relationship between the specific features of the supramolecular organization of the hydrated salts and their solubility was observed and discussed.
KW - Mechanochemistry
KW - XRD
PY - 2020
U6 - https://doi.org/10.1039/D0CE00514B
VL - 22
IS - 25
SP - 4238
EP - 4249
AN - OPUS4-51818
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Opitz, P.
A1 - Asta, M.
A1 - Fernandez-Martinez, A.
A1 - Panthöfer, M.
A1 - Kabelitz, Anke
A1 - Emmerling, Franziska
A1 - Mondeshki, M.
A1 - Tremel, W.
T1 - Monitoring a Mechanochemical Syntheses of Isostructural Luminescent Cocrystals of 9-Anthracenecarboxylic Acid with two Dipyridines Coformers
N2 - Amorphous calcium carbonate (ACC) is an important precursor in the biomineralization of crystalline CaCO3. In nature, it serves as a storage material or as a permanent structural element, whose lifetime is regulated by an organic matrix. The relevance of ACC in materials science is primarily related to our understanding of CaCO3 crystallization pathways and CaCO3/(bio)polymer nanocomposites. ACC can be synthesized by liquid–liquid phase separation, and it is typically stabilized with macromolecules. We have prepared ACC by milling calcite in a planetary ball mill. Phosphate “impurities” were added in the form of monetite (CaHPO4) to substitute the carbonate anions, thereby stabilizing ACC by substitutional disorder. The phosphate anions do not simply replace the carbonate anions. They undergo shear-driven acid/base and condensation reactions, where stoichiometric (10%) phosphate contents are required for the amorphization to be complete. The phosphate anions generate a strained network that hinders ACC recrystallization kinetically. The amorphization reaction and the structure of BM-ACC were studied by quantitative Fourier transform infrared spectroscopy and solid state 31P, 13C, and 1H magic angle spinning nuclear magnetic resonance spectroscopy, which are highly sensitive to symmetry changes of the local environment. In the first—and fast—reaction step, the CO32– anions are protonated by the HPO42– groups. The formation of unprecedented hydrogen carbonate (HCO3–) and orthophosphate anions appears to be the driving force of the reaction, because the phosphate group has a higher Coulomb energy and the tetrahedral PO43– unit can fill space more efficiently. In a competing second—and slow—reaction step, pyrophosphate anions are formed in a condensation reaction. No pyrophosphates are formed at higher carbonate contents. High strain leads to such a large energy barrier that any reaction is suppressed. Our findings aid in the understanding of the mechanochemical amorphization of calcium carbonate and emphasize the effect of impurities for the stabilization of the amorphous phases in general. Our approach allowed the synthesis of new amorphous alkaline earth defect variants containing the unique HCO3– anion. Our approach outlines a general strategy to obtain new amorphous solids for a variety of carbonate/phosphate systems that offer promise as biomaterials for bone regeneration.
KW - Crystallization
KW - Mechanochemistry
KW - PDF
PY - 2020
U6 - https://doi.org/10.1021/acs.cgd.0c00912
VL - 20
IS - 10
SP - 6831
EP - 6846
PB - American Chemical Society
AN - OPUS4-51819
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - de Oliveira Guilherme Buzanich, Ana
A1 - Kulow, Anicó
A1 - Kabelitz, Anke
A1 - Grunewald, C.
A1 - Seidel, R.
A1 - Chapartegui-Arias, Ander
A1 - Radtke, Martin
A1 - Reinholz, Uwe
A1 - Emmerling, Franziska
A1 - Beyer, S.
T1 - Observation of early ZIF-8 crystallization stages with X-ray absorption spectroscopy
N2 - The present study investigates early stages of ZIF-8 crystallization up to 5 minutes post mixing of precursor solutions. Dispersive X-ray Absorption Spectroscopy (DXAS) provides a refined understanding of the evolution of the coordination environment during ZIF-8 crystallization. Linear Combination Fiting (LCF) suggests tetrakis(1-methylimidazole)zinc2+ to be a suitable and stable mononuclear structure analogue for some early stage ZIF-8 intermediates. Our results pave the way for more detailed studies on physico-chemical aspects of ZIF-8 crystallization to better control tailoring ZIF-8 materials for specific applications.
KW - In-situ
KW - XANES
KW - ZIF-8
KW - Crystallization
PY - 2020
U6 - https://doi.org/10.1039/D0SM01356K
SN - 1744-6848
VL - 17
IS - 2
SP - 331
EP - 334
PB - Royal Scociety of Chemistry
AN - OPUS4-51723
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - de Olivera, Paulo
A1 - Michalchuk, Adam
A1 - Marquardt, Julien
A1 - Feiler, Torvid
A1 - Prinz, Carsten
A1 - Torresi, R.
A1 - Camargo, P.
A1 - Emmerling, Franziska
T1 - Investigating the role of reducing agents on mechanosynthesis of Au nanoparticles
N2 - Control over the bottom up synthesis of metal nanoparticles (NP) depends on many experimental factors, including the choice of stabilising and reducing agents. By selectively manipulating these species, it is possible to control NP characteristics through solution-phase synthesis strategies. It is not known, however, whether NPs produced from mechanochemical syntheses are governed by the same rules. Using the Au NPs mechanosynthesis as a model system, we investigate how a series of common reducing agents affect both the reduction kinetics and size of Au NPs. It is shown that the relative effects of reducing agents on mechanochemical NP synthesis differ significantly from their role in analogous solution-phase reactions. Hence, strategies developed for control over NP growth in solution are not directly transferrable to environmentally benign mechanochemical approaches. This work demonstrates a clear need for dedicated, systematic studies on NP mechanosynthesis.
KW - Mechanochemistry
KW - Metal nanoparicels
PY - 2020
U6 - https://doi.org/10.1039/d0ce00826e
VL - 22
IS - 38
SP - 6261
EP - 6267
PB - Royal Society of Chemistry
AN - OPUS4-51757
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - de Olivera, Paulo
A1 - Michalchuk, Adam
A1 - de Oliveira Guilherme Buzanich, Ana
A1 - Bienert, Ralf
A1 - Torresi, R.
A1 - Camargo, P.
A1 - Emmerling, Franziska
T1 - Tandem X-ray absorption spectroscopy and scattering for in situ time-resolved monitoring of gold nanoparticle mechanosynthesis
N2 - Current time-resolved in situ approaches limit the scope of mechanochemical investigations possible. Here we develop a new, general approach to simultaneously follow the evolution of bulk atomic and electronic structure during a mechanochemical synthesis. This is achieved by coupling two complementary synchrotron-based X-ray methods: X-ray absorption spectroscopy (XAS) and X-ray diffraction. We apply this method to investigate the bottom-up mechanosynthesis of technologically important Au micro and nanoparticles in the presence of three different reducing agents, hydroquinone, sodium citrate, and NaBH4. Moreover, we show how XAS offers new insight into the early stage generation of growth species (e.g. monomers and clusters), which lead to the subsequent formation of nanoparticles. These processes are beyond the detection capabilities of diffraction methods. This combined X-ray approach paves the way to new directions in mechanochemical research of advanced electronic materials.
KW - Mechanochemistry
KW - XANES
KW - X-ray diffraction
KW - Nano particles
PY - 2020
U6 - https://doi.org/10.1039/d0cc03862h
SN - 1364-548X
VL - 56
SP - 10329
EP - 10332
PB - Royal Society of Chemistry
AN - OPUS4-51760
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Opitz, P.
A1 - Besch, L.
A1 - Panthöfer, M.
A1 - Kabelitz, Anke
A1 - Unger, R.
A1 - Emmerling, Franziska
A1 - Mondeshki, M.
A1 - Tremel, W.
T1 - Insights into the In Vitro Formation of Apatite from Mg‐Stabilized Amorphous Calcium Carbonate
N2 - A protein‐free formation of bone‐like apatite from amorphous precursors through ball‐milling is reported. Mg2+ ions are crucial to achieve full amorphization of CaCO3. Mg2+ incorporation generates defects which strongly retard a recrystallization of ball‐milled Mg‐doped amorphous calcium carbonate (BM‐aMCC), which promotes the growth of osteoblastic and endothelial cells in simulated body fluid and has no effect on endothelial cell gene expression. Ex situ snapshots of the processes revealed the reaction mechanisms. For low Mg contents (<30%) a two phase system consisting of Mg‐doped amorphous calcium carbonate (ACC) and calcite “impurities” was formed. For high (>40%) Mg2+ contents, BM‐aMCC follows a different crystallization path via magnesian calcite and monohydrocalcite to aragonite. While pure ACC crystallizes rapidly to calcite in aqueous media, Mg‐doped ACC forms in the presence of phosphate ions bone‐like hydroxycarbonate apatite (dahllite), a carbonate apatite with carbonate substitution in both type A (OH−) and type B (PO43−) sites, which grows on calcite “impurities” via heterogeneous nucleation. This process produces an endotoxin‐free material and makes BM‐aMCC an excellent “ion storage buffer” that promotes cell growth by stimulating cell viability and metabolism with promising applications in the treatment of bone defects and bone degenerative diseases.
KW - Total Scattering
KW - XRD
KW - Mechanochemistry
PY - 2020
U6 - https://doi.org/10.1002/adfm.202007830
VL - 31
IS - 3
SP - 7830
PB - Wiley VHC-Verlag
AN - OPUS4-51761
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Kulow, Anicó
A1 - de Oliveira Guilherme Buzanich, Ana
A1 - Reinholz, Uwe
A1 - Emmerling, Franziska
A1 - Hampel, S.
A1 - Fittschen, U.E.A.
A1 - Streli, C.
A1 - Radtke, Martin
T1 - Comparison of three reconstruction methods based on deconvolution, iterative algorithm and neural network for X-ray fluorescence imaging with coded apertures
N2 - X-ray imaging methods are used in many fields of research, as they allow a non-destructive Investigation of the elemental content of various samples. As for every imaging method, for X-ray imaging the optics are of crucial importance. However, these optics can be very expensive and laborious to build, as the requirements on surface roughness and precision are extremely high. Angles of reflection and refraction are often in the range of a few mrad, making a compact design hard to achieve. In this work we present a possibility to simplify X-ray imaging. We have adapted the coded aperture method, a high energy radiation imaging method that has its origins in astrophysics, to full field X-ray fluorescence imaging. In coded aperture imaging, an object is projected through a known mask, the coded aperture, onto an area sensitive detector. The resulting image consists of overlapping projections of the object and a reconstruction step is necessary to obtain the information from the recorded image. We recorded fluorescence images of different samples with an energy-dispersive 2D detector (pnCCD) and investigated different reconstruction methods. With a small coded aperture with 12 holes we could significantly increase the count rate compared to measurements with a straight polycapillary optic. We show that the reconstruction of two different samples is possible with a deconvolution approach, an iterative algorithm and a neural network. These results demonstrate that X-ray fluorescence imaging with coded apertures has the potential to deliver good results without scanning and with an improved count rate, so that measurement times can be shortened compared to established methods.
KW - X-ray fluorescence imaging
KW - Coded apertures
KW - Imaging
KW - Elemental mapping
KW - Image reconstruction
PY - 2020
U6 - https://doi.org/10.1039/d0ja00146e
VL - 35
IS - 7
SP - 1423
EP - 1434
PB - Royal Society of Chemistry
CY - United Kingdom
AN - OPUS4-51518
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Akhmetova, Irina
A1 - Beyer, Sebastian
A1 - Schutjajew, K.
A1 - Tichter, T.
A1 - Wilke, Manuel
A1 - Prinz, Carsten
A1 - B. Martins, Inês C.
A1 - Al-Sabbagh, Dominik
A1 - Roth, C.
A1 - Emmerling, Franziska
T1 - Cadmium benzylphosphonates - the close relationship between structure and properties
N2 - Cadmium benzylphosphonate Cd(O3PBn)·H2O and its fluorinated derivates Cd(O3PBn-3F)·H2O, Cd(O3PBn-4F)·H2O, and Cd(O3PBn-F5)·H2O were synthesized mechanochemically. The Crystal structures of the compounds were determined based on powder X-ray diffraction (PXRD) data. The influence of the ligand substitution on the crystal structure of the metal phosphonate was determined. The hydrophobicity as a function of degree of fluorination was investigated using dynamic vapor sorption.
KW - Mechanochemistry
KW - Metal phosphonates
KW - PXRD
KW - DVS
PY - 2019
U6 - https://doi.org/10.1039/c9ce00776h
VL - 21
SP - 5958
EP - 5964
PB - RSC Royal Society of Chemistry
AN - OPUS4-49930
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Kumari, N.
A1 - Bhattacharya, Biswajit
A1 - Roy, P.
A1 - Michalchuk, Adam
A1 - Ghosh, A.
A1 - Emmerling, Franziska
T1 - Enhancing the Pharmaceutical Properties of Pirfenidone by Mechanochemical Cocrystallization
N2 - Pirfenidone is an important drug molecule used in the treatment of idiopathic lung fibrosis. Although approved by the USFDA in 2014, pirfenidone’s aqueous solubility is too high and must be mitigated by additives. In this work, the cocrystallization of pirfenidone is explored as an alternative approach to reducing its solubility. Herein, an anhydrous form of pirfenidone is reported, alongside its first two reported cocrystals. The new crystalline solids are thoroughly characterized by single crystal X-ray diffraction (SCXRD), powder X-ray diffraction analysis (PXRD), Fourier transform infrared (FTIR) spectroscopy, differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA).
Equilibrium solubility and intrinsic dissolution rates (IDR) are studied for the cocrystals and compared to that of the parent drug. Both cocrystal forms exhibit drastically lower aqueous solubility (by up to 90%) and dissolution rates, rationalized based on both lattice energy calculations and consideration of intermolecular interactions in the solid state. Furthermore, we compare the physicochemical properties of solution-based material with that of material produced mechanochemically. Importantly, no differences are observed between the two production methods. This work demonstrates the strength of crystal Engineering strategies to beneficially modify important pharmaceutical properties and highlights the potential of mechanochemistry to facilitate this in an environmentally benign way.
KW - Mechanochemistry
PY - 2019
U6 - https://doi.org/10.1021/acs.cgd.9b00932
VL - 19
IS - 11
SP - 6482
EP - 6492
PB - ACS Publications
AN - OPUS4-49828
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Bhattacharya, Biswajit
A1 - Michalchuk, Adam
A1 - Emmerling, Franziska
T1 - Revealing Mechanical Plastic Bending in Coordination Polymer Crystals
N2 - Crystalline molecular materials with mechanical flexibility are promising for technological development. This is particularly true for the development of advanced materials with optoelectronic and biomedical applications. While a growing number of mechanically flexible crystalline molecular materials are being reported,1 they remain scarce. At present, most discoveries are serendipitous, as limited design strategies are currently known. Amongst these strategies Desiraju et. al. suggested that elastic materials must contain herringbone structures.2 For plastic crystals, the so-called ‘shape-synthon’ strategy has been developed, in which weak non-covalent interactions are introduced into structures to facilitate mobility of molecules.3 This includes formation of slip planes. Generally, these models have performed very well at predicting and rationalizing the mechanical properties of new materials. Recently, however, a family of one-dimensional covalent networks (coordination polymers; CPs) has been described, which show mechanical elasticity. With drastically different structural chemistry, these systems do not seem to adhere to the currently established rules. Herein, we present the first such system: a plastically bendable crystal of a 1D CP, [Zn(-Cl)2(3,5-Cl2Py)2]n (where 3,5-Cl2Py = 3,5-dichloro pyridine). This CP crystallizes in a tetragonal, and can therefore be bent over two major faces to acute angles without fracturing. We conducted bending and indentation experiments to quantify the mechanical properties of the CP crystal. This was complimented by Vibrational (Raman and Terahertz) spectroscopy and theoretical calculations for deeper understanding of molecular level structural deformation.
T2 - 32nd European Crystallographic Meeting (ECM32)
CY - University of Vienna, Vienna, Austria
DA - 18.08.2019
KW - Mechanical Flexiblity
KW - Crystal engineering
KW - Coordination Polymers
PY - 2019
AN - OPUS4-49875
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Haferkamp, Sebastian
A1 - Emmerling, Franziska
A1 - Akhmetova, Irina
A1 - Kulla, H.
A1 - Rademann, K.
T1 - Insights into mechanochemical Knoevenagel condensations
N2 - Mechanochemistry paves the way to simple, fast, and green syntheses. Despite considerable effort, there is a lack in understanding of the underlying mechanisms. In situ investigations help to understand these mechanisms, which occur during a mechanochemical reaction. Here we present a universal strategy for simultaneous real-time in situ analysis, combining X-ray diffraction, Raman spectroscopy, and thermography. The potential of of our approach is shown for diffrent model reactions.
T2 - Adlershofer Forschungsforum 2019
CY - Berlin, Germany
DA - 11.11.2019
KW - Mechanochemistry
KW - In situ
KW - Knoevenagel condensation
PY - 2019
AN - OPUS4-49694
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Chewle, Surahit
A1 - Emmerling, Franziska
A1 - Weber, M.
T1 - Effect of choice of solvent on crystallization pathway of paracetamol: An experimental and theoretical case study
N2 - The choice of solvents influences crystalline solid formed during the crystallization of active pharmaceutical ingredients (API). The underlying effects are not always well understood because of the complexity of the systems. Theoretical models are often insufficient to describe this phenomenon. In this study, the crystallization behavior of the model drug paracetamol in different solvents was studied based on experimental and molecular dynamics data. The crystallization process was followed in situ using time-resolved Raman spectroscopy. Molecular dynamics with simulated annealing algorithm was used for an atomistic understanding of the underlying processes. The experimental and theoretical data indicate that paracetamol molecules adopt a particular geometry in a given solvent predefining the crystallization of certain polymorphs
KW - Crystallization
KW - Nucleation
KW - Polymorphism
KW - Raman spectroscopy
KW - Cassical nucleation theory
PY - 2021
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-520052
SN - 2073-4352
VL - 10
IS - 12
SP - 1
EP - 10
PB - MDPI
CY - Basel
AN - OPUS4-52005
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Simões, R. G.
A1 - Melo, P. L. T.
A1 - Bernardes, C. E. S.
A1 - Heilmann, Maria
A1 - Emmerling, Franziska
A1 - Minas da Piedade, M. E.
T1 - Linking Aggregation in Solution, Solvation, and Solubility of Simvastatin: An Experimental and MD Simulation Study
N2 - The solubility is generally thought to be higher if the solvent effectively solvates solute molecules that are well-separated from each other. The present work suggests, however, that the formation of large solute aggregates does not necessarily imply less effective solvation and lower solubility. Measurements of the solubility of simvastatin (one of the most commonly prescribed antihyperlipidemic drugs) in three solvents with different polarities and protic characters, led to the solubility order acetone > ethyl acetate > ethanol, in the full temperature range covered by the experiments (283–308 K). An analysis of the structures of the different solutions on the basis of molecular dynamics simulation results indicated that this trend seems to be determined by a balance between the solute tendency toward aggregation and the ability of the solvent to efficiently solvate it, by integrating the cluster structures, regardless of their size, and effectively establishing solvent–solute interactions.
KW - Simvastatin
KW - Solubility
KW - API
KW - Aggregation
PY - 2021
U6 - https://doi.org/10.1021/acs.cgd.0c01325
VL - 21
IS - 1
SP - 544
EP - 551
AN - OPUS4-52185
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Michalchuk, Adam
A1 - Boldyreva, E.
A1 - Belenguer, A. M.
A1 - Emmerling, Franziska
A1 - Boldyrev, V. V.
T1 - Tribochemistry, mechanical alloying, mechanochemistry: what is in a name?
N2 - Over the decades, the application of mechanical force to influence chemical reactions has been called by various names: mechanochemistry, tribochemistry, mechanical alloying, to name but a few. The evolution of these terms has largely mirrored the understanding of the field. But what is meant by these terms, why have they evolved, and does it really matter how a process is called? Which parameters should be defined to describe unambiguously the experimental conditions such that others can reproduce the results, or to allow a meaningful comparison between processes explored under different conditions? Can the information on the process be encoded in a clear, concise, and self-explanatory way? We address these questions in this Opinion contribution, which we hope will spark timely and constructive discussion across the international mechanochemistry community.
KW - Mechanochemistry
KW - Tribochemistry
KW - Mechanical alloying
KW - Tribology
KW - Mechanical activation
KW - Nomenclature
KW - Mechanochemical pictographs
PY - 2021
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-523291
SN - 2296-2646
VL - 9
SP - 1
EP - 29
PB - Frontiers Media
CY - Lausanne
AN - OPUS4-52329
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Zänker, Steffen
A1 - Scholz, G.
A1 - Xu, W.
A1 - Kemnitz, E.
A1 - Emmerling, Franziska
T1 - Structure and properties of fluorinated and non-fluorinated Ba-coordination polymers - the position of fluorine makes the difference
N2 - As the most electronegative element, fluorine has a strong influence on material properties such as absorption behaviour or chemical and thermal stability. Fluorine can be easily integrated into coordination polymers (CPs) via a fluorinated acetate, here trifluoroacetate in Ba(CF3COO)2, or directly via a metal fluorine bond (BaF(CH3COO)). In the present study both possibilities of fluorine integration were tested and their effect on structure and properties of barium coordination polymers was investigated in comparison with the non-fluorinated barium acetate (Ba(CH3COO)2). In addition to the study of their thermal behaviour and their decomposition temperature, the CPs structures were tested for their application as possible anode materials in lithium ion batteries and for their sorption of water and ammonia. The properties of the CPs can be traced back to the individual structural motifs and could thus trigger new design ideas for CPs in LIBs and/or catalysis.
KW - Alkaline earth metal coordination polymers
KW - Lithium-ion battery
KW - Water stability
KW - Fluorine coordination
PY - 2020
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-524041
SN - 0044-2313
VL - 647
IS - 9
SP - 1014
EP - 1024
PB - Wiley-VCH GmbH
AN - OPUS4-52404
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Stroh, Julia
A1 - Emmerling, Franziska
ED - Plank, J.
ED - Lei, L.
T1 - Direct insight into the admixture activity during cement hydration using levitated droplets
N2 - Chemical admixtures are widely used to adjust properties of the cementitious mixtures. Different superplasticizers (SP) are typically added to improve the flowability of the fresh cement paste. Their working period is the initial stage of the cement hydration from its beginning until stiffening. Currently, polycarboxylate-based SP (PCE-SP) are the most effective ones. They can act beyond their aimed function causing changes in the hydration course, e. g. retardation effects. The exact mechanisms and influencing factors are still under investigation. However, the occurrence of the retardation effect indicates the involvement of PCE in the hydration reactions. Some observations indicate, that the retardation depends on the type, molecular structure and concentration of PCE, and the presence of other admixtures (stabiliser, ST). These factors influence further the working time of admixture and its amount related efficacy in the flow improvement.
We investigate the cement hydration process in situ in levitated droplets. High resolution synchrotron X-ray diffraction allows gathering temporal course of the hydration reactions. The measurement setup is based on an ultrasonic levitator allowing in situ investigation of the temporal changes of the phase composition in the hydrating cementitious system. Further, the hydration can be followed ab initio avoiding the time loss for the sample preparation and filling in the sample holder. The collected data allows to conclude about the mechanisms of the admixture action and their involvement into the ongoing hydration process.
T2 - 2nd International Conference on Polycarboxylate Superplasticizers (PCE 2017)
CY - München, Germany
DA - 28.09.2017
KW - Portland cement
KW - Initial hydration
KW - Acoustic levitator
KW - Admixtures
KW - Time resolution
PY - 2017
SN - 978-3-9816240-6-9
SP - 185
EP - 193
AN - OPUS4-43167
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Kraffert, K.
A1 - Kabelitz, Anke
A1 - Siemensmeyer, K.
A1 - Schmack, R.
A1 - Bernsmeier, D.
A1 - Emmerling, Franziska
A1 - Kraehnert, R.
T1 - Nanocasting of superparamagnetic iron oxide films with ordered mesoporosity
N2 - Maghemite and magnetite show superparamagnetic behavior when synthesized in a nanostructured form. The material’s inducible magnetization enables applications ranging from contrast enhancing agents for magnetic resonance imaging to drug delivery systems, magnetic hyperthermia, and separation. Superparamagnetic iron oxides with templated porosity have been synthesized so far only in the form of hard-templated powders, where silicon retained from the template severely degrades the material’s magnetic properties. Here, for the first time, the synthesis of superparamagnetic iron oxides with soft-templated mesopore structure is reported. The synthesis of nanostructured maghemite and magnetite films succeeds using micelles of amphiphilic block-copolymers as templates. A thermal treatment of the initially formed mesoporous ferrihydrite in nitrogen produces maghemite, which can be partly reduced to magnetite via thermal treatment in hydrogen while retaining the templated mesopore structure. The resulting materials feature a unique combination of high surface area, controlled pore diameter, and tunable magnetic properties.
KW - Iron oxide films
KW - Mesoporosity
KW - Soft-templated
PY - 2018
U6 - https://doi.org/10.1002/admi.201700960
SN - 2196-7350
VL - 5
IS - 3
SP - 1700960, 1
EP - 1700960, 7
PB - Wiley-VCH
CY - Weinheim
AN - OPUS4-43560
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Emmerling, Franziska
T1 - Licht ins Dunkle - In situ Untersuchungen mechanochemischer Reaktionen
N2 - Mechanochemistry is increasingly used for synthesizing soft matter materials including metal organic compounds and cocrystals. The ever-increasing interest in this method is contrasted by a limited mechanistic understanding of the mechanochemical reactivity and selectivity. Time-resolved in situ investigations of milling reactions provide direct insights in the underlying mechanisms. We recently introduced a setup enabling in situ investigation of mechanochemical reactions using synchrotron XRD combined with Raman spectroscopy. The specific combination allows to study milling processes comprehensively on the level of the molecular and crystalline structure and thus obtaining reliable data for mechanistic studies. In this contribution, I will discuss our recent results investigating the formation of (polymorphic) cocrystals and metal phosphonates. First investigations of a mechanochemical synthesis under controlled temperature which allow determining the activation barrier are presented. Furthermore, in situ Raman spectroscopy coupled with thermography revealed a low temperature increase during milling reactions due to the mechanical impact and clear temperature increases as a result of the reaction heat.5 Our results indicate that in situ investigation of milling reactions offer a new approach to tune and optimize mechanochemically synthesized compounds.
T2 - PRORA Fachtagung Prozessnahe Röntgenanalytik
CY - Berlin, Germany
DA - 30.11.2017
KW - Mechanochemie
KW - XRD
KW - In situ
PY - 2017
AN - OPUS4-43562
LA - deu
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Emmerling, Franziska
A1 - Kulla, Hannes
A1 - Wilke, Manuel
T1 - In situ investigations of mechanochemical reactions - new insights in formation pathways
N2 - Mechanochemistry is increasingly used for synthesizing soft matter materials including metal organic compounds and cocrystals. The ever-increasing interest in this method is contrasted by a limited mechanistic understanding of the mechanochemical reactivity and selectivity. Time-resolved in situ investigations of milling reactions provide direct insights in the underlying mechanisms. We recently introduced a setup enabling in situ investigation of mechanochemical reactions using synchrotron XRD combined with Raman spectroscopy. The specific combination allows to study milling processes comprehensively on the level of the molecular and crystalline structure and thus obtaining reliable data for mechanistic studies. In situ Raman spectroscopy coupled with thermography revealed a low temperature increase during milling reactions due to the mechanical impact and clear temperature increases because of the reaction heat.
Based on the data, temperature rises as postulated in the magma plasma and hot spot theory can be excluded for soft matter milling syntheses. Our results indicate that in situ investigation of milling reactions offer a new approach to tune and optimize mechanochemically synthesized compounds.
T2 - Wissenschaftsforum Chemie
CY - Berlin, Germany
DA - 10.09.17
KW - Mechanochemistry
KW - In situ
PY - 2017
AN - OPUS4-43563
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Emmerling, Franziska
T1 - New insights in formation pathways: in situ investigations of mechanochemical reactions
N2 - Mechanochemistry is increasingly used for synthesizing soft matter materials including metal organic compounds and cocrystals.1 The ever-increasing interest in this method is contrasted by a limited mechanistic understanding of the mechanochemical reactivity and selectivity. Time-resolved in situ investigations of milling reactions provide direct insights in the underlying mechanisms.2,3 We recently introduced a setup enabling in situ investigation of mechanochemical reactions using synchrotron XRD combined with Raman spectroscopy. The specific combination allows to study milling processes comprehensively on the level of the molecular and crystalline structure and thus obtaining reliable data for mechanistic studies. In this contribution, I will discuss our recent results investigating the formation of (polymorphic) cocrystals and metal phosphonates.4 First investigations of a mechanochemical synthesis under controlled temperature which allow determining the activation barrier are presented. Furthermore, in situ Raman spectroscopy coupled with thermography revealed a low temperature increase during milling reactions due to the mechanical impact and clear temperature increases as a result of the reaction heat.5 Our results indicate that in situ investigation of milling reactions offer a new approach to tune and optimize mechanochemically synthesized compounds.
T2 - International Conference on Mechanochemistry and Mechanical Alloying, INCOME 2017
CY - Kosice, Slovakia
DA - 03.09.2017
KW - Mechanochemistry
KW - In situ
PY - 2017
AN - OPUS4-43564
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Emmerling, Franziska
T1 - In situ investigations of mechanochemical reactions
N2 - Mechanochemistry is increasingly used for synthesizing soft matter materials including metal organic compounds and cocrystals.1,2 The ever-increasing interest in this method is contrasted by a limited mechanistic understanding of the mechanochemical reactivity and selectivity. Time-resolved in situ investigations of milling reactions provide direct insights in the underlying mechanisms.3,4 We recently introduced a setup enabling in situ investigation of mechanochemical reactions using synchrotron XRD combined with Raman spectroscopy (Fig.1a) The specific combination allows to study milling processes comprehensively on the level of the molecular and crystalline structure and thus obtaining reliable data for mechanistic studies. In this talk I will discuss our recent results investigating the formation of (polymorphic) cocrystals.6-7 First investigations of a mechanochemical synthesis under controlled temperature (Fig 2a) which allow determining the activation barrier are presented.8 Furthermore, in situ Raman spectroscopy coupled with thermography revealed a low temperature increase during milling reactions due to the mechanical impact and clear temperature increases as a result of the reaction heat.
T2 - Kolloquium Anorganische und Analytische Chemie Universität Freiburg
CY - Freiburg, Germany
DA - 20.12.2017
KW - In situ
KW - Mechanochemistry
KW - Rietveld
PY - 2017
AN - OPUS4-43566
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Emmerling, Franziska
T1 - In situ investigations of mechanochemical syntheses: New insights in formation pathways
N2 - Mechanochemistry is increasingly used for synthesizing soft matter materials including metal organic compounds and cocrystals.1,2 The ever-increasing interest in this method is contrasted by a limited mechanistic understanding of the mechanochemical reactivity and selectivity. Time-resolved in situ investigations of milling reactions provide direct insights in the underlying mechanisms.3,4 We recently introduced a setup enabling in situ investigation of mechanochemical reactions using synchrotron XRD combined with Raman spectroscopy (Fig.1a) The specific combination allows to study milling processes comprehensively on the level of the molecular and crystalline structure and thus obtaining reliable data for mechanistic studies. In this talk I will discuss our recent results investigating the formation of (polymorphic) cocrystals.
T2 - CF@Bo2017 Crystal Forms Bologna 2017
CY - Bologna, Italy
DA - 04.06.2017
KW - Mechanochemistry
PY - 2017
AN - OPUS4-43567
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Seidel, R.
A1 - Kraffert, K.
A1 - Kabelitz, Anke
A1 - Pohl, M.N.
A1 - Kraehnert, R.
A1 - Emmerling, Franziska
A1 - Winter, B.
T1 - Detection of the electronic structure of iron-(III)-oxo oligomers forming in aqueous solutions
N2 - The nature of the small iron-oxo oligomers in iron-(III) aqueous solutions has a determining effect on the chemical processes that govern the formation of nanoparticles in aqueous phase. Here we report on a liquid-Jet photoelectron-spectroscopy experiment for the investigation of the electronic structure of the occurring iron-oxo oligomers in FeCl3 aqueous solutions. The only iron species in the as-prepared 0.75 M solution are Fe3+ monomers. Addition of NaOH initiates Fe3+ hydrolysis which is followed by the formation of iron-oxo oligomers. At small enough NaOH concentrations, corresponding to approximately [OH]/[Fe] = 0.2–0.25 ratio, the iron oligomers can be stabilized for several hours without engaging in further aggregation. Here, we apply a combination of non-resonant as well as iron 2p and Oxygen 1s resonant photoelectron spectroscopy from a liquid microjet to detect the electronic structure of the occurring species. Specifically, the oxygen 1s partial electron yield X-ray absorption (PEY-XA) spectra are found to exhibit a peak well below the onset of liquid water and OH (aq) absorption. The iron 2p absorption gives rise to signal centered between the main absorption bands typical for aqueous Fe3+. Absorption bands in both PEY-XA spectra are found to correlate with an enhanced photoelectron Peak near 20 eV binding energy, which demonstrates the sensitivity of resonant photoelectron (RPE) spectroscopy to mixing between iron and ligand orbitals. These various signals from the iron-oxo oligomers exhibit Maximum intensity at [OH]/[Fe] = 0.25 ratio. For the same ratio, we observe changes in the pH as well as in complementary Raman spectra, which can be assigned to the Transition from monomeric to oligomeric species. At approximately [OH]/[Fe] = 0.3 we begin to observe particles larger than 1 nm in radius, detected by small-angle X-ray scattering.
KW - Iron-oxo oligomers
KW - XPS
KW - Electronic structure
PY - 2017
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-433468
SN - 1463-9076
SN - 1463-9084
VL - 19
IS - 48
SP - 32226
EP - 32234
AN - OPUS4-43346
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Joester, Maike
A1 - Seifert, Stephan
A1 - Emmerling, Franziska
A1 - Kneipp, Janina
T1 - Physiological influence of silica on germinating pollen as shown by Raman spectroscopy
N2 - The process of silicification in plants and the biochemical
effects of silica in plant tissues are largely unknown. To
study the molecular changes occurring in growing cells
that are exposed to higher than normal concentration of
silicic acid, Raman spectra of germinating pollen grains of
three species (Pinus nigra, Picea omorika, and Camellia
japonica) were analyzed in a multivariate classification
approach that takes into account the variation of biochemical
composition due to species, plant tissue structure,
and germination condition. The results of principal
component analyses of the Raman spectra indicate differences
in the utilization of stored lipids, a changed mobilization
of storage carbohydrates in the pollen grain bodies,
and altered composition and/or structure of cellulose of
the developing pollen tube cell walls. These biochemical
changes vary in the different species.
KW - Silica
KW - Raman spectroscopy
KW - Principal component analysis
PY - 2017
U6 - https://doi.org/10.1002/jbio.201600011
SN - 1864-063X
SN - 1864-0648
VL - 10
IS - 4
SP - 542
EP - 552
AN - OPUS4-40090
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Joseph, A.
A1 - Bernardes, C. E. S.
A1 - Druzhinina, A. I.
A1 - Varushchenko, R. M.
A1 - Nguyen, Thi Yen
A1 - Emmerling, Franziska
A1 - Yuan, L.
A1 - Dupray, V.
A1 - Coquerel, G.
A1 - Minas da Piedade, M. E.
T1 - Polymorphic phase transition in 4′-hydroxyacetophenone: Equilibrium temperature, kinetic barrier, and the relative stability of Z′=1 and Z′=2 forms
N2 - Particularly relevant in the context of polymorphism is understanding how structural, thermodynamic, and kinetic factors dictate the stability domains of polymorphs, their tendency to interconvert through phase transitions, or their possibility to exist in metastable states. These three aspects were investigated here for two 4′-hydroxyacetophenone (HAP) polymorphs, differing in crystal system, space group, and number and conformation of molecules in the asymmetric unit. The results led to a ΔfGm°-T phase diagram highlighting the enantiotropic nature of the system and the fact that the Z′=1 polymorph is not necessarily more stable than its Z′=2 counterpart. It was also shown that the form II → form I transition is entropy driven and is likely to occur through a nucleation and growth mechanism, which does not involve intermediate phases, and is characterized by a high activation energy. Finally, although it has been noted that conflicts between hydrogen bond formation and close packing are usually behind exceptions from the hypothesis of Z′=1 forms being more stable than their higher Z′ analogues, in this case, the HAP polymorph with stronger hydrogen bonds (Z′=2) is also the one with higher density.
KW - Polymorphism
KW - Polymorphic transition
KW - 4'-hydroxyacetophenone
PY - 2017
U6 - https://doi.org/10.1021/acs.cgd.6b01876
SN - 1528-7483
SN - 1528-7505
VL - 17
IS - 4
SP - 1918
EP - 1932
PB - ACS
AN - OPUS4-40167
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Juribašić, M.
A1 - Halasz, I.
A1 - Budimir, A.
A1 - Užarević, K.
A1 - Lukin, S.
A1 - Monas, A.
A1 - Emmerling, Franziska
A1 - Plavec, J.
A1 - Ćurić, M.
T1 - Reversible Gas−Solid Ammonia N−H Bond Activation Mediated by an Organopalladium Complex
N2 - N−H bond activation of gaseous ammonia is achieved at room temperature in a reversible solvent-free reaction using a solid dicyclopalladated azobenzene complex. Monitoring of the gas−solid reaction in real-time by in situ solid-state Raman spectroscopy enabled a detailed insight into the stepwise activation pathway proceeding to the final amido complex via a stable diammine intermediate. Gas−solid synthesis allowed for isolation and subsequent structural characterization of the intermediate and the final amido product, which presents the first dipalladated complex with the PdII−(μ-NH2)−PdII bridge. Gas−solid reaction is readily followed via color changes associated with conformational switching of the palladated azobenzene backbone. The reaction proceeds analogously in solution and was characterized by UV−vis and NMR spectroscopies showing the same stepwise route to the amido complex. Combining the experimental data with density functional theory calculations we propose a stepwise mechanism of this heterolytic N−H bond activation assisted by exogenous ammonia.
KW - In situ
KW - Mechanochemistry
PY - 2017
U6 - https://doi.org/10.1021/acs.inorgchem.7b00422
VL - 56
SP - 5342
EP - 5351
PB - American Chemical Society
CY - Washington, DC, USA
AN - OPUS4-40464
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Kulla, Hannes
A1 - Greiser, Sebastian
A1 - Benemann, Sigrid
A1 - Rademann, K.
A1 - Emmerling, Franziska
T1 - Knowing When To Stop-Trapping Metastable Polymorphs in Mechanochemical Reactions
N2 - The cocrystal formation of pyrazinamide (PZA) with malonic acid (MA) was studied in situ. The mechanochemical reaction proceeds via conversion of a crystalline intermediate (PZA:MA II) into the thermodynamically more stable form (PZA:MA I) upon further grinding. The information derived from in situ powder X-ray diffraction (PXRD) enabled the isolation of this new metastable polymorph. On the basis of the PXRD data, the crystal structure of the 1:1 cocrystal PZA:MA II was solved. The polymorphs were further characterized and compared by Raman spectroscopy, solid-state NMR spectroscopy, differential thermal analysis/thermogravimetric analysis, and scanning electron microscopy. Our study demonstrates how monitoring mechanochemical reactions by in situ PXRD can direct the discovery and isolation of even short-lived intermediates not yet accessed by conventional methods.
KW - Mechanochemistry
KW - Polymorphs
KW - Metastable
KW - In situ PXRD
KW - Cocrystal
KW - Pyrazinamide
PY - 2017
U6 - https://doi.org/10.1021/acs.cgd.6b01572
SN - 1528-7483
SN - 1528-7505
VL - 17
IS - 3
SP - 1190
EP - 1196
AN - OPUS4-39420
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Fischer, Franziska
A1 - Fendel, Nicole
A1 - Greiser, Sebastian
A1 - Rademann, Klaus
A1 - Emmerling, Franziska
T1 - Impact is important - Systematic investigation of the influence of milling balls in mechanochemical reactions
N2 - A newly established in situ technique using Raman spectroscopy was employed for the detailed kinetic investigation of mechanochemical reaction pathways. This approach was applied for the systematic investigation of the direct influence of colliding balls on the reaction rate constants of a mechanochemical cocrystallization reaction. As a model reaction, the mechanochemical cocrystallization of felodipine and the coformer imidazole was investigated. Keeping the total ball mass constant by varying the number of milling balls, our study reveals that the impact of each single collision has a more significant influence on the reaction kinetics than expected.
KW - Mechanochemistry
KW - In situ
KW - Cocrystal
PY - 2017
UR - http://pubs.acs.org/doi/abs/10.1021/acs.oprd.6b00435
U6 - https://doi.org/10.1021/acs.oprd.6b00435
SN - 1083-6160
SN - 1520-586X
VL - 21
IS - 4
SP - 655
EP - 659
AN - OPUS4-40355
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Kulla, Hannes
A1 - Wilke, Manuel
A1 - Fischer, Franziska
A1 - Röllig, Mathias
A1 - Maierhofer, Christiane
A1 - Emmerling, Franziska
T1 - Warming up for mechanosynthesis – temperature development in ball mills during synthesis
N2 - We present a first direct measurement of the temperature during milling combined with in situ Raman spectroscopy monitoring. The data reveal a low temperature increase due to the mechanical impact and clear temperature increases as a consequence of the reaction heat. Based on the data, temperature rises as postulated in the magma plasma and hot spot theory can be excluded for soft matter milling syntheses.
KW - Thermography
KW - Milling
KW - Mechanochemistry
KW - Soft matter
PY - 2017
U6 - https://doi.org/10.1039/c6cc08950j
SN - 1364-548X
SN - 1359-7345
SN - 0009-241X
VL - 53
IS - 10
SP - 1664
EP - 1667
AN - OPUS4-39251
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Wilke, Manuel
A1 - Bach, S.
A1 - Gorelik, T.
A1 - Kolb, U.
A1 - Tremel, W.
A1 - Emmerling, Franziska
T1 - Divalent metal phosphonates – new aspects for syntheses, in situ characterization and structure solution
N2 - Divalent metal phosphonates are promising hybrid materials with a broad field of application. The rich coordination chemistry of the phosphonate linkers enables the formation of structures with different dimensionalities ranging from isolated complexes and layered structures to porous frameworks incorporating various functionalities through the choice of the building blocks.
In brief, metal phosphonates offer an interesting opportunity for the design of multifunctional materials. Here, we provide a short review on the class of divalent metal phosphonates discussing their syntheses, structures, and applications. We present the advantages of the recently introduced mechanochemical pathway for the Synthesis of divalent phosphonates as a possibility to generate new, in certain cases metastable compounds. The benefits of in situ investigation of synthesis mechanisms as well as the implementation of sophisticated methods for the structure analysis of the resulting compounds are discussed.
KW - Metal phosphonate
KW - Mechanochemistry
PY - 2017
U6 - https://doi.org/10.1515/zkri-2016-1971
SN - 2194-4946
SN - 2196-7105
VL - 232
IS - 1-3
SP - 209
EP - 222
PB - De Gruyter
AN - OPUS4-40003
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Schulz, K.
A1 - Schmack, R.
A1 - Klemm, H. W.
A1 - Kabelitz, Anke
A1 - Schmidt, T.
A1 - Emmerling, Franziska
A1 - Kraehnert, R.
T1 - Mechanism and kinetics of hematite crystallization in air: Linking bulk and surface models via mesoporous films with defined nanostructure
N2 - Iron can form numerous oxides, hydroxides, and oxide−hydroxides. Despite their relevance, many of the transformation processes between these phases are still poorly understood. In particular the crystallization of quasi-amorphous hydroxides and oxide−hydroxides is difficult to assess, since typical diffraction and scattering methods provide only sampleaveraged information about the crystallized phases. We report a new approach for the investigation of the crystallization of oxide−hydroxides. The approach relies on model-type films that comprise a defined homogeneous nanostructure. The nanostructure allows quantitative linking of Information obtained by bulk-averaging diffraction techniques (XRD, SAXS) with locally resolved information, i.e., Domain sizes (SEM, TEM, LEEM) and phase composition (SAED). Using time-resolved imaging and diffraction we deduce mechanism and kinetics for the crystallization of ferrihydrite into hematite. Hematite forms via nucleation of hematite domains and subsequent Domain growth that terminates only upon complete transformation. A Johnson−Mehl−Avrami−Kolmogorov model describes the kinetics over a wide temperature range. The derived understanding enables the first synthesis of ferrihydrite films with ordered mesoporosity and quantitative control over the films’ hematite and ferrihydrite content.
KW - Iron oxide
KW - Crystallization
KW - Mesoporous films
KW - Nanostructure
PY - 2017
U6 - https://doi.org/10.1021/acs.chemmater.6b05185
SN - 0897-4756
SN - 1520-5002
VL - 29
IS - 4
SP - 1724
EP - 1734
AN - OPUS4-39690
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Nguyen, Thi Yen
A1 - Roessler, Ernst
A1 - Rademann, Klaus
A1 - Emmerling, Franziska
T1 - Control of organic polymorph formation: crystallization pathways in acoustically levitated droplets
N2 - Theoretical and experimental studies indicate that crystal nucleation can take more complex pathways than expected on the ground of the classical nucleation theory. Among these pathways are the formation of pre-nucleation clusters and amorphous precursor phases. A direct in situ observation of the different pathways of nucleation from solution is challenging since the paths can be influenced by heterogeneous nucleation sites, such as container walls. Here, we provide insights into the crystallization process using the in situ combination of an acoustic levitator, Raman spectroscopy, and X-ray scattering. The contactless sample holder enables the observation of homogeneous crystallization processes and the detection of intermediates and final crystalline forms. We provide evidence for the existence of multiple pathways of nucleation based on the investigation of the crystallization of organic molecules from different solvents. Starting from a diluted solution, a supersaturation is reached during the experiment due to the evaporation of the solvent. The highly supersaturated solution reveals different pathways of crystallization. Depending on the degree of supersaturation either the thermodynamically stable or the metastable crystal form is observed.
KW - Crystallization
KW - In situ XRD
KW - Polymorphism
KW - Polyamorphism
KW - Raman spectroscopy
PY - 2017
U6 - https://doi.org/10.1515/zkri-2016-1964
SN - 2194-4946
SN - 2196-7105
VL - 232
IS - 1-3
SP - 15
EP - 24
PB - De Gruyter
CY - Berlin
AN - OPUS4-39708
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Dietzsch, Michael
A1 - Andrusenko, Iryna
A1 - Branscheid, Robert
A1 - Emmerling, Franziska
A1 - Kolb, Ute
A1 - Tremel, Wolfgang
T1 - Snapshots of calcium carbonate Formation - a step by step analysis
N2 - Recent advances in our understanding of CaCO, nucleation from solution have provoked new and challenging questions. We have studied CaC03 formation using precipitation by carbonate ester hydrolysis which ensures precipitation from a strictly homogeneous solution state and allows “titrating” carbonate to a solution with a given Ca2+ concentration on a timescale suited for kinetic studies. Nucleation and crystallization were traced by combining dynamic light Scattering (DLS) and transmission electron microscopy (TEM). DLS served as in situ technique to identify the nucleation time, to monitor particle size evolution, to discriminate different precipitation mechanisms and to validate reproducibility. TEM snapshots taken during different stages of the precipitation process identified different phases and morphologies. At a high level of supersaturation homogeneous nucleation in solution led to the formation of amorphous CaC03 particles (diameter=30 nm), which transformed via vaterite to calcite. Nucleation occurred uniformly in solution which appears to be unique for the CaC03 System. In the presence of Na-polymethacrylate (Na-PMA), heterogeneous nucleation was suppressed and Ca-polymer aggregates were formed in the prenucleation stage. Beyond a critical threshold supersaturation CaC03 particles formed in solution outside of these aggregates. The nucleation process resembled that without additive, indicating that Na-PMA exerts only a minor effect on the CaC03 nucleation. In the postnucleation stage, the polymer led to the formation of extended liquid-like networks, which served as a precursor phase for solid ACC particles that formed alongside the network.
KW - biomineralization
KW - calcium carbonate
KW - nucleation
KW - polymer additives
PY - 2017
U6 - https://doi.org/10.1515/zkri-2016-1973
SN - 2194-4946
SN - 2196-7105
VL - 232
IS - 1-3
SP - 255
EP - 265
PB - De Gruyter
CY - Berlin
AN - OPUS4-39863
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Fischer, Franziska
A1 - Emmerling, Franziska
T1 - Synthesen in der Kugelmühle
N2 - Wärme, Licht und Elektrizität sind die typischen Energiequellen chemischer Synthesen. In den letzten Jahren haben sich aber auch mechanische Kräfte etabliert: Mechanochemie braucht kein Lösungsmittel und funktioniert bei Raumtemperatur. Über die zugrundeliegenden Prozesse ist bislang wenig bekannt.
KW - Mechanochemie
PY - 2016
U6 - https://doi.org/10.1002/nadc.20164046717
SN - 1439-9598
SN - 1868-0054
VL - 64
IS - 5
SP - 509
EP - 513
AN - OPUS4-39282
LA - deu
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Wilke, Manuel
A1 - Akhemtova, Irina
A1 - Rademann, K.
A1 - Emmerling, Franziska
T1 - Mechanochemical synthesis of cerium(IV)-phosphonates
N2 - The syntheses and crystal structures of two cerium(IV) phosphonates are presented. Cerium(IV) bis(phenylphosphonate) Ce(O3PC6H5)2 1 can be formed from precipitation and mechanochemical reaction, whereas cerium(IV) bis(carboxymethylphosphonate) monohydrate Ce(O3PCH2COOH)2 H2O 2 is only accessible via ball milling. All reactions proceed very fast and are completed within a short time span. In situ measurements for the syntheses of 1 show that the product occurs within seconds or a few minutes, respectively. The structures were solved from powder X-ray diffraction data.
KW - In situ studies
KW - Mechanochemistry
KW - XRD
PY - 2018
U6 - https://doi.org/10.1007/s10853-018-2507-x
SN - 0022-2461
SN - 1573-4803
VL - 53
IS - 19
SP - 13733
EP - 13741
PB - Springer Science + Business Media B.V.
AN - OPUS4-45672
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Akhmetova, Irina
A1 - Schuzjajew, K.
A1 - Wilke, M.
A1 - de Oliveira Guilherme Buzanich, Ana
A1 - Rademann, K.
A1 - Roth, C.
A1 - Emmerling, Franziska
T1 - Synthesis, characterization and in situ monitoring of the mechanochemical reaction process of two manganese(II)-phosphonates with N-containing ligands
N2 - Two divalent manganese aminophosphonates, manganese mono (nitrilotrimethylphosphonate) (MnNP3) and manganese bis N-(carboxymethyl)iminodi(methylphosphonate)) (Mn(NP2AH)2), have been prepared by mechanochemical synthesis and characterized by powder X-ray diffraction (PXRD). The structure of the novel compound Mn(NP2AH)2 was determined from PXRD data. MnNP3 as well as Mn(NP2AH)2 exhibits a chain-like structure.
In both cases, the manganese atom is coordinated by six oxygen atoms in a distorted octahedron. The local coordination around Mn was further characterized by extended X-ray absorption fine structure. The synthesis process was followed in situ by synchrotron X-ray diffraction revealing a three-step reaction mechanism. The asprepared manganese(II) phosphonates were calcined on air.
All samples were successfully tested for their suitability as catalyst material in the oxygen evolution reaction.
KW - Mechanochemistry
KW - In situ
KW - XRD
PY - 2018
U6 - https://doi.org/10.1007/s10853-018-2608-6
SN - 0022-2461
SN - 1573-4803
VL - 53
IS - 19
SP - 13390
EP - 13399
PB - Springer Science + Business Media B.V.
AN - OPUS4-45673
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Emmerling, Franziska
T1 - In situ studies of mechanochemistry: a force of synthesis
N2 - Recent results in the field of mechanisms and kinetics of mechanochemical reactions.
T2 - Seminar GFZ Potsdam
CY - Postdam, Germany
DA - 28.03.2018
KW - In situ
KW - XRD
KW - Rietveld
PY - 2018
AN - OPUS4-46992
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Emmerling, Franziska
T1 - Synchrotron X-ray Investigations
N2 - Summary of the techniques available at the BAMline and µspot BEamline.
T2 - Workshop Humboldt University and Hebrew University of Jerusalem
CY - Berlin, Germany
DA - 09.10.2018
KW - In situ
KW - XRD
PY - 2018
AN - OPUS4-46993
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Emmerling, Franziska
T1 - New insights in mechanochemical processes using real-time In situ investigations
N2 - Mechanochemistry is a fast and efficient method applicable for the synthesis of new organic[1], metal-organic[2], and inorganic[3] compounds. The direct monitoring of milling reactions is still challenging. The underlying reaction mechanisms remain often unclear. In the last years, have established a tandem in situ approach for investigating mechanochemical reactions using time-resolved in situ XRD coupled with Raman spectroscopy.[4] Here, we present an in situ coupling of synchrotron XRD, Raman spectroscopy, and thermography allowing the observation of mechanochemical reactions in real time.[5] Information on the crystalline, molecular, and temperature state of the materials during grinding could be collected. The chemical composition of the reaction mixture was found to be directly correlated with changes in the temperature profile of the reaction. Furthermore, the presented setup allows the detection of crystalline, amorphous, eutectic as well as liquid intermediates. The resulting deeper kinetic and thermodynamic understanding of milling processes is the key for future optimization of mechanochemical syntheses.
T2 - 5th International Conference "Fundamental Bases of Mechanochemical Technologies"
CY - Novosibirsk, Russia
DA - 25.06.2018
KW - Mechanochemistry
KW - XRD
KW - Kinetic
KW - Coordination polymers
PY - 2018
AN - OPUS4-46994
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Emmerling, Franziska
T1 - In situ characterization of nucleation, growth, crystallization and dissolution of nanoscaled iron oxides
N2 - Nucleation and growths of iorn oxide nanoparticles studied in situ using XRD, XRF, SAXS and XANES.
T2 - International CRC meeting
CY - Berlin, Germany
DA - 10.10.2018
KW - XRD
KW - XANES
PY - 2018
AN - OPUS4-46995
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Emmerling, Franziska
T1 - May the Force be with you - Mechanochemical syntheses studied in situ
N2 - Mechanochemistry is a fast and efficient method applicable for the synthesis of new organic, metal-organic, and inorganic compounds. The direct monitoring of milling reactions is still challenging. The underlying reaction mechanisms remain often unclear. In the last years, have established a tandem in situ approach for investigating mechanochemical reactions using time-resolved in situ XRD coupled with Raman spectroscopy. Here, we present an in situ coupling of synchrotron XRD, Raman spectroscopy, and thermography allowing the observation of mechanochemical reactions in real time. Information on the crystalline, molecular, and temperature state of the materials during grinding could be collected. The chemical composition of the reaction mixture was found to be directly correlated with changes in the temperature profile of the reaction. Furthermore, the presented setup allows the detection of crystalline, amorphous, eutectic as well as liquid intermediates. The resulting deeper kinetic and thermodynamic understanding of milling processes is the key for future optimization of mechanochemical syntheses.
T2 - Seminar Universität Montpellier
CY - Montpellier, France
DA - 24.01.2019
KW - Mechanochemistry
KW - In situ
PY - 2019
AN - OPUS4-47261
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Emmerling, Franziska
T1 - New insights in mechanochemical processes using real-time in situ investigations
N2 - Use of synchrotron radiation for special sample conditions.
Recent work of the group at BESSY II.
T2 - DESY Usermeeting Satelite Workshop
CY - Hamburg, Germany
DA - 22.01.2019
KW - XRD
KW - In situ
KW - Rietveld
KW - Synchrotron
PY - 2019
AN - OPUS4-47262
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Haferkamp, Sebastian
A1 - Fischer, Franziska
A1 - Kraus, Werner
A1 - Emmerling, Franziska
T1 - Mechanochemical Knoevenagel condensation investigated in situ
N2 - The mechanochemical Knoevenagel condensation of malononitrile with p-nitrobenzaldehyde was studied in situ using a tandem approach. X-ray diffraction and Raman spectroscopy were combined to yield time-resolved information on the milling process. Under solvent-free conditions, the reaction leads to a quantitative conversion to p-nitrobenzylidenemalononitrile within 50 minutes. The in situ data indicate that the process is fast and proceeds under a direct conversion. After stopping the milling process, the reaction continues until complete conversion. The continuous and the stopped milling process both result in crystalline products suitable for single crystal X-ray diffraction.
KW - Mechanochemistry
KW - Ball milling
KW - C–C coupling
KW - In situ
KW - Knoevenagel condensation
PY - 2017
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-425388
VL - 13
SP - 2010
EP - 2014
PB - Beilstein-Institut
AN - OPUS4-42538
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Al-Terkawi, Abdal-Azim
A1 - Scholz, G.
A1 - Emmerling, Franziska
A1 - Kemnitz, E.
T1 - Strontium-coordination polymers based on tetrafluorophthalic and phthalic acids: mechanochemical synthesis, ab initio structures determination, and spectroscopic characterization
N2 - Two strontium-based dicarboxylate systems [Sr(oBDC-F4)(H2O)2] (1) and [{Sr(oBDC)(H2O)2)·H2O] (2) were synthesized mechanochemically via milling of Sr(OH)2·8H2O with tetrafluorophthalic acid (H2oBDC-F4) or phthalic acid (H2oBDC), respectively. The new structures were determined ab initio from the powder X-ray diffraction (PXRD) data. Both compounds 1 and 2 crystallize in the monoclinic space group P21 /c as two-dimensional coordination polymers (2D-CPs). The determined structures were validated by extended X-ray absorption (EXAFS) data. Compounds 1 and 2 show different thermal stabilities. The fluorinated CP 1 is decomposed at 300 °C while the nonfluorinated CP 2 transforms into a new phase after thermal treatment at 400 °C. The two hydrated CPs exhibit small surface areas which increase after the thermal posttreatment for 1 but remains unchanged for the dehydrated sample of 2. Dynamic vapor sorption (DVS) experiments indicate that both the dehydrated and hydrated samples of 2 depict no significant differences in their adsorption isotherms. The DVS of water indicates that the phase transition after thermal posttreatment of 2 is irreversible.
KW - Mechanochemistry
KW - XRD
KW - NMR
PY - 2017
U6 - https://doi.org/10.1039/c7dt02564e
SN - 1477-9226
SN - 1477-9234
VL - 46
IS - 37
SP - 12574
EP - 12587
PB - The Royal Society of Chemistry
CY - Cambridge
AN - OPUS4-42261
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Wilke, Manuel
A1 - Kabelitz, Anke
A1 - Zimathies, Annett
A1 - Rademann, K.
A1 - Emmerling, Franziska
T1 - Crystal structure and in situ investigation of a mechanochemical synthesized 3D zinc N-(phosphonomethyl)glycinate
N2 - The mechanochemical synthesis of the zinc N-(phosphonomethyl)glycinate Zn(O₃PCH₂NH₂CH₂CO₂) H₂O is presented. The structure was solved from powder X-ray diffraction (PXRD) data. In the three-dimensional pillared structure, the Zn atoms are coordinated tetrahedrally. In situ investigations of the reaction process with synchrotron PXRD and Raman spectroscopy reveal a two-step process including the formation of an intermediate.
KW - Mechanochemistry
KW - Metal phosphonate
KW - In situ
PY - 2017
U6 - https://doi.org/10.1007/s10853-017-1121-7
SN - 0022-2461
SN - 1573-4803
VL - 52
IS - 20
SP - 12013
EP - 12020
PB - Springer
CY - New York
AN - OPUS4-41490
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Peplinski, Burkhard
A1 - Adamczyk, Burkart
A1 - Formanek, P.
A1 - Meyer, Christian
A1 - Krüger, O.
A1 - Scharf, Holger
A1 - Reinsch, Stefan
A1 - Ostermann, Markus
A1 - Nofz, Marianne
A1 - Jäger, Christian
A1 - Adam, Christian
A1 - Emmerling, Franziska
T1 - Nanocrystalline and stacking-disordered beta-cristobalite AlPO4 chemically stabilized at room temperature: synthesis, physical characterization, and X-ray powder diffraction data
N2 - This paper reports the first successful synthesis and the structural characterization of nanocrystalline and stacking-disordered β-cristobalite AlPO4 that is chemically stabilized down to room temperature and free of crystalline impurity phases. Several batches of the title compound were synthesized and thoroughly characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy, selected area electron diffraction, energy dispersive X-ray spectroscopy mapping in SEM, solid-state 31P nuclear magnetic resonance (31P-NMR) spectroscopy including the TRAPDOR method, differential thermal analysis (DTA), gas-sorption methods, optical Emission spectroscopy, X-ray fluorescence spectroscopy, and ion chromatography. Parameters that are critical for the synthesis were identified and optimized. The synthesis procedure yields reproducible results and is well documented. A high-quality XRD pattern of the title compound is presented, which was collected with monochromatic copper radiation at room temperature in a wide 2θ range of 5°–100°.
KW - Stabilization of high-temperature phase at RT
KW - Nanochrystalline AlPO4
KW - Beta-christobalite structure type
KW - High-cristobalite form
KW - Aluminium phosphate
PY - 2017
U6 - https://doi.org/10.1017/S0885715617000537
SN - 1945-7413
SN - 0885-7156
VL - 32
IS - S1
SP - S193
EP - S200
PB - JCPDS-ICDD
CY - Cambridge
AN - OPUS4-42235
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Santos de Freitas, M.
A1 - Araghi, R. R.
A1 - Brandenburg, E.
A1 - Leiterer, Jork
A1 - Emmerling, Franziska
A1 - Folmert, K.
A1 - Gerling-Driessen, U. I. M.
A1 - Bardiaux, B.
A1 - Böttcher, C.
A1 - Pagel, K.
A1 - Diehl, A.
A1 - v. Berlepsch, H.
A1 - Oschkinat, H.
A1 - Koksch, B.
T1 - The protofilament architecture of a de novo designed coiled coil-based amyloidogenic peptide
N2 - Amyloid fibrils are polymers formed by proteins under specific conditions and in many cases they are related to pathogenesis, such as Parkinson’s and Alzheimer’s diseases. Their hallmark is the presence of a β-sheet structure. High resolution structural data on these systems as well as information gathered from multiple complementary analytical techniques is needed, from both a fundamental and a pharmaceutical perspective. Here, a previously reported de novo designed, pH-switchable coiled coil-based peptide that undergoes structural transitions resulting in fibril formation under physiological conditions has been exhaustively characterized by transmission electron microscopy (TEM), cryo-TEM, atomic force microscopy (AFM), wide-angle X-ray scattering (WAXS) and solid-state NMR (ssNMR). Overall, a unique 2-dimensional carpet-like assembly composed of large coexisiting ribbon-like, tubular and funnel-like structures with a clearly resolved protofilament substructure is observed. Whereas electron microscopy and scattering data point somewhat more to a hairpin model of β-fibrils, ssNMR data obtained from samples with selectively labelled peptides are in agreement with both, hairpin structures and linear arrangements.
KW - Amyloid
KW - Elektronenmikroskopie
PY - 2018
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-458713
UR - https://www.sciencedirect.com/science/article/pii/S1047847718301333
SN - 1047-8477
VL - 203
IS - 3
SP - 263
EP - 272
PB - Elsevier
AN - OPUS4-45871
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Emmerling, Franziska
T1 - Mechanochemical Syntheses of Metal Phosphonates
N2 - Mechanochemistry is a suitable method for synthesizing a variety of metal phosphonates. By varying the ratio of the reactants, it is possible to control the reaction pathway. With this approach targeted synthesis of a certain composition is possible. Several new metal phosphonate structures were solved from the powder X-ray diffraction data including molecular metal phosphonates. The results demonstrate a new fast, facile, and environmental friendly alternative for the preparation of metal phosphonates. In situ investigations of the milling processes provided insights into the formation process of metal phosphonates. A multi-step diffusion mechanism was identified for most systems. Crystalline phases were obtained intermediately, suggesting that the synthesis is following Ostwald’s rules of stages.
T2 - 1st European Workshop on Metalphophantes
CY - Swanse, UK
DA - 18.09.2018
KW - Mechanochemistry
PY - 2018
AN - OPUS4-46382
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Emmerling, Franziska
T1 - Mechanistic investigations of mechanosyntheses
N2 - Mechanochemistry is a fast and efficient method applicable for the synthesis of new organic, metal-organic, and inorganic compounds. The direct monitoring of milling reactions is still challenging. The underlying reaction mechanisms often remain unclear. In the last years, we have established a tandem in situ approach for investigating mechanochemical reactions using time-resolved in situ XRD coupled with Raman spectroscopy. A further development is the in situ coupling of synchrotron XRD, Raman spectroscopy, and thermography allowing the observation of mechanochemical reactions in real time. [5] Information on the crystalline, molecular, and temperature state of the materials during grinding could be collected. The chemical composition of the reaction mixture was found to be directly correlated with changes in the temperature profile of the reaction. Furthermore, the presented setup allows the detection of crystalline, amorphous, eutectic as well as liquid intermediates. Based on these data, metastable polymorphs of cocrystals and coordination polymorphs could be isolated and struc-turally characterized. A multi-step diffusion mechanism was identified for most systems. Crystalline phases were obtained intermediately, suggesting that the synthesis is following Ostwald’s rules of stages. The resulting deeper kinetic and thermodynamic understanding of milling processes is the key for future optimization of mechanochemical syntheses.
T2 - Beilstein Symposium MECHANOCHEMISTRY: MICROSCOPIC AND MACROSCOPIC ASPECTS
CY - Rüdesheim, Germany
DA - 13.11.2018
KW - Mechanochemistry
KW - Phosphonates
KW - In situ
PY - 2018
AN - OPUS4-46758
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Simoes, R.
A1 - Bernades, C.
A1 - Joseph, A.
A1 - Piedade, F.
A1 - Kraus, Werner
A1 - Emmerling, Franziska
A1 - Diogo, H.
A1 - da Piedade, M.
T1 - Polymorphism in simvastatin: Twinning, disorder, and enantiotropic phase transitions
N2 - : Simvastatin is one of the most widely used active pharmaceutical ingredients for the treatment of hyperlipidemias. Because the compound is employed as a solid in drug formulations, particular attention should be given to the characterization of different polymorphs, their stability domains, and the nature of the phase transitions that relate them. In this work, the phase transitions delimiting the stability domains of three previously reported simvastatin forms were investigated from structural, energetics, and dynamical points of view based on single crystal X-ray diffraction (SCXRD), hot stage microscopy (HSM), and differential scanning calorimetry (DSC) experiments (conventional scans and heat capacity measurements), complemented with molecular dynamics (MD) simulations. Previous assignments of the crystal forms were confirmed by SCXRD: forms I and II were found to be orthorhombic (P212121, Z′/Z = 1/4) and form III was monoclinic (P21, Z′/Z = 2/4). The obtained results further indicated that (i) the transitions between different forms are observed at 235.9 ± 0.1 K (form III → form II) and at 275.2 ± 0.2 K (form II → form I) in DSC runs carried out at 10 K min−1 and close to these values when other types of techniques are used (e.g., HSM). (ii) They are enantiotropic (i.e., there is a transition temperature relating the two phases before fusion at which the stability order is reversed), fast, reversible, with very little hysteresis between heating and cooling modes, and occur under single crystal to single crystal conditions. (iii) A nucleation and growth mechanism seems to be followed since HSM experiments on single crystals evidenced the propagation of an interface, accompanied by a change of birefringence and crystal contraction or expansion (more subtle in the case of form III → form II), when the phase transitions are triggered. (iv) Consistent with the reversible and small hysteresis nature of the phase transitions, the SCXRD results indicated that the molecular packing is very similar in all forms and the main structural differences are associated with conformational changes of the “ester tail”. (v) The MD simulations further suggested that the tail is essentially “frozen” in two conformations below the III → II transition temperature, becomes progressively less hindered throughout the stability domain of form II, and acquires a large conformational freedom above the II → I transition. Finally, the fact that these transitions were found to be fast and reversible suggests that polymorphism is unlikely to be a problem for pharmaceutical formulations employing crystalline simvastatin because, if present, the III and II forms will readily convert to form I at ambient temperature.
KW - Polymorphism
KW - Twinning
KW - Disorder
KW - Simvastatine
PY - 2018
U6 - https://doi.org/10.1021/acs.molpharmaceut.8b00818
SN - 1543-8384
SN - 1543-8392
VL - 15
IS - 11
SP - 5349
EP - 5360
PB - American Chemical Society
CY - Washington, DC
AN - OPUS4-46927
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Emmerling, Franziska
A1 - Tumanov, N.
A1 - Tumanova, N.
A1 - Fischer, Franziska
A1 - Morelle, F.
A1 - Ban, V.
A1 - Robeyns, K.
A1 - Filinchuk, Y.
A1 - Wouters, J.
A1 - Leyssens, T.
T1 - Exploring polymorphism and stoichiometric diversity in naproxen/proline cocrystals
N2 - We present naproxen/proline cocrystals discovered when combining enantiopure and racemic naproxen and proline. Using liquid-assisted grinding as the main method to explore the variety of crystal forms in this system, we found 17 cocrystals, of which the structures of only four of them were previously known. The naproxen/proline system exhibited multiple polymorphs of 1 : 1 stoichiometry as well as more rare cocrystals with 1 : 2 and 2 : 3 stoichiometries, two cocrystal hydrates and one cocrystal solvate. In situ ballmilling, used to monitor liquid-assisted grinding reactions, revealed that the solvent dictates the reaction intermediates even if the final reaction product stays the same. Synchrotron X-ray diffraction data collected in situ upon heating allowed us to monitor directly the phase changes upon heating and gave access to pure diffraction patterns of several cocrystals, thus enabling their structure determination from powder X-ray diffraction data; this method also confirmed the formation of a conglomerate in the RS-naproxen/DL-proline system. Proline in cocrystals kept its ability to form charge-assisted head-to-tail
N-H⋯O hydrogen bonds, typical of pure crystalline amino acids, thus increasing the percentage of strong chargeassisted interactions in the structure and consequently providing some of the cocrystals with higher melting points as compared to pure naproxen. The majority of drugs are chiral, and hence, these data are of importance to the pharmaceutical industry as they provide insight into the challenges of chiral cocrystallization.
KW - In situ
KW - Mechanochemistry
KW - XRD
PY - 2018
UR - https://pubs.rsc.org/en/Content/ArticleLanding/CE/2018/C8CE01338A#!divAbstract
U6 - https://doi.org/10.1039/c8ce01338a
SN - 1466-8033
VL - 20
IS - 45
SP - 7308
EP - 7321
PB - Royal Society of Chemistry
CY - London
AN - OPUS4-46913
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Emmerling, Franziska
T1 - In-situ investigations of mechanochemical reactions
N2 - Mechanochemistry is a fast and efficient method applicable for the synthesis of new organic[1], metal-organic[2], and inorganic[3] compounds. The direct monitoring of milling reactions is still challenging. The underlying reaction mechanisms remain often unclear. In the last years, have established a tandem in situ approach for investigating mechanochemical reactions using time-resolved in situ XRD coupled with Raman spectroscopy.[4] Here, we present an in situ coupling of synchrotron XRD, Raman spectroscopy, and thermography allowing the observation of mechanochemical reactions in real time.[5] Information on the crystalline, molecular, and temperature state of the materials during grinding could be collected. The chemical composition of the reaction mixture was found to be directly correlated with changes in the temperature profile of the reaction. Furthermore, the presented setup allows the detection of crystalline, amorphous, eutectic as well as liquid intermediates. The resulting deeper kinetic and thermodynamic understanding of milling processes is the key for future optimization of mechanochemical syntheses.
T2 - ACS Conference Boston
CY - Boston, USA
DA - 19.08.2018
KW - Mechanochemistry
KW - In situ
KW - Kinetic
PY - 2018
AN - OPUS4-46989
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Emmerling, Franziska
T1 - New insights in mechanochemical processes using real-time in situ investigations
N2 - Mechanochemistry is increasingly used for synthesizing various materials including metal organic compounds and cocrystals. Although this synthesis approach offers a fast and pure synthesis in high yields, there is a lack in understanding the mechanisms of milling reactions. The necessary data can only be obtained in in situ experiments, which were only recently established for milling reactions. Herein, we present a novel setup enabling a combined in situ investigation of mechanochemical reactions using synchrotron XRD and Raman spectroscopy.
T2 - ECM31
CY - Oviedo, Spain
DA - 18.08.2018
KW - Mechanochemistry
KW - In situ
PY - 2018
AN - OPUS4-46990
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Emmerling, Franziska
T1 - In situ investigations of mechanochemical reactions
N2 - Presentation of the recent results in the context of in situ investigations of reactions using X-ray diffraction.
T2 - Germany Brazil Workshop: New light on mechanisms of chemical reactions
CY - Kiel, Germany
DA - 31.07.2018
KW - In situ
KW - XRD
PY - 2018
AN - OPUS4-46991
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Al-Terkawi, Abdal-Azim
A1 - Scholz, G.
A1 - de Oliveira Guilherme Buzanich, Ana
A1 - Reinsch, Stefan
A1 - Kemnitz, E.
A1 - Emmerling, Franziska
T1 - Ca- and Sr- tetrafluoroisophthalates: mechanochemical synthesis, characterization, and ab initio structure determination
N2 - New fluorinated coordination polymers were prepared mechanochemically by milling the alkaline earth metal hydroxides MII(OH)2·xH2O (MII: Ca, Sr) with tetrafluoroisophthalic acid (H2mBDC-F4). The structures of [{Ca(mBDC-F4)(H2O)2}·H2O] and [{Sr(mBDC-F4)(H2O)2}·H2O] were determined based on ab initio calculations and their powder X-ray diffraction (PXRD) data. The compounds are isomorphous and crystallize in the orthorhombic space group P212121. The determined structures were validated by using extended X-ray absorption (EXAFS) data. The new materials were thoroughly characterized using elemental analysis, thermal analysis, magic angle spinning NMR, and attenuated total reflection-infrared spectroscopy. Further characterization methods such as BET, dynamic vapor sorption, and scanning electron microscopy imaging were also used. Our investigations indicate that mechanochemistry is an efficient method for preparing such materials.
KW - Mechanochemistry
KW - In situ
KW - XRD
KW - Coordination polymers
PY - 2017
UR - http://pubs.rsc.org/-/content/articlehtml/2017/dt/c7dt00734e
U6 - https://doi.org/10.1039/c7dt00734e
VL - 46
IS - 18
SP - 6003
EP - 6012
AN - OPUS4-41516
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Matoga, D.
A1 - Roztocki, K.
A1 - Wilke, Manuel
A1 - Emmerling, Franziska
A1 - Oszajca, M.
A1 - Fitta, M.
A1 - Bałanda, M.
T1 - Crystalline bilayers unzipped and rezipped: solid-state reaction cycle of a metal–organic framework with triple rearrangement of intralayer bonds
N2 - We present a series of remarkable structural transformations for a family of layered metal–organic frameworks (MOFs) in a three-step solid-state reaction cycle. The cycle represents new dynamic behavior of 2D coordination polymers and involves the sequence of reactions: {[Mn2(ina)4(H2O)2]·2EtOH}n (JUK-1) → {(NH4)2[Mn(ina)2(NCS)2]}n·xH2O (JUK-2) → {[Mn2(ina)2(Hina)2(NCS)2]}n (JUK-3) → JUK-1 (Hina = isonicotinic acid), each accompanied by rearrangement of intralayer coordination bonds and each induced by a different external stimulus. In situ investigation of the first step of the cycle by combined synchrotron X-ray diffraction and Raman spectroscopy reveals direct mechanochemical unzipping of JUK-1 bilayers to respective JUK-2 layers with reaction rates dependent on the milling conditions. In contrast, the reverse zipping of JUK-2 layers involves two steps and proceeds through a new MOF (JUK-3) whose structure was elucidated by powder X-ray diffraction. Magnetic measurements confirm conversions of manganese nodes in the reaction cycle. The findings indicate the possibility of developing coordination-based assemblies with large structural responses for use in smart stimuli-responsive systems and sensor technologies.
KW - Mechanochemistry
KW - In situ
KW - XRD
KW - MOF
PY - 2017
UR - http://pubs.rsc.org/is/content/articlehtml/2017/ce/c7ce00655a
U6 - https://doi.org/10.1039/C7CE00655A
VL - 19
SP - 2987
EP - 2995
AN - OPUS4-41517
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Kulla, Hannes
A1 - Fischer, Franziska
A1 - Benemann, Sigrid
A1 - Rademann, K.
A1 - Emmerling, Franziska
T1 - The effect of the ball to reactant ratio on mechanochemical reaction times studied by in situ PXRD
N2 - The effect of the reactant powder mass on reaction times for the mechanochemical formation of a soft matter model system was studied by in situ PXRD. The syntheses were performed at a constant ball mass in a shaker mill with and without glassy SiO2 as an inert additive. Reaction times decreased with the increase of the ball to reactant ratio (BRR). The kinetic influence of the SiO2 powder was excluded. The decrease in the reaction time with decreasing mass of reactants was related to the rise in the stress energy transferred to the powder by a higher ball impact. The BRR had no effect on the induction time. But the product conversion was accelerated by raising the BRR. While a certain temperature is needed for the activation of reactants in the induction phase, the conversion of soft matter reactants is rather controlled by impact than temperature.
KW - XRD
KW - Mechanochemistry
PY - 2017
UR - http://pubs.rsc.org/en/content/articlehtml/2017/ce/c7ce00502d
U6 - https://doi.org/10.1039/c7ce00502d
VL - 19
IS - 28
SP - 3902
EP - 3907
AN - OPUS4-41197
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Grunert, B.
A1 - Saatz, Jessica
A1 - Hoffmann, Katrin
A1 - Appler, F.
A1 - Lubjuhn, Dominik
A1 - Jakubowski, Norbert
A1 - Resch-Genger, Ute
A1 - Emmerling, Franziska
A1 - Briel, A.
T1 - Multifunctional rare-earth element nanocrystals for cell labeling and multimodal imaging
N2 - In this work, we describe a simple solvothermal route for the synthesis of Eu3+-doped gadolinium orthovanadate nanocrystals (Eu:GdVO4−PAA) functionalized with poly(acrylic)acid (PAA), that are applicable as cell labeling probes for multimodal cellular imaging. The Eu3+ doping of the vanadate matrix provides optical functionality, due to red photoluminescence after illumination with UV light. The Gd3+ ions of the nanocrystals reduce the T1 relaxation time of surrounding water protons, allowing these nanocrystals to act as a positive MRI contrast agent with a r1 relaxivity of 1.97 mM−1 s−1. Low background levels of Eu3+, Gd3+, and V5+ in biological systems make them an excellent label for elemental microscopy by Laser Ablation (LA)-ICP-MS. Synthesis resulted in polycrystalline nanocrystals with a hydrodynamic diameter of 55 nm and a crystal size of 36.7 nm, which were further characterized by X-ray diffraction (XRD), photoluminescence spectroscopy (PL) and transmission electron microscopy (TEM). The multifunctional nanocrystals were subsequently used for intracellular labeling of both human adipose-derived stem cells (MSCs) and A549 (adenocarcinomic human alveolar basal epithelial) cells.
KW - Bioimaging
KW - Nanoparticle
KW - Multimodal
KW - Lanthanide
PY - 2018
U6 - https://doi.org/10.1021/acsbiomaterials.8b00495
SN - 2373-9878
VL - 4
IS - 10
SP - 3578
EP - 3587
PB - ACS Publications
CY - Washington, USA
AN - OPUS4-46244
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Haferkamp, Sebastian
A1 - Emmerling, Franziska
A1 - Akhmetova, Irina
A1 - Kulla, Hannes
A1 - Rademann, K.
T1 - In situ investigations of mechanochemical reactions
N2 - Mechanochemistry paves the way to simple, fast, and green syntheses. Despite considerable effort, there remains a lack in understanding of the underlying mechanisms. In situ investigations help to understand these mechanisms, which occur during a mechanochemical reaction. Here we present a universal strategy for simultaneous real-time in situ analysis, combining X-ray diffraction, Raman spectroscopy, and thermography. The potential of our approach is shown for different model reactions.
T2 - ANAKON 2019
CY - Münster, Germany
DA - 25.03.2019
KW - In situ
KW - Mechanochemistry
KW - Milling
PY - 2019
AN - OPUS4-47701
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Stroh, Julia
A1 - Ali, Naveed Zafar
A1 - Maierhofer, Christiane
A1 - Emmerling, Franziska
T1 - Ettringite via Mechanochemistry: A Green and Rapid Approach for Industrial Application
N2 - Here, we report on a first mechanochemical synthesis of ettringite, an important cement hydrate phase. The mineral compound ettringite ([Ca3Al(OH)6]2·(SO4)3·26H2O) occurs rarely in nature, but is common for cement-based materials. Ettringite has wide technical application in the ceramic and paper industry. However, its typical wet-chemical synthesis is cumbersome and produces waste water and CO2 emissions. Here, we investigate the first mechanochemical synthesis of ettringite for developing an easy and sustainable alternative for industrial application. The mechanosynthesis was monitored in situ by coupled synchrotron X-ray diffraction (XRD) and infrared thermography (IRT). The consumption of the reactants and the formation of the reaction product were monitored with time-resolved XRD. IRT showed the temperature increase based on the exothermic reaction. The reaction conversion was significantly improved changing the strategy of the mechanosynthesis from a one- to a two-step process. The latter included neat pregrinding of solid reactants followed by a delayed addition of the stoichiometric amount of water. Thus, an increase of reaction conversion from 34 to 94% of ettringite could be achieved.
KW - XRD
KW - Mechanochemistry
KW - Ettringite
KW - In situ
PY - 2019
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-479016
SN - 2470-1343
VL - 4
IS - 4
SP - 7734
EP - 7737
PB - ACS Publications
CY - Washington, DC
AN - OPUS4-47901
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Surov, Artem O.
A1 - Vasilev, Nikita A.
A1 - Churakov, Andrei V.
A1 - Stroh, Julia
A1 - Emmerling, Franziska
A1 - Perlovich, German L.
T1 - Solid Forms of Ciprofloxacin Salicylate: Polymorphism, Formation Pathways, and Thermodynamic Stability
N2 - The crystallization of ciprofloxacin - an antibacterial fluoroquinolone compound - with salicylic acid resulted in the isolation of five distinct solid forms of the drug, namely, an anhydrous salt, two polymorphic forms of the salt monohydrate, methanol and acetonitrile solvates, and the salt-cocrystal hydrate. The salicylate salts were investigated by different analytical techniques ranging from powder and single crystal X-ray diffractometry, differential scanning calorimetry, thermogravimetric analysis, variable temperature powder X-ray diffraction, dynamic vapor sorption analysis, dissolution, and solubility investigations. Real-time in situ Raman spectroscopy was used to investigate the mechanochemical formation pathways of the different solid polymorphs of ciprofloxacin salicylate. The mechanism of the phase transformation between the crystalline forms was evaluated under mechanochemical conditions. It was found that the formation pathway and kinetics of the grinding process depend on the form of the starting material and reaction conditions. The analysis of the solid-state thermal evolution of the hydrated salts revealed the two-step mechanism of dehydration process, which proceeds through a formation of the distinct intermediate crystalline products.
KW - Cocrystal
KW - Polymorphism
KW - Ciprofloxacin
KW - XRD
KW - DSC
PY - 2019
U6 - https://doi.org/10.1021/acs.cgd.9b00185
SN - 1528-7483
VL - 19
IS - 5
SP - 2979
EP - 2990
PB - American Chemical Society
AN - OPUS4-47903
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Scheurrell, Kerstin
A1 - B. Martins, Inês C.
A1 - Murray, Claire
A1 - Emmerling, Franziska
T1 - Exploring the role of solvent polarity in mechanochemical Knoevenagel condensation: in situ investigation and isolation of reaction intermediates
N2 - Mechanochemistry has proven to be a highly effective method for the synthesis of organic compounds. We studied the kinetics of the catalyst-free Knoevenagel reaction between 4-nitrobenzaldehyde and malononitrile, activated and driven by ball milling. The reaction was investigated in the absence of solvents (neat grinding) and in the presence of solvents with different polarities (liquid-assisted grinding). The reaction was monitored using time-resolved in situ Raman spectroscopy and powder X-ray diffraction (PXRD). Our results indicate a direct relationship between solvent polarity and reaction kinetics, with higher solvent polarity leading to faster product (2-(4-nitrobenzylidone)malononitrile) formation. For the first time, we were able to isolate and determine the structure of an intermediate 2-(hydroxy(4-nitrophenyl)methyl)malononitrile based on PXRD data.
KW - Physical and Theoretical Chemistry
KW - General Physics and Astronomy
PY - 2023
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-588071
SN - 1463-9076
VL - 25
IS - 35
SP - 23637
EP - 23644
PB - Royal Society of Chemistry (RSC)
AN - OPUS4-58807
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Manoharan, Deepak
A1 - Ahmad, Shamim
A1 - Tothadi, Srinu
A1 - Emmerling, Franziska
A1 - Bhattacharya, Biswajit
A1 - Ghosh, Soumyajit
T1 - Linker size dependent mechanical properties of di-imine based molecular crystals
N2 - We have demonstrated the ability to modify the mechanical flexibility of molecular crystals by modulating the length of intervening linker moieties while keeping the terminal shape synthons the same.
KW - Mechanically flexible molecular crystals
KW - Mechanical properties
KW - Crystal Engineering
PY - 2023
U6 - https://doi.org/10.1039/D3CE00928A
SN - 1466-8033
SP - 1
EP - 8
PB - RSC
CY - London
AN - OPUS4-58836
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Bhattacharya, Biswajit
A1 - Akhmetova, Irina
A1 - Rautenberg, Max
A1 - Emmerling, Franziska
T1 - Mechanochemical synthesis of phosphonate-based proton conducting metal organic frameworks and hydrogen-bonded metal phosphonates
N2 - Proton exchange membrane fuel cells (PEMFCs) are one of the most promising alternative green energy technologies that deliver high energy density without CO2 emissions. The proton conductivity of proton exchange membranes (PEM) contributes to the overall efficiency of a PEMFC. Materials being used as PEMs must exhibit high proton conductivity at the working conditions of the targeted PEMFC. To date, Nafion and Nafion-like polymers with acidic functionality are widely used as membrane materials due to their high proton conductivity in the range of 10-1 to 10-2 Scm-1 at higher relative humidity. However, these materials suffer from high costs, hazardous production process, and poor performance at high temperatures, limiting their versatility.
In this context, crystalline porous materials are recognized as promising proton conductors for the proton exchange membrane (PEM) in fuel cell technology, owing to their tunable framework structure. However, it is still challenging bulk synthesis for real-world applications of these materials. Herein, we present mechanochemical gram-scale synthesis of series of mixed ligand metal organic frameworks (MOFs) and metal hydrogen‐bonded organic frameworks (MHOFs) using phenylene diphosphonic acid and 1-hydroxyethylidene-1,1-diphosphonic acid with different bipyridyl type of ligands, respectively. In all cases, the existence of extensive hydrogen bonds with amphiprotic uncoordinated phosphonate hydroxyl and oxygen atoms, the frameworks exhibited high proton conductivity. The study demonstrates the potential of green mechanosynthesis for preparations of framework-based proton conducting materials in bulk scale for green energy generation.
T2 - 4th International Conference on Phosphonate Chemistry, Science and Technology, ICOPHOS-4
CY - Crete, Greece
DA - 02.10.2023
KW - Proton exchange membrane fuel cells
KW - Metal organic frameworks
KW - Proton conducting materials
PY - 2023
AN - OPUS4-58837
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - de Oliveira Guilherme Buzanich, Ana
A1 - Cakir, Cafer Tufan
A1 - Radtke, Martin
A1 - Haider, M. Bilal
A1 - Emmerling, Franziska
A1 - F. M. Oliveira, P.
A1 - Michalchuk, Adam A. L.
T1 - Dispersive x-ray absorption spectroscopy for time-resolved in situ monitoring of mechanochemical reactions
N2 - X-ray absorption spectroscopy (XAS) provides a unique, atom-specific tool to probe the electronic structure of solids. By surmounting long-held limitations of powder-based XAS using a dynamically averaged powder in a Resonant Acoustic Mixer (RAM), we demonstrate how time-resolved in situ (TRIS) XAS provides unprecedented detail of mechanochemical synthesis. The use of a custom-designed dispersive XAS (DXAS) setup allows us to increase the time resolution over existing fluorescence measurements from ∼15 min to 2 s for a complete absorption spectrum. Hence, we here establish TRIS-XAS as a viable method for studying mechanochemical reactions and sampling reaction kinetics. The generality of our approach is demonstrated through RAM-induced (i) bottom-up Au nanoparticle mechanosynthesis and (ii) the synthesis of a prototypical metal organic framework, ZIF-8. Moreover, we demonstrate that our approach also works with the addition of a stainless steel milling ball, opening the door to using TRIS-DXAS for following conventional ball milling reactions. We expect that our TRIS-DXAS approach will become an essential part of the mechanochemical tool box.
KW - In situ studies
KW - Dipsersive XAS
KW - Mechanochemistry
KW - Time-resolved
PY - 2022
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-567659
SN - 1089-7690
VL - 157
IS - 21
SP - 1
EP - 12
PB - American Institute of Physics
CY - Melville, NY
AN - OPUS4-56765
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Cakir, Cafer Tufan
A1 - Piotrowiak, T.
A1 - Reinholz, Uwe
A1 - Ludwig, A.
A1 - Emmerling, Franziska
A1 - Streli, C.
A1 - de Oliveira Guilherme Buzanich, Ana
A1 - Radtke, Martin
T1 - Exploring the Depths of Corrosion: A Novel GE-XANES Technique for Investigating Compositionally Complex Alloys
N2 - In this study, we propose the use of nondestructive, depth-resolved, element-specific characterization using grazing exit X-ray absorption near-edge structure spectroscopy (GE-XANES) to investigate the corrosion process in compositionally complex alloys (CCAs). By combining grazing exit X-ray fluorescence spectroscopy (GE-XRF) geometry and a pnCCD detector, we provide a scanning-free, nondestructive, depth-resolved analysis in a sub-micrometer depth range, which is especially relevant for layered materials, such as corroded CCAs. Our setup allows for spatial and energy-resolved measurements and directly extracts the desired fluorescence line, free from scattering events and other overlapping lines. We demonstrate the potential of our approach on a compositionally complex CrCoNi alloy and a layered reference sample with known composition and specific layer thickness. Our findings indicate that this new GE-XANES approach has exciting opportunities for studying surface catalysis and corrosion processes in real-world materials.
KW - Degradation mechanisms
KW - Grazin exit XANES
KW - Depth resolved XANES
KW - Compositional complex alloys
KW - Corrosion
PY - 2023
U6 - https://doi.org/10.1021/acs.analchem.3c00404
VL - 95
SP - 4810
EP - 4818
PB - ACS Publications
AN - OPUS4-57823
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - de Oliveira Guilherme Buzanich, Ana
A1 - Radtke, Martin
A1 - Yusenko, Kirill
A1 - Stawski, Tomasz
A1 - Kulow, Anicó
A1 - Cakir, Cafer Tufan
A1 - Röder, Bettina
A1 - Naese, Christoph
A1 - Britzke, Ralf
A1 - Sintschuk, Michael
A1 - Emmerling, Franziska
T1 - BAMline - A real-life sample materials research beamline
N2 - With increasing demand and environmental concerns, researchers are exploring new materials that can perform as well or better than traditional materials while reducing environmental impact. The BAMline, a real-life sample materials research beamline, provides unique insights into materials’ electronic and chemical structure at different time and length scales. The beamline specializes in x-ray absorption spectroscopy, x-ray fluorescence spectroscopy, and tomography experiments. This enables real-time optimization of material properties and performance for various applications, such as energy transfer, energy storage, catalysis, and corrosion resistance. This paper gives an overview of the analytical methods and sample environments of the BAMline, which cover non-destructive testing experiments in materials science, chemistry, biology, medicine, and cultural heritage. We also present our own synthesis methods, processes, and equipment developed specifically for the BAMline, and we give examples of synthesized materials and their potential applications. Finally, this article discusses the future perspectives of the BAMline and its potential for further advances in sustainable materials research.
KW - Extended X-ray absorption fine structure
KW - Energy storage
KW - Environmental impacts
KW - Nondestructive testing techniques
KW - X-ray fluorescence spectroscopy
KW - Corrosion
KW - Near edge X-ray absorption fine structure spectroscopy
KW - X-ray absorption spectroscopy
PY - 2023
U6 - https://doi.org/10.1063/5.0157194
VL - 158
IS - 24
SP - 1
EP - 22
PB - AIP Publishing
AN - OPUS4-57824
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Bhattacharya, Biswajit
A1 - Michalchuk, Adam A. L.
A1 - Silbernagl, Dorothee
A1 - Yasuda, N.
A1 - Feiler, Torvid
A1 - Sturm, Heinz
A1 - Emmerling, Franziska
T1 - An atomistic mechanism for elasto-plastic bending in molecular crystals
N2 - Mechanically flexible single crystals of molecular materials offer potential for a multitude of new directions in advanced materials design. Before the full potential of such materials can be exploited, insight into their mechanisms of action must be better understood. Such insight can be only obtained through synergistic use of advanced experimentation and simulation. We herein report the first detailed mechanistic study of elasto-plastic flexibility in a molecular solid. An atomistic origin for this mechanical behaviour is proposed through a combination of atomic force microscopy, μ-focus synchrotron X-ray diffraction, Raman spectroscopy, ab initio simulation, and computed elastic tensors. Our findings suggest that elastic and plastic bending are intimately linked and result from extensions of the same molecular deformations. The proposed mechanism bridges the gap between contested mechanisms, suggesting its applicability as a general mechanism for elastic and plastic bending in organic molecular crystals.
KW - Mechanical property
KW - Mechanical flexibility
KW - Organic crystal
PY - 2023
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-577722
SN - 2041-6520
VL - 14
IS - 13
SP - 3441
EP - 3450
PB - Royal Society of Chemisty (RSC)
CY - London/Cambridge
AN - OPUS4-57772
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Manoharan, D.
A1 - Megha, S. N.
A1 - Kiran, M. S. R. N.
A1 - Emmerling, Franziska
A1 - Bhattacharya, Biswajit
A1 - Ghosh, S.
T1 - Designing the Mechanical Plasticity of Benzylidene Indanones Based Molecular Crystals by Crystal Engineering
N2 - Mechanically flexible molecular crystals have important implications in flexible optoelectronics, optical waveguides, etc. We report a series of 2-benzylidene 1-indanone based plastic crystals. Moreover, we have shown how plasticity can be fine-tuned through controlling intermolecular interactions.
KW - Mechanical flexibility
KW - Organic crystal
KW - Mechanical property
PY - 2023
U6 - https://doi.org/10.1021/acs.cgd.2c01137
SN - 1528-7483
VL - 23
SP - 657
EP - 661
PB - ACS Publications
AN - OPUS4-57773
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Rautenberg, Max
A1 - Akhmetova, Irina
A1 - Das, Chayanika
A1 - Bhattacharya, Biswajit
A1 - Emmerling, Franziska
T1 - Synthesis and In Situ Monitoring of Mechanochemical Preparation of Highly Proton Conductive Hydrogen-Bonded Metal Phosphonates
N2 - Crystalline porous materials are recognized as promising proton conductors for the proton exchange membrane (PEM) in fuel cell technology owing to their tunable framework structure. However, it is still a challenging bulk synthesis for real-world applications of these materials. Herein, we report the mechanochemical gram-scale synthesis of two isostructural metal hydrogen-bonded organic frameworks (MHOFs) of Co(II) and Ni(II) based on 1-hydroxyethylidenediphosphonic acid (HEDPH4) with 2,2′-bipyridine (2,2′-bipy): Co(HEDPH3)2(2,2′-bipy)·H2O (1) and Ni(HEDPH3)2(2,2′-bipy)·H2O (2). In situ monitoring of the mechanochemical synthesis using different synchrotron-based techniques revealed a one-step mechanism – the starting materials are directly converted to the product. With the existence of extensive hydrogen bonds with amphiprotic uncoordinated phosphonate hydroxyl and oxygen atoms, both frameworks exhibited proton conduction in the range of 10–4 S cm–1 at room temperature under humid conditions. This study demonstrates the potential of green mechanosynthesis for bulk material preparation of framework-based solid-state proton conductors.
KW - Mechanochemistry
KW - Proton conductivity
KW - Metal Organic Frameworks
PY - 2023
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-577777
VL - 8
IS - 19
SP - 16687
EP - 16693
PB - ACS Publications
AN - OPUS4-57777
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Karafiludis, Stephanos
A1 - de Oliveira Guilherme Buzanich, Ana
A1 - Heinekamp, Christian
A1 - Smales, Glen Jacob
A1 - Hodoroaba, Vasile-Dan
A1 - ten Elshof, J. E.
A1 - Emmerling, Franziska
A1 - Stawski, Tomasz
T1 - Template-free synthesis of mesoporous, amorphous transition metal phosphate materials
N2 - We present how mesoporosity can be engineered in transition metal phosphate (TMPs) materials in a template-free manner. The method involves a transformation of a precursor metal phosphate phase, called M-struvite (NH4MPO4·6H2O, M = Mg2+, Ni2+, Co2+, NixCo1-x2+). It relies on the thermal decomposition of crystalline M-struvite precursors to an amorphous and simultaneously mesoporous phase, which forms while degassing of NH3 and H2O. The temporal evolution of mesoporous frameworks and the response of the metal coordination environment were followed with in-situ and ex-situ scattering and diffraction, as well as X -ray spectroscopy. Despite sharing the same precursor struvite structure, different amorphous and mesoporous structures were obtained depending on the involved transition metal. We highlight the systematic differences in absolute surface area, pore shape, pore size, and phase transitions depending on a metal cation present in the analogous M-struvites. The amorphous structures of thermally decomposed Mg-, Ni- and NixCo1-x-struvites exhibit high surface areas and pore volumes (240 m²g-1 and 0.32 cm-3 g-1 for Mg and 90 m²g-1 and 0.13 cm-3 g-1 for Ni). We propose that the low-cost, environmentally friendly M-struvites could be obtained as recycling products from industrial and agricultural wastewaters. These waste products could be then upcycled into mesoporous TMPs through a simple thermal treatment for further applications, for instance, in (electro)catalysis.
KW - Struvite
KW - Pphosphates
KW - Transition metal
KW - In-situ SAXS/WAXS
KW - Mesoporosity
PY - 2023
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-569503
SN - 2040-3364
SP - 1
EP - 15
PB - Royal Society of Chemistry (RSC)
AN - OPUS4-56950
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Getenet, M.
A1 - Otálora, F.
A1 - Emmerling, Franziska
A1 - Al-Sabbagh, Dominik
A1 - García-Ruiz, J. M.
T1 - Mineral precipitation and hydrochemical evolution through evaporitic processes in soda brines (East African Rift Valley)
N2 - Soda lakes of the East African Rift Valley are hyperalkaline, hypersaline lakes extremely enriched in Na+, K+, Cl−, CO32−, HCO3−, and SiO2. In this paper, we investigate the chemical evolution in these lakes and the production of chemical sediments by salt precipitation via evaporation. Water samples from tributary springs and three lakes (Magadi, Nasikie Engida and Natron) have been experimentally studied by in-situ X-ray diffraction during evaporation experiments to characterize the sequence of mineral precipitation. These data are complemented by ex-situ diffraction studies, chemical analyses and thermodynamic hydrochemical calculations producing detailed information on the activity of all solution species and the saturation state of all minerals potentially generated by the given composition. Major minerals precipitating from these samples are sodium carbonates/bicarbonates as well as halite. The CO3/HCO3 ratio, controlled by pH, is the main factor defining the Na‑carbonates precipitation sequence: in lake brines where CO3/HCO3 > 1, trona precipitates first whereas in hot springs, where CO3/HCO3 ≪ 1, nahcolite precipitates instead of trona, which forms later via partial dissolution of nahcolite. Precipitation of nahcolite is possible only at lower pH values (pCO2 higher than −2.7) explaining the distribution of trona and nahcolite in current lakes and the stratigraphic sequences. Later, during evaporation, thermonatrite precipitates, normally at the same time as halite, at a very high pH (>11.2) after significant depletion of HCO3− due to trona precipitation. The precipitation of these soluble minerals increases the pH of the brine and is the main factor contributing to the hyperalkaline and hypersaline character of the lakes. Villiaumite, sylvite, alkaline earth carbonates, fluorapatite and silica are also predicted to precipitate, but most of them have not been observed in evaporation experiments, either because of the small amount of precipitates produced, kinetic effects delaying the nucleation of some phases, or by biologically induced effects in the lake chemistry that are not considered in our calculations. Even in these cases, the chemical composition in the corresponding ions allows for discussion on their accumulation and the eventual precipitation of these phases. The coupling of in-situ and ex-situ experiments and geochemical modelling is key to understanding the hydrogeochemical and hydroclimatic conditions of soda lakes, evaporite settings, and potentially soda oceans of early Earth and other extraterrestrial bodies.
KW - Crystallization sequence
KW - Hydrochemical evolution
KW - Alkaline brines
KW - Sodium carbonate minerals
KW - Soda lakes
KW - Evaporite deposits
PY - 2023
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-568431
SN - 0009-2541
VL - 616
SP - 1
EP - 13
PB - Elsevier
CY - New York, NY
AN - OPUS4-56843
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Karafiludis, Stephanos
A1 - Ryll, T. W.
A1 - Buzanich, Ana Guilherme
A1 - Emmerling, Franziska
A1 - Stawski, Tomasz Maciej
T1 - Phase stability studies on transition metal phosphates aided by an automated synthesis
N2 - Transition metal phosphates (TMPs) have attracted interest as materials for (electro-) catalysis, and electrochemistry due to their low-cost, stability, and tunability. In this work, an automated synthesis platform was used for the preparation of transition metal phosphate crystals to efficiently explore the multidimensional parameter space, determining the phase selection, crystal sizes, shapes. By using X-ray diffraction and spectroscopy-based methods and electron microscopy imaging, a complete characterization of the phase stability fields, phase transitions, and crystal morphology/sizes was achieved. In an automated three-reactant synthesis, the individual effect of each reactant species NH4+, M2+, and PO43- on the formation of transition metal phosphate phases: M-struvite NH4MPO4·6H2O, M-phosphate octahydrate M3(PO4)2·8H2O with M = Ni, Co and an amorphous phase, was investigated. The NH4+ concentration dictates the phase composition, morphology, and particle size in the Ni-system (crystalline Ni-struvite versus amorphous Ni-PO4 phase), whereas in the Co-system all reactant species - NH4+, Co2+, and PO43- - influence the reaction outcome equivalently (Co-struvite vs. Co-phosphate octahydrate). The coordination environment for all crystalline compounds and of the amorphous Ni-PO4 phase was resolved by X-ray absorption spectroscopy, revealing matching characteristics to its crystalline analogue, Ni3(PO4)2·8H2O. The automated synthesis turned out to be significantly advantageous for the exploration of phase diagrams due to its simple modularity, facile traceability, and enhanced reproducibility compared to a typical manual synthesis.
KW - Automated synthesis
KW - Phase diagrams
KW - Transition metals
KW - Phosphates
KW - Local structure
KW - Struvite
PY - 2023
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-579151
VL - 25
IS - 30
SP - 4333
EP - 4344
PB - CrystEngComm
CY - London
AN - OPUS4-57915
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Somasundaram, S. K.
A1 - Buzanich, Ana
A1 - Emmerling, Franziska
A1 - Krishnan, S.
A1 - Senthilkumar, K.
A1 - Joseyphus, R.J.
T1 - New insights into pertinent Fe-complexes for the synthesis of iron via the instant polyol process
N2 - Chemically synthesized iron is in demand for biomedical applications due to its large saturation magnetization compared to iron oxides. The polyol process, suitable for obtaining Co and Ni particles and their alloys, is laborious in synthesizing Fe. The reaction yields iron oxides, and the reaction pathway remains unexplored. This study shows that a vicinal polyol, such as 1,2-propanediol, is suitable for obtaining Fe rather than 1,3-propanediol owing to the formation of a reducible Fe intermediate complex. X-ray absorption spectroscopy analysis reveals the ferric octahedral geometry and tetrahedral geometry in the ferrous state of the reaction intermediates in 1,2-propanediol and 1,3-propanediol, respectively. The final product obtained using a vicinal polyol is Fe with a γ-Fe2O3 shell, while the terminal polyol is favourable for Fe3O4. The distinct Fe–Fe and Fe–O bond lengths suggest the presence of a carboxylate group and a terminal alkoxide ligand in the intermediate of 1,2-propanediol. A large Fe–Fe bond distance suggests diiron complexes with bidentate carboxylate bridges. Prominent high-spin and low-spin states indicate the possibility of transition, which favors the reduction of iron ions in the reaction using 1,2-propanediol.
KW - XAS
KW - Nanoparticle
PY - 2023
U6 - https://doi.org/10.1039/D3CP01969A
SN - 1463-9076
VL - 25
IS - 33
SP - 21970
EP - 21980
PB - Royal Society of Chemistry (RSC)
AN - OPUS4-58073
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Fink, Friedrich
A1 - Stawski, Tomasz M.
A1 - Stockmann, Jörg M.
A1 - Emmerling, Franziska
A1 - Falkenhagen, Jana
T1 - Surface Modification of Kraft Lignin by Mechanochemical Processing with Sodium Percarbonate
N2 - In this article, we present a novel one-pot mechanochemical reaction for the surface activation of lignin.
The process involves environmentally friendly oxidation with hydrogen peroxide, depolymerization of fractions with high molecular mass, and introduction of new carbonyl functions into the lignin backbone. Kraft lignin was ground with sodium percarbonate and sodium hydroxide in a ball mill at different time intervals. Analyses by infrared spectroscopy (IR), nuclear magnetic resonance spectroscopy (NMR), size exclusion chromatography (SEC), dynamic vapor sorption (DVS), and small-angle X-ray scattering (SAXS) showed significant improvements. After only 5 min of reaction, there was a 47% reduction in mass-average molecular weight and an increase in carboxyl functionalities.
Chemical activation resulted in an approximately 2.8-fold increase in water adsorption. Principal component analysis (PCA) provided further insight into the correlations between IR spectra and SAXS parameters
KW - Kraft Lignin
KW - Mechanochemical oxidation
KW - SEC
KW - FTIR
KW - SAXS
KW - PCA
PY - 2023
U6 - https://doi.org/10.1021/acs.biomac.3c00584
SN - 1525-7797
SP - 1
EP - 11
PB - American Chemical Society
AN - OPUS4-58074
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Karafiludis, Stephanos
A1 - Bhattacharya, Biswajit
A1 - de Oliveira Guilherme Buzanich, Ana
A1 - Fink, Friedrich
A1 - Feldmann, Ines
A1 - ten Elshof, J. E.
A1 - Emmerling, Franziska
A1 - Stawski, Tomasz
T1 - Thermally processed Ni-and Co-struvites as functional materials for proton conductivity
N2 - We present how mesoporosity can be engineered in transition metal phosphate (TMPs) materials in a template-free manner. The method involves the transformation of a precursor metal phosphate phase, called M-struvite (NH4MPO4·6H2O, M = Mg2+, Ni2+, Co2+, NixCo1−x2+). It relies on the thermal decomposition of crystalline M-struvite precursors to an amorphous and simultaneously mesoporous phase, which forms during degassing of NH3 and H2O. The temporal evolution of mesoporous frameworks and the response of the metal coordination environment were followed by in situ and ex situ scattering and diffraction, as well as X-ray spectroscopy. Despite sharing the same precursor struvite structure, different amorphous and mesoporous structures were obtained depending on the involved transition metal. We highlight the systematic differences in absolute surface area, pore shape, pore size, and phase transitions depending on the metal cation present in the analogous M-struvites. The amorphous structures of thermally decomposed Mg-, Ni- and NixCo1−x-struvites exhibit high surface areas and pore volumes (240 m2 g−1 and 0.32 cm−3 g−1 for Mg and 90 m2 g−1 and 0.13 cm−3 g−1 for Ni). We propose that the low-cost, environmentally friendly M-struvites could be obtained as recycling products from industrial and agricultural wastewaters. These waste products could be then upcycled into mesoporous TMPs through a simple thermal treatment for further application, for instance in (electro)catalysis.
KW - Struvite
KW - Phosphates
KW - Transition metals
KW - Proton conductivity
PY - 2023
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-575862
SN - 1477-9226
SP - 1
EP - 13
PB - Royal Society of Chemisty (RSC)
CY - London/Cambridge
AN - OPUS4-57586
LA - deu
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Manoharan, D.
A1 - Ahmad, S.
A1 - Emmerling, Franziska
A1 - Bhattacharya, Biswajit
A1 - Ghosh, S.
T1 - Stress and light sensitive dual-mechanical property of acylhydrazone crystal
N2 - Mechanically dual-responsive molecular crystals have gained ubstantial interest among researchers due to their significant applications in various fields. However, incorporation of disparate mechanical responses in the same crystalline material is still a challenging issue and is continuously being explored. Here, we report long acicular crystals derived from 4-bromobenzhydrazide and 9-anthraldehyde exhibit both stressinduced mechanical bending and blue-light induced photomechanical bending. Furthermore, the crystals show thermal back isomerization upon gradual heating. These two distinct mechanical responses in the crystalline phase have been studied and their structure–property correlation have been established.
KW - Light sensitive crystal
KW - Mechanical flexibility
KW - Organic crystal
PY - 2023
U6 - https://doi.org/10.1039/d3ce00296a
VL - 25
IS - 21
SP - 3237
EP - 3244
PB - Royal Society of Chemisty (RSC)
CY - London/Cambridge
AN - OPUS4-57593
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Peters, Stefan
A1 - Kunkel, Benny
A1 - Cakir, Cafer Tufan
A1 - Kabelitz, Anke
A1 - Witte, Steffen
A1 - Bernstein, Thomas
A1 - Bartling, Stephan
A1 - Radtke, Martin
A1 - Emmerling, Franziska
A1 - Abdel-Mageed, Ali Mohamed
A1 - Wohlrab, Sebastian
A1 - Guilherme Buzanich, Ana
T1 - Time-, space- and energy-resolved in situ characterization of catalysts by X-ray absorption spectroscopy
N2 - A novel setup for dispersive X-ray absorption spectroscopy (XAS) with simultaneous resolution of space, time and energy for in situ characterization of solid materials is demonstrated.
KW - Dispersive XAS
KW - Catalysis
KW - In situ
KW - Structure analysis
PY - 2023
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-584924
SN - 1359-7345
SP - 1
EP - 4
PB - Royal Society of Chemistry (RSC)
AN - OPUS4-58492
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Karafiludis, Stephanos
A1 - Scoppola, E.
A1 - Wolf, S.E.
A1 - Kochovski, Z.
A1 - Matzdorff, D.
A1 - Van Driessche, A. E. S.
A1 - Hövelmann, J.
A1 - Emmerling, Franziska
A1 - Stawski, Tomasz M.
T1 - Evidence for liquid-liquid phase separation during the early stages of Mg-struvite formation
N2 - The precipitation of struvite, a magnesium ammonium phosphate hexahydrate (MgNH₄PO₄ · 6H₂O) mineral, from wastewater is a promising method for recovering phosphorous. While this process is commonly used in engineered environments, our understanding of the underlying mechanisms responsible for the formation of struvite crystals remains limited. Specifically, indirect evidence suggests the involvement of an amorphous precursor and the occurrence of multi-step processes in struvite formation, which would indicate non-classical paths of nucleation and crystallization. In this study, we use synchrotron-based in situ x-ray scattering complemented by cryogenic transmission electron microscopy to obtain new insights from the earliest stages of struvite formation. The holistic scattering data captured the structure of an entire assembly in a time-resolved manner. The structural features comprise the aqueous medium, the growing struvite crystals, and any potential heterogeneities or complex entities. By analysing the scattering data, we found that the onset of crystallization causes a perturbation in the structure of the surrounding aqueous medium. This perturbation is characterized by the occurrence and evolution of Ornstein-Zernike fluctuations on a scale of about 1 nm, suggesting a non-classical nature of the system. We interpret this phenomenon as a liquid-liquid phase separation, which gives rise to the formation of the amorphous precursor phase preceding actual crystal growth of struvite. Our microscopy results confirm that the formation of Mg-struvite includes a short-lived amorphous phase, lasting >10 s.
KW - Physical and theoretical chemistry
KW - Non-classical crystallization
KW - Struvite
KW - Liquid-liquid-phase-separation
KW - Nucleation
KW - Crystallization
KW - In-situ scattering
PY - 2023
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-584766
SN - 1089-7690
VL - 159
IS - 13
SP - 1
EP - 12
PB - AIP Publishing
CY - Woodbury, NY
AN - OPUS4-58476
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Bernardes, C. E. S.
A1 - Feliciano, I.O.
A1 - Naese, Christoph
A1 - Emmerling, Franziska
A1 - Minas da Piedade, M.
T1 - Energetics of dehydroepiandrosterone polymorphs I and II from solution and drop-sublimation Calvet microcalorimetry measurements
N2 - The lattice enthalpies and monotropic relationship of two dehydroepiandrosterone (DEHA) polymorphs (forms I and II) were evaluated through a combination of differential scanning calorimetry (DSC), isothermal solution microcalorimetry, and drop-sublimation Calvet microcalorimetry experiments. The standard molar enthalpy of transition between both forms was determined as ΔtrsHom (II→I, 298.15 K) = - 0.90 ± 0.07 kJ mol-1 and ΔtrsHom (II→I, 417.8 K) = - 1.7 ± 1.0 kJ mol- 1, from measurements of standard molar enthalpies of solution in dimethyl sulfoxide and enthalpies of fusion, respectively. Drop-sublimation Calvet microcalorimetry experiments on form I led to ΔsubHom (cr I, 298.15 K) = 132.0±3.3 kJ mol - 1. This result, when combined with the more precise ΔtrsHom (II→I) value obtained by solution calorimetry, afforded ΔsubHom (cr II, 298.15 K) = 131.1±3.3 kJ mol - 1. The overall data indicate that on enthalpic grounds form I is more stable than form II from 298.15 K up to fusion. This conclusion, and the fact that DSC experiments indicated that form I has also a considerably higher temperature fusion, namely, Tfus(cr I)= 422.5±0.2 K and Tfus(cr II) = 413.1±0.2 K, suggest that the two polymorphs are monotropically related.
KW - Calorimetry
KW - Polymorphism
KW - Enthalpy of solution
KW - Enthalpy of sublimation
KW - Thermochemistry
KW - Lattice enthalpy
PY - 2023
U6 - https://doi.org/10.1016/j.jct.2023.107137
SN - 0021-9614
SN - 1096-3626
VL - 186
SP - 1
EP - 7
PB - Elsevier
AN - OPUS4-58418
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Bui, M.
A1 - Hoffmann, K. F.
A1 - Braun, T.
A1 - Riedel, S.
A1 - Heinekamp, Christian
A1 - Scheurell, K.
A1 - Scholz, G.
A1 - Stawski, Tomasz
A1 - Emmerling, Franziska
T1 - An Amorphous Teflate Doped Aluminium Chlorofluoride:
A Solid Lewis-Superacid for the Dehydrofluorination of
Fluoroalkanes
N2 - Ananion-dopedaluminiumchlorofluoride AlCl0.1F2.8(OTeF5)0.1(ACF-teflate) was synthesized.The material contains pentafluor-oorthotellurate(teflate)groups, which mimic fluoride ions electronically, but are sterically more demanding. They are embedded into the amorphous structure. The latter was studied by PDF analysis, EXAFS data and MAS NMR spectroscopy. The mesoporous powder is a Lewis superacid, and ATR-IR spectra of adsorbed CD3CN reveal a blue-shift of the adsorption band by73 cm-1, which is larger than the shift for SbF5. Remarkably,ACF-teflate catalyzes dehydrofluorination reactions of mono-fluoroalkanes to yield olefins in C6D6. In these cases,no Friedel-Crafts products were formed.
KW - Aluminium fluorides
KW - Aluminium teflates
KW - C-F bond activation
KW - Lewis superacids
KW - Silanes
PY - 2023
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-572290
SN - 1867-3880
SP - 1
EP - 7
PB - Wiley VHC-Verlag
AN - OPUS4-57229
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Manoharan, Deepak
A1 - Ranjan, Subham
A1 - Emmerling, Franziska
A1 - Bhattacharya, Biswajit
A1 - Takamizawa, Satoshi
A1 - Ghosh, Soumyajit
T1 - Elasto-plastic behaviour with reversible thermosalient expansion in acrylonitrile-based organic crystals
N2 - Crystalline materials that exhibit reversible mechanical responses upon exposure to external stimuli have garnered significant attention owing to their potential applications in various fields. Herein, we report a crystal of (2Z,2′Z)-2,2′-(1,4-phenylene)bis(3-(4-bromophenyl)acrylonitrile) (DSBr), which displays simultaneous elasto-plastic behaviour and reversible thermosalient effects. While elasto-plastic behaviour is attributed to underlying packing features, reversible thermosalient expansion is attributed to uniaxial expansion mediated by heat. Exceptional length increase and contraction upon cooling is due to the restorative nature of weak interactions through a cooperative effect. The cooperative movement of molecules is reflected in the unidirectional expansion of the habit plane. Thermosalient reversible expansion–contraction in elasto-plastic crystals have not been discussed in the literature so far. Detailed analysis reported herein provides a comprehensive understanding of the underlying mechanism of flexibility and thermosalient responses. This crystal's unique blend of reversible thermal expansion with flexibility holds substantial promise for applications in flexible thermal actuators.
KW - Materials Chemistry
KW - General Chemistry
PY - 2024
U6 - https://doi.org/10.1039/D3TC04272C
SN - 2050-7526
SP - 1
EP - 11
PB - Royal Society of Chemistry (RSC)
AN - OPUS4-59527
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Emmerling, Franziska
T1 - Understanding mechanochemical reactions: Real-time insights and collaborative research
N2 - Mechanochemistry emerges as a potent, environmentally friendly, and straightforward approach for crafting novel multicomponent crystal systems. Various milling parameters, including milling frequency, time, filling degree of the milling jar, ball diameter, vessel size, degree of milling ball filling, and material of jars, are recognized influencers on the mechanisms and rates of product formation. Despite the growing interest in mechanochemistry, there exists a gap in understanding the mechanistic aspects of mechanochemical reactivity and selectivity. To address this, diverse analytical methods and their combinations, such as powder X-ray diffraction, X-ray absorption spectroscopy, NMR, Raman spectroscopy, and thermography, have been developed for real-time, in situ monitoring of mechanochemical transformations.
This discussion centers on our recent findings, specifically investigating the formation of (polymorphic) cocrystals and metal-organic frameworks. Through these studies, we aim to unravel the impact of milling parameters and reaction sequences on the formation mechanism and kinetics. Notably, in the mechanochemical chlorination reaction of hydantoin, normalizing kinetic profiles to the volume of the milling ball unequivocally demonstrates the conservation of milling reaction kinetics. In this ball-milling transformation, physical kinetics outweigh chemical factors in determining reaction rates. Attempting to interpret such kinetics solely through chemical terms poses a risk of misinterpretation. Our results highlight that time-resolved in situ investigations of milling reactions provide a novel avenue for fine-tuning and optimizing mechanochemical processes.
T2 - PhD Seminar
CY - Online meeting
DA - 12.10.2023
KW - Mechanochemistry
KW - In situ
PY - 2023
AN - OPUS4-59022
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Dietzmann, Simon
A1 - Mehmood, Asad
A1 - Guilherme Buzanich, Ana
A1 - Emmerling, Franziska
A1 - Fellinger, Tim-Patrick
A1 - Thomas, A.
T1 - Characterization of Solid-State Complexes by XAS
N2 - Atomically dispersed metal-nitrogen doped carbons (M-N-C) are
promising catalysts for the activation of small molecules such as O2
and CO2. These single atom catalysts (SAC) operate at the interface
between homogenous and heterogenous catalysts. Currently, many
examples of M-N-C are known with good oxygen reduction reaction
activity but lacking a controlled synthesis of the specific active sites of
the precatalyst. Recently, our group facilitated the synthesis of pure
pyrrolic M-N4 sites using Zn ions as imprinters.[1] These amorphous
materials obtained by active site imprinting method are characterized
at the BAMline (Bessy II) by X-ray absorption spectroscopy (XAS).
In-situ/operando measurements will be crucial in future work for a
better understanding of the dynamic changes of the active site.
T2 - InSynX Workshop 2023
CY - Sao Paulo, Brazil
DA - 06.03.2023
KW - Solid-State Complexes
PY - 2023
AN - OPUS4-58933
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Goswami, Juli Nanda
A1 - Haque, Najirul
A1 - Seikh, Asiful H.
A1 - Bhattacharya, Biswajit
A1 - Emmerling, Franziska
A1 - Bar, Nimai
A1 - Ifseisi, Ahmad A.
A1 - Biswas, Surajit
A1 - Dolai, Malay
T1 - Carboxylative cyclization of propargyl alcohols with carbon dioxide for the synthesis of α-alkylidene cyclic carbonates in presence of Co(III) schiff base complex catalyst
N2 - A cobalt(III) complex, [Co(L)3](DMF) (1) of Schiff base ligand HL, 2-((E)-(benzylimino)methyl)-4-bromophenol is prepared and single crystal X-ray structural analysis have also been performed. The structures of complex 1 showed hexa-coordinated mononuclear systems that adopt octahedral geometry. The complex has also exhibited the supramolecular networks through non-covalent interactions like H-bonding, C–Hπ stacking. Moreover, the complex 1 is very effective in the catalytic fixation of carbon dioxide in propergyl alcohols to produce α-alkylidene cyclic carbonates. The catalytic production of α-alkylidene cyclic carbonates have been carried out through carboxylative cyclization of propargyl alcohols using CO2 balloon of 1 atm pressure at 80 ◦C. Solvent free condition (green synthesis) made this catalytic protocol eco-friendly towards the environment. Utilizing various substrates of propargyl alcohols moderate to high percentage yield (62–95%) of respective α-alkylidene cyclic carbonates product have been isolated over this catalytic reaction. Besides, the theoretical calculations (DFT) was performed for the prediction of probable mechanism of the catalytic reaction
KW - Catalytic fixation of carbon dioxide
KW - Carboxylative cyclization of propargyl alcohols
KW - Cobalt (III) Schiff base complex
KW - X-ray crystal analysis
PY - 2024
U6 - https://doi.org/10.1016/j.molstruc.2023.136868
SN - 0022-2860
VL - 1296
IS - Part 1
SP - 1
EP - 8
PB - Elsevier B.V.
AN - OPUS4-58947
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Emmerling, Franziska
T1 - Investigating the mechanism and kinetics of the mechanochemical synthesis of multi-component systems
N2 - Mechanochemistry is a promising and environmentally friendly approach for synthesizing (novel) multicomponent crystal systems. Various milling parameters, such as milling frequency, milling time, and ball diameter have been shown to influence the mechanisms and rates of product formation. Despite increasing interest in mechanochemistry, there is still limited understanding of the underlying reactivity and selectivity mechanisms.
Various analytical techniques have been developed to gain insight into the mechanochemical transformations, including powder X-ray diffraction, X-ray adsorption spectroscopy, NMR, Raman spectroscopy and thermography. Using these techniques, we have studied the formation of (polymorphic) cocrystals, organometallic compounds and salts, and elucidated the influence of milling parameters and reaction sequences on the formation mechanism and kinetics.
For example, our study of the mechanochemical chlorination reaction of hydantoin revealed that normalisation of the kinetic profiles to the volume of the grinding ball clearly showed that physical kinetics dominate the reaction rates in a ball-milling transformation. Attempts to interpret such kinetics in purely chemical terms risk misinterpretation of the results.
Our results suggest that time-resolved in situ investigation of milling reactions is a promising way to fine-tune and optimise mechanochemical processes.
T2 - ISIC 2023
CY - Glasgow, Scotland
DA - 05.09.2023
KW - Mechanochemistry
KW - Polymorphy
KW - In situ
PY - 2023
AN - OPUS4-59023
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Emmerling, Franziska
T1 - Understanding mechanochemical reactions: Real-time insights and collaborative research
N2 - Mechanochemistry emerges as a potent, environmentally friendly, and straightforward approach for crafting novel multicomponent crystal systems. Various milling parameters, including milling frequency, time, filling degree of the milling jar, ball diameter, vessel size, degree of milling ball filling, and material of jars, are recognized influencers on the mechanisms and rates of product formation. Despite the growing interest in mechanochemistry, there exists a gap in understanding the mechanistic aspects of mechanochemical reactivity and selectivity. To address this, diverse analytical methods and their combinations, such as powder X-ray diffraction, X-ray absorption spectroscopy, NMR, Raman spectroscopy, and thermography, have been developed for real-time, in situ monitoring of mechanochemical transformations.
This discussion centers on our recent findings, specifically investigating the formation of (polymorphic) cocrystals and metal-organic frameworks. Through these studies, we aim to unravel the impact of milling parameters and reaction sequences on the formation mechanism and kinetics. Notably, in the mechanochemical chlorination reaction of hydantoin, normalizing kinetic profiles to the volume of the milling ball unequivocally demonstrates the conservation of milling reaction kinetics. In this ball-milling transformation, physical kinetics outweigh chemical factors in determining reaction rates. Attempting to interpret such kinetics solely through chemical terms poses a risk of misinterpretation. Our results highlight that time-resolved in situ investigations of milling reactions provide a novel avenue for fine-tuning and optimizing mechanochemical processes.
T2 - Brimingham Green chemsistry
CY - Birmingham, England
DA - 08.09.2023
KW - Mechanochemistry
KW - Green Chemistry
PY - 2023
AN - OPUS4-59024
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Emmerling, Franziska
T1 - Combination of complementary methods For in situ studies
N2 - This talk explores the synergistic application of complementary synchrotron methods for in situ investigations, providing a comprehensive approach to enhance analytical capabilities in materials research and characterization.
T2 - INSYNX - DEUTSCH-BRASILIANISCHER WORKSHOP ON BREAKING BOUNDARIES OF IN SITU SYNCHROTRON X-RAY METHODS
CY - Sao Paulo, Brazil
DA - 06.03.2023
KW - In situ
KW - Synchrotron
PY - 2023
AN - OPUS4-59025
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Emmerling, Franziska
T1 - Understanding mechanochemical reactions: Real-time insights and collaborative research
N2 - Mechanochemistry has become a compelling method for producing (new) molecule s and mate-rials, but the inner workings of the milling jars remain a fascinating mystery. Advances in this field include tailor-made chemical systems and real-time revelations using techniques such as XRD and Raman spectroscopy.
This talk will discuss our recent progress in using X-ray diffraction and sophisticated spectros-copy to observe reactions in various material systems during ball milling and extrusion in real-time.
The complexity of mechanochemical reactions spans multiple scales and requires a holistic ap-proach. The categorisation of reactions by investigative methods precedes the exploration of real-time analysis that reveals macroscopic processes using synchrotron techniques.
During this exploration, one resounding realisation remains: We are on the threshold of under-standing. The complexity of mechanochemistry requires a collective effort, drawing on the ex-pertise of a diverse community. As we unravel the web of mechanochemical phenomena, we acknowledge the collaborative nature of this ongoing journey.
T2 - CMCC Mechanochemistry Discussions
CY - Online meeting
DA - 21.09.2023
KW - Mechanochemistry
KW - In situ
PY - 2023
AN - OPUS4-59026
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Emmerling, Franziska
T1 - Connecting the nodes: networks and networking
N2 - This talk explores the intricate connections between scientists, focusing on the networking dynamics within the realm of metal-organic frameworks (MOFs). The study delves into the collaborative networks formed among scientists, shedding light on the synergistic relationships that contribute to advancements in MOF research.
T2 - WINS School 2023 Frameworks and networks
CY - Blossin, Germany
DA - 02.06.2023
KW - Metal-organic frameworks
PY - 2023
AN - OPUS4-59028
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Stawski, Tomasz
A1 - Karafiludis, Stephanos
A1 - Pimentel, Carlos
A1 - Montes-Hernández, German
A1 - Kochovski, Zdravko
A1 - Bienert, Ralf
A1 - Weimann, Karin
A1 - Emmerling, Franziska
A1 - Scoppola, Ernesto
A1 - Van Driessche, Alexander E.S.
T1 - Solution-driven processing of calcium sulfate: The mechanism of the reversible transformation of gypsum to bassanite in brines
N2 - Here, we show that calcium sulfate dihydrate (gypsum) can be directly, rapidly and reversibly converted to calcium sulfate hemihydrate (bassanite) in high salinity solutions (brines). The optimum conditions for the efficient production of bassanite in a short time (<5 min) involve the use of brines with c(NaCl) > 4 M and maintaining a temperature, T > 80 °C. When the solution containing bassanite crystals is cooled down to around room temperature, eventually gypsum is formed. When the temperature is raised again to T > 80 °C, bassanite is rapidly re-precipitated. This contrasts with the better-known behaviour of the bassanite phase in low-salt environments. In low-salinity aqueous solutions, bassanite is considered to be metastable with respect to gypsum and anhydrite, and therefore gypsum-to-bassanite conversion does not occur in pure water. Interestingly, the high-salinity transformation of gypsum-to-bassanite has been reported by many authors and used in practice for several decades, although its very occurrence actually contradicts numerical thermodynamic predictions regarding solubility of calcium sulfate phases. By following the evolution of crystalline phases with in situ and time-resolved X-ray diffraction/scattering and Raman spectroscopy, we demonstrated that the phase stability in brines at elevated temperatures was inaccurately represented in the thermodynamic databases. Most notably for c(NaCl) > 4 M, and T > 80 °C gypsum becomes readily more soluble than bassanite, which induces the direct precipitation of the latter from gypsum. The fact that these transformations are controlled by the solution provides extensive opportunities for precise manipulation of crystal formation. Our experiments confirmed that bassanite remained the sole crystalline phase for many hours before reverting into gypsum. This property is extremely advantageous for practical processing and efficient crystal extraction in industrial scenarios.
KW - Industrial and Manufacturing Engineering
KW - Strategy and Management
KW - General Environmental Science
KW - Renewable Energy, Sustainability and the Environment
KW - Building and Construction
KW - Calcium sulfate
KW - Gypsum
KW - Bassanite
KW - Scattering
KW - Raman
KW - In situ
KW - Synchrotron
KW - BESSY
KW - MySpot
PY - 2024
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-594698
UR - https://www.sciencedirect.com/science/article/pii/S0959652624004591#appsec1
SN - 0959-6526
VL - 440
SP - 1
EP - 12
PB - Elsevier B.V.
AN - OPUS4-59469
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Zuffa, Caterina
A1 - Cappuccino, Chiara
A1 - Casali, Lucia
A1 - Emmerling, Franziska
A1 - Maini, Lucia
T1 - Liquid reagents are not enough for liquid assisted grinding in the synthesis of (AgBr)(n-pica) n
N2 - This study investigates the mechanochemical reactions between AgBr 3-picolylamine and 4-picolylamine. The use of different stoichiometry ratios of the reagents allows [(AgBr)(n-pica)]n and [(AgBr)2(n-pica)]n to be obtained, and we report the new structures of [(AgBr)2(3-pica)]n and [(AgBr)2(4-pica)]n which are characterized by the presence of the following: (a) infinite inorganic chains, (b) silver atom coordinated only by bromide atoms and (c) argentophilic interactions. Furthermore, we studied the interconversion of [(AgBr)(n-pica)]n/[(AgBr)2(n-pica)]n by mechanochemical and thermal properties. The in situ experiments suggest that [(AgBr)(3-pica)]n is kinetically favoured while [(AgBr)2(3-pica)]n is converted into [(AgBr)(3-pica)]n only with a high excess of the ligand. Finally, the liquid nature of the ligands is not sufficient to assist the grinding process, and the complete reaction is observed with the addition of a small quantity of acetonitrile.
KW - Mechanochemistry
KW - Complex
PY - 2024
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-594755
SN - 1463-9076
SP - 1
EP - 10
PB - Royal Society of Chemistry (RSC)
AN - OPUS4-59475
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Emmerling, Franziska
T1 - Why shaken, not stirred, makes the difference: insights into mechanochemical reactions from in situ investigations
N2 - Mechanochemistry is an effective, environmentally benign, and facile method for the synthesis of new multicomponent crystal systems. Different milling parameters are known to affect the mechanisms and rates of product formation: milling frequency, milling time, filling degree of the milling jar, ball diameter and vessel size, degree of milling ball filling, and material of jars. The increasing interest in mechanochemistry is contrasted by a limited mechanistic understanding of the mechanochemical reactivity and selectivity.
Different analytical methods and their combinations have been developed for the time resolved in situ monitoring of mechanochemical transformations, including powder X-ray diffraction, X-ray adsorption spectroscopy, NMR, Raman spectroscopy, and thermography.
Here we will discuss our recent results investigating the formation of (poly-morphic) cocrystals[1,3], metal-organic compounds, and salts, thereby elucidating the influence of milling parameters and reaction sequences on the formation mechanism and kinetics. For the mechanochemical chlorination reaction of hydantoin normalizing the kinetic profiles to the volume of the milling ball showed clearly that milling reaction kinetics are conserved. Here physical kinetics dominate reaction rates in a ball-milling transformation. Attempting to interpret such kinetics in purely chemical terms risk misinterpreting the results.
Our results indicate that time-resolved in situ investigation of milling reactions offer a new approach to tune and optimize mechanochemical processes.
T2 - GdCh Vortrag Universität Potsdam
CY - Potsdam, Germany
DA - 05.06.2023
KW - Mechanochemistry
KW - In Situ
PY - 2023
AN - OPUS4-58982
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Heinekamp, Christian
A1 - Kneiske, Sönke
A1 - Guilherme Buzanich, Ana
A1 - Ahrens, Mike
A1 - Braun, Thomas
A1 - Emmerling, Franziska
T1 - A fluorolytic sol-gel route to access an amorphous Zr fluoride catalyst: A useful tool for C-F bond activation
N2 - A route to a ZrF4 catalyst active in room temperature Friedel–Crafts and dehydrofluorination reactions was developed via a fluorolytic sol–gel route, which was followed by a postfluorination step using a stream of CHClF2. The behaviour of different Zr(IV) precursors in a sol–gel reaction with anhydrous isopropanol/HF solution was investigated. The subsequent post-fluorination step was optimised in its temperature ramp and confirmed the necessity of a fluorination of the generated xerogels to obtain catalytic activity. The process is discussed in the context of the analysis of the materials using Brunauer–Emmett–Teller analysis (BET), powder X-ray diffraction (XRD), infrared spectroscopy (IR), thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The local structure of the amorphous catalyst was elucidated by extended X-ray absorption fine structure spectroscopy (EXAFS).
KW - Catalysis
KW - Heterogeneous catalysis
KW - C-F bond activation
KW - Postfluorination
PY - 2024
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-593433
SN - 2044-4761
SP - 1
EP - 8
PB - Royal Society of Chemistry (RSC)
AN - OPUS4-59343
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - GEN
A1 - Prinz, Carsten
A1 - Zimathies, Annett
A1 - Emmerling, Franziska
T1 - Experimantal raw data sets associated with certified reference material BAM-P116 (titanium dioxide) for comparison of nitrogen and argon sorption, available in the universal adsorption information format (AIF)
N2 - These data sets serve as models for calculating the specific surface area (BET method) using gas sorption in accordance with ISO 9277.
The present measurements were carried out with nitrogen at 77 Kelvin and argon at 87 Kelvin.
It is recommended to use the following requirements for the molecular cross-sectional area:
Nitrogen: 0.1620 nm²
Argon: 0.1420 nm²
Titanium dioxides certified with nitrogen sorption and additionally measured with argon for research purposes were used as sample material.
The resulting data sets are intended to serve as comparative data for own measurements and show the differences in sorption behaviour and evaluations between nitrogen and argon.
These data are stored in the universal AIF format (adsorption information file), which allows flexible use of the data.
KW - Physisorption
KW - Surface area
KW - AIF
KW - Argon
KW - Nitrogen
PY - 2023
U6 - https://doi.org/10.5281/zenodo.10199628
PB - Zenodo
CY - Geneva
AN - OPUS4-59102
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Linberg, Kevin
A1 - Szymoniak, Paulina
A1 - Schönhals, Andreas
A1 - Emmerling, Franziska
A1 - Michalchuk, Adam A. L.
T1 - The Origin of Delayed Polymorphism in Molecular Crystals Under Mechanochemical Conditions
N2 - We show that mechanochemically driven polymorphic transformations can require extremely long induction periods, which can be tuned from hours to days by changing ball milling energy. The robust design and interpretation of ball milling experiments must account for this unexpected kinetics that arises from energetic phenomena unique to the solid state. Detailed thermal analysis, combined with DFT simulations, indicates that these marked induction periods are associated with processes of mechanical activation. Correspondingly, we show that the pre‐activation of reagents can also lead to marked changes in the length of induction periods. Our findings demonstrate a new dimension for exerting control over polymorphic transformations in organic crystals. We expect mechanical activation to have a much broader implication across organic solid‐state mechanochemistry.
KW - General Chemistry
KW - Catalysis
KW - Organic Chemistry
PY - 2023
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-589219
SN - 0947-6539
SP - e202302150
PB - Wiley
AN - OPUS4-58921
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Edzards, Joshua
A1 - Saßnick, Holger-Dietrich
A1 - Buzanich, Ana Guilherme
A1 - Valencia, Ana M.
A1 - Emmerling, Franziska
A1 - Beyer, Sebastian
A1 - Cocchi, Caterina
T1 - Effects of Ligand Substituents on the Character of Zn-Coordination in Zeolitic Imidazolate Frameworks
N2 - Due to their favorable properties and high porosity, zeolitic imidazolate frameworks (ZIFs) have recently received much limelight for key technologies such as energy storage, optoelectronics, sensorics, and catalysis. Despite widespread interest in these materials, fundamental questions regarding the zinc coordination environment remain poorly understood. By focusing on zinc(II)2-methylimidazolate (ZIF-8) and its tetrahedrally coordinated analogues with Br-, Cl-, and H-substitution in the 2-ring position, we aim to clarify how variations in the local environment of Zn impact the charge distribution and the electronic properties of these materials. Our results from densityfunctional theory confirm the presence of a Zn coordinative bond with a large polarization that is quantitatively affected by different substituents on the organic ligand. Moreover, our findings suggest that the variations in the Zn coordination induced by the functionalization have a negligible effect on the electronic structure of the considered compounds. On the other hand, halogen terminations of the ligands lead to distinct electronic contributions in the vicinity of the frontier region which ultimately reduce the band gap size by a few hundred millielectron volts. Experimental results obtained from X-ray absorption spectroscopy (Zn K-edge) confirm the trends predicted by theory and, together with them, contribute to a better understanding of the structure−property relationships that are needed to tailor ZIFs for target applications.
KW - Surfaces
KW - Physical and Theoretical Chemistry
KW - General Energy
KW - Electronic
KW - Coatings and Films
KW - Optical and Magnetic Materials
PY - 2023
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-589117
SN - 1932-7447
VL - 127
IS - 43
SP - 21456
EP - 21464
PB - American Chemical Society (ACS)
AN - OPUS4-58911
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Karafiludis, Stephanos
A1 - Kochovski, Z.
A1 - Scoppola, E.
A1 - Retzmann, Anika
A1 - Hodoroaba, Vasile-Dan
A1 - ten Elshof, J. E.
A1 - Emmerling, Franziska
A1 - Stawski, Tomasz Maciej
T1 - Nonclassical Crystallization Pathway of Transition Metal Phosphate Compounds
N2 - Here, we elucidate nonclassical multistep crystallization pathways of transition metal phosphates from aqueous solutions. We followed precipitation processes of M-struvites, NH4MPO4·6H2O, and M-phosphate octahydrates, M3(PO4)2·8H2O, where M = Ni, Co, or NixCo1–x, by using in situ scattering and spectroscopy-based techniques, supported by elemental mass spectrometry analyses and advanced electron microscopy. Ni and Co phosphates crystallize via intermediate colloidal amorphous nanophases, which change their complex structures while agglomerating, condensing, and densifying throughout the extended reaction times. We reconstructed the three-dimensional morphology of these precursors by employing cryo-electron tomography (cryo-ET). We found that the complex interplay between metastable amorphous colloids and protocrystalline units determines the reaction pathways. Ultimately, the same crystalline structure, such as struvite, is formed. However, the multistep process stages vary in complexity and can last from a few minutes to several hours depending on the selected transition metal(s), their concentration, and the Ni/Co ratio.
KW - Non-classical crystallization theory
KW - Transition metals
KW - Phosphates
KW - Amorphous phases
KW - Intermediate phases
PY - 2023
U6 - https://doi.org/10.1021/acs.chemmater.3c02346
SN - 1520-5002
VL - 35
IS - 24
SP - 10645
EP - 10657
PB - American Chemical Society (ACS)
CY - Washington D.C.
AN - OPUS4-59135
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Emmerling, Franziska
A1 - Chewle, S.
A1 - Weber, M.
T1 - Revealing Kinetics of Paracetamol Crystallization Using Time Resolved Raman Spectroscopy, Orthogonal Time-Lapse Photography, and Non-Negative Matrix Factorization (OSANO)
N2 - Crystallization is a complex phenomenon with farreaching implications for the production and formulation of active pharmaceutical ingredients. Understanding this process is critical for achieving control over key physicochemical properties that can affect, for example, the bioavailability and stability of a drug. In this study, we were able to reveal intricate and diverse dynamics of the formation of metastable intermediates of paracetamol crystallization varying with the choice of solvent. We demonstrate the efficacy of our novel approach utilizing an objective function-based non-negative matrix factorization technique for the analysis of time-resolved Raman
spectroscopy data, in conjunction with time-lapse photography.
Furthermore, we emphasize the crucial importance of integrating Raman spectroscopy with supplementary experimental instrumentation for the mathematical analysis of the obtained spectra.
KW - Polymorphism
KW - Crystallization
KW - Measurement
KW - Algorithm
PY - 2023
U6 - https://doi.org/10.1021/acs.cgd.3c00617
SN - 1528-7483
VL - 23
SP - 6737
EP - 6746
PB - ACS Publications
AN - OPUS4-58193
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Feiler, Torvid
A1 - Yasuda, N.
A1 - Michalchuk, Adam
A1 - Emmerling, Franziska
A1 - Bhattacharya, Biswajit
T1 - Mechanistic Investigation of an Elastically Flexible Organic Crystal
N2 - Mechanical flexibility in molecular crystals is a fascinating behavior with potential for developing advanced technologies. However, the phenomenon of mechanical bending is poorly understood. We explore for the first time the atomistic origin of elastic bending in a single component organic crystal using a combination of μ-focus synchrotron X-ray diffraction and ab initio simulation.
KW - Flexible crystals
KW - DFT calculation
KW - Bending mechanism
PY - 2023
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-581949
SN - 1528-7483
VL - 23
IS - 9
SP - 6244
EP - 6249
PB - ACS Publications
AN - OPUS4-58194
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Heinekamp, Christian
A1 - Guilherme Buzanich, Ana
A1 - Ahrens, M.
A1 - Braun, T.
A1 - Emmerling, Franziska
T1 - An amorphous Lewis-acidic zirconium chlorofluoride as HF shuttle: C–F bond activation and formation
N2 - An exceptional HF transfer reaction by C–F bond activation of fluoropentane and a subsequent hydrofluorination of alkynes at room temperature is reported. An amorphous Lewis-acidic Zr chlorofluoride serves as heterogeneous catalyst, which is characterised by an eightfold coordination environment at Zr including chlorine atoms. The studies are seminal in establishing sustainable fluorine chemistry.
KW - ZCF
KW - Heterogeneous catalysis
KW - C-F bond activation
KW - HF-shuttle
PY - 2023
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-582249
SN - 1359-7345
VL - 59
IS - 75
SP - 11224
EP - 11227
PB - RSC
CY - Cambridge
AN - OPUS4-58224
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Bornemann-Pfeiffer, Martin
A1 - Wolf, Jakob
A1 - Meyer, Klas
A1 - Kern, S.
A1 - Angelone, D.
A1 - Leonov, A.
A1 - Cronin, L.
A1 - Emmerling, Franziska
T1 - Standardization and control of Grignard reactions in a universal chemical synthesis machine using online NMR
T1 - Standardisierung und Kontrolle von Grignard-Reaktionen mittels Online-NMR in einer universellen chemischen Syntheseplattform
N2 - A big problem with the chemistry literature is that it is not standardized with respect to precise operational parameters, and real time corrections are hard to make without expert knowledge. This lack of context means difficult reproducibility because many steps are ambiguous, and hence depend on tacit knowledge. Here we present the integration of online NMR into an automated chemical synthesis machine (CSM aka. “Chemputer” which is capable of small-molecule synthesis using a universal programming language) to allow automated analysis and adjustment of reactions on the fly. The system was validated and benchmarked by using Grignard reactions which were chosen due to their importance in synthesis. The system was monitored in real time using online-NMR, and spectra were measured continuously during the reactions. This shows that the synthesis being done in the Chemputer can be dynamically controlled in response to feedback optimizing the reaction conditions according to the user requirements.
N2 - Ein Problem der chemischen Literatur ist die fehlende Standardisierung bezüglich genauer Bedingungen, auch Echtzeit-Korrekturen sind ohne Expertenwissen nur schwer möglich. Dieser Mangel an Details erschwert experimentelle Reproduzierbarkeit, da Schritte oft mehrdeutig sind und daher von implizitem Wissen abhängen. Hier präsentieren wir die Integration von Online-NMR Spektroskopie in eine automatisierte chemische Syntheseplattform (CSM aka. “Chemputer”, unter Verwendung einer universellen Programmiersprache zur Synthese kleiner Moleküle fähig), um eine automatisierte Analyse und Anpassung von Reaktionen im laufenden Betrieb zu ermöglichen. Das System wurde anhand von Grignard-Reaktionen, die aufgrund ihrer Bedeutung für die Synthese ausgewählt wurden, validiert und einem Härtetest unterzogen. Synthesen wurden in Echtzeit mit Online-NMR überwacht, und die Spektren wurden während der Reaktionen kontinuierlich aufgenommen und analysiert. Dies zeigt, dass der Chemputer dynamisch mittels einer Regelung kontrolliert werden kann, um die Reaktionsbedingungen entsprechend den Anforderungen des Benutzers zu optimieren.
KW - Grignard reaction
KW - NMR spectroscopy
KW - Process analytical technology
KW - Process control
KW - Grignard-Reaktion
KW - NMR-Spektroskopie
KW - Prozessanalytik
KW - Prozesskontrolle
PY - 2021
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-531260
SN - 1521-3773
SN - 1433-7851
N1 - Bibliografische Angaben für die deutsche Version: Angewandte Chemie 2021, Jg. 133, S. 1–7, ISSN 0044-8249, ISSN 1521-3757, https://doi.org/10.1002/ange.202106323 - Bibliographic information for the German version: Angewandte Chemie 2021, vol. 133, p. 1–7, ISSN 0044-8249, ISSN 1521-3757, https://doi.org/10.1002/ange.202106323
VL - 60
IS - 43
SP - 1
EP - 6
PB - Wiley-VCH
CY - Weinheim
AN - OPUS4-53126
LA - mul
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Gugin, Nikita
A1 - Villajos Collado, José Antonio
A1 - Dautain, O.
A1 - Maiwald, Michael
A1 - Emmerling, Franziska
T1 - Optimizing the Green Synthesis of ZIF-8 by Reactive Extrusion Using In Situ Raman Spectroscopy
N2 - We report the scale-up of a batch solid synthesis of zeolitic imidazolate framework-8 (ZIF-8) for reactive extrusion. The crystalline product forms in the extruder directly under the mixture of solid 2-methylimidazole and basic zinc carbonate in the presence of a catalytic amount of liquid. The process parameters such as temperature, liquid type, feeding rate, and linker excess were optimized using the setup specifically designed for in situ Raman spectroscopy. Highly crystalline ZIF-8 with a Brunauer–Emmett–Teller (BET) surface area of 1816 m2 g–1 was quantitatively prepared at mild temperature using a catalytic amount of ethanol and a small excess of the linker. Finally, we developed a simple and comprehensive approach to evaluating the environmental friendliness and scalability of metal–organic framework (MOF) syntheses in view of their large-scale production.
KW - Mechanochemistry
KW - In situ Raman
KW - Large-scale processing
KW - Metal−organic frameworks
KW - Twin-screw extrusion (TSE)
PY - 2023
U6 - https://doi.org/10.1021/acssuschemeng.2c07509
SN - 2168-0485
VL - 11
IS - 13
SP - 5175
EP - 5183
PB - ACS Publications
AN - OPUS4-57366
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Zientek, Nicolai
A1 - Batzdorf, Lisa
A1 - Kraume, M.
A1 - Emmerling, Franziska
A1 - Maiwald, Michael
T1 - Online-NMR-Methoden zur Analyse des Auflösungsverhaltens von pharmazeutischen Cokristallen
T2 - 8. Kolloquium Arbeitskreis Prozessanalytik
CY - Berlin, Germany
DA - 2012-12-03
KW - Quantitative Online-NMR-Spektroskopie
KW - Cokristalle
KW - Auflösungskinetik
PY - 2012
SN - 978-3-9815360-1-0
N1 - Geburtsname von Batzdorf, Lisa: Tröbs, L. - Birth name of Batzdorf, Lisa: Tröbs, L.
IS - P12
SP - 40
AN - OPUS4-28267
LA - deu
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Batzdorf, Lisa
A1 - Zientek, Nicolai
A1 - Rump, Doreen
A1 - Fischer, Franziska
A1 - Maiwald, Michael
A1 - Emmerling, Franziska
T1 - Make and break - Facile synthesis of cocrystals and comprehensive dissolution studies
N2 - Mechanochemistry is increasingly used as a ‘green alternative’ for synthesizing various materials including pharmaceutical cocrystals. Herein, we present the mechanochemical synthesis of three new cocrystals containing the API carbamazepine (cocrystals CBZ:Indometacin 1:1, CBZ:Benzamide 1:1, and CBZ:Nifedipine 1:1). The mechanochemical reaction was investigated in situ documenting a fast and complete reaction within one minute. Online NMR spectroscopy proved the direct influence of the dissolution behaviour of the coformers to the dissolution behaviour of the API carbamazepine. The dissolution behaviour of the organic cocrystals is compared to the behaviour of the pure drug indicating a general applicability of this approach for detailed cocrystal dissolution studies.
KW - Cocrystals
KW - Carbamazepine
KW - Mechanochemistry
KW - Powder diffraction
KW - Online NMR spectroscopy
PY - 2017
U6 - https://doi.org/10.1016/j.molstruc.2016.11.063
SN - 0022-2860
SN - 1872-8014
VL - 1133
SP - 18
EP - 23
AN - OPUS4-38664
LA - deu
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Villajos Collado, José Antonio
A1 - Bienert, M.
A1 - Gugin, Nikita
A1 - Emmerling, Franziska
A1 - Maiwald, Michael
T1 - A database to select affordable MOFs for volumetric hydrogen cryoadsorption considering the cost of their linkers
N2 - Physical adsorption at cryogenic temperature (cryoadsorption) is a reversible mechanism that can reduce the pressure of conventional compressed gas storage systems. Metal–organic framework (MOF) materials are remarkable candidates due to the combination of high specific surface area and density which, in some cases, provide a high volumetric storage capacity. However, such extensive use of MOFs for this application requires the selection of affordable structures, easy to produce and made from feasible metallic and organic components. Herein, we introduce a MOF database detailing the crystallographic and porous properties of 3600 existing MOFs made from industrially relevant metals and their organic composition. The comparison of the available minimum costs of linkers allowed the creation of a database to select affordable structures with high potential for volumetric hydrogen storage by cryoadsorption, considering their composition based on individual or mixed building blocks. A user inter� face, available online, facilitates the selection of MOFs based on the properties or names of structures and linkers.
KW - MOF´s
PY - 2023
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-583619
VL - 4
IS - 18
SP - 4226
EP - 4237
PB - Royal Society of Chemistry (RSC)
AN - OPUS4-58361
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Martins, Inês C.B.
A1 - Al-Sabbagh, Dominik
A1 - Meyer, Klas
A1 - Maiwald, Michael
A1 - Scholz, G.
A1 - Emmerling, Franziska
T1 - Insight into the Structure and Properties of Novel Imidazole-Based Salts of Salicylic Acid
N2 - The preparation of new active pharmaceutical ingredient (API) multicomponent Crystal forms, especially co-crystals and salts, is being considered as a reliable strategy to improve API solubility and bioavailability. In this study, three novel imidazole-based salts of the poorly water-soluble salicylic acid (SA) are reported exhibiting a remarkable improvement in solubility and dissolution rate properties. All structures were solved by powder X-ray diffraction. Multiple complementary techniques were used to solve co-crystal/salt ambiguities: density functional Theory calculations, Raman and 1H/13C solid-state NMR spectroscopies. In all molecular salts, the Crystal packing interactions are based on a common charged assisted +N-H SA)...O-(co-former) hydrogen bond interaction. The presence of an extra methyl group in different positions of the co-former, induced different supramolecular arrangements, yielding salts with different physicochemical properties.
All salts present much higher solubility and dissolution rate than pure SA. The most promising results were obtained for the salts with imidazole and 1-methylimidazole co-formers.
KW - Salicylic acid
KW - Imidazole
KW - Salts
KW - Powder X-ray diffraction
KW - SsNMR
KW - DFT
PY - 2019
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-502825
VL - 24
IS - 22
SP - 4144
PB - MDPI
AN - OPUS4-50282
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -