TY - JOUR
A1 - Donskyi, Ievgen
A1 - Nie, C.
A1 - Ludwig, K.
A1 - Trimpert, J.
A1 - Ahmed, R.
A1 - Quaas, E.
A1 - Achazi, K.
A1 - Radnik, Jörg
A1 - Adeli, M.
A1 - Haag, R.
A1 - Osterrieder, K.
T1 - Graphene Sheets with Defined Dual Functionalities for the Strong SARS-CoV-2 Interactions
N2 - Search of new strategies for the inhibition of respiratory viruses is one of the urgent health challenges worldwide, as most of the current therapeutic agents and treatments are inefficient. Severe acute respiratory syndrome coronavirus 2 (SARSCoV-2) has caused a pandemic and has taken lives of approximately two Million people to date. Even though various vaccines are currently under development, virus, and especially its spike glycoprotein can mutate, which highlights a Need for a broad-spectrum inhibitor. In this work, inhibition of SARS-CoV-2 by graphene platforms with precise dual sulfate/alkyl functionalities is investigated. A series of graphene derivatives with different lengths of aliphatic chains is synthesized and is investigated for their ability to inhibit SARS-CoV-2 and feline coronavirus.
Graphene derivatives with long alkyl chains (>C9) inhibit coronavirus replication by virtue of disrupting viral envelope. The ability of these graphene platforms to rupture viruses is visualized by atomic force microscopy and cryogenic electron microscopy. A large concentration window (10 to 100-fold) where graphene platforms display strongly antiviral activity against native SARS-CoV-2 without significant toxicity against human cells is found. In this concentration range, the synthesized graphene platforms inhibit the infection of enveloped viruses efficiently, opening new therapeutic and metaphylactic avenues against SARS-CoV-2.
KW - Graphene
KW - Graphene-based polyglycerol sulfates
KW - SARS-CoV2 inhibitor
KW - Virucidality
PY - 2021
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-520858
DO - https://doi.org/10.1002/smll.202007091
VL - 17
IS - 11
SP - 7091
PB - Wiley VCH
AN - OPUS4-52085
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Hünger, K.-J.
A1 - Kositz, M.
A1 - Danneberg, M.
A1 - Radnik, Jörg
T1 - Enrichment of aluminium in the near‐surface region of natural quartzite rock after aluminium exposure
N2 - Alkali–silica reaction (ASR) is an ongoing problem that causes damage to concrete constructions and reduces their durability. Therefore, minimizing this undesired reaction is of great interest for both safety and economic reasons. Additives containing high aluminium content are very effective in reducing the release of silica and enhancing the durability of concrete; however, the mechanism for this effect is still under discussion. In this study, an enrichment of aluminium in the near‐surface region was observed for natural quartzite rock after storage in Al (OH)3 and metakaolin as aluminium sources, from which we conclude that the formation of aluminosilicate sheets of a few nanometres inhibits the silica release; this hypothesis is supported by high‐resolution spectra of Al 2p, Si 2p and O 1s.
KW - Alkali-silica reaction
KW - Quartzite rock
KW - X-ray photoelectron spectroscopy
PY - 2020
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-519394
DO - https://doi.org/10.1002/sia.6918
SN - 0142-2421
SP - 1
EP - 7
PB - Wiley VCH
AN - OPUS4-51939
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Radnik, Jörg
A1 - Knigge, Xenia
A1 - Andresen, Elina
A1 - Resch-Genger, Ute
A1 - Cant, D.J.H.
A1 - Shard, A.G.
A1 - Clifford, C.A.
T1 - Composition, thickness, and homogeneity of the coating of core–shell nanoparticles—possibilities, limits, and challenges of X-ray photoelectron spectroscopy
N2 - Core–shell nanoparticles have attracted much attention in recent years due to their unique properties and their increasing importance in many technological and consumer products. However, the chemistry of nanoparticles is still rarely investigated in comparison to their size and morphology. In this review, the possibilities, limits, and challenges of X-ray photoelectron spectroscopy (XPS) for obtaining more insights into the composition, thickness, and homogeneity of nanoparticle coatings are discussed with four examples: CdSe/CdS quantum dots with a thick coating and a small core; NaYF4-based upconverting nanoparticles with a large Yb-doped core and a thin Er-doped coating; and two types of polymer nanoparticles with a poly(tetrafluoroethylene) core with either a poly(methyl methacrylate) or polystyrene coating. Different approaches for calculating the thickness of the coating are presented, like a simple numerical modelling or a more complex simulation of the photoelectron peaks. Additionally, modelling of the XPS background for the investigation of coating is discussed. Furthermore, the new possibilities to measure with varying excitation energies or with hard-energy X-ray sources (hard-energy X-ray photoelectron spectroscopy) are described. A discussion about the sources of uncertainty for the determination of the thickness of the coating completes this review.
KW - X-ray spectroscopy
KW - Nanoparticles
KW - Spectroscopy / Instrumentation
KW - Spectroscopy / Theory
PY - 2022
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-548305
DO - https://doi.org/10.1007/s00216-022-04057-9
VL - 414
IS - 15
SP - 4331
EP - 4345
PB - SpringerNature
AN - OPUS4-54830
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Page, T.M.
A1 - Nie, C.
A1 - Neander, L.
A1 - Povolotsky, T.L.
A1 - Sahoo, A.K.
A1 - Nickl, Philip
A1 - Adler, J.M.
A1 - Bawadkji, O.
A1 - Radnik, Jörg
A1 - Achazi, K.
A1 - Ludwig, K.
A1 - Lauster, D.
A1 - Netz, R.R.
A1 - Trimpert, J.
A1 - Kaufer, B.
A1 - Haag, R.
A1 - Donskyi, Ievgen
T1 - Functionalized Fullerene for Inhibition of SARS-CoV-2 Variants
N2 - As virus outbreaks continue to pose a challenge, a nonspecific viral inhibitor can provide significant benefits, especially against respiratory viruses. Polyglycerol sulfates recently emerge as promising agents that mediate interactions between cells and viruses through electrostatics, leading to virus inhibition.
Similarly, hydrophobic C60 fullerene can prevent virus infection via interactions with hydrophobic cavities of surface proteins. Here, two strategies are combined to inhibit infection of SARS-CoV-2 variants in vitro. Effective inhibitory concentrations in the millimolar range highlight the significance of bare fullerene’s hydrophobic moiety and electrostatic interactions of polysulfates with surface proteins of SARS-CoV-2. Furthermore, microscale thermophoresis measurements support that fullerene linear polyglycerol sulfates interact with the SARS-CoV-2 virus via its spike protein, and highlight importance of electrostatic interactions within it. All-atom molecular dynamics simulations reveal that the fullerene binding site is situated close to the receptor binding domain, within 4 nm of polyglycerol sulfate binding sites, feasibly allowing both portions of the material to interact simultaneously.
KW - Covalent functionalization
KW - Fullerene
KW - SARS-CoV 2
KW - Sulfated materials
KW - Virus inhibition
PY - 2023
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-568672
DO - https://doi.org/10.1002/smll.202206154
SN - 1613-6810
SP - 1
EP - 8
PB - Wiley VCH
AN - OPUS4-56867
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Bawadkji, O.
A1 - Cherri, M.
A1 - Schäfer, A.
A1 - Herziger, S.
A1 - Nickl, Philip
A1 - Achazi, K.
A1 - Donskyi, Ievgen
A1 - Adeli, M.
A1 - Haag, R.
T1 - One-pot covalent functionalization of 2D black phosphorus by anionic ring opening polymerization
N2 - In this work, a one-pot approach for the covalent functionalization of few-layer black phosphorus (BP) by anionic ring opening polymerization of glycidol to obtain multifunctional BP-polyglycerol (BP-PG) with high amphiphilicity for near-infrared-responsive drug delivery and biocompatibility is reported. Straightforward synthesis in combination with exceptional biological and physicochemical properties designates functionalized BP-PG as a promising candidate for a broad range of biomedical applications.
KW - 2D nanomaterial
KW - Amphiphilicity
KW - Black phosphorus
KW - Hyperbranched
KW - Polyglycerol
KW - Water dispersibility
PY - 2022
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-568833
DO - https://doi.org/10.1002/admi.202201245
SN - 2196-7350
VL - 9
SP - 1
EP - 8
PB - Wiley-VCH
CY - Weinheim
AN - OPUS4-56883
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Knigge, Xenia
A1 - Radnik, Jörg
T1 - 1,3-Dimethyl-imidazolium dimethyl phosphate ([MMIM]+[DMP]−) analyzed by XPS and HAXPES
N2 - The ionic liquid 1,3-dimethyl-imidazolium-dimethylphosphate ([MMIM]+[DMP]−) was analyzed using (hard) x-ray photoelectron spectroscopy.
Here, XPS and HAXPES spectra are shown in comparison. For the acquisition of the XPS spectra, monochromatic Al Kα radiation at 1486.6 eV was used, while for the acquisition of the HAXPES spectra, monochromatic Cr Kα radiation at 5414.8 eV was applied. Here, survey scans and high-resolution spectra of P 2p, P 2s, C 1s, O 1s, and N 1s for both methods and P 1s, P KL2,3L2,3, and P KL1L2,3 for HAXPES are shown.
KW - C7H15N2O4P
KW - [MMIM]+[DMP]−
KW - Lonic liquid
KW - Hard x-ray photoelectron spectroscopy
KW - HAXPES
KW - XPS
PY - 2023
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-571604
DO - https://doi.org/10.1116/6.0002297
VL - 30
IS - 1
SP - 1
EP - 20
PB - AIP Publishing
AN - OPUS4-57160
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Chen, Z.
A1 - Perez, J. P. H.
A1 - Smales, Glen Jacob
A1 - Blukis, R.
A1 - Pauw, Brian Richard
A1 - Stammeier, J. A.
A1 - Radnik, Jörg
A1 - Smith, A. J.
A1 - Benning, L. G.
T1 - Impact of organic phosphates on the structure and composition of short-range ordered iron nanophases
N2 - Organic phosphates (OP) are important nutrient components for living cells in natural environments, where they readily interact with ubiquitous iron phases such as hydrous ferric oxide, ferrihydrite (FHY). FHY partakes in many key bio(geo)chemical reactions including iron-mediated carbon storage in soils, or iron-storage in living organisms. However, it is still unknown how OP affects the formation, structure and properties of FHY. Here, we document how β-glycerophosphate (GP), a model OP ligand, affects the structure and properties of GP–FHY nanoparticles synthesized by coprecipitation at variable nominal molar P/Fe ratios (0.01 to 0.5). All GP–FHY precipitates were characterized by a maximum solid P/Fe ratio of 0.22, irrespective of the nominal P/Fe ratio. With increasing nominal P/Fe ratio, the specific surface area of the GP–FHY precipitates decreased sharply from 290 to 3 m2 g−1, accompanied by the collapse of their pore structure. The Fe–P local bonding environment gradually transitioned from a bidentate binuclear geometry at low P/Fe ratios to monodentate mononuclear geometry at high P/Fe ratios. This transition was accompanied by a decrease in coordination number of edge-sharing Fe polyhedra, and the loss of the corner-sharing Fe polyhedra. We show that Fe(III) polymerization is impeded by GP, and that the GP–FHY structure is highly dependent on the P/Fe ratio. We discuss the role that natural OP-bearing Fe(III) nanophases have in biogeochemical reactions between Fe–P and C species in aquatic systems.
KW - Organic phosphates
KW - Iron nanophases
KW - Scattering
KW - Diffraction
KW - Nanomaterials
KW - Coprecipitation
KW - Carbon storage
PY - 2024
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-599399
DO - https://doi.org/10.1039/d3na01045g
SN - 2516-0230
SP - 1
EP - 13
PB - Royal Society of Chemistry (RSC)
CY - Cambridge
AN - OPUS4-59939
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Bennet, Francesca
A1 - Opitz, R.
A1 - Ghoreishi, N.
A1 - Plate, K.
A1 - Barnes, J.-P.
A1 - Bellew, A.
A1 - Bellu, A.
A1 - Ceccone, G.
A1 - de Vito, E.
A1 - Delcorte, A.
A1 - Franquet, A.
A1 - Fumageli, F.
A1 - Gilliland, D.
A1 - Jungnickel, H.
A1 - Lee, T.G.
A1 - Poleunis, C.
A1 - Rading, D.
A1 - Shon, H.K.
A1 - Spampinato, V.
A1 - Son, J.G.
A1 - Wang, F.
A1 - Wang, Y.-C. A.
A1 - Zhao, Y.
A1 - Roloff, A.
A1 - Tentschert, J.
A1 - Radnik, Jörg
T1 - VAMAS TWA2 interlaboratory comparison: Surface analysis of TiO2 nanoparticles using ToF-SIMS
N2 - Due to the extremely high specific surface area of nanoparticles and corresponding potential for adsorption, the results of surface analysis can be highly dependent on the history of the particles, particularly regarding sample preparation and storage. The sample preparation method has, therefore, the potential to have a significant influence on the results. This report describes an interlaboratory comparison (ILC) with the aim of assessing which sample preparation methods for ToF-SIMS analysis of nanoparticles provided the most intra- and interlaboratory consistency and the least amount of sample contamination. The BAM reference material BAM-P110 (TiO2 nanoparticles with a mean Feret diameter of 19 nm) was used as a sample representing typical nanoparticles. A total of 11 participants returned ToF-SIMS data,in positive and (optionally) negative polarity, using sample preparation methods of “stick-and-go” as well as optionally “drop-dry” and “spin-coat.” The results showed that the largest sources of variation within the entire data set were caused by adventitious hydrocarbon contamination or insufficient sample coverage, with the spin-coating protocol applied in this ILC showing a tendency toward insufficient sample coverage; the sample preparation method or the participant had a lesser influence on results.
KW - Secondary Ion Mass Spectrometry
KW - VMAAS
KW - Titania
KW - Interlaboratory comparison
KW - Reproducibility
PY - 2023
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-582290
DO - https://doi.org/10.1116/6.0002814
SN - 0734-2101
VL - 41
IS - 5
SP - 053210-1
EP - 053210-13
PB - AIP (American Institute of Physics)
AN - OPUS4-58229
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Hirahara, Kenta
A1 - Bonse, Jörn
A1 - Krüger, Jörg
A1 - Weise, Matthias
A1 - Ermilova, Elena
A1 - Schusterbauer, Robert
A1 - Unterreiner, Andreas-Neil
A1 - Hertwig, Andreas
T1 - A multi-method study of femtosecond laser modification and ablation of amorphous hydrogenated carbon coatings
N2 - e present a study on femtosecond laser treatment of amorphous hydrogen-containing carbon coatings (a-C:H). The coatings were deposited on silicon wafers by a plasma-assisted chemical vapour deposition (PA-CVD), resulting in two different types of material with distinct properties (referred to as “absorbing” and “semi-transparent” coatings in the following).
The samples were laser-treated with single fs-laser pulses (800 nm center wavelength, 35 fs pulse duration) in the ablative regime. Through a multi-method approach using topometry, Raman spectroscopy, and spectroscopic imaging ellipsometry, we can identify zones and thresholds of diferent fuence dependent efects and have access to the local dielectric function.
The two coating materials react signifcantly diferent upon laser treatment. We determined the (non-ablative) modifcation threshold fuence for the absorbing coating as 3.6 × 10−2 Jcm−2 and its ablation threshold as 0.22 Jcm−2. The semi-transparent coating does not show such a low-fuence modifcation but exhibits a characteristic interference-based intra-flm ablation mechanism with two distinguishable ablation thresholds at 0.25 and 0.28 Jcm−2, respectively. The combination of tailored layer materials and correlative imaging spectroscopic methods delivers new insights into the behaviour of materials when treated with ultrashort-pulse laser radiation
KW - Amorphous Hydrogenated Carbon Coatings
KW - Correlative Imaging Measurement Techniques
KW - Hybrid Metrology
KW - Imaging Spectroscopy
KW - Spectroscopic Ellipsometry
KW - Ultra-short Pulse Laser Materials Processing
PY - 2024
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-617829
DO - https://doi.org/10.1007/s00339-024-07980-z
VL - 130
IS - 12
SP - 1
EP - 17
PB - Springer Science and Business Media LLC
AN - OPUS4-61782
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Broicher, Cornelia
A1 - Zeng, F.
A1 - Pfänder, N.
A1 - Frisch, M.
A1 - Bisswanger, T.
A1 - Radnik, Jörg
A1 - Stockmann, Jörg M.
A1 - Palkovits, S.
A1 - Beine, A. K.
A1 - Palkovits, R.
T1 - Iron and Manganese Containing Multi-Walled Carbon Nanotubes as Electrocatalysts for the Oxygen Evolution Reaction - Unravelling Influences on Activity and Stability
N2 - Hydrogen economy is a central aspect of future energy supply, as hydrogen can be used as energy storage and fuel. In order tomake water electrolysis efficient, the limiting oxygen evolution reaction (OER) needs to be optimized. Therefore, C-based composite materials containing earth-abundant Fe and Mn were synthesized, characterized and tested in the OER. For pyrolysis temperatures above 700°C N-rich multi-walled carbon nanotubes (MWCNT) are obtained. Inside the tubes Fe3C particles are formed, Fe and Mn oxides are incorporated in the carbon matrix and metal spinel nanoparticles cover the outer surface. The best catalyst prepared at 800°C achieves a low overpotential of 389 mV (at 10 mA/cm2) and high stability (22.6 h). From electrochemical measurements and characterization it can be concluded that the high activity is mainly provided by MWCNT, Fe3C and the metal oxides in the conductive carbon matrix. The metal spinel nanoparticles in
contrast protect the MWCNT from oxidation and thereby contribute to the high stability.
KW - Oxygen Evolution Reaction
KW - Carbon Nanotubes
KW - Stability
PY - 2020
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-513955
DO - https://doi.org/10.1002/cctc.202000944
VL - 12
IS - 21
SP - 1
EP - 8
PB - Wiley Online Libary
AN - OPUS4-51395
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Stockmann, Jörg M.
A1 - Radnik, Jörg
A1 - Bütefisch, S.
A1 - Busch, I.
A1 - Weimann, T.
A1 - Passiu, C.
A1 - Rossi, A.
A1 - Unger, Wolfgang
T1 - A new test specimen for the determination of the field of view of small-area X-ray photoelectron spectrometers
N2 - Small-area/spot photoelectron spectroscopy (SAXPS) is a powerful tool for the investigation of small surface features like microstructures of electronic devices, sensors or other functional surfaces, and so forth. For evaluating the quality of such microstructures, it is often crucial to know whether a small signal in a spectrum is an unwanted contamination of the field of view (FoV), defined by the instrument settings, or it originated from outside. To address this issue, the d80/20 parameter of a line scan across a chemical edge is often used. However, the typical d80/20 parameter does not give information on contributions from the long tails of the X-ray beam intensity distribution or the electron-optical system as defined by apertures. In the VAMAS TWA2 A22 project “Applying planar, patterned, multi-metallic samples to assess the impact of analysis area in surface-chemical analysis,” new test specimen was developed and tested. The here presented testing material consists of a silicon wafer substrate with an Au-film and embedded Cr circular and square spots with decreasing dimensions from 200 μm down to 5 μm. The spot sizes are traceable to the length unit due to size measurements with a metrological SEM. For the evaluation of the FoV, we determined the Au4f intensities measured with the center of the FoV aligned with the center of the spot and normalized to the Au4f intensity determined on the Au-film. With this test specimen, it was possible to characterize, as an example, the FoV of a Kratos AXIS Ultra DLD XPS instrument.
T2 - ECASIA 2019
CY - Dresden, Germany
DA - 15.09.2019
KW - Field of view
KW - Reference material
KW - Selected area XPS
KW - Small-area XPS
KW - Small-spot XPS
PY - 2020
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-509902
DO - https://doi.org/10.1002/sia.6831
SN - 1096-9918
VL - 52
IS - 12
SP - 890
EP - 894
PB - John Wiley & Sons Ltd
AN - OPUS4-50990
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Broichert, C.
A1 - Klingenhof, M.
A1 - Frisch, M.
A1 - Dresp, S.
A1 - Kubo, N.M.
A1 - Artz, J.
A1 - Radnik, Jörg
A1 - Palkovits, S.
A1 - Beine, A.K.
A1 - Strasser, P.
A1 - Palkovits, R.
T1 - Particle size-controlled synthesis of highperformance MnCo-based materials for alkaline OER at fluctuating potentials
N2 - For the large-scale generation of hydrogen via water electrolysis the design of long term stable and active catalysts for the oxygen evolution reaction (OER) remains a key challenge. Most catalysts suffer from severe structural corrosion that becomes even more pronounced at fluctuating potentials. Herein, MnCo based cubic particles were prepared via a hydrothermal approach, in which the edge length of the micron-sized particles can be controlled by changing the pH value of the precursor solution. The cubes are composed of varying amounts of MnCo2O4, CoCO3 and a mixed (Mn/Co)CO3 phase. Structure–activity relationships were deduced revealing a volcano-type behavior for the intrinsic OER activity and fraction of spinel oxide phase.
A low overpotential of 0.37 V at 10 mA cm−2 and a stability of more than 25 h was achieved in 1.0 M KOH using a rotating disc electrode (RDE) setup. The best performing catalyst material was successfully tested under dynamic process conditions for 9.5 h and shows a superior catalytic activity as anode for the Overall water splitting in an electrolyser setup in 1.0 M KOH at 333 K compared to a reference NiCo-spinel catalyst.
KW - Water electrolysis
KW - Oxygen evolution reaction
KW - Structure activity relationships
PY - 2021
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-536050
DO - https://doi.org/10.1039/d1cy00905b
SN - 2044-4753
VL - 11
IS - 12
SP - 7278
EP - 7286
PB - Royal Society of Chemistry
AN - OPUS4-53605
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
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-504755
DO - https://doi.org/10.1002/anie.201914798
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 - 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
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-523291
DO - https://doi.org/10.3389/fchem.2021.685789
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 - 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
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-512080
DO - https://doi.org/10.1039/D0TA05183G
VL - 8
IS - 32
SP - 16114
AN - OPUS4-51208
LA - eng
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
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-518226
DO - https://doi.org/10.3390/cryst10100889
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 - 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
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-508360
DO - https://doi.org/10.1002/chem.202001627
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 - 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
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-510821
DO - https://doi.org/10.1002/chem.202002653
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 - 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
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-512707
DO - https://doi.org/10.1002/chem.202002653
VL - 26
IS - 44
SP - 10133
EP - 10139
AN - OPUS4-51270
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Tantardini, C.
A1 - Michalchuk, Adam
A1 - Samtsevich, A.
A1 - Rota, C.
A1 - Kvashnin, A. G.
T1 - The Volumetric Source Function: Looking Inside van der Waals Interactions
N2 - The study of van der Waals interactions plays a central role in the understanding of bonding across a range of biological, chemical and physical phenomena. The presence of van der Waals interactions can be identified through analysis of the reduced density gradient, a fundamental parameter at the core of Density Functional Theory. An extension of Bader’s Quantum Theory of Atoms in Molecules is developed here through combination with the analysis of the reduced density gradient. Through this development, a new quantum chemical topological tool is presented: the volumetric source function.
This technique allows insight into the atomic composition of van der Waals interactions, offering the first route towards applying the highly successful source function to these disperse interactions. A new algorithm has been implemented in the open-source code, CRITIC2, and tested on acetone, adipic and maleic acids molecular crystals, each stabilized by van der Waals interactions. This novel technique for studying van der Waals interactions at an atomic level offers unprecedented opportunities in the fundamental study of intermolecular interactions and molecular design for crystal engineering, drug design and bio-macromolecular processes.
KW - Noncovalent interactions
PY - 2020
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-507911
DO - https://doi.org/10.1038/s41598-020-64261-4
VL - 10
IS - 1
SP - 7816
AN - OPUS4-50791
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
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-532089
DO - https://doi.org/10.1021/acssuschemeng.1c02063
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 - 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
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-531260
DO - https://doi.org/10.1002/anie.202106323
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 - Christopher, I
A1 - Michalchuk, Adam
A1 - Pulham, C.
A1 - Morrison, C.
T1 - Towards Computational Screening for New Energetic Molecules: Calculation of Heat of Formation and Determination of Bond Strengths by Local Mode Analysis
N2 - The reliable determination of gas-phase and solid-state heats of formation are important considerations in energetic materials research. Herein, the ability of PM7 to calculate the gas-phase heats of formation for CNHO-only and inorganic compounds has been critically evaluated, and for the former, comparisons drawn with isodesmic equations and Atom equivalence methods. Routes to obtain solid-state heats of formation for a range of singlecomponent molecular solids, salts, and co-crystals were also evaluated. Finally, local vibrational mode analysis has been used to calculate bond length/force constant curves for seven different chemical bonds occurring in CHNO-containing molecules, which allow for rapid identification of the weakest bond, opening up great potential to rationalise decomposition pathways. Both metrics are important tools in rationalising the design of new energetic materials through computational screening processes.
KW - Energetic materials
KW - Density functional theory
PY - 2021
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-530371
DO - https://doi.org/10.3389/fchem.2021.726357
VL - 9
SP - 726357
AN - OPUS4-53037
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
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-532075
DO - https://doi.org/10.1039/d1ce00642h
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 - 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
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-524041
DO - https://doi.org/10.1002/zaac.202000360
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 - 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
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-533855
DO - https://doi.org/10.1002/cmtd.202100028
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 - 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
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-507531
DO - https://doi.org/10.3390/nano10040713
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 - 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
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-520052
DO - https://doi.org/10.3390/cryst10121107
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 - 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
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-530360
DO - https://doi.org/10.1038/s41467-021-24165-x
VL - 12
IS - 1
SP - 3871
AN - OPUS4-53036
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Wurzler, Nina
A1 - Sobol, Oded
A1 - Altmann, Korinna
A1 - Radnik, Jörg
A1 - Özcan Sandikcioglu, Özlem
T1 - Preconditioning of AISI 304 stainless steel surfaces in the presence of flavins—Part I: Effect on surface chemistry and corrosion behavior
N2 - Stainless steel AISI 304 surfaces were studied after a mild anodic polarization for oxide growth in the presence and absence of two derivatives of vitamin B2 (riboflavin and flavin mononucleotide) that can be secreted by metal‐reducing bacteria and act as a chelating agent for iron species. The alterations in oxide chemistry were studied by means of surface‐sensitive techniques such as X‐ray photoelectron spectroscopy and time‐of‐flight secondary ion mass spectrometry analysis. The complementary electrochemical characterization revealed a preferential growth of an oxide/hydroxide iron‐rich film that is responsible for an altered pit initiation and nucleation behavior. These findings suggest that as the corrosion behavior is determined by the interplay of the chemical and electronic properties, only a mild anodic polarization in the presence of redox‐active molecules is able to alter the chemical and electronic structure of the passive film formed on stainless steel AISI 304. This helps to achieve a profound understanding of the mechanisms of microbially influenced corrosion (MIC) and especially the possible effects of the redox‐active biomolecules, as they may play an important role in the corrosion susceptibility of stainless steel surfaces.
KW - Corrosion
KW - Stainless steel
KW - Surface analysis
PY - 2021
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-528117
DO - https://doi.org/10.1002/maco.202012191
VL - 72
IS - 6
SP - 974
EP - 982
PB - Wiley
AN - OPUS4-52811
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
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-546712
DO - https://doi.org/10.1021/acs.cgd.1c01391
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 - Fahmy, A.
A1 - Anis, B.
A1 - Szymoniak, Paulina
A1 - Altmann, Korinna
A1 - Schönhals, Andreas
T1 - Graphene Oxide/Polyvinyl Alcohol–Formaldehyde Composite Loaded by Pb Ions: Structure and Electrochemical Performance
N2 - An immobilization of graphene oxide (GO) into a matrix of polyvinyl formaldehyde (PVF) foam as an eco-friendly, low cost, superior, and easily recovered sorbent of Pb ions from an aqueous solution is described. The relationships between the structure and electrochemical properties of PVF/GO composite with implanted Pb ions are discussed for the first time. The number of alcohol groups decreased by 41% and 63% for PVF/GO and the PVF/GO/Pb composite, respectively, compared to pure PVF. This means that chemical bonds are formed between the Pb ions and the PVF/GO composite based on the OH groups. This bond formation causes an increase in the Tg values attributed to the formation of a strong surface complexation between adjacent layers of PVF/GO composite. The conductivity increases by about 2.8 orders of magnitude compared to the values of the PVF/GO/Pb composite compared to the PVF. This means the presence of Pb ions is the main factor for enhancing the conductivity where the conduction mechanism is changed from ionic for PVF to electronic conduction for PVF/GO and PVF/GO/Pb.
KW - Graphene oxide
KW - Polyvinyl formaldehyde
KW - Lead ions
KW - Conductivity
PY - 2022
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-549588
DO - https://doi.org/10.3390/polym14112303
SN - 2073-4360
VL - 14
IS - 11
SP - 1
EP - 16
PB - MDPI
CY - Basel
AN - OPUS4-54958
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
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-546833
DO - https://doi.org/10.3389/fchem.2022.840758
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 - 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
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-546823
DO - https://doi.org/10.1002/chem.202200079
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 - 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
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-546803
DO - https://doi.org/10.1038/s41598-022-09774-w
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 - 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
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-547397
DO - https://doi.org/10.1002/zaac.202200026
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 - 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
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-549984
DO - https://doi.org/10.1002/anie.202203579
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 - 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
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-549934
DO - https://doi.org/10.1039/D2CE00393G
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 - 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
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-546841
DO - https://doi.org/10.1039/D2RA00740A
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 - 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
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-568431
DO - https://doi.org/10.1016/j.chemgeo.2022.121222
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 - 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
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-569503
DO - https://doi.org/10.1039/D2NR05630E
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 - 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
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-575862
DO - https://doi.org/10.1039/D3DT00839H
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 - Karafiludis, Stephanos
A1 - Ryll, T. W.
A1 - de Oliveira Guilherme Buzanich, Ana
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
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-579151
DO - https://doi.org/10.1039/D3CE00386H
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 - 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
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-577777
DO - https://doi.org/10.1021/acssuschemeng.2c07509
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 - 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
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-572290
DO - https://doi.org/10.1002/cctc.202300350
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 - Altmann, Korinna
A1 - Goedecke, Caroline
A1 - Bannick, C.-G.
A1 - Abusafia, A.
A1 - Scheid, C.
A1 - Steinmetz, H.
A1 - Paul, Andrea
A1 - Beleites, C.
A1 - Braun, U.
T1 - Identification of microplastic pathways within a typical European urban wastewater system
N2 - In recent years, thermoextraction/desorption-gas chromatography/mass spectrometry (TED-GC/MS) has been developed as a rapid detection method for the determination of microplastics (MP) mass contents in numerous environmentally relevant matrices and, in particular, for the measurement of polymers in water samples without time-consuming sample preparation. The TED-GC/MS method was applied to investigate a typical European municipal wastewater system for possible MP masses. Such investigations are important in view of the recent revision of the Urban Wastewater Treatment Directive. Four different representative sampling sites were selected: greywater (domestic wastewater without toilet), combined sewer, and influent and effluent of a wastewater treatment plant (WWTP). All samples were collected by fractional filtration. Filtration was carried out over mesh sizes of 500, 100, 50, and in some cases, 5 µm. Polyethylene (PE), polypropylene (PP), and polystyrene (PS) were detected in all samples, with the PE fraction dominating in all cases. Styrene-butadiene rubber which serves as an indication of tire abrasion, was only found in the influent of the WWTP. The highest MP mass contents were found in the combined sewer, so MP can become a source of pollution during heavy rain events when the capacity limits of the effluent are reached, and the polluted effluent is released uncontrolled into the environment. Based on the studies, MP retention from the WWTP could be estimated to be approximately 96%. Few trends in polymer type or mass contents were detected within the different fractions of the samples or when comparing samples to each other.
KW - Microplastics
KW - Microplastic analysis
KW - TED-GC/MS
KW - Microplastic pathways
KW - Mass contents
PY - 2023
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-568289
DO - https://doi.org/doi.org/10.1002/appl.202200078
SP - 1
EP - 10
PB - Wiley-VCH
CY - Weinheim
AN - OPUS4-56828
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Heinekamp, Christian
A1 - de Oliveira 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
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-582249
DO - https://doi.org/10.1039/D3CC03164K
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 - Oksal-Kilinc, Sefine
A1 - Altmann, Korinna
A1 - Seiwert, Bettina
A1 - Reemtsma, Thorsten
A1 - Ruess, Liliane
T1 - Grinding method and oxidative aging modulate the impact of tire wear microplastics on the reproduction of the nematode C. elegans
N2 - Rationale Tire abrasion is one of the largest sources of microplastic in aquatic and terrestrial environments. Despite this fact, research on tire wear microplastic (TWP) and its effects on soil ecosystems is scarce, especially regarding natural weathering processes. This leaves a large knowledge gap on the interactions of TWP with soil biota. Methodology Cryo-milled tire tread (CMTT) and diamond-ground tire tread (DGTT) were artificially weathered through dry ozone treatment and heat exposure. Particles were analyzed via scanning electron microscopy, particle size distribution, and shape characterization. TWP leachate composition was examined using liquid chromatography–mass spectrometry. The impact on the reproduction of the nematode Caenorhabditis elegans, a widely used toxicological model, was tested for leachate concentration, exposure duration and TWP aging status, using offspring per adult as the endpoint. Results The comminution method significantly influenced TWP particle size distribution, with diamond grinding yielding smaller particles and a more structured surface morphology than cryo-milling. Aging with ozone (180 min) and heat (20 min at 100 °C) reduced DGTT particle sizes by 27-58%, but not in CMTT. Additionally, aging increased carboxylic functional groups and led to a brittle structure in both TWP types. Leachate composition varied with comminution method and aging. Benzothiazole, N-Cyclo-N-phenylurea, and aniline were more abundant in pristine and aged CMTT and aged DGTT. Diphenylguanidine had the highest concentration in all leachates. Aged TWP leachates, regardless of comminution, had significant toxic effects on C. elegans. Leachate from pristine CMTT was more toxic than from pristine DGTT. Nematode offspring correlated negatively with ozone exposure duration in aged DGTT. Tests with aged CMTT leachate showed even short-term exposure reduced offspring numbers. Discussion The results underscore the importance of oxidative and mechanical weathering in TWP toxicity and challenge the use of pristine particles in toxicological assays for risk assessment in the natural environment.
KW - Microplastics
KW - Tire abrasion
KW - Environment
PY - 2025
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-654672
DO - https://doi.org/10.1071/EN25051
SN - 1448-2517
VL - 23
IS - 2
SP - 1
EP - 16
PB - CSIRO Publishing
AN - OPUS4-65467
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Miliūtė, Aistė
A1 - Bustamante, Joana
A1 - Karafiludis, Stephanos
A1 - Zöllner, Moritz
A1 - Eddah, Mustapha
A1 - Emmerling, Franziska
A1 - Mieller, Björn
A1 - George, Janine
A1 - Stawski, Tomasz M.
T1 - Synthesis and phase purity of the negative thermal expansion material ZrV2O7
N2 - Synthesis of pure, homogeneous, and reproducible materials is key for the comprehensive understanding, design, and tailoring of material properties. In this study, we focus on the synthesis of ZrV2O7, a material known for its negative thermal expansion properties. We investigate the influence of solid-state and wet chemistry synthesis methods on the purity and homogeneity of ZrV2O7 samples. Our findings indicate that different synthesis methods significantly impact the material's characteristics. The solid-state reaction provided high-purity material through extended milling time and repeated calcination cycles, while the sol-gel reaction enabled a “near-atomic” level of mixing and, therefore, homogenous phase-pure ZrV2O7. We confirmed purity via X-ray diffraction and Raman spectroscopy, highlighting differences between phase-pure and multiphase ceramics. These analytical techniques allowed us to distinguish subtle differences in the structure of the material. Based on ab initio simulated phonon data, we were able to interpret the Raman spectra and visualise Raman active atom vibrations. We show that phase purity enables the unbiased characterisation of material properties such as negative thermal expansion.
KW - NTE
KW - Sol-gel
KW - Solid-state
KW - Ab-initio
KW - XRD
KW - Raman
PY - 2024
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-624013
DO - https://doi.org/10.1039/d4tc04095c
SN - 2050-7534
SP - 1
EP - 13
PB - Royal Society of Chemistry (RSC)
AN - OPUS4-62401
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Heinekamp, Christian
A1 - Palmer, Tahlia M.
A1 - Al‐Sabbagh, Dominik
A1 - May, Anastasia
A1 - Prinz, Carsten
A1 - Michalik, Stefan
A1 - Michalchuk, Adam
A1 - Emmerling, Franziska
T1 - Pre‐Activation as a Route for Tuning the Kinetics of Mechanochemical Transformations
N2 - Learning to control reaction kinetics is essential for translating any chemical technology into real‐world application. Based on time‐resolved in situ powder X‐ray diffraction data, we demonstrate the opportunity to tune mechanochemical reaction rates through the pre‐activation of the starting reagents. For three model co‐crystal systems, the pre‐activation of the most stable reagent yields up to a ca 10‐fold increase in the reaction rate, whilst negligible kinetic enhancement is seen when the less stable reagent is pre‐activated. Moreover, we demonstrate how the polymorphic outcome of mechano‐co‐crystallization is also sensitive to pre‐activation of the starting material. Our results suggest that reproducibility of mechanochemical processes requires detailed understanding over the origin and history of reagent powders, whilst providing a new conceptual framework to design and control mechanochemical reactions.
KW - Mechanochemistry
KW - In situ synthesis
PY - 2025
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-649409
DO - https://doi.org/10.1002/anie.202516632
SN - 1433-7851
SP - 1
EP - 7
PB - Wiley VHC-Verlag
AN - OPUS4-64940
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Michalchuk, Adam
T1 - The Mechanochemical Excitation of Crystalline LiN3
N2 - Mechanochemical reactions are driven by the direct absorption of mechanical energy by a solid (often crystalline) material. Understanding how this energy is absorbed and ultimately causes a chemical transformation is essential for understanding the elementary stages of mechanochemical transformations. Using as a model system the energetic material LiN3 we here consider how vibrational energy flows through the crystal structure. By considering the compression response of the crystalline material we identify the partitioning of energy into an initial vibrational excitation. Subsequent energy flow is based on concepts of phonon–phonon scattering, which we calculate within a quasi-equilibrium model facilitated by phonon scattering data obtained from Density Functional Theory (DFT). Using this model we demonstrate how the moments (picoseconds) immediately following mechanical impact lead to significant thermal excitation of crystalline LiN3, sufficient to drive marked changes in its electronic structure and hence chemical reactivity. This work paves the way towards an ab initio approach to studying elementary processes in mechanochemical reactions involving crystalline solids.
KW - Energetic materials
KW - Ab initio simulation
KW - DFT
KW - Mechanochemistry
PY - 2022
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-559310
DO - https://doi.org/10.1039/d2fd00112h
SP - 1
EP - 20
PB - Royal Society of Chemistry
AN - OPUS4-55931
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
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
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-567659
DO - https://doi.org/10.1063/5.0130673
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 - 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
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-565302
DO - https://doi.org/10.1002/adom.202201518
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 - Bhattacharya, Biswajit
A1 - Michalchuk, Adam
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
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-577722
DO - https://doi.org/10.1039/D2SC06470G
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 - 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
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-564728
DO - https://doi.org/10.1039/d2fd00115b
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 - 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
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-581949
DO - https://doi.org/10.1021/acs.cgd.3c00473
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 - 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
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-565276
DO - https://doi.org/10.1021/acs.cgd.2c01227
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 - Liu, Yuanbin
A1 - Zhou, Yuxing
A1 - Ademuwagun, Richard
A1 - Walterbos, Luc
A1 - George, Janine
A1 - Elliott, Stephen R.
A1 - Deringer, Volker L.
T1 - Medium-Range Structural Order in Amorphous Arsenic
N2 - Medium-range order (MRO) is a key structural feature of amorphous materials, but its origin and nature remain elusive. Here, we reveal the MRO in amorphous arsenic (a-As) using advanced atomistic simulations, based on machine-learned potentials derived using automated workflows. Our simulations accurately reproduce the experimental structure factor of a-As, especially the first sharp diffraction peak (FSDP), which is a signature of MRO. We compare and contrast the structure of a-As with that of its lighter homologue, red amorphous phosphorus (a-P): we find that a-As has a more uniform dihedral-angle distribution, and so we confirm that its structure can be thought of as a 3-fold coordinated continuous random network in first approximation, in contrast to the more molecular-cluster-like structure of a-P. The pressure-dependent structural behaviors of a-As and a-P differ as well, and the origin of the FSDP is closely correlated with the size and spatial distribution of voids in the amorphous networks. Our work provides fundamental insights into MRO in an amorphous elemental system, and more widely it illustrates the usefulness of automation for machine-learning-driven atomistic simulations.
KW - Machine Learned Interatomic Potentials
KW - Amorphous
KW - Advanced Materials
KW - Automation
KW - Digitalisation
KW - Structure-Property- Relationships
PY - 2026
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-655952
DO - https://doi.org/10.1021/jacs.5c18688
SN - 0002-7863
SP - 1
EP - 13
PB - American Chemical Society (ACS)
AN - OPUS4-65595
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Völzke, Jule L.
A1 - Hodjat Shamami, Parya
A1 - Gawlitza, Kornelia
A1 - Feldmann, Ines
A1 - Zimathies, Annett
A1 - Meyer, Klas
A1 - Weller, Michael G.
T1 - High-purity corundum as support for affinity extractions from complex samples
N2 - Nonporous corundum powder, known as an abrasive material in the industry, was functionalized covalently with protein binders to isolate and enrich specific proteins from complex matrices. The materials based on corundum were characterized by TEM, ESEM, BET, DLS, EDS, and zeta potential measurements. The strong Al-O-P bonds between the corundum surface and amino phosphonic acids were used to introduce functional groups for further conjugations. The common crosslinker glutaraldehyde was compared with a hyperbranched polyglycerol (PG) of around 10 kDa. The latter was oxidized with periodate to generate aldehyde groups that can covalently react with the amines of the surface and the amino groups from the protein via a reductive amination process. The amount of bound protein was quantified via aromatic amino acid analysis (AAAA). This work shows that oxidized polyglycerol can be used as an alternative to glutaraldehyde. With polyglycerol, more of the model protein bovine serum albumin (BSA) could be attached to the surface under the same conditions, and lower non-specific binding (NSB) was observed. As a proof of concept, IgG was extracted with protein A from crude human plasma. The purity of the product was examined by sodium dodecyl sulfate-polyacrylamide gel electrophoresis (SDS-PAGE). A binding capacity of 1.8 mg IgG per gram of corundum powder was achieved. The advantages of corundum include the very low price, extremely high physical and chemical stability, pressure resistance, favorable binding kinetics, convenient handling, and flexible application.
KW - Corundum
KW - Sapphire
KW - Affinity chromatography
KW - Antibodies
KW - Self-assembled monolayers (SAM)
KW - Polyglycerol
KW - Dendrimer
KW - Nonspecific binding (NSB)
KW - Purification
KW - Solid-phase extraction (SPE)
PY - 2022
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-559342
DO - https://doi.org/10.3390/separations9090252
VL - 9
IS - 9
SP - 1
EP - 13
PB - MDPI
CY - Basel
AN - OPUS4-55934
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Tannenberg, Robert
A1 - Paul, Martin
A1 - Röder, Bettina
A1 - Gande, S. L.
A1 - Sreeramulu, S.
A1 - Saxena, K.
A1 - Richter, C.
A1 - Schwalbe, H.
A1 - Swart, C.
A1 - Weller, Michael G.
T1 - Chemiluminescence biosensor for the determination of cardiac troponin I (cTnI)
N2 - Cardiac troponin I (cTnI) is a crucial biomarker for diagnosing cardiac vascular diseases, including acute myocardial infarction (AMI). This study presents a proof-of-concept chemiluminescence-based immunosensor for rapid and accurate measurement of cTnI, with the potential for online monitoring. The immunosensor incorporates a flow cell design and a sensitive complementary metal-oxide-semiconductor (CMOS) camera for optical readout. A microfluidic setup was established to enable selective and quasi-online determination of cTnI within ten minutes. The sensor was tested with recombinant cTnI in phosphate buffer, demonstrating measurements in the concentration range of 2–25 µg/L, with a limit of detection (LoD) of 0.6 µg/L (23 pmol/L) achieved using the optimized system. The immunosensor exhibited high selectivity, as no cross-reactivity was observed with other recombinant proteins such as cTnT and cTnC at a concentration of 16 µg/L. Measurements with diluted blood plasma and serum yielded an LoD of 60 µg/L (2.4 nmol/L) and 70 µg/L (2.9 nmol/L), respectively. This biosensor offers a promising approach for the rapid and sensitive detection of cTnI, contributing to the diagnosis and management of acute myocardial infarction and other cardiac vascular diseases.
N2 - Das kardiale Troponin I (cTnI) ist ein wichtiger Biomarker für die Diagnose von Herz-Kreislauf-Erkrankungen, einschließlich des akuten Myokardinfarkts (AMI). In dieser Studie wird ein auf Chemilumineszenz basierender Immunsensor für die schnelle und genaue Messung von cTnI vorgestellt, der das Potenzial für eine Online-Überwachung hat. Der Immunsensor besteht aus einer Durchflusszelle und einer empfindlichen CMOS-Kamera (Complementary Metal-Oxide-Semiconductor) zur optischen Detektion. Es wurde ein mikrofluidischer Aufbau entwickelt, der eine selektive und quasi Online-Bestimmung von cTnI innerhalb von zehn Minuten ermöglicht. Der Sensor wurde mit rekombinantem cTnI in Phosphatpuffer getestet und zeigte einen Messbereich von 2-25 µg/L, wobei mit dem optimierten System eine Nachweisgrenze (LoD) von 0,6 µg/L (23 pmol/L) erreicht wurde. Der Immunsensor zeigte eine hohe Selektivität, da keine Kreuzreaktivität mit anderen rekombinanten Proteinen wie cTnT und cTnC bei einer Konzentration von 16 µg/L beobachtet wurde. Messungen mit verdünntem Blutplasma und Serum ergaben einen LoD von 60 µg/L (2,4 nmol/L) bzw. 70 µg/L (2,9 nmol/L). Dieser Biosensor bietet einen vielversprechenden Ansatz für den schnellen und empfindlichen Nachweis von cTnI, der zur Diagnose und Behandlung des akuten Myokardinfarkts und anderer kardialer Gefäßerkrankungen beitragen kann.
KW - Acute myocardial infarction
KW - Heart attack
KW - Emergency
KW - Diagnosis
KW - Cardiac troponin
KW - Biomarker
KW - Immunosensor
KW - Biosensor
KW - Chemiluminescence
KW - Luminol
KW - Peroxidase
KW - Monoclonal antibodies
KW - Flow injection immunoassay
KW - Immunometric assay
KW - Immunometric biosensor
KW - Microfluidic system
KW - Monolithic column
KW - Online biosensor
PY - 2023
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-575471
DO - https://doi.org/10.3390/bios13040455
SN - 2079-6374
VL - 13
IS - 4
SP - 1
EP - 20
PB - MDPI
CY - Basel
AN - OPUS4-57547
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Raab, A. R.
A1 - Grießler, T. R.
A1 - Rück, D.
A1 - Li, Z.
A1 - Zens, A.
A1 - Bruckner, J. R.
A1 - Huber, P.
A1 - Schönhals, Andreas
A1 - Szymoniak, Paulina
A1 - Laschat, S.
T1 - Salt complexation drives liquid crystalline selfassembly in crown ether–amino acid hybrids
N2 - Crown ether–amino acid hybrids represent a promising class of amphiphilic molecules combining ion recognition with self-assembly capabilities. Despite extensive studies on their binding properties, the influence of inorganic salt complexation on their liquid crystalline behaviour remains underexplored. Here we synthesized amphiphilic [18]-crown-6 derivatives of L-dihydroxyphenylalanine and tetrahydroisoquinoline analogues, systematically investigating the effects of alkyl chain length and salt type on mesophase formation. Complexation with various salts induced liquid crystalline phases, transitioning from smectic A to columnar hexagonal structures as anion size and alkyl chain length increased.
Structural analyses and electron density mapping revealed assembly into charged superdiscs forming columnar stacks with tunable ion channels. Broadband dielectric spectroscopy highlighted differences in molecular mobility and conductivity linked to molecular design. These findings establish salt complexation as a key strategy to control self-assembly and ion transport in crown ether–amino acid hybrids, advancing their potential in responsive soft materials and ion-conductive applications.
KW - Ionic liquid crystals
PY - 2026
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-655986
DO - https://doi.org/10.1039/d5tc04129e
SP - 1
EP - 18
PB - Royal Society of Chemistry (RSC)
AN - OPUS4-65598
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Frechilla, A.
A1 - Martínez, E.
A1 - del Moral, J.
A1 - López-Santos, C.
A1 - Frechilla, J.
A1 - Nuñez-Gálvez, F.
A1 - López-Flores, V.
A1 - de la Fuente, G.F.
A1 - Hülagü, Deniz
A1 - Bonse, Jörn
A1 - González-Elipe, A.R.
A1 - Borrás, A.
A1 - Angurel, L.A.
T1 - Influence of near-edge Laser-Induced Periodic Surface Structures (LIPSS) on the electrical properties of fs-laser-machined ITO microcircuits
N2 - Scalable, cost-effective methods for processing transparent electrodes at the microscale are pivotal to advancing in electrochemistry, optoelectronics, microfluidics, and energy harvesting. In these fields, the precise fabrication of micrometric circuits and patterns plays a critical role in determining device performance, material compatibility, and integration with added-value substrates. In this context, Laser Subtractive Manufacturing stands out as a suitable microfabrication technique for its adaptability to diverse materials and complex configurations, as well as its straightforward scalability, affordability, and eco-friendly nature. However, a challenge in micromachining metals and metal oxides is the inherent formation of Laser-Induced Periodic Surface Structures (LIPSS), which can significantly impair electrical conductivity, particularly when circuit dimensions fall within the micrometer range. Herein, we investigate the micromachining of electrical microcircuits using ultrashort pulse laser systems applied to transparent indium tin oxide (ITO) thin films. We analyze the formation of LIPSS at the edges of the micromachined regions associated with the Gaussian distribution of the energy within the laser spot, and the impact of these structures on the electrical properties of the circuits. Thus, we systematically evaluate the influence of LIPSS orientation and periodicity by fabricating various circuit patterns using femtosecond lasers at green (515 nm) and ultraviolet (UV) (343 nm) wavelengths. A correlation between electrical resistivity measurements and microstructure analysis, as determined by field emission scanning electron and transmission electron microscopy, reveals distinct effects of the formed nanostructures depending on the laser source and its polarization. For the green wavelength, the edge side regions where LIPSS are oriented perpendicular to the ITO track exhibit a resistance higher by a factor just above two compared to those where LIPSS are parallel. Additionally, UV laser processing results in a pronounced reduction of ITO thickness at the boundary between the LIPSS region and the substrate. The mechanisms for the formation of LIPSS with both wavelengths are also discussed. Furthermore, we have determined that in narrow conductive tracks with a width ranging from 6 to 8 µm, the impact of LIPSS is particularly significant because the LIPSS structured region occupies a dominant fraction of the total width.
KW - ITO
KW - Laser-induced periodic surface structures (LIPSS)
KW - Laser subtractive manufacturing
KW - fs-laser processing
KW - Electrical properties
PY - 2026
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-655921
DO - https://doi.org/10.1016/j.apsusc.2026.166415
SN - 0169-4332
VL - 731
SP - 1
EP - 13
PB - Elsevier B.V.
AN - OPUS4-65592
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Altmann, Korinna
A1 - Portela, Raquel
A1 - Barbero, Francesco
A1 - Breuninger, Esther
A1 - Camassa, Laura Maria Azzurra
A1 - Velickovic, Tanja Cirkovic
A1 - Charitidis, Costas
A1 - Costa, Anna
A1 - Fadda, Marta
A1 - Fengler, Petra
A1 - Fenoglio, Ivana
A1 - Giovannozzi, Andrea M.
A1 - Haugen, Øyvind Pernell
A1 - Kainourgios, Panagiotis
A1 - von der Kammer, Frank
A1 - Kirchner, Markus J.
A1 - Lomax-Vogt, Madeleine
A1 - Lujic, Tamara
A1 - Milczewski, Frank
A1 - Moussawi, Mhamad Aly
A1 - Ortelli, Simona
A1 - Parac-Vogt, Tatjana N.
A1 - Potthoff, Annegret
A1 - Reinosa, Julian J.
A1 - Röschter, Sophie
A1 - Sacco, Alessio
A1 - Wimmer, Lukas
A1 - Zanoni, Ilaria
A1 - Dailey, Lea Ann
T1 - Characterizing nanoplastic suspensions of increasing complexity: Inter-laboratory comparison of size measurements using dynamic light scattering
N2 - Understanding the potential human health risks associated with micro- and nanoplastic exposure is currently a priority research area. Nanoplastic toxicity studies are complicated by the lack of available, well-characterized test and reference materials. Further, many nanoplastic test materials are inherently more polydisperse and heterogenous in shape compared to polystyrene beads, making accurate and representative size distribution measurements particularly challenging. The aim of this study was to conduct an inter-laboratory comparison of dynamic light scattering measurements, the most commonly used particle sizing method for nanomaterials. Using a published standard operating procedure, size measurements in water and a standardized cell culture medium (CCM) were generated for spherical, carboxy-functionalized polystyrene nanoparticles (PS-COOH; 50 nm; benchmark material), and for increasingly complex in-house produced spherical poly(ethylene terephthalate) (nanoPET) and irregular shaped polypropylene (nanoPP) test materials. The weighted mean of hydrodynamic diameters of PS-COOH dispersed in water (55 ± 5 nm) showed moderate variation between labs (coefficient of variation, CV = 8.2%) and were similar to literature reports. Measurements of nanoPET (82 ± 6 nm) and nanoPP (182 ± 12 nm) in water exhibited similar CV values (nanoPET: 7.3% and nanoPP; 6.8%). Dispersion of PS-COOH and nanoPET in CCM increased the CV to 15.1 and 14.2%, respectively, which is lower than literature reports (CV = 30%). We conclude with a series of practical recommendations for robust size measurements of nanoplastics in both water and complex media highlighting that strict adherence to a standard operating procedure is required to prevent particle agglomeration in CCM
KW - Nanoplastics
KW - Reference materials
KW - Polypropylene
PY - 2025
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-644571
DO - https://doi.org/10.1039/d5en00645g
SN - 2051-8153
SP - 1
EP - 15
PB - Royal Society of Chemistry (RSC)
CY - Cambridge
AN - OPUS4-64457
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Hickel, Tilmann
A1 - Waske, Anja
A1 - Tehranchi, Ali
A1 - Bhattacharya, Biswajit
A1 - Stawski, Tomasz M.
A1 - Fellinger, Tim-Patrick
A1 - Mehmood, Asad
A1 - Witt, Julia
A1 - Ozcan, Ozlem
A1 - Guilherme Buzanich, Ana
A1 - Kumar, Sourabh
A1 - Mishra, Rajesh Kumar
A1 - Holzer, Marco
A1 - Stucchi de Camargo, Andrea Simone
A1 - Agudo Jácome, Leonardo
A1 - Manzoni, Anna
A1 - Fantin, Andrea
A1 - John, Elisabeth
A1 - Hodoroaba, Vasile-Dan
A1 - Bührig, Sophia
A1 - Murugan, Jegatheesan
A1 - Marschall, Niklas
A1 - George, Janine
A1 - Darvishi Kamachali, Reza
A1 - Maaß, Robert
A1 - Emmerling, Franziska
T1 - Chemically complex materials enable sustainable high-performance materials
N2 - Chemically complex materials (CCMats) including high-entropy alloys, oxides, and related multi-principal element systems offer a paradigm shift in materials design by leveraging chemical diversity to simultaneously optimize functional, structural, and sustainability criteria. The vastness of the compositional and structural space in CCMats propels the field into an expanding exploratory state. To reconcile functional and structural performance across this immense parameter space remains an open challenge. This Perspective evaluates the opportunities and challenges associated with harnessing chemical complexity across a broad spectrum of applications, such as hydrogen storage, ionic conductors, catalysis, magnetics, dielectrics, semiconductors, optical materials, and multifunctional structural systems. It is delineated how three central design strategies: targeted substitution (SUB), defect engineering (DEF), and diversity management (DIV) enable the reconciliation of high functional performance with long-term structural stability and environmental responsibility.
Advances in computational thermodynamics, microstructure simulations, machine learning, and multimodal characterization are accelerating the exploration and optimization of CCMats, while robust data infrastructures and automated synthesis workflows are emerging as essential tools for navigating their complex compositional space. By fostering cross-disciplinary knowledge transfer and embracing data-driven design, CCMats are poised to deliver next-generation materials solutions that address urgent technological, energy, and
environmental demands.
KW - Chemically complex materials
KW - Structural stability
KW - Functional performance
KW - Design strategies
KW - Sustainability
PY - 2026
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-655598
UR - https://www.sciencedirect.com/science/article/pii/S1359028626000033?via%3Dihub
DO - https://doi.org/10.1016/j.cossms.2026.101256
SN - 1359-0286
VL - 42
SP - 1
EP - 26
PB - Elsevier Ltd.
CY - Amsterdam
AN - OPUS4-65559
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Stolar, Tomislav
A1 - Alić, Jasna
A1 - Casali, Lucia
A1 - Gugin, Nikita
A1 - Baláž, Matej
A1 - Michalchuk, Adam
A1 - Emmerling, Franziska
ED - Stolar, Tomislav
T1 - Mechanochemistry: Looking back and ahead
N2 - Starting with the discovery of fire and the preparation of food in prehistoric times, mechanochemistry is the oldest form of chemistry that humans have controlled. Mechanochemical practices, such as grinding with a mortar and pestle, continued into the Middle Ages until dedicated scientific studies began in the 19th century. Since then,research in mechanochemistry has shown that many chemicalreactions can be performed via mechanical force without or with small amounts of solvent. Besides being time, material, and energy efficient, mechanochemical reactions often yield products that differ from those obtained in solution. Therefore, not only is mechanochemistry greener and more sustainable than conventional solution chemistry, but it also has the added value of providing new reactivity and selectivity. This is especially important today, when chemists need to invent high-performance materials, intermediates, and products with the use of sustainable feedstocks and develop environmental remediation pathways. At the same time, time-resolved in situ monitoring and computational modeling are necessary for addressing fundamental questions about the atomistic, molecular, and electronic nature of mechanochemical reactivity. Integrating digitalization, robotics, and artificial intelligence tools promises to increase the reproducibility and scalability of mechanochemical processes. Further evolution of mechanochemistry is expected to have a transformative effect on the chemical industry.
KW - Mechanochemistry
PY - 2026
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-653962
DO - https://doi.org/10.1016/j.chempr.2025.102880
SN - 2451-9294
VL - 12
IS - 2
SP - 1
EP - 27
PB - Elsevier BV
AN - OPUS4-65396
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Casali, Lucia
A1 - Carta, Maria
A1 - Michalchuk, Adam
A1 - Delogu, Francesco
A1 - Emmerling, Franziska
T1 - Kinetics of the mechanically induced ibuprofen–nicotinamide co-crystal formation by in situ X-ray diffraction
N2 - Mechanochemistry is drawing attention from the pharmaceutical industry given its potential for sustainable material synthesis and manufacture. Scaling mechanochemical processes to industrial level remains a challenge due to an incomplete understanding of their underlying mechanisms. We here show how time-resolved in situ powder X-ray diffraction data, coupled with analytical kinetic modelling, provides a powerful approach to gain mechanistic insight into mechanochemical reactions. By using the ibuprofen–nicotinamide co-crystal mechanosynthesis as a benchmark system, we investigate the behaviour of the solids involved and identify the factors that promote the reaction. As mechanochemical mechanisms become increasingly clear, it promises to become a breakthrough in the industrial preparation of advanced pharmaceuticals.
KW - Mechanochemistry
KW - Kinetics
PY - 2024
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-608820
DO - https://doi.org/10.1039/D4CP01457J
SN - 1463-9084
VL - 26
SP - 22041
EP - 22048
PB - Royal Society of Chemistry (RSC)
CY - Cambridge
AN - OPUS4-60882
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
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-558878
DO - https://doi.org/10.1039/d2fd00115b
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 - Haugen, Øyvind P.
A1 - Polanco-Garriz, Itziar
A1 - Alcolea-Rodriguez, Victor
A1 - Portela, Raquel
A1 - Bæra, Rita
A1 - Sadeghiankaffash, Hamed
A1 - Hildebrandt, Jana
A1 - Ciornii, Dmitri
A1 - Altmann, Korinna
A1 - Barbero, Francesco
A1 - Fenoglio, Ivana
A1 - Reinosa, Julián J.
A1 - Fernández, José F.
A1 - Katsumiti, Alberto
A1 - Camassa, Laura M.A.
A1 - Wallin, Håkan
A1 - Zienolddiny-Narui, Shan
A1 - Afanou, Anani K.
T1 - Activation of Toll-like receptor 2 reveals microbial contamination beyond endotoxins on micro- and nanoplastics
N2 - Current literature on health hazards associated with micro- and nanoplastics (MNPs) is largely influenced by studies that insufficiently account for potential microbial contamination of their test materials. This may lead to misinterpretation of outcomes, as the test materials may be incorrectly considered pristine MNPs. The present study screened eight MNP test materials for microbial contaminants using Toll-like receptor (TLR) reporter cells for TLR2 and TLR4 and the commonly used Limulus amebocyte lysate (LAL) assay. Our results show that MNPs testing negative for endotoxins, based on the absence of TLR4 activation and negative LAL results, may still contain microbial ligands that selectively activate TLR2. Moreover, five of the eight MNP test materials contained microbial ligands capable of activating TLR2 and/or TLR4. Compared to the LAL assay, TLR4-based screening effectively detected endotoxin contamination. Overall, we found that the TLR reporter cell assay provides broader coverage than the LAL assay in detecting microbial ligands, which appear to be highly prevalent in MNP test materials.
KW - Nanoplastics
KW - Microplastics
KW - Microbial contamination
PY - 2026
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-653286
DO - https://doi.org/10.1016/j.tiv.2025.106190
SN - 0887-2333
VL - 112
SP - 1
EP - 8
PB - Elsevier Ltd.
AN - OPUS4-65328
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Putzu, Mara
A1 - Wiesner, Yosri
A1 - Weimann, Christiane
A1 - Hodoroaba, Vasile-Dan
A1 - Muniategui Lorenzo, Soledad
A1 - Fernández-Gonzáles, Verónica
A1 - Booth, Andy M.
A1 - Igartua, Amaia
A1 - Benismail, Nizar
A1 - Coïc, Laureen
A1 - Chivas-Joly, Carine
A1 - Fenoglio, Ivana
A1 - Rossi, Andrea Mario
A1 - Giovannozzi, Andrea Mario
A1 - Altmann, Korinna
T1 - Optimization of tablet processing as a reference material for microplastic detection methods
N2 - Reference materials (RMs) are essential and highly demanded tools for the development and validation of methods for microplastic (MP) quantification in complex matrices, to ensure comparable and harmonized approaches aligned with EU commission criteria for monitoring MPs (e.g., Drinking Water Directive and Urban Wastewater Treatment Directive). This study investigates different approaches for optimizing the production of polypropylene (PP) RMs in the form of water-soluble tablets, which were carefully evaluated for their homogeneity and stability according to ISO Guide 30, ISO 33401, and ISO 33405. PP particles (1–100 μm) were produced by cryomilling and embedded in a lactose/PEG matrix, then pressed into tablets (18 µg theoretical PP mass). The production process was optimized by varying (i) the size distribution of the matrix components and (ii) the mixer instrument. The materials obtained were characterized by thermogravimetric analysis to assess the homogeneity distribution of MPs with respect to PP mass in the individual tablets and their stability over a 4-month period. The most promising approach, with a homogenous mass of 19 μg (standard deviation of 4 μg), relative standard deviation of 19%, was further investigated for homogeneity by comparison with thermo-analytical mass determination methods, such as TED-GC/MS (thermal extraction desorption-gas chromatography/mass spectrometry) and Py-GC/MS (pyrolysis-gas chromatography-mass spectrometry), and for number-based characterization using micro-Raman spectroscopy. Material characterization was also examined using laser diffraction, scanning electron microscopy, and ATR-FTIR. Based on the results, the optimized processing protocol yields a PP RM suitable for quality control and method performance studies supporting standardization.
KW - Microplastics
KW - TED-GC/MS
KW - Reference materials
KW - Polypropylene
PY - 2025
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-653290
DO - https://doi.org/10.1007/s00216-025-06271-7
SN - 1618-2642
SP - 1
EP - 14
PB - Springer Science and Business Media LLC
AN - OPUS4-65329
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Wiesner, Yosri
A1 - Eisentraut, Paul
A1 - Altmann, Korinna
T1 - One Year Observation of Microplastic Concentrations in the River Rhine
N2 - In recent years, the quantification of microplastics (MP) in aquatic environments has gained increasing attention, particularly regarding their environmental distribution and potential exposure levels. Environmentally relevant exposure data are still essential for a realistic risk assessment of the harmful health potential of microplastics in freshwater systems. This study addresses a large data set of MP concentrations analyzed and processed under statistical aspects and provides mass concentrations as well as associated size fractions of the detected MP. Over a 12 month period, samples were collected at three locations and analyzed across three particle size fractions (100−500 μm, 50−100 μm, and 10−50 μm) using thermalextraction desorption-gas chromatography/mass spectrometry (TED-GC/MS). The most prevalent polymers identified were polyethylene (PE), polypropylene (PP), polystyrene (PS), styrene−butadiene rubber (SBR), and natural rubber (NR). Statistical analyses, including principal component and cluster analysis, revealed size-dependent patterns,minor seasonal variation and spatial variations. These findings are particularly significant for ecotoxicological research and regulatory development, especially regarding tire abrasion a rarely quantified but potentially harmful MP source. The study contributes aluable data for future environmental monitoring and supports EU directives on wastewater and drinking water quality
KW - TED-GC/MS
KW - Microplastics
KW - Environment
KW - Monitoring
KW - Reference data
PY - 2026
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-654669
DO - https://doi.org/10.1021/acsestwater.5c00530
SN - 2690-0637
SP - 1
EP - 10
PB - American Chemical Society (ACS)
AN - OPUS4-65466
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Hemingway, Jack M.
A1 - Quayle, Heather M.
A1 - Byrne, Cian
A1 - Pulham, Colin R.
A1 - Mondal, Subrata
A1 - Michalchuk, Adam
A1 - Morrison, Carole A.
T1 - Predicting impact sensitivities for an extended set of energetic materials via the vibrational up-pumping model: Molecular-based structure–property relationships identified
N2 - We have applied the vibrational up-pumping model to predict the mechanically-induced impact sensitivities of 33 molecular energetic crystals. Overall, the current model successfully identifies and ranks the compounds that are most sensitive to mechanical initiation, but offers poorer differentiation between compounds with lower sensitivity. Further developments to include the effects of trigger bond activation led to significant improvements in predictive capability. We show that this structure–property model highlights the importance of molecular flexibility in predicting impact sensitivity, and furthermore, we show that the Kier molecular flexibility index, which can be obtained from a SMILES string, offers a simple molecular-based descriptor that goes some way towards predicting the sensitivity of energetic materials.
KW - Vibrational
KW - Pyrazoles
KW - Comprising
KW - Electronic
PY - 2025
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-632651
DO - https://doi.org/10.1039/d5cp00852b
SN - 1463-9076
VL - 27
IS - 22
SP - 11640
EP - 11648
PB - Royal Society of Chemistry (RSC)
CY - Cambridge
AN - OPUS4-63265
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Ghiringhelli, Luca M.
A1 - Baldauf, Carsten
A1 - Bereau, Tristan
A1 - Brockhauser, Sandor
A1 - Carbogno, Christian
A1 - Chamanara, Javad
A1 - Cozzini, Stefano
A1 - Curtarolo, Stefano
A1 - Draxl, Claudia
A1 - Dwaraknath, Shyam
A1 - Fekete, Ádám
A1 - Kermode, James
A1 - Koch, Christoph T.
A1 - Kühbach, Markus
A1 - Ladines, Alvin Noe
A1 - Lambrix, Patrick
A1 - Himmer, Maja-Olivia
A1 - Levchenko, Sergey V.
A1 - Oliveira, Micael
A1 - Michalchuk, Adam
A1 - Miller, Ronald E.
A1 - Onat, Berk
A1 - Pavone, Pasquale
A1 - Pizzi, Giovanni
A1 - Regler, Benjamin
A1 - Rignanese, Gian-Marco
A1 - Schaarschmidt, Jörg
A1 - Scheidgen, Markus
A1 - Schneidewind, Astrid
A1 - Sheveleva, Tatyana
A1 - Su, Chuanxun
A1 - Usvyat, Denis
A1 - Valsson, Omar
A1 - Wöll, Christof
A1 - Scheffler, Matthias
T1 - Shared metadata for data-centric materials science
N2 - The expansive production of data in materials science, their widespread sharing and repurposing requires educated support and stewardship. In order to ensure that this need helps rather than hinders scientific work, the implementation of the FAIR-data principles (Findable, Accessible, Interoperable, and Reusable) must not be too narrow. Besides, the wider materials-science community ought to agree on the strategies to tackle the challenges that are specific to its data, both from computations and experiments. In this paper, we present the result of the discussions held at the workshop on “Shared Metadata and Data Formats for Big-Data Driven Materials Science”. We start from an operative definition of metadata, and the features that a FAIR-compliant metadata schema should have. We will mainly focus on computational materials-science data and propose a constructive approach for the FAIRification of the (meta)data related to ground-state and excited-states calculations, potential-energy sampling, and generalized workflows. Finally, challenges with the FAIRification of experimental (meta)data and materials-science ontologies are presented together with an outlook of how to meet them.
KW - Library and Information Sciences
KW - Statistics, Probability and Uncertainty
KW - Computer Science Applications
KW - Education
KW - Information Systems
KW - Statistics and Probability
PY - 2023
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-584846
DO - https://doi.org/10.1038/s41597-023-02501-8
VL - 10
IS - 1
SP - 1
EP - 18
PB - Springer Science and Business Media LLC
AN - OPUS4-58484
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Michalchuk, Adam
T1 - On the physical processes of mechanochemically induced transformations in molecular solids
N2 - Initiating or sustaining physical and chemical transformations with mechanical force – mechanochemistry – provides an opportunity for more sustainable chemical processes, and access to new chemical reactivity.
KW - Molecular solids
KW - Transformation
KW - Destabilisation
KW - Instabilities
KW - Common phenomenon
PY - 2024
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-621755
DO - https://doi.org/10.1039/d4cc04062g
IS - 99
SP - 1
EP - 12
PB - Royal Society of Chemistry (RSC)
AN - OPUS4-62175
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Driscoll, Laura L.
A1 - Driscoll, Elizabeth H.
A1 - Dong, Bo
A1 - Sayed, Farheen N.
A1 - Wilson, Jacob N.
A1 - O’Keefe, Christopher A.
A1 - Gardner, Dominic J.
A1 - Grey, Clare P.
A1 - Allan, Phoebe K.
A1 - Michalchuk, Adam
A1 - Slater, Peter R.
T1 - Under pressure: offering fundamental insight into structural changes on ball milling battery materials
N2 - Synthesis of Li ion battery materials via ball milling has been a huge area of growth, leading to new high-capacity electrode materials, such as a number of promising disordered rocksalt (DRS) phases. In prior work, it was generally assumed that the synthesis was facilitated simply by local heating effects during the milling process. In this work, we show that ball milling Li2MoO4 leads to a phase transformation to the high pressure spinel polymorph and we report electrochemical data for this phase. This observation of the formation of a high pressure polymorph shows that local heating effects alone cannot explain the phase transformation observed (phenakite to spinel) and so indicates the importance of other effects. In particular, we propose that when the milling balls collide with the material, the resulting shockwaves exert a localised pressure effect, in addition to local heating. To provide further support for this, we additionally report ball milling results for a number of case studies (Li2MnO3, Li2SnO3, Nb2O5) which reinforces the conclusion that local heating alone cannot explain the phase transformations observed. The work presented thus provides greater fundamental understanding of milling as a synthetic pathway and suggests potential strategies to prepare such samples without milling (e.g., doping to create internal chemical pressure). In addition, we suggest that further research is needed into the effect of the use of milling as a route to smaller particles, since we believe that such milling may also be affecting the surface structure of the particles through the influence of the shockwaves generated.
KW - Pollution
KW - Nuclear Energy and Engineering
KW - Sustainability and the Environment
KW - Environmental Chemistry
KW - Renewable Energy
PY - 2023
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-590086
DO - https://doi.org/10.1039/d3ee00249g
VL - 16
IS - 11
SP - 5196
EP - 5209
PB - Royal Society of Chemistry (RSC)
AN - OPUS4-59008
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Dudziak, Mateusz
A1 - Riechers, Birte
A1 - Maaß, Robert
A1 - Michalchuk, Adam
A1 - Schönhals, Andreas
A1 - Szymoniak, Paulina
T1 - Beyond conventional calorimetry: Unlocking thermal characterization with fast scanning techniques
N2 - Fast scanning calorimetry (FSC) has emerged as a transformative technique in thermal analysis, enabling the investigation of rapid and kinetically driven thermal transitions that are inaccessible to conventional differential scanning calorimetry. This review highlights the capabilities enabled by FSC for studying a wide range of materials under extreme thermal conditions, including polymers, pharmaceuticals, metallic glasses, nanocomposites, and hydrogels. By employing ultrafast heating and cooling rates, FSC allows for the suppression of crystallization, resolution of weak transitions, and analysis of thermally labile or size-limited samples. The technique is particularly valuable for probing glass transitions, relaxation phenomena, and phase behavior in systems with complex morphologies or confined geometries. Case studies demonstrate the use of FSC in characterizing vitrification, physical aging, and interfacial dynamics, as well as its application in emerging fields such as additive manufacturing, supramolecular systems, and neuromorphic materials. Together, these examples underscore the role that FSC plays in advancing the understanding of structure-property relationships across diverse material classes.
KW - Flash DSC
KW - Calorimetry
KW - Glass transition
PY - 2025
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-647405
DO - https://doi.org/10.1016/j.tca.2025.180177
VL - 754
SP - 1
EP - 14
PB - Elsevier B.V.
AN - OPUS4-64740
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
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
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-589219
DO - https://doi.org/10.1002/chem.202302150
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 - Gugin, Nikita
A1 - Yusenko, Kirill
A1 - King, Andrew
A1 - Meyer, Klas
A1 - Al-Sabbagh, Dominik
A1 - Villajos Collado, José Antonio
A1 - Emmerling, Franziska
T1 - Lighting up industrial mechanochemistry: Real-time in situ monitoring of reactive extrusion using energy-dispersive X-ray diffraction
N2 - Mechanochemistry is an environmentally friendly synthetic approach that enables the sustainable production of a wide range of chemicals while reducing or eliminating the need for solvents. Reactive extrusion aims to move mechanochemistry from its conventional gram-scale batch reactions, typically performed in laboratory ball mills, to a continuous, large-scale process. Meeting this challenge requires in situ monitoring techniques to gain insights into reactive extrusion and its underlying processes. While the effectiveness of in situ Raman spectroscopy in providing molecular-level information has been demonstrated, our study uses energy-dispersive X-ray diffraction to monitor reactive extrusion in real time at the crystalline level. Our results provide previously unavailable control over the reactive extrusion process, promoting its perception as an industrially feasible green alternative to traditional solvent-based syntheses.
KW - Mechanochemistry
KW - Reactive extrusion
KW - Green chemistry
KW - In situ studies
KW - Time-resolved in situ
KW - TRIS
KW - Synchrotron radiation
KW - Scalable synthesis
KW - Solid-state reactions
KW - Reaction mechanisms
PY - 2024
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-613969
DO - https://doi.org/10.1016/j.chempr.2024.07.033
VL - 10
IS - 11
SP - 1
EP - 16
PB - Elsevier B.V.
AN - OPUS4-61396
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Wimmer, L
A1 - Hoang, M V N
A1 - Schwarzinger, J
A1 - Jovanovic, V
A1 - Adelkovic, B
A1 - Velickovic, T C
A1 - Meisel, T C
A1 - Waniek, T
A1 - Weimann, Christiane
A1 - Altmann, Korinna
A1 - Dailey, L A
T1 - A quality-by-design inspired approach to develop PET and PP nanoplastic test materials for use in in vitro and in vivo biological assays
N2 - Micro- and nanoplastics have become environmental pollutants of concern, receiving increased attention from consumers, scientists, and policymakers. The lack of knowledge about possible impacts on wildlife and human health requires further research, for which well-characterized testmaterials are needed. A quality-bydesign (QbD) driven approachwas used to produce sterile, endotoxinmonitored nanoplastics of polyethylene terephthalate (PET) and polypropylene (PP) with a size fraction of >90% below 1 μm and high yield of >90%. Glycerol was used as a versatile and biocompatible liquid storage medium which requires no further exogenous dispersing agent andmaintained colloidal stability, sterility (0 CFU mL−1), and low endotoxin levels (<0.1 EU mL−1) for more than one year of storage at room temperature. Further, the glycerol vehicle showed no biological effect on the tested human bronchial cell line Calu-3 up to 0.8% (w/v). Given the concentration of 40 mg g−1 nanoplastics in the glycerol stock, this corresponds to a nanoplastic concentration of 320 μg mL−1. The surfactant-free nanoplastics are dispersible in bio-relevant media from the glycerol stock without changing size characteristics and are suitable for in vitro and in vivo research.
KW - Microplastics
KW - Reference materials
KW - Nanoplastics
KW - Polymer 3R
KW - Glycerol
PY - 2025
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-629934
DO - https://doi.org/10.1039/D4EN01186D
SN - 2051-8161
VL - 12
IS - 5
SP - 2667
EP - 2686
PB - Royal Society of Chemistry
CY - Cambridge
AN - OPUS4-62993
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Starkholm, A.
A1 - Al-Sabbagh, Dominik
A1 - Sarisozen, S
A1 - von Reppert, A
A1 - Rössle, M
A1 - Ostermann, Markus
A1 - Unger, E
A1 - Emmerling, Franziska
A1 - Kloo, L
A1 - Svensson, P
A1 - Lang, F
A1 - Maslyanchuk, O.
T1 - Green Fabrication of Sulfonium-Containing Bismuth Materials for High-Sensitivity X-Ray Detection
N2 - Organic–inorganic hybrid materials based on lead and bismuth have recently been proposed as novel X- and gamma-ray detectors for medical imaging, non-destructive testing, and security, due to their high atomic numbers and facile preparation compared to traditional materials like amorphous selenium and Cd(Zn)Te. However, challenges related to device operation, excessively high dark currents, and long-term stability have delayed commercialization. Here, two novel semiconductors incorporating stable sulfonium cations are presented, [(CH3CH2)3S]6Bi8I30 and [(CH3CH2)3S]AgBiI5, synthesized via solvent-free ball milling and fabricated into dense polycrystalline pellets using cold isostatic compression, two techniques that can easily be upscaled, for X-ray detection application. The fabricated detectors exhibit exceptional sensitivities (14 100–15 190 µC Gyair−1 cm−2) and low detection limits (90 nGyair s−1 for [(CH3CH2)3S]6Bi8I30 and 78 nGyair s−1 for [(CH3CH2)3S]AgBiI5), far surpassing current commercial detectors. Notably, they maintain performance after 9 months of ambient storage. The findings highlight [(CH3CH2)3S]6Bi8I30 and [(CH3CH2)3S]AgBiI5 as scalable, cost-effective and highly stable alternatives to traditional semiconductor materials, offering great potential as X-ray detectors in medical and security applications.
KW - Mechanochemistry
KW - X-ray detectors
PY - 2025
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-630306
DO - https://doi.org/10.1002/adma.202418626
SP - 1
EP - 10
PB - Wiley VHC-Verlag
AN - OPUS4-63030
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Rodríguez-Sánchez, Noelia
A1 - Bhattacharya, Biswajit
A1 - Emmerling, Franziska
A1 - Prinz, Carsten
A1 - Prieto-Laria, P.
A1 - Ruiz-Salvador, A.R.
A1 - Ballesteros, M.
T1 - Engineering a multivariate cobalt metal–organic framework for high photocatalytic activity: the impact of mixed ligands and metal incorporation in a visible light-driven heterogeneous photo-Fenton reaction for water treatment
N2 - Metal–organic frameworks (MOFs) have attracted increasing attention for the removal of organic pollutants in wastewater via photocatalysis. Here, we design a multivariate modification of ZIF-9 to tune its electronic properties for use in visible light photocatalysis. A controllable synthesis of ZIF-9 and its multivariate forms with the incorporation of copper and the 2-imidazolecarboxaldehyde (ica) ligand was carried out. The materials are tested for the removal of the model dye methylene blue (MB) by a heterogeneous photo-Fenton-like reaction at neutral pH and room temperature. Cu-ZIF-9-ica (UPO-3) shows high photocatalytic activity under both visible and ultraviolet A (UVA) light, achieving 94% MB degradation in 45 min, compared to 65% MB degradation in 120 min using bare ZIF-9. The study revealed a first-order rate constant of 0.0475 min−1 for Cu-ZIF-9-ica compared to 0.0088 min−1 for ZIF-9 under visible light. The improvement of the catalyst was clearly attributed to the co-incorporation of Cu and the ica ligand in the MOF, which reduces the band gap, in agreement with DFT calculations. Reproducibility and recyclability tests proved that Cu-ZIF-9-ica can be used for at least 3 cycles without a significant loss of efficiency, making it a promising material for the study and application of wastewater treatment.
KW - Metal-Organic Framework (MOF)
KW - Heterogeneous photo-Fenton
KW - ZIF-9
KW - Methylene Blue
PY - 2025
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-630797
DO - https://doi.org/10.1039/d4na00954a
SN - 2516-0230
VL - 7
IS - 8
SP - 2255
EP - 2265
PB - Royal Society of Chemistry
AN - OPUS4-63079
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Tscheuschner, Georg
A1 - Ponader, Marco
A1 - Raab, Christopher
A1 - Weider, Prisca S.
A1 - Hartfiel, Reni
A1 - Kaufmann, Jan Ole
A1 - Völzke, Jule L.
A1 - Bosc-Bierne, Gaby
A1 - Prinz, Carsten
A1 - Schwaar, T.
A1 - Andrle, Paul
A1 - Bäßler, Henriette
A1 - Nguyen, Khoa
A1 - Zhu, Y.
A1 - Mey, A. S. J. S.
A1 - Mostafa, A.
A1 - Bald, I.
A1 - Weller, Michael G.
T1 - Efficient Purification of Cowpea Chlorotic Mottle Virus by a Novel Peptide Aptamer
N2 - The cowpea chlorotic mottle virus (CCMV) is a plant virus explored as a nanotechnological platform. The robust self-assembly mechanism of its capsid protein allows for drug encapsulation and targeted delivery. Additionally, the capsid nanoparticle can be used as a programmable platform to display different molecular moieties. In view of future applications, efficient production and purification of plant viruses are key steps. In established protocols, the need for ultracentrifugation is a significant limitation due to cost, difficult scalability, and safety issues. In addition, the purity of the final virus isolate often remains unclear. Here, an advanced protocol for the purification of the CCMV from infected plant tissue was developed, focusing on efficiency, economy, and final purity. The protocol involves precipitation with PEG 8000, followed by affinity extraction using a novel peptide aptamer. The efficiency of the protocol was validated using size exclusion chromatography, MALDI-TOF mass spectrometry, reversed-phase HPLC, and sandwich immunoassay. Furthermore, it was demonstrated that the final eluate of the affinity column is of exceptional purity (98.4%) determined by HPLC and detection at 220 nm. The scale-up of our proposed method seems to be straightforward, which opens the way to the large-scale production of such nanomaterials. This highly improved protocol may facilitate the use and implementation of plant viruses as nanotechnological platforms for in vitro and in vivo applications.
N2 - Das Cowpea Chlorotic Mottle Virus (CCMV) ist ein Pflanzenvirus, das als nanotechnologische Plattform erforscht wird. Der robuste Selbstorganisationsmechanismus seines Kapsidproteins ermöglicht die Verkapselung und gezielte Abgabe von Medikamenten. Darüber hinaus kann das Kapsid-Nanopartikel als programmierbare Plattform für die Präsentation verschiedener molekularer Komponenten verwendet werden. Im Hinblick auf künftige Anwendungen ist eine effiziente Produktion und Reinigung von Pflanzenviren von entscheidender Bedeutung. In etablierten Protokollen stellt die notwendige Ultrazentrifugation aufgrund von Kosten, schwieriger Skalierbarkeit und Sicherheitsaspekten eine erhebliche Einschränkung dar. Darüber hinaus bleibt die Reinheit des endgültigen Virusisolats oft unklar. Hier wurde ein fortschrittliches Protokoll für die Reinigung von CCMV aus infiziertem Pflanzengewebe entwickelt, wobei der Schwerpunkt auf Effizienz, Wirtschaftlichkeit und Reinheit lag. Das Protokoll beinhaltet eine Fällung mit Polyethylenglycol (PEG 8000), gefolgt von einer Affinitätsextraktion mit einem neuartigen Peptid-Aptamer. Die Effizienz des Protokolls wurde mithilfe von Größenausschluss-Chromatographie (SEC), MALDI-TOF-Massenspektrometrie, Umkehrphasen-HPLC und Sandwich-Immunoassay validiert. Darüber hinaus wurde nachgewiesen, dass das endgültige Eluat der Affinitätssäule eine außergewöhnliche Reinheit (98,4 %) aufweist, die durch HPLC und Detektion bei 220 nm bestimmt wurde. Die Skalierung der von uns vorgeschlagenen Methode scheint einfach zu sein, was den Weg für eine größer angelegte Produktion solcher Nanomaterialien ebnet. Dieses stark verbesserte Protokoll könnte die Verwendung und Umsetzung von Pflanzenviren als nanotechnologische Plattformen für In-vitro- und In-vivo-Anwendungen erleichtern.
KW - Affinity chromatography
KW - Nanoparticles
KW - Nanoscience
KW - Carrier protein
KW - Encapsulation
KW - Combinatorial peptide library
KW - Peptide binder
KW - Vigna unguiculata
KW - Augenbohne
KW - Schlangenbohne
KW - Pflanzenvirus
KW - Plant virus
KW - Upscaling
KW - Commercialization
KW - Reference material
KW - Nanocarrier
PY - 2023
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-572645
DO - https://doi.org/10.3390/v15030697
VL - 15
IS - 3
SP - 1
EP - 24
PB - MDPI
CY - Basel, Schweiz
AN - OPUS4-57264
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Liu, Yanchen
A1 - de Oliveira Guilherme Buzanich, Ana
A1 - Montoro, Luciano A.
A1 - Liu, Hao
A1 - Liu, Ye
A1 - Emmerling, Franziska
A1 - Russo, Patrícia A.
A1 - Pinna, Nicola
T1 - A partially disordered crystallographic shear block structure as fast-charging negative electrode material for lithium-ion batteries
N2 - A well-ordered crystalline structure is crucial in battery electrodes, as the dimensionality and connectivity of the interstitial sites inherently influence Li+ ions diffusion kinetics. Niobium tungsten oxides block structures, composed of ReO3-type blocks of specific sizes with well-defined metal sites, are promising fast-charging negative electrode materials. Structural disorder is generally detrimental to conductivity or ion transport. However, here, we report an anomalous partially disordered Nb12WO33 structure that significantly enhances Li-ion storage performance compared to the known monoclinic Nb12WO33 phase. The partially disordered phase consists of corner-shared NbO6 octahedra blocks of varied sizes, including 5×4, 4×4, and 4×3, with a disordered arrangement of distorted WO4 tetrahedra at the corners of the blocks. This structural arrangement is robust during lithiation/delithiation, exhibiting minor local structure changes during cycling. It enables accelerated Li-ion migration, resulting in promising fast-charging performance, namely, 62.5 % and 44.7 % capacity retention at 20 C and 80 C, respectively. This study highlights the benefits of introducing disorder into niobium tungsten oxide shear structures, through the establishment of clear structure-performance correlations, offering guidelines for designing materials with targeted properties.
KW - Lithium ion batteries
KW - Oxides
KW - XANES
KW - XRD
PY - 2025
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-637994
DO - https://doi.org/10.1038/s41467-025-61646-9
SN - 2041-1723
VL - 16
IS - 1
SP - 1
EP - 15
PB - Springer Science and Business Media LLC
AN - OPUS4-63799
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Heinekamp, Christian
A1 - Roy, Arkendu
A1 - Karafiludis, Stephanos
A1 - Kumar, Sourabh
A1 - de Oliveira Guilherme Buzanich, Ana
A1 - Stawski, Tomasz M.
A1 - Miliūtė, Aistė
A1 - von der Au, Marcus
A1 - Ahrens, Mike
A1 - Braun, Thomas
A1 - Emmerling, Franziska
T1 - Zirconium fluoride-supported high-entropy fluoride: a catalyst for enhanced oxygen evolution reaction
N2 - Extended hydrogen initiatives promote the urgency of research on water splitting technologies and, therein, oxygen evolution reaction catalysts being developed. A route to access a ZrF4 supported high-entropy fluoride catalyst using a facile sol–gel route is presented. The high-entropy character of the catalyst was confirmed by scanning transmission electron microscopy and energy dispersive X-ray spectroscopy (STEM-EDX) as well as inductively coupled plasma-mass spectrometry (ICP-MS). Additional investigations on the local structure were performed using extended X-ray absorption fine structure spectroscopy (EXAFS) and pair distribution function (PDF) analysis. The catalyst shows significant potential for oxygen evolution reaction (OER) in alkaline media with a current density of 100 mA cm−2 at approximately 1.60 V, thus outperforming benchmark materials such as IrO2, despite a significant reduction in electrochemical mass loading. A potential mechanism is suggested based on free energy calculation using DFT calculations.
KW - OER
KW - HEA
KW - CCMAT
PY - 2025
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-637116
DO - https://doi.org/10.1039/D4TA08664C
SN - 2050-7488
VL - 13
IS - 26
SP - 20383
EP - 20393
PB - Royal Society of Chemistry (RSC)
AN - OPUS4-63711
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Dittmar, Stefan
A1 - Weyrauch, Steffen
A1 - Reemtsma, Thorsten
A1 - Eisentraut, Paul
A1 - Altmann, Korinna
A1 - Ruhl, Aki S.
A1 - Jekel, Martin
T1 - Settling Velocities of Tire and Road Wear Particles: Analyzing Finely Graded Density Fractions of Samples from a Road Simulator and a Highway Tunnel
N2 - The terminal settling velocity is considered the most critical parameter determining the transport of tire and road wear particles (TRWP) in aquatic environments. Nonetheless, no respective empirical data has been reported so far. In this study, particle samples from a road simulator and a highway tunnel were investigated with a validated imaging method. Different density and size fractions of both samples were measured separately, acquiring sizes and settling velocities of more than 30,000 individual particles. In addition, tire marker polymers were analyzed for each fraction via thermal extraction desorption-gas chromatography/mass spectrometry. Finally, the acquired particle data was combined according to the fractions’ estimated tire contents in order to deduce detailed probability distributions of particle size and settling velocity for the actual TRWP from both samples. Weighted by TRWP-incorporated tire mass, median diameters of 54 and 44 μm as well as median settling velocities of 0.65 and 0.22 mm/s were found for TRWP from the road simulator and highway tunnel, respectively. This study thus provides the first ever empirical data on TRWP settling velocities in water, which can be highly valuable input for modeling the environmental transport of TRWP and for dimensioning TRWP retention systems.
KW - Microplastics
KW - TED-GC/MS
KW - Sinking velocities
KW - Transport
PY - 2025
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-635449
DO - https://doi.org/10.1021/acs.est.5c04165
SN - 0013-936X
VL - 59
IS - 26
SP - 13434
EP - 13446
PB - American Chemical Society (ACS)
AN - OPUS4-63544
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Das, Prasenjit
A1 - Chakraborty, Gouri
A1 - Yang, Jin
A1 - Roeser, Jérôme
A1 - Küçükkeçeci, Hüseyin
A1 - Nguyen, Anh Dung
A1 - Schwarze, Michael
A1 - Gabriel, Jose
A1 - Penschke, Christopher
A1 - Du, Shengjun
A1 - Weigelt, Vincent
A1 - Khalil, Islam E.
A1 - Schmidt, Johannes
A1 - Saalfrank, Peter
A1 - Oschatz, Martin
A1 - Rabeah, Jabor
A1 - Schomäcker, Reinhard
A1 - Emmerling, Franziska
A1 - Thomas, Arne
T1 - The Effect of Pore Functionality in Multicomponent Covalent Organic Frameworks on Stable Long‐Term Photocatalytic H2 Production
N2 - AbstractIn nature, organic molecules play a vital role in light harvesting and photosynthesis. However, regarding artificial water splitting, the research focus is primarily on inorganic semiconductors. Although organic photocatalysts have high structural variability, they tend to exhibit lower quantum efficiencies for water splitting than their inorganic counterparts. Multicomponent reactions (MCRs) offer an attractive route to introduce different functional units into covalent organic frameworks (COFs) and enable semiconducting properties and high chemical stability, creating promising materials for long‐term photocatalytic applications, such as H2 production. Herein, five highly crystalline donor‐acceptor based, 4‐substituted quinoline‐linked MCR‐COFs are presented that are prepared via the three‐component Povarov reaction. The pore functionality is varied by applying different vinyl derivatives (e.g., styrene, 2‐vinyl pyridine, 4‐vinylpyridine, 4‐vinyl imidazole, 2,3,4,5,6‐pentafluorostyrene), which has a strong influence on the obtained photocatalytic activity. Especially an imidazole‐functionalized COF displays promising photocatalytic performance due to its high surface area, crystallinity, and wettability. These properties enable it to maintain its photocatalytic activity even in a membrane support. Furthermore, such MCR‐COFs display dramatically enhanced (photo)chemical stability even after long‐term solar light irradiation and exhibit a high and steady H2 evolution for at least 15 days.
KW - Sstability
KW - Covalent organic frameworks
KW - Pore functionality
KW - Long-term H2 production
KW - Multicomponent reactions
PY - 2025
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-639787
DO - https://doi.org/10.1002/aenm.202501193
SN - 1614-6832
SP - 1
EP - 10
PB - Wiley VHC-Verlag
AN - OPUS4-63978
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Visileanu, Emilia
A1 - Altmann, Korinna
A1 - Stepa, Raluca
A1 - Haiducu, Maria
A1 - Miclea, Paul Tiberiu
A1 - Vladu, Alina
A1 - Dondea, Felicia
A1 - Grosu, Marian Catalin
A1 - Scarlat, Razvan
T1 - Comparative Analysis of Airborne Particle Concentrations in Textile Industry Environments Throughout the Workday
N2 - This paper addresses the growing concern surrounding microplastic pollution, particularly within the textile industry, and the associated potential health risks linked to the inhalation and ingestion of microplastic particles. Microplastics, defined as plastic particles smaller than five millimeters, are increasingly found not only in aquatic environments, but also in soils, air, and food. Although research on the health impacts of microplastics is still emerging, early studies indicate that these particles could contribute to health issues, including oxidative stress, inflammation, and cardiovascular diseases. Notably, individuals with higher concentrations of plastics in arterial plaques are more susceptible to heart attacks and strokes. In the textile industry, synthetic fibers such as polyester, nylon, and acrylic release microplastics into the air during production. The paper discusses a study conducted in a textile company that processes polyester yarns, where airborne microplastic concentrations were measured at various locations throughout the day. Particle sizes ranging from 0.3 nm to 10 nm were analyzed, revealing the presence of polyester polymers in the particulate matter. These findings underscore the widespread nature of microplastic pollution, particularly in industrial settings, and raise concerns about the health risks associated with prolonged exposure to airborne microplastics. While further research is necessary to fully understand the extent of these health impacts, preliminary data suggest a troubling link between microplastic inhalation and cardiovascular conditions.
KW - Microplastics
KW - Textiles
KW - Airborne particles
PY - 2025
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-635269
DO - https://doi.org/10.3390/microplastics4020034
SN - 2673-8929
VL - 4
IS - 2
SP - 1
EP - 17
PB - MDPI AG
AN - OPUS4-63526
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Rodríguez-Sánchez, Noelia
A1 - Domínguez-Santos, J. Enrique
A1 - Bhattacharya, Biswajit
A1 - Prinz, Carsten
A1 - Canosa, Inés
A1 - Flores, Amando
A1 - Jiménez-Rodríguez, Antonia
A1 - Ruiz-Salvador, A. Rabdel
A1 - Emmerling, Franziska
A1 - Ballesteros, Menta
T1 - Mechanochemical synthesis of multivariate UPO-3 (Cu-ZIF-9-ica) MOF for inactivation of antibiotic-resistant bacteria and irrigation-quality water production via heterogeneous photo-Fenton catalysis
N2 - Water scarcity and pollution are critical global challenges, particularly in agriculture, the largest consumer of water. The development of sustainable, effective, and environmentally friendly disinfection methods is essential to address the risks posed by antibiotic-resistant bacteria and to ensure safe reuse of water for irrigation. In this study, we report the synthesis of the metal-organic framework (MOF) Universidad Pablo de Olavide-3 (UPO-3) via a mechanochemical approach, a scalable and sustainable method compared to traditional solvothermal synthesis. The resulting UPO-3/H2O2 system exhibits robust photocatalytic properties under visible light, achieving effective and broad-spectrum antibacterial activity. The disinfection efficiency of the catalyst was evaluated against Escherichia coli as a model of microbial pathogen in two saline matrices, considering the key parameters of the heterogeneous photo-Fenton process, including catalyst dosage, initial H2O2 concentration, and light irradiation. Notably, it inactivated two important virulent and antibiotic-resistant bacterial pathogens (Staphylococcus aureus and Pseudomonas aeruginosa). Furthermore, UPO-3 shows exceptional performance under real-world conditions, such as river water disinfection, achieving >5-log reduction of E. coli, fulfilling a critical criterion for Class A water reuse under Regulation (EU) 2020/741. These results highlight UPO-3 as a versatile and sustainable solution for water reuse, addressing water scarcity and advancing efforts to achieve United Nations Sustainable Development Goal 6.
KW - Water reuse
KW - Antibiotic-resistant bacteria
KW - Water disinfection
KW - Mechanochemical synthesis
KW - Metal organic framework
PY - 2025
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-639766
DO - https://doi.org/10.1016/j.chemosphere.2025.144610
SN - 0045-6535
VL - 386
SP - 1
EP - 11
PB - Elsevier Ltd.
AN - OPUS4-63976
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Go, Eun Sul
A1 - Hong, Eun Ji
A1 - Lee, Ji Yeong
A1 - Stolar, Tomislav
A1 - Peterson, Gregory I.
A1 - Emmerling, Franziska
A1 - Kim, Kyoungsoo
A1 - Kim, Jeung Gon
T1 - Insights into Mechanochemical Solid-State Ball-Milling Reaction: Monitoring Transition from Heterogeneous to Homogeneous Conditions
N2 - As mechanochemical synthesis has advanced significantly, there has been intense interest in understanding the underlying mechanisms of these reactions. Given that many mechanochemical processes are conducted in the solid-state without solvation yet sometimes yield faster reactions than those in solution, we sought to address the following question: Are mechanochemical reactions homo- or heterogeneous? To investigate, we employed a model system involving the mixing and copolymerization of l-lactide (LLA) and d-lactide (DLA), monitored through powder X-ray diffraction (PXRD), nuclear magnetic resonance, and differential scanning calorimetry. In situ and ex situ PXRD analyses of the mixture of LLA and DLA showed that vibratory ball milling rapidly transformed the initially heterogeneous lactide mixture into a homogeneous phase within one min due to collisions between the balls and the jar. By varying the milling conditions, we were able to regulate the level of mixing, which subsequently influenced the copolymerization outcomes. In the solid-state ball-milling copolymerization of LLA and DLA in the presence of a catalyst and initiator, multiblock copolymers of poly(l-lactic acid) and poly(d-lactic acid) were formed within one min during the early stage of the reaction, when incomplete mixing of the monomers led to a process governed by phase heterogeneity. In contrast, prolonged polymerization promoted conditions approaching homogeneity, ultimately yielding atactic poly(lactic acid). This transition from heterogeneous to homogeneous reactions is a distinctive feature compared to conventional homogeneous reactions, potentially leading to mechano-exclusive reaction designs.
KW - Mechanochemistry
KW - Ball-milling
KW - Homogeneous reaction
KW - Heterogeneous reaction
PY - 2025
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-638008
DO - https://doi.org/10.1021/jacsau.5c00322
SN - 2691-3704
VL - 5
IS - 6
SP - 2720
EP - 2727
PB - American Chemical Society (ACS)
AN - OPUS4-63800
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Fink, Friedrich
A1 - Stawski, Tomasz M.
A1 - Emmerling, Franziska
A1 - Falkenhagen, Jana
T1 - A novel machine-learning approach to unlock technical lignin classification by NIR spectroscopy - bench to handheld
N2 - In this research, the utilization of near-infrared (NIR) spectroscopy in conjunction with advanced machine learning methods is investigated for categorizing technical lignins obtained from different biomass sources and industrial procedures. Technical lignins, such as kraft, organosolv and lignosulfonates, have different chemical compositions, which continue to make uniform characterization and application in sustainable sectors extremely difficult. Fast, universally accessible analytics combined with data analysis is still an open question. For the first time three distinct NIR spectrometers—a high-performance benchtop system, a mid-priced compact device, and an economical handheld unit—were utilized to record NIR spectra of 31 unique lignin samples. The spectra underwent pre-processing through standard normal variate (SNV) transformation and Savitzky-Golay derivatives to amplify spectral features and decrease noise. Principal component analysis (PCA) was employed to reduce data complexity and extract crucial characteristics for classification purposes. Subsequently, four machine learning algorithms—Support Vector Machines (SVM), Gaussian Naive Bayes (GNB), Gaussian Process Classification (GPC), and Decision Tree Classification (DTC)—were implemented for the classification of the lignin samples. The DTC model exhibited the highest accuracy among them across different spectrometers. Although the benchtop spectrometer produced the most precise outcomes, the compact NeoSpectra system also displayed potential as a cost-efficient option. Nonetheless, the restricted spectral coverage of the handheld NIRONE spectrometer resulted in reduced classification accuracy. Our discoveries highlight the capability of NIR spectroscopy, combined with robust data analysis techniques, for the swift and non-destructive classification of technical lignins, facilitating their improved utilization in sustainable fields.
KW - Technical lignins
KW - NIR spectroscopy
KW - Classification
KW - Machine-learning
KW - PCA
PY - 2025
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-634518
DO - https://doi.org/10.1016/j.chemolab.2025.105467
SN - 0169-7439
VL - 264
SP - 1
EP - 10
PB - Elsevier B.V.
CY - Amsterdam
AN - OPUS4-63451
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Feiler, Torvid
A1 - Emmerling, Franziska
A1 - Bhattacharya, Biswajit
T1 - Sustainable mechanochemical approach for the selective synthesis of multicomponent organic solids: real-time in situ insights
N2 - Crystalline multicomponent organic solids (MOSs) such as cocrystals and ionic cocrystals hold immense potential in diverse functional applications, ranging from pharmaceuticals to optoelectronics. However, conventional solution-based crystallization methods often result in polymorphic mixtures and lack precise control over product composition. Herein, we report a comparative investigation of solution crystallization versus mechanochemical synthesis for constructing MOSs from 9-anthracenecarboxylic acid (ACA) and 4,4 '-bipyridine (BPY). Solution-based approaches consistently yielded concomitant formation of neutral cocrystal (CC) and ionic cocrystal (ICC) forms, regardless of the solvent used. The resulting multicomponent solids were comprehensively characterized using a combination of single crystal X-ray diffraction, powder X-ray diffraction, Fourier-transform infrared spectroscopy, differential thermal analysis, and thermogravimetric analysis. In contrast, mechanochemical methods, including neat grinding (without solvent) and liquid-assisted grinding (with minimum solvent), enabled selective formation of either a phase pure CC or ICC form. Less polar and nonpolar organic solvents favor the kinetic CC, while polar water promotes formation of the thermodynamically stable ICC. Time-resolved in situ powder X-ray diffraction (TRIS-PXRD) captures the dynamic evolution of solid-state phases and reveals the complete transformation of the CC into ICC under neat grinding or water-assisted conditions. This study highlights the powerful role of mechanochemistry and in situ monitoring in steering solid-state reactivity and offers a sustainable pathway for the targeted and scalable synthesis of pure multicomponent organic materials.
KW - Cocrystal
KW - Synchrotron X-ray powder diffraction
KW - Time-resolved in situ investigation
PY - 2025
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-641409
DO - https://doi.org/10.1039/D5CE00663E
SN - 1466-8033
SP - 1
EP - 9
PB - Royal Society of Chemistry (RSC)
CY - Cambridge
AN - OPUS4-64140
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
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-584766
DO - https://doi.org/10.1063/5.0166278
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 - 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
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-594698
UR - https://www.sciencedirect.com/science/article/pii/S0959652624004591#appsec1
DO - https://doi.org/10.1016/j.jclepro.2024.141012
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 - Edzards, Joshua
A1 - Saßnick, Holger-Dietrich
A1 - de Oliveira Guilherme Buzanich, Ana
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
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-589117
DO - https://doi.org/10.1021/acs.jpcc.3c06054
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 - 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
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-594755
DO - https://doi.org/10.1039/d3cp04791a
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 - 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
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-583619
DO - https://doi.org/10.1039/d3ma00315a
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 - 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
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-588071
DO - https://doi.org/10.1039/D3CP02883F
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 - 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 - de Oliveira 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
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-584924
DO - https://doi.org/10.1039/d3cc03277a
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 - Wiesner, Yosri
A1 - Bednarz, Marius
A1 - Braun, Ulrike
A1 - Bannick, Claus Gerhard
A1 - Ricking, Mathias
A1 - Altmann, Korinna
T1 - A promising approach to monitor microplastic masses in composts
N2 - Inputs of plastic impurities into the environment via the application of fertilizers are regulated in Germany and the EU by means of ordinances. Robust and fast analytical methods are the basis of legal regulations. Currently, only macro- and large microplastic contents (>1 mm) are measured. Microplastics (1–1,000 µm), are not yet monitored. Thermal analytical methods are suitable for this purpose, which can determine the mass content and can also be operated fully automatically in routine mode. Thermal extraction desorption-gas chromatography/mass spectrometry (TED-GC/MS) allows the identification of polymers and the determination of mass contents in solid samples from natural environments. In accordance with the German or European Commission (EC) Fertiliser Ordinance, composting plants should be monitored for microplastic particles with this method in the future. In this context a compost plant was sampled. At the end of the rotting process, the compost was sieved and separated in a coarse (>1 mm) and a fine fraction (<1 mm). The fine fraction was processed using density separation comparing NaCl and NaI as possible salt alternative and screened for microplastic masses by TED-GC/MS with additional validation and quality assurance experiments. With TED-GC/MS total microplastics mass contents of 1.1–3.0 μg/mg in finished compost could be detected with polyethylene mainly. What differs much to the total mass of plastics in the coarse fraction with up to 60 μg/mg, which were visually searched, identified via ATR-FTIR and gravimetrically weighted.
KW - Microplastics
KW - TED-GC/MS
KW - Compost
KW - Monitoring
KW - Soil
PY - 2023
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-586688
DO - https://doi.org/10.3389/fenvc.2023.1281558
SN - 2673-4486
VL - 4
SP - 1
EP - 12
PB - Frontiers Media
CY - Lausanne
AN - OPUS4-58668
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Heinekamp, Christian
A1 - Kneiske, Sönke
A1 - de Oliveira 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
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-593433
DO - https://doi.org/10.1039/D3CY01439H
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 - JOUR
A1 - Paul, Sagar
A1 - Dolai, Malay
A1 - Nanda Goswami, Juli
A1 - Bhattacharya, Biswajit
A1 - Emmerling, Franziska
A1 - Drew, Michael G. B.
A1 - Chattopadhyay, Shouvik
A1 - Sarkar, Rabi Sankar
A1 - Sunil, Appu
A1 - Novitchi, Ghenadie
A1 - Moreno-Pineda, Eufemio
A1 - Wernsdorfer, Wolfgang
T1 - From strong to weak interaction: Reconciling SQUID and μSQUID-EPR data in anomalous Co(ii) dimers
N2 - Magnetic molecules have been proposed as scaffolds for novel quantum technologies, ranging from quantum sensing and quantum memory to multilevel quantum bits (qudits) and fault-tolerant quantum computation. Integration of magnetic molecules into cutting-edge applications hinges on a deep understanding and tunability of their spin states. To date, the strategic manipulation of the local environment of the ion and careful selection of the magnetic core have enabled the desired tunability and scalability of the spin states. For such goals, however, extracting the anisotropic parameters that dictate the characteristics of the Spin Hamiltonian is challenging, especially for molecules consisting of multiple magnetic cores. We address these challenges by studying two cobalt(II) dinuclear systems, complicated by inherent spin–orbit coupling. We explore the magnetic properties of these systems in two temperature regimes: (i) at sub-Kelvin temperatures employing single crystals at 30 mK using a unique μSQUID-EPR technique that examines the microwave absorption peaks in the magnetisation data and their variation with field angle and frequency; and (ii) in bulk employing convectional SQUID magnetometry above 2 K i.e., χMT(T) and M(H). Unexpectedly, sub-Kelvin temperature investigations reveal a negligible interaction, whereas the SQUID data reveal a much stronger interaction between the Co(II) ions. An understanding of these data is developed based on a strong coupling model and the coupling of two moieties with a spin-effective ground state.
KW - cOBALT(II)-complex
KW - In situ complex formation
KW - Magnetic property
KW - Crystal structure
PY - 2025
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-641421
DO - https://doi.org/10.1039/D5QI01387A
SN - 2052-1553
SP - 1
EP - 13
PB - Royal Society of Chemistry (RSC)
CY - Cambridge
AN - OPUS4-64142
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -