TY - JOUR
A1 - de Olivera, Paulo
A1 - Michalchuk, Adam
A1 - de Oliveira Guilherme Buzanich, Ana
A1 - Bienert, Ralf
A1 - Torresi, R.
A1 - Camargo, P.
A1 - Emmerling, Franziska
T1 - Tandem X-ray absorption spectroscopy and scattering for in situ time-resolved monitoring of gold nanoparticle mechanosynthesis
N2 - Current time-resolved in situ approaches limit the scope of mechanochemical investigations possible. Here we develop a new, general approach to simultaneously follow the evolution of bulk atomic and electronic structure during a mechanochemical synthesis. This is achieved by coupling two complementary synchrotron-based X-ray methods: X-ray absorption spectroscopy (XAS) and X-ray diffraction. We apply this method to investigate the bottom-up mechanosynthesis of technologically important Au micro and nanoparticles in the presence of three different reducing agents, hydroquinone, sodium citrate, and NaBH4. Moreover, we show how XAS offers new insight into the early stage generation of growth species (e.g. monomers and clusters), which lead to the subsequent formation of nanoparticles. These processes are beyond the detection capabilities of diffraction methods. This combined X-ray approach paves the way to new directions in mechanochemical research of advanced electronic materials.
KW - Mechanochemistry
KW - XANES
KW - X-ray diffraction
KW - Nano particles
PY - 2020
DO - https://doi.org/10.1039/d0cc03862h
SN - 1364-548X
VL - 56
SP - 10329
EP - 10332
PB - Royal Society of Chemistry
AN - OPUS4-51760
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Radtke, Martin
A1 - Rakotondrajoa, A.
T1 - Machine learning based quantification of synchrotron radiation-induced X-ray fluorescence measurements - a case study
N2 - In this work, we describe the use of artificial neural networks for the quantification of X-ray fluorescence measurements. The training data were generated using Monte Carlo simulation, which avoided the use of adapted reference materials. The extension of the available data set by means of an ANN to generate additional data was demonstrated. Particular emphasis was put on the comparability of simulated and experimental data and how the influence of deviations can be reduced. The search for the optimal hyperparameter, manual and automatic, is also described. For the presented case, we were able to train a network with a mean absolute error of 0.1 weight percent for the synthetic data and 0.7 weight percent for a set of experimental data obtained with certified reference materials.
KW - Machine learning
KW - BAMline
KW - XRF
KW - Synchrotron
KW - Neural network
PY - 2020
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-519008
DO - https://doi.org/10.1088/2632-2153/abc9fb
SP - 1
EP - 16
PB - IOP Publishing
AN - OPUS4-51900
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Smekhova, A.
A1 - Kuzmin, A.
A1 - Siemensmeyer, K.
A1 - Luo, C.
A1 - Taylor, J.
A1 - Thakur, S.
A1 - Radu, F.
A1 - Weschke, E.
A1 - de Oliveira Guilherme Buzanich, Ana
A1 - Xiao, B.
A1 - Savan, A.
A1 - Yusenko, Kirill
A1 - Ludwig, A.
T1 - Local structure and magnetic properties of a nanocrystalline Mn-rich Cantor alloy thin film down to the atomic scale
N2 - The huge atomic heterogeneity of high-entropy materials along with a possibility to unravel the behavior of individual components at the atomic scale suggests a great promise in designing new compositionally complex systems with the desired multi-functionality. Herein, we apply multi-edge X-ray absorption spectroscopy (extended X-ray absorption fine structure (EXAFS), X-ray absorption near edge structure (XANES), and X-ray magnetic circular dichroism (XMCD)) to probe the structural, electronic, and magnetic properties of all individual constituents in the single-phase face-centered cubic (fcc)-structured nanocrystalline thin film of Cr20Mn26Fe18Co19Ni17 (at.%) high-entropy alloy on the local scale. The local crystallographic ordering and component-dependent lattice displacements were explored within the reverse Monte Carlo approach applied to EXAFS spectra collected at the K absorption edges of several constituents at room temperature. A homogeneous short-range fcc atomic environment around the absorbers of each type with very similar statistically averaged interatomic distances (2.54–2.55 Å) to their nearest-neighbors and enlarged structural relaxations of Cr atoms were revealed. XANES and XMCD spectra collected at the L2,3 absorption edges of all principal components at low temperature from the oxidized and in situ cleaned surfaces were used to probe the oxidation states, the changes in the electronic structure, and magnetic behavior of all constituents at the surface and in the sub-surface volume of the film. The spin and orbital magnetic moments of Fe, Co, and Ni components were quantitatively evaluated. The presence of magnetic phase transitions and the co-existence of different magnetic phases were uncovered by conventional magnetometry in a broad temperature range.
KW - Magnetism
KW - High-entropy alloys
KW - Reverse Monte Carlo (RMC)
KW - Element-specific spectroscopy
KW - Extended X-ray absorption fine structure (EXAFS),
KW - X-ray magnetic circular dichroism (XMCD),
PY - 2022
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-578254
DO - https://doi.org/10.1007/s12274-022-5135-3
SN - 1998-0124
SP - 5626
PB - Springer
AN - OPUS4-57825
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 - 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 - 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 - 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 - 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 - 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 - 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 - Zänker, Steffen
A1 - Scholz, Gudrun
A1 - Krahl, Thoralf
A1 - Prinz, Carsten
A1 - Emmerling, Franziska
A1 - Kemnitz, E.
T1 - Luminescent properties of Eu3+/Tb3+ doped fluorine containing coordination polymers
N2 - Lanthanides doped coordination polymers (CPs) with different binding motifs were synthesized to investigate the influence of the different fluorine positions in the structure on the decay time τ of the excited states. Fluorine can be integrated into the network mechanochemically via a fluorinated organic linker, here barium tetrafluoroterephthalate Ba(p-BDC-F4)2 or directly via a metal-fluorine bond (barium terephthalate fluoride BaF(p-BDC)0.5). The CP with a metal-fluorine bond shows the highest lifetime of the excited states of lanthanides (Eu3+, Tb3+ or Eu3+& Tb3+). The excitation of the lanthanides can be performed directly via the excitation wavelength typical for lanthanides and via the excitation wavelength of the linker. This enabled the simultaneous excitation of Eu3+ and Tb3+ in one CP. In the emission spectra (λem = 393 nm) of the mixed doped CPs (Eu3+ and Tb3+) the bands of both lanthanides can be observed. The integration into the crystal lattice and the homogeneous distribution of the lanthanides in the CPs is shown by X-ray diffraction, TEM, STEM-EDS measurements and the long decay times.
KW - Alkaline earth metal coordination polymers
KW - Fluorine coordination polymers
KW - Lanthanides doped coordination polymers
KW - Luminescence
PY - 2021
DO - https://doi.org/10.1016/j.solidstatesciences.2021.106614
VL - 117
SP - 106614
PB - Elsevier Masson SAS
AN - OPUS4-52559
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Emmerling, Franziska
A1 - Michalchuk, Adam
A1 - Bhattacharya, Biswajit
A1 - Rodríguez Sánchez, Noelia
A1 - Gugin, Nikita
T1 - Advancing sustainable synthesis through in situ monitoring and industrial scale-up of mechanochemical processes
N2 - Mechanochemistry has emerged as a powerful approach for sustainable materials synthesis and processing, with significant potential to meet the UN Sustainable Development Goals. This presentation will highlight our recent advancements in understanding, monitoring, and scaling-up mechanochemical transformations, focusing on the balance between fundamental understanding of reaction mechanisms and its practical applications in energy storage and energy transfer materials.
Our research has made significant strides in elucidating the fundamental mechanisms of mechanochemical reactions. We have investigated delayed polymorphism under mechanochemical conditions, revealing new insights into the interplay between mechanical impact, thermal effects, and structural transformations in molecular crystals. By employing variable temperature ball milling, we have demonstrated unprecedented control over polymorphic forms in organic cocrystals, opening new avenues for tailoring material properties.
A central focus of our work has been the development and application of time-resolved in situ monitoring techniques for mechanochemical processes. Our research on real-time synchrotron X-ray diffraction has enabled unprecedented insights into reaction pathways and kinetics. Recently, we have successfully applied energy-dispersive X-ray diffraction for time-resolved in situ monitoring of reactive extrusion, marking a significant step towards ‘lighting up’ industrial-scale mechanochemistry.
Bridging fundamental understanding with practical applications, we have explored the mechanochemical synthesis of functional materials for energy storage and transfer, making process in the mechanochemical synthesis of highly proton-conductive metal phosphonates, demonstrating the potential of mechanochemistry to manufacture advanced materials for energy applications. Addressing the challenges of industrial scale-up, we have investigated the role of solvent polarity in mechanochemical reactions, providing valuable guidance for optimizing organic syntheses such as the Knoevenagel condensation. This work contributes to our broader efforts to develop more efficient and sustainable chemical manufacturing processes.
Looking to the future, we will discuss emerging directions in mechanochemistry, including the development of continuous flow processes and the integration of machine learning approaches for reaction prediction and optimization. As we anticipate the next decade of research, we envision mechanochemistry playing an increasingly crucial role in sustainable chemical manufacturing and materials processing, with far-reaching implications for addressing global energy and environmental challenges.
T2 - Mech’cheM 2025: New forces in Mechanochemistry Conference
CY - Montpellier, France
DA - 04.06.2025
KW - Phosphonates
KW - Biocomposites
PY - 2025
AN - OPUS4-64845
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Emmerling, Franziska
A1 - Michalchuk, Adam
A1 - Bhattacharya, Biswajit
A1 - Rodríguez Sánchez, Noelia
A1 - Gugin, Nikita
T1 - Mechanochemical innovations for sustainable synthesis of framework materials and industrial scaleup
N2 - Mechanochemistry has emerged as a powerful approach for sustainable materials synthesis and processing, with significant potential to meet the UN Sustainable Development Goals. This presentation will highlight our recent advancements in understanding, monitoring, and scaling-up mechanochemical synthesis of framework materials, focusing on the balance between fundamental understanding of reaction mechanisms and its practical applications in energy storage and energy transfer materials.
A central focus of our work has been the development and application of time-resolved in situ monitoring techniques for mechanochemical processes. Our research on real-time synchrotron X-ray diffraction has enabled unprecedented insights into reaction pathways and kinetics. Recently, we have successfully applied energy-dispersive X-ray diffraction for time-resolved in situ monitoring of reactive extrusion, marking a significant step towards ‘lighting up’ industrial-scale mechanochemistry.
Bridging fundamental understanding with practical applications, we have explored the mechanochemical synthesis of functional materials for energy storage and transfer, making process in the mechanochemical synthesis of highly proton-conductive metal phosphonates, demonstrating the potential of mechanochemistry to manufacture advanced materials for energy applications.
T2 - 17. international-conference für Materialchemie
CY - Edinburgh, United Kingdom
DA - 07.07.2025
KW - MOF
KW - Synchrotron
KW - ZIF
PY - 2025
AN - OPUS4-64841
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 - Mazzeo, P
A1 - Lampronti, G
A1 - Michalchuk, Adam
A1 - Belenguer, A
A1 - Bacchi, A
A1 - Emmerling, Franziska
T1 - Accurate extrinsic and intrinsic peak broadening modelling for time-resolved in situ ball milling reactions via synchrotron powder X-ray diffraction
N2 - The debate on the mechanisms which underpin mechanochemical reactions via ball mill grinding is still open. Our ability to accurately measure the microstructural (crystal size and microstrain) evolution of materials under milling conditions as well as their phase composition as a function of time is key to the in-depth understanding of the kinetics and driving forces of mechanochemical transformations. Furthermore, all ball milling reactions end with a steady state or milling equilibrium – represented by a specific phase composition and relative microstructure – that does not change as long as the milling conditions are maintained. The use of a standard sample is essential to determine the instrumental contribution to the X-ray powder diffraction (XRPD) peak broadening for time-resolved in situ (TRIS) monitoring of mechanochemical reactions under in operando conditions. Using TRIS-XRPD on a ball milling setup, coupled with low-energy synchrotron radiation, we investigated different data acquisition and analysis strategies on a silicon standard powder. The diffraction geometry and the microstructural evolution of the standard itself have been studied to model the instrumental contribution to XRPD peak broadening throughout the grinding activity. Previously proposed functions are here challenged and further developed. Importantly, we show that minor drifts of the jar position do not affect the instrumental resolution function significantly. We here report and discuss the results of such investigations and their application to TRIS-XRPD datasets of inorganic and organic ball mill grinding reactions.
KW - Mechanochemistry
KW - In situ diffraction
KW - Synchrotron radiation
KW - Sustainable chemisry
PY - 2022
DO - https://doi.org/10.1039/d2fd00104g
SP - 1
EP - 17
PB - Royal Society of Chemistry
AN - OPUS4-55932
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - 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 - Lakshmipathi, M.
A1 - Dey, S.
A1 - Emmerling, Franziska
A1 - Bhattacharya, Biswajit
A1 - Michalchuk, Adam
T1 - Designing Dual Mechanical Response in Molecular Crystals through Cocrystallization
N2 - Two isomorphous crystals are reported based on a naphthylvinylpyridine coformer. The crystals are mechanically flexible and exhibit photosalient response to UV irradiation. We therefore show how multiple mechanical phenomena can be simultaneously designed into a single material by cocrystallization.
KW - Cocrystal
KW - Mechanical response
PY - 2022
DO - https://doi.org/10.1021/acs.cgd.2c00913
SN - 1528-7483
VL - 22
SP - 6838
EP - 6843
PB - ACS Publ.
CY - Washington, DC
AN - OPUS4-56561
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - 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 - 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 - CONF
A1 - Ruehle, Bastian
T1 - A Self-Driving Lab for Nano and Advanced Materials Synthesis in a Self-Driving Lab
N2 - In this contribution, we present our Self-Driving Lab (SDL) for Nano and Advanced Materials, that integrates robotics for batched autonomous synthesis – from molecular precursors to fully purified nanomaterials – with automated characterization and data analysis, for a complete and reliable nanomaterial synthesis workflow. By fully automating the processing steps for seven different materials from five representative, completely different classes of nano- and advanced materials (metal, metal oxide, silica, metal organic framework, and core–shell particles) that follow different reaction mechanisms, we demonstrate the great versatility and flexibility of the platform. The system also exhibits high modularity and adaptability in terms of reaction scales and incorporates in-line characterization measurement of hydrodynamic diameter, zeta potential, and optical properties (absorbance, fluorescence). We discuss the excellent reproducibility of the various materials synthesized on the platform in terms of particle size and size distribution, and the adaptability and modularity that allows access to a diverse set of nanomaterial classes.
We also present several key aspects of the central backend that orchestrates the (parallelized) syntheses workflows. One key feature is the resource management or “traffic control” for scheduling and executing parallel reactions in a multi-threaded environment. Another is the interface with data analysis algorithms from in-line, at-line, and off-line measurements. Here, we will give examples of how automatic image segmentation of electron microscopy images with the help of AI can be used for reducing the “data analysis bottleneck” from an off-line measurement. We will also discuss various machine learning (ML) algorithms that are currently implemented in the backend and can be used for ML-guided, closed-loop material optimization in our SDL. Lastly, we will show our recent efforts in making the workflow generation on SDLs more user-friendly by using large language models to generate executable workflows automatically from synthesis procedures given in natural language and user-friendly graphical user interfaces based on node editors that also allow for knowledge graph extraction from the workflows. In this context, we are currently also working on a common description or ontology for representing the process steps and parameters of the workflows, which will greatly facilitate the semantic description and interoperability of workflows between different SDL hardware and software platforms.
T2 - Series on Digitalisation-Meet the Experts | Special Topic: Automation
CY - Berlin, Germany
DA - 27.02.2026
KW - Self-Driving Labs
KW - Materials Acceleration Platforms
KW - Advanced Materials
KW - Nanomaterials
KW - Automation
KW - Digitalization
PY - 2026
AN - OPUS4-65604
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Völzke, Jule L.
T1 - Corundum as a novel affinity platform for the isolation of human IgG from plasma
N2 - Nonporous corundum powder was functionalized covalently with protein binders to isolate and enrich specific proteins from complex matrices.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). As a proof of concept, IgG was extracted with protein A from crude human plasma. 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.
T2 - Adlershofer Forschungsforum 2022
CY - Berlin, Germany
DA - 11.11.2022
KW - Affinity support
KW - Affinity chromatography
KW - Affinity extraction
KW - Phosphonic acids
KW - Polyglycerol
KW - Reductive amination
KW - Amino acid analysis
KW - Tyrosine
KW - Protein quantification
KW - SDS-PAGE
KW - Antibodies
KW - Antibody purification
KW - Downstream processing
KW - Bovine serum albumin
KW - BSA
KW - Protein a
KW - TEM
KW - ESEM
KW - Aluminum oxide
KW - Sapphire
KW - Human plasma
KW - Protein immobilization
KW - Protein hydrolysis
KW - Glutaraldehyde
KW - Aromatic amino acid analysis AAAA
PY - 2022
AN - OPUS4-56154
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - INPR
A1 - Völzke, Jule L.
A1 - Hodjat Shamami, Parya
A1 - Gawlitza, Kornelia
A1 - Feldmann, Ines
A1 - Zimathies, Annett
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, and zeta potential measurements. The strong Al-O-P bonds between the corundum surface and amino phosphonic acids are used to introduce functional groups for further conjugations. The common cross-linker glutaraldehyde was compared with a hyperbranched polyglycerol (PG) of around 10 kDa. The latter is 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 nonspecific 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 SDS-PAGE. A binding capacity of 1.8 mg IgG per g of corundum powder was achieved. The advantages of corundum are the very low price, extremely high physical and chemical stability, pressure resistance, favorable binding kinetics, and flexible application.
KW - Protein
KW - Bioseparation
KW - Purification
KW - Immunoprecipitation
KW - Affinity chromatography
KW - Polyglycerol
KW - Glutaraldehyde
KW - Linker
KW - Bioconjugation
KW - Self-assembled monolayer (SAM)
KW - Periodate oxidation
KW - Reductive amination
KW - Antibodies
KW - Igg
KW - Immunoglobulins
KW - Carrier
KW - Solid phase
KW - Hyperbranched polymer
KW - Aromatic amino acid analysis aaaa
PY - 2022
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-555142
DO - https://doi.org/10.20944/preprints202208.0004.v1
SN - 2310-287X
SP - 1
EP - 13
PB - MDPI
CY - Basel
AN - OPUS4-55514
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 - CONF
A1 - Ryll, Tom William
T1 - Researching automation of gypsum recycling
N2 - This poster illustrates the recent work on a setup for automated in-situ analysis of gypsum recycling processes. Analysis in synchrotron X-rays, Raman- and UV-vis spectroscopy are made possible with this compact and mobile setup. First results from Raman spectroscopy on the conversion of gypsum to bassanite in hypersaline solutions are presented and future plans on optimization are formulated.
T2 - ANAKON 2025
CY - Leipzig, Germany
DA - 10.03.2025
KW - Recycling
KW - Automation
KW - Synchrotron-X-ray-diffraction
KW - Raman-spectroscopy
KW - Gypsum
PY - 2025
AN - OPUS4-62706
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Speight, Isaiah R.
A1 - Ardila-Fierro, Karen J.
A1 - Hernández, José G.
A1 - Emmerling, Franziska
A1 - Michalchuk, Adam
A1 - García, Felipe
A1 - Colacino, Evelina
A1 - Mack, James
T1 - Ball milling for mechanochemical reactions
N2 - Mechanochemistry is an emerging field with the potential to pave the way for sustainable chemistry. Although the use of mechanical force to initiate chemical reactions has been recognized for millennia, it has often taken a backseat to thermal and photonic methods. Over the past 30 years, mechanochemistry has seen a resurgence of interest, attracting researchers across the globe. Despite its proven ability to address numerous challenges within the chemical community, mechanochemistry remains on the periphery. This Primer serves as a valuable guide for conducting mechanochemical reactions by ball milling, offering an overview of the processes, methods, tools and terminology necessary to embark on research in this field. It also highlights persistent hurdles such as equipment standardization, understanding the impact of new discoveries and the lack of predictability of reaction outcomes. The Primer’s focus is on how mechanochemical ball milling is used in various chemical transformations, distinguishing it from other forms of mechanochemistry discussed in the literature. With a promising future, this Primer serves as a gateway for those aspiring to contribute to the field’s advancement.
KW - Mechanochemistry
KW - Ball milling
KW - Upscaling
PY - 2025
DO - https://doi.org/10.1038/s43586-025-00401-2
SN - 2662-8449
VL - 5
IS - 1
SP - 1
EP - 18
PB - Springer Science and Business Media LLC
AN - OPUS4-63447
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 - 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 - Michalchuk, Adam
A1 - Delogu, Francesco
T1 - Fundamental basis of mechanochemical reactivity
N2 - This themed collection includes a collection of articles on the fundamental basis of mechanochemical reactivity.
KW - Mechanochemical
KW - Metal-organic
KW - Transformation
KW - Dimerization
PY - 2024
DO - https://doi.org/10.1039/d4cp90153c
SP - 1
EP - 3
PB - Royal Society of Chemistry (RSC)
AN - OPUS4-61500
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Emmerling, Franziska
A1 - Michalchuk, Adam
A1 - Casali, Lucia
A1 - May, Anastasia
T1 - Real-Time Monitoring and Temperature Control for Optimized Polymorph Engineering
N2 - Integrating real-time monitoring with precise temperature control and mechanochemical processing represents a transformative approach to the controlled engineering of polymorphic forms in molecu-lar solids. Combining these methodologies overcomes the limitations of traditional solution-based or purely thermal approaches, enabling access to metastable or otherwise elusive polymorphs under milder and more sustainable conditions. Recent studies have shown that mechanochemical trans-formations proceed through distinct kinetic stages, including prolonged induction periods that can be tuned by adjusting the mechanical energy input[1]. These induction periods are associated with pro-cesses of mechanical activation, such as the accumulation of defects and increased surface energy, which lower the effective energy barriers for polymorphic transitions. Crucially, it is the total accumu-lated mechanical energy, rather than the duration or intensity of milling alone, that dictates the onset of polymorphic conversion, offering a new dimension of kinetic control[2-5].
Variable temperature ball milling reveals that the temperature required to induce polymorphic trans-formations can be significantly lower than under conventional thermal methods. For instance, tran-sitions that typically require high temperatures under equilibrium conditions can be achieved at sub-stantially lower temperatures in the presence of mechanical activation. This has been demonstrated in cocrystal systems such as nicotinamide-pimelic acid and isonicotinamide-glutaric acid, where the transition temperature was lowered by up to 25°C[2,3]. Real-time, in situ powder X-ray diffraction and temperature monitoring are essential for capturing transient phases and elucidating the interplay between thermal and mechanical effects. This confirms that combining mechanical energy with con-trolled temperature not only accelerates transformation kinetics, but also expands the accessible polymorphic landscape [2,3].
Collectively, these advances underscore the potential of real-time monitored, temperature-controlled mechanochemistry as a robust platform for the selective design and manufacturing of polymorphs. This approach provides unprecedented control over solid-state reactivity and opens new avenues for the sustainable and targeted engineering of functional materials and pharmaceuticals.
T2 - 13th Bologna´s convention on Crystal Forms - CF@Bo n.13 University of Bologna
CY - Bologna, Italy
DA - 07.09.2025
KW - Plymorhism
KW - Pre-activation
PY - 2025
AN - OPUS4-64839
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - INPR
A1 - Miliūtė, Aistė
ED - Bustamante, Joana
ED - Karafiludis, Stephanos
ED - Zöllner, Moritz
ED - Eddah, Mustapha
ED - Emmerling, Franziska
ED - Mieller, Björn
ED - George, Janine
ED - Stawski, Tomasz
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:b43-613643
DO - https://doi.org/10.26434/chemrxiv-2024-d4sj9
SN - 2573-2293
VL - 2024
SP - 1
EP - 60
PB - American Chemical Society
CY - Washington, D.C.
AN - OPUS4-61364
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 - 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 - CONF
A1 - de Oliveira Guilherme Buzanich, Ana
A1 - Radtke, Martin
A1 - Emmerling, Franziska
ED - Rogge, Andreas
ED - Meng, Birgit
T1 - Exploring new materials for Green Intelligent Building - How can our BAMline help?
N2 - In the scope of exploring and characterizing new materials related to Green Intelligent Building (GIB), we will provide an overview of the X-ray spectroscopy and diffraction analytical methods available at the BAMline /1/. and Myspot beamlines. These are two universal beamlines at the Berlin Synchrotron BESSY-II, where BAM has access and supervision role. Overarching electronic and structural properties at different time and length scales, such measurements enable a real-time characterization of materials properties. We will show-case in situ and ex situ deterioration and hydration studies on cement-based constructure materials.
T2 - 11. Jahrestagung des DAfStb mit 63. Forschungskolloquium der BAM Green Intelligent Building
CY - Berlin, Germany
DA - 16.10.2024
KW - BAMline
KW - Scope of exploring
KW - Green intelligent building
PY - 2024
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-612882
SN - 978-3-9818564-7-7
SP - 30
EP - 36
PB - Bundesanstalt für Materialforschung und -prüfung (BAM)
CY - Berlin
AN - OPUS4-61288
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 - 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 - 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 - 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 - 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 - 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 -
TY - JOUR
A1 - Mishra, Rajesh K.
A1 - Minussi, F.B.
A1 - Kumari, Priyanka
A1 - Shahi, Rohit R.
A1 - Yadav, R.P.
A1 - Emmerling, Franziska
A1 - Araújo, E.B.
T1 - Effect of sintering temperature on structural, microstructural, and dielectric properties of (Co0.2Fe0.2Ni0.2Al0.2Ti0.2)3O4 multi-cations high entropy oxides
N2 - The study reports the effect of sintering temperature on structural, microstructural, and dielectric properties of (Co0.2Fe0.2Ni0.2Al0.2Ti0.2)3O4 spinel high-entropy oxides (HEOs) synthesized through the solid-state mechanochemistry method. The sintering of the ceramic powders was accomplished at three different temperatures (1000 ◦C, 1100 ◦C, and 1250 ◦C), followed by air quenching. XRD analysis along with Le-Bail refinement confirms that 1100 ◦C and 1250 ◦C sintered oxides comprised of a single cubic spinel phase (Fd3m), while 1000 ◦C sintered oxide contains constituent oxides and a spinel phase. The phase formation of oxides sintered at 1100 ◦C and 1250 ◦C has also been confirmed by Raman spectroscopic analysis. Microstructural analysis revealed that the aggregated particle size increases with the rise in sintering temperature. With the change in sintering temperature, the dielectric behavior of the ceramic changed extensively. The 1100 ◦C sintered ceramic exhibits high frequency-dependent behavior, whereas the 1250 ◦C sintered ceramic yields low frequency-dependent behavior. The 1250 ◦C sintered HEO exhibits low-loss tangent (tan δ = 0.01) with higher dielectric permittivity (εʹ = 44) at high frequency (1 MHz) compared to the 1100 ◦C sintered ceramic and many other conventional dielectrics.
Fractal concept and impedance analysis have been employed to correlate the microstructure-dielectric property relation of (Co0.2Fe0.2Ni0.2Al0.2Ti0.2)3O4 spinel HEOs. The found Hurst exponent values for both different temperature-sintered HEOs are less than 0.5, indicating the anti-persistent behavior. This signifies that the height variations at neighboring pixels are negatively correlated. The present work is of fundamental importance in employing fractal analysis for the first time on spinel HEOs and correlating their properties. It also shows that processing conditions can effectively tailor the dielectric properties of the materials.
KW - Multi-cations high entropy oxide
KW - Mechanochemistry
KW - Spinel structure
KW - Fractal and impedance spectroscopic analysis
PY - 2025
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-647584
DO - https://doi.org/10.1016/j.ceramint.2025.09.256
SN - 0272-8842
VL - 51
IS - 27
SP - 55341
EP - 55354
PB - Elsevier Ltd.
AN - OPUS4-64758
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Karafiludis, Stephanos
A1 - Standl, Jacob
A1 - Ryll, Tom W.
A1 - Schwab, Alexander
A1 - Prinz, Carsten
A1 - Wolf, Jakob B.
A1 - Kruschwitz, Sabine
A1 - Emmerling, Franziska
A1 - Völker, Christoph
A1 - Stawski, Tomasz M.
T1 - High-Entropy Phosphate Synthesis: Advancements through Automation and Sequential Learning Optimization
N2 - Transition metal phosphates (TMPs) are extensively explored for electrochemical and catalytical applications due to their structural versatility and chemical stability. Within this material class, novel high-entropy metal phosphates (HEMPs)─containing multiple transition metals combined into a single-phase structure─are particularly promising, as their compositional complexity can significantly enhance functional properties. However, the discovery of suitable HEMP compositions is hindered by the vast compositional design space and complex or very specific synthesis conditions. Here, we present a data-driven strategy combining automated wet-chemical synthesis with a Sequential Learning App for Materials Discovery (SLAMD) framework (Random Forest regression model) to efficiently explore and optimize HEMP compositions. Using a limited set of initial experiments, we identified multimetal compositions in a single-phase crystalline solid. The model successfully predicted a novel Co0.3Ni0.3Fe0.2Cd0.1Mn0.1 phosphate octahydrate phase, validated experimentally, demonstrating the effectiveness of the machine learning approach. This work highlights the potential of integrating automated synthesis platforms with data-driven algorithms to accelerate the discovery of high-entropy materials, offering an efficient design pathway to advanced functional materials.
KW - Metal phosphates
KW - High entropy
KW - Sequential learning
KW - Automated synthesis
KW - MAP
KW - Random forest
KW - Machine learning
PY - 2025
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-641554
DO - https://doi.org/10.1021/acs.cgd.5c00549
SN - 1528-7483
VL - 25
IS - 19
SP - 7989
EP - 8001
PB - American Chemical Society (ACS)
CY - Washington, DC
AN - OPUS4-64155
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Batteas, James
A1 - Blank, Kerstin G.
A1 - Colacino, Evelina
A1 - Emmerling, Franziska
A1 - Friščić, Tomislav
A1 - Mack, James
A1 - Moore, Jeffrey
A1 - Rivas, Maria Elena
A1 - Tysoe, Wilfred
T1 - Moving mechanochemistry forward
N2 - Arguably mechanochemistry is one of the oldest, and at the same time one of the newest, areas of chemistry. One of the oldest, because it has been theorized that early hominids were able to develop rapidly due to their ability to heat and mechanically process their food to make it easier to digest. Old, because the ancient Greeks knew that mechanically activating stones (consisting of cinnabar) with vinegar in a copper pestle and mortar caused them to convert into mercury. We might be forgiven for thinking that this could have led our alchemical forbears to wonder if there were other stones that might also be persuaded to convert into gold. Early chemical luminaries such as Michael Faraday and Wilhelm Röntgen dabbled in mechanochemistry. However, in the late 19th and early 20th centuries, the field developed separately in many areas. Perhaps most significantly, synthetic chemists realized that reactions could be carried out with surprisingly high yields and selectivities by shaking them in a ball mill, and that they could even make novel compounds that their colleagues just using heat were not able to. Physicists were mechanically rearranging atoms into new configurations (i.e., doing chemistry) using exotic means such as atomic force microscope tips and optical tweezers. Scientists and engineers studying the formation of lubricious and anti-wear films realized that they were mechanochemically formed. Biochemists found molecular motor proteins, such as myosin and kinesin, that were able to convert chemical energy into motion or, vice versa, mechanical energy into the biochemical energy storage molecule adenosine triphosphate. In 2023, this confluence of advances convinced the Royal Society of Chemistry that the time was ripe to establish a new journal dedicated to the field of mechanochemistry. It is rare that a journal has the privilege of helping to create a new sub-branch of chemistry but, having done so, it has the obligation of helping to define the field and, optimistically, suggesting how the field might develop. This editorial has two major goals. The first is to bring to the attention of the scientific community the challenges faced by the field to set people thinking about how they might contribute and, second, to form the basis for more thorough discussions in the future. The sub-topics below outline current thoughts brought forward from members of our editorial board. We lay out areas and topics here with the intent of establishing a new editorial series, which we invite the community to contribute to, and outline topics and hopefully lay out challenges, which will enable us as a community to come together to move mechanochemistry forward.
KW - Mechanochemistry
PY - 2025
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-646086
DO - https://doi.org/10.1039/d4mr90021a
SN - 2976-8683
VL - 2
IS - 1
SP - 10
EP - 19
PB - Royal Society of Chemistry (RSC)
AN - OPUS4-64608
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Rodríguez-Sánchez, Noelia
A1 - Prinz, Carsten
A1 - Bienert, Ralf
A1 - Ballesteros, Menta
A1 - Ruiz Salvador, A. Rabdel
A1 - Bhattacharya, Biswajit
A1 - Emmerling, Franziska
T1 - Mechanochemical ZIF-9 formation: in situ analysis and photocatalytic enhancement evaluation
N2 - Efficient treatment of persistent pollutants in wastewater is crucial for sustainable water management and environmental protection. This study addresses this challenge by investigating the mechanochemical synthesis and photocatalytic performance of ZIF-9, a cobalt-based zeolitic imidazolate framework. Using synchrotron-based powder X-ray diffraction, we provide real-time insights into the formation dynamics of ZIF-9 during mechanosynthesis. Our results show that mechanochemically synthesised ZIF-9 exhibits superior photocatalytic activity compared to its solvothermally prepared counterpart, achieving a 2-fold increase in methylene blue degradation rate. This research not only advances our understanding of the synthesis and properties of ZIF-9, but also demonstrates the potential of mechanochemical approaches in the development of high-performance, sustainably produced materials for water treatment and other environmental applications.
KW - MOFs
KW - ZIF
KW - Time-resolved in situ investigation
KW - Photocatalysis synchrotron X-ray powder diffraction
PY - 2025
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-641416
DO - https://doi.org/10.1039/D4MR00114A
SN - 2976-8683
VL - 2
IS - 1
SP - 116
EP - 126
PB - Royal Society of Chemistry (RSC)
CY - Cambridge
AN - OPUS4-64141
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Lopes, Chrystal
A1 - Casali, Lucia
A1 - Emmerling, Franziska
A1 - Leyssens, Tom
A1 - Dupray, Valérie
A1 - Brandel, Clement
A1 - Cartigny, Yohann
T1 - Efficient racemization of the pharmaceutical compound Levetiracetam using solvent-free mechanochemistry
N2 - We present the racemization of an active pharmaceutical ingredient Levetiracetam using a novel approach. We demonstrate the design of a 100% solvent-free process that proceeds by high energy milling inside a regular mixer mill. The kinetics of the racemization process is drastically improved compared to the solution-based approach and illustrates the tremendous potential of mechanochemistry. In this study, we highlight the importance of mixing efficiency regarding data reproducibility, and we show, in particular, that water contamination has a negative impact on the reaction rate. Moreover, in situ X-ray diffraction gives us first insights into the mechanisms involved in the solid state during the mechanochemical racemization process.
KW - Mechanochemistry
PY - 2025
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-646108
DO - https://doi.org/10.1039/d4mr00103f
SN - 2976-8683
VL - 2
IS - 1
SP - 83
EP - 90
PB - Royal Society of Chemistry (RSC)
AN - OPUS4-64610
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Macchietti, Laura
A1 - Casali, Lucia
A1 - Emmerling, Franziska
A1 - Braga, Dario
A1 - Grepioni, Fabrizia
T1 - Deriving kinetic insights from mechanochemically synthesized compounds using multivariate analysis (MCR-ALS) of powder X-ray diffraction data
N2 - Kinetics information on the progress of the mechanochemical reactions is key to their understanding and subsequent scale-up. For crystalline materials, the most robust and tested method for obtaining kinetic data is the Quantitative Phase Analysis (QPA) via Rietveld refinement. In this work, we tested the feasibility of the Multivariate Curve Resolution-Alternating Least Squares (MCR-ALS) method on powder X-ray diffraction (PXRD) data of mechanochemical processes by studying the system theophylline (TP) and malonic acid (MA) in a 1 : 1 stoichiometric ratio at different milling conditions. We have highlighted the strengths and weaknesses of the MCR-ALS method, and we demonstrated why it may be an alternative route to obtain quantitative information on mechanochemical kinetics.
KW - Mechanochemistry
PY - 2024
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-646115
DO - https://doi.org/10.1039/d3mr00013c
SN - 2976-8683
VL - 1
IS - 1
SP - 106
EP - 115
PB - Royal Society of Chemistry (RSC)
AN - OPUS4-64611
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Pavlidis, Sotirios
A1 - Teutloff, Christian
A1 - de Oliveira Guilherme Buzanich, Ana
A1 - Krause, Konstantin B.
A1 - Emmerling, Franziska
A1 - Bittl, Robert
A1 - Abbenseth, Josh
T1 - A Crystalline Bismuth(II) Radical Anion: Synthesis, Characterization, and Reactivity
N2 - AbstractWe report the synthesis of a planarized tris‐amidobismuthane supported by a rigid, bulky NNN pincer ligand, which enforces a T‐shaped geometry at the bismuth center. The Bi(NNN) complex features a low‐lying LUMO with distinct Bi(6p) orbital character as shown by DFT calculations. Cyclic voltammetry reveals a fully reversible one‐electron reduction at E1/2 = –1.85 V versus Fc0/+ in THF. Chemical reduction with KC8 in the presence of 4,7,13,16,21,24‐hexaoxa‐1,10‐diazabicyclo[8.8.8]hexacosane (222‐crypt) enables the isolation of an unprecedented Bi(II) radical anion in high isolated yields. Multi‐frequency EPR, X‐ray absorption spectroscopy and SQUID magnetometry complemented by theoretical calculations confirm localization of the unpaired electron on the bismuth center. Preliminary reactivity studies display radical reactivity as shown by single‐electron transfer chemistry and radical coupling reactions.
KW - Bi(III)
PY - 2025
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-644143
DO - https://doi.org/10.1002/anie.202515545
SN - 1433-7851
VL - 64
IS - 49
SP - 1
EP - 6
PB - Wiley VHC-Verlag
AN - OPUS4-64414
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Chapartegui-Arias, Ander
A1 - Raysyan, A.
A1 - Belenguer, A. M.
A1 - Jaeger, Carsten
A1 - Tchipilov, Teodor
A1 - Prinz, Carsten
A1 - Abad Andrade, Carlos Enrique
A1 - Beyer, S.
A1 - Schneider, Rudolf
A1 - Emmerling, Franziska
T1 - Tailored mobility in a zeolite imidazolate framework (ZIF) antibody conjugate
N2 - Zeolitic imidazolate framework (ZIF) hybrid fluorescent nanoparticles and ZIF antibody conjugates have been synthesized, characterized, and employed in lateral-flow immunoassay (LFIA). The bright fluorescence of the conjugates and the possibility to tailor their mobility gives a huge potential for diagnostic assays. An enzyme-linked immunosorbent assay (ELISA) with horseradish peroxidase (HRP) as label, proved the integrity, stability, and dispersibility of the antibody conjugates, LC-MS/MS provided evidence that a covalent link was established between these metal-organic frameworks and lysine residues in IgG antibodies.
KW - ZIF
KW - ELISA
PY - 2021
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-532096
DO - https://doi.org/10.1002/chem.202100803
SN - 0947-6539
SN - 1521-3765
VL - 27
IS - 36
SP - 9414
EP - 9421
PB - Wiley-VCH
CY - Weinheim
AN - OPUS4-53209
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Casali, L.
A1 - Broll, V.
A1 - Ciurili, S.
A1 - Braga, D.
A1 - Emmerling, Franziska
A1 - Gepioni, F.
T1 - Facilitating Nitrification Inhibition through Green, Mechanochemical Synthesis of a Novel Nitrapyrin Complex
N2 - Nitrapyrin (NP) is applied to cultivated soils to inhibit the enzymatic activity of ammonia monooxygenase (AMO), but its poor aqueous solubility and high volatility severely limit its application. β-Cyclodextrin (β-CD) is commonly used to form inclusion complexes with hydrophobic molecules, improving water solubility and stability upon complexation. Here we report on the mechanochemical synthesis of the inclusion complex β-CD·NP, characterized via a combination of solid-state techniques, including exsitu and in situ X-ray diffraction, Raman and NMR spectroscopies, transmission electron microscopy, and energy dispersive X-ray spectroscopy. The pure inhibitor NP was also structurally characterized. The β-CD·NP complex presents improved solubility and thermal stability, and still inhibits the enzymatic activity of AMO with high efficacy. All results indicate that the inclusion of NP into β-CD represents a viable route for the preparation of a novel class of inhibitors, with improved properties related to stability, water solubility, and good inhibition activity.
KW - Mechanochemistry
KW - Nitrification
PY - 2021
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-537154
DO - https://doi.org/10.1021/acs.cgd.1c00681
SN - 1528-7505
VL - 21
IS - 10
SP - 5792
EP - 5799
PB - ACS Publications
AN - OPUS4-53715
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Heilmann, Maria
A1 - Prinz, Carsten
A1 - Bienert, Ralf
A1 - Wendt, R.
A1 - Kunkel, B.
A1 - Radnik, Jörg
A1 - Hoell, A.
A1 - Wohlrab, S.
A1 - de Oliveira Guilherme Buzanich, Ana
A1 - Emmerling, Franziska
T1 - Size-Tunable Ni–Cu Core–Shell Nanoparticles—Structure, Composition, and Catalytic Activity for the Reverse Water–Gas Shift Reaction
N2 - A facile and efficient methodology is described for the solvothermal synthesis of size-tunable, stable, and uniform NiCu core–shell nanoparticles (NPs) for application in catalysis. The diameter of the NPs is tuned in a range from 6 nm to 30 nm and to adjust the Ni:Cu ratio from 30:1 to 1:1. Furthermore, the influence of different reaction parameters on the final NPs is studied. The NPs are structurally characterized by a method combination of transmission electron microscopy, anomalous small-angle X-ray scattering, X-ray absorption fine structure, and X-ray photoelectron spectroscopy. Using these analytical methods, it is possible to elucidate a core–shell–shell structure of all particles and their chemical composition. In all cases, a depletion from the core to the shell is observed, with the core consisting of NiCu alloy, surrounded by an inner Ni-rich shell and an outer NiO shell. The SiO2-supported NiCu core–shell NPs show pronounced selectivity of >99% for CO in the catalytic reduction of CO2 to CO using hydrogen as reactant (reverse water–gas shift reaction) independent of size and Ni:Cu ratio.
KW - Nanoparticles
KW - Core-shell
KW - Catalysis
PY - 2022
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-543606
DO - https://doi.org/10.1002/adem.202101308
SN - 1438-1656
SP - 1
EP - 13
PB - Wiley VCH
AN - OPUS4-54360
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Yusenko, Kirill
A1 - Kabelitz, Anke
A1 - Schokel, Alexander
A1 - Wagner, Ralf
A1 - Prinz, Carsten
A1 - Kemnitz, E
A1 - Emmerling, Franziska
A1 - Krahl, Thoralf
A1 - de Oliveira Guilherme Buzanich, Ana
T1 - Local Structure of Europium-Doped Luminescent Strontium Fluoride Nanoparticles: Comparative X-ray Absorption Spectroscopy and Diffraction Study
N2 - Rare-earth based luminescent materials are key functional components for the rational design of light-conversion smart devices. Stable Eu3+-doped strontium fluoride (SrF2) nanoparticles were prepared at room temperature in ethylene glycol. Their luminescence depends on the Eu content and changes after heat treatment. The crystallinity of heat-treated material increases in comparison with as-synthesized samples. Particles were investigated in solution using X-ray diffraction, small-angle X-ray scattering, and X-ray spectroscopy. After heat treatment, the size of the disordered nanoparticles increases together with a change of their local structure. Interstitial fluoride ions can be localized near Eu3+ ions. Therefore, non-radiative relaxation from other mechanisms is decreased. Knowledge about the cation distribution is key information for understanding the luminescence properties of any material.
KW - SrF2
KW - EXAFS
KW - Eu
PY - 2021
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-540094
DO - https://doi.org/10.1002/cnma.202100281
VL - 7
IS - 11
SP - 1221
EP - 1229
PB - Wiley Online Library
AN - OPUS4-54009
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Lampronti, G.
A1 - Michalchuk, Adam
A1 - Mazzeo, P.
A1 - Belenguer, Ana
A1 - Sanders, J. K. M.
A1 - Bacchi, A.
A1 - Emmerling, Franziska
T1 - Changing the game of time resolved X-ray diffraction on the mechanochemistry playground by downsizing
N2 - Time resolved in situ (TRIS) monitoring has revolutionised the study of mechanochemical transformations but has been limited by available data quality. Here we report how a combination of miniaturised grinding jars together with innovations in X-ray powder diffraction data collection and state-of-the-art analysis strategies transform the power of TRIS synchrotron mechanochemical experiments. Accurate phase compositions, comparable to those obtained by ex situ measurements, can be obtained with small sample loadings. Moreover, microstructural parameters (crystal size and microstrain) can be also determined with high confidence. This strategy applies to all chemistries, is readily implemented, and yields high-quality diffraction data even using a low energy synchrotron source. This offers a direct avenue towards the mechanochemical investigation of reactions comprising scarce, expensive, or toxic compounds. Our strategy is applied to model systems, including inorganic, metal-organic, and organic mechanosyntheses, resolves previously misinterpreted mechanisms in mechanochemical syntheses, and promises broad, new directions for mechanochemical research.
KW - Mechanochemistry
KW - Synchrotron radiation
KW - Material synthesis
PY - 2021
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-535932
DO - https://doi.org/10.1038/s41467-021-26264-1
SN - 2041-1723
VL - 12
IS - 1
SP - 1
EP - 9
PB - Nature Publishing Group
CY - London
AN - OPUS4-53593
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Feiler, Torvid
A1 - Michalchuk, Adam
A1 - Schröder, V.
A1 - List-Kratochvil, E.
A1 - Emmerling, Franziska
A1 - Bhattacharya, Biswajit
T1 - Elastic Flexibility in an Optically Active Naphthalidenimine-Based Single Crystal
N2 - Organic single crystals that combine mechanical flexibility and optical properties are important for developing flexible optical devices, but examples of such crystals remain scarce. Both mechanical flexibility and optical activity depend on the underlying crystal packing and the nature of the intermolecular interactions present in the solid state. Hence, both properties can be expected to be tunable by small chemical modifications to the organic molecule. By incorporating a chlorine atom, a reportedly mechanically flexible crystal of (E)-1-(4-bromo-phenyl)iminomethyl-2-hydroxylnaphthalene (BPIN) produces (E)-1-(4-bromo-2-chloro-phenyl)iminomethyl-2-hydroxyl-naphthalene (BCPIN). BCPIN crystals show elastic bending similar to BPIN upon mechanical stress, but exhibit a remarkable difference in their optical properties as a result of the chemical modification to the backbone of the organic molecule. This work thus demonstrates that the optical properties and mechanical flexibility of molecular materials can, in principle, be tuned independently.
KW - Elastic Crystal
PY - 2021
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-539040
DO - https://doi.org/10.3390/cryst11111397
VL - 11
IS - 11
SP - 1397
PB - MDPI
AN - OPUS4-53904
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Gernhard, M.
A1 - Rautenberg, Max
A1 - Hörner, G.
A1 - Weber, B.
A1 - Emmerling, Franziska
A1 - Roth, C.
T1 - Mechanochemical Synthesis as a Greener Way to ProduceIron-based Oxygen Reduction Catalysts
N2 - Iron-based catalysts have been reported manifold and studied as platinum group metal (PGM) free alternatives for the catalysis of the oxygen reduction reaction (ORR). However, their sustainable preparation by greener synthesis approaches is usually not discussed. In this work, we propose a new method for the sustainable preparation of such catalysts by using a mechanochemical approach, with no solvents and non-toxic chemicals. The materials obtained from low temperature carbonization (700 °C) exhibit considerable and stable catalytic performance for ORR in alkaline medium. A catalyst obtained
from iron hydroxide, tryptophan, dicyandiamide, and ammonium nitrate shows the best electrocatalytic Performance with an overpotential of 921 mV vs. RHE at 0.1 mA/cm2 and an electron transfer number of 3.4.
KW - PGM-free catalyst
KW - Oxygen Reduction Reaction
KW - AEMFC
KW - Mössbauer Spectroscopy
KW - Sustainable Synthesis
PY - 2021
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-535326
DO - https://doi.org/10.1002/zaac.202100194
VL - 647
IS - 22
SP - 2080
EP - 2087
PB - Weinheim-VCH GmbH
AN - OPUS4-53532
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Michalchuk, Adam
A1 - Rudic, S.
A1 - Pulham, C.
A1 - Morrison, C.
T1 - Predicting the impact sensitivity of a polymorphic high explosive: the curious case of FOX-7
N2 - The impact sensitivity (IS) of FOX-7 polymorphs is predicted by phonon up-pumping to decrease as layers of FOX-7 molecules flatten. Experimental validation proved anomalous owing to a phase transition during testing, raising questions regarding Impact sensitivity measurement and highlighting the need for models to predict IS of polymorphic energetic materials.
KW - Energetic materials
KW - Density functional theory
KW - Inelastic Neutron Scattering Spectroscopy
KW - Impact Sensitivity
PY - 2021
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-535558
DO - https://doi.org/10.1039/d1cc03906g
SN - 1364-548X
VL - 57
IS - 85
SP - 11213
EP - 11216
PB - Royal Society of Chemistry
AN - OPUS4-53555
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Loges, A.
A1 - Scholz, G.
A1 - de Sousa Amadeu, Nader
A1 - Jingjing, S.
A1 - Emmerling, Franziska
A1 - John, T.
A1 - Paulus, B.
A1 - Braun, T.
T1 - Studies on the local structure of the F/OH site in topaz by magic angle spinning nuclear magnetic resonance and Raman spectroscopy
N2 - he mutual influence of F and OH groups in neighboring sites in topaz (Al2SiO4(F,OH)2) was investigated using magic angle spinning nuclear magnetic resonance (MAS NMR) and Raman spectroscopy. The splitting of 19F and 1H NMR signals, as well as the OH Raman band, provides evidence for hydrogen bond formation within the crystal structure. Depending on whether a given OH group has another OH group or fluoride as its neighbor, two different hydrogen bond constellations may form: either OH···O···HO or F···H···O. The proton accepting oxygen was determined to be part of the SiO4 tetrahedron using 29Si MAS NMR. Comparison of the MAS NMR data between an OH-bearing and an OH-free topaz sample confirms that the 19F signal at −130 ppm stems from F− ions that take part in H···F bonds with a distance of ∼ 2.4 Å, whereas the main signal at −135 ppm belongs to fluoride ions with no immediate OH group neighbors. The Raman OH sub-band at 3644 cm−1 stems from OH groups neighboring other OH groups, whereas the sub-band at 3650 cm−1 stems from OH groups with fluoride neighbors, which are affected by H···F bridging. The integrated intensities of these two sub-bands do not conform to the expected ratios based on probabilistic calculations from the total OH concentration. This can be explained by a difference in the polarizability of the OH bond between the different hydrogen bond constellations or partial order or unmixing of F and OH, or a combination of both. This has implications for the quantitative interpretation of Raman data on OH bonds in general and their potential use as a probe for structural (dis-)order. No indication of tetrahedrally coordinated Al was found with 27Al MAS NMR, suggesting that the investigated samples likely have nearly ideal Al/Si ratios, making them potentially useful as high-density electron microprobe reference materials for Al and Si, as well as for F.
KW - Topas
KW - NMR
KW - XRD
PY - 2022
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-561863
DO - https://doi.org/10.5194/ejm-34-507-2022
SN - 1617-4011
VL - 34
IS - 5
SP - 507
EP - 521
PB - Copernicus Publications
CY - Göttingen
AN - OPUS4-56186
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Dittmann, D.
A1 - Saal, L.
A1 - Zietschmann, F.
A1 - Mai, M.
A1 - Altmann, Korinna
A1 - Al-Sabbagh, Dominik
A1 - Schuhmann, P.
A1 - Ruhl, A.
A1 - Jekel, M.
A1 - Braun, U.
T1 - Characterization of activated carbons for water treatment using TGA‑FTIR for analysis of oxygen‑containing functional groups
N2 - Water treatment with activated carbon (AC) is an established method for the removal of organic micropollutants and natu ral organic matter. However, it is not yet possible to predict the removal of individual pollutants. An appropriate material characterization, matching adsorption processes in water, might be the missing piece in the puzzle. To this end, this study examined 25 diferent commercially available ACs to evaluate their material properties. Frequently reported analyses, including N2 adsorption/desorption, CHNS(O), point of zero charge (PZC) analysis, and X-ray photoelectron spectroscopy, were conducted on a selected subset of powdered ACs. Inorganic elements examined using X-ray fuorescence and X-ray difraction spectroscopy revealed that relative elemental contents were distinctive to the individual AC’s raw material and activation procedure. This study also is the frst to use thermogravimetric analysis (TGA) coupled to Fourier-transform infrared spectroscopy (FTIR) to conduct quantitative analyses of functional surface oxygen groups (SOGs: carboxylic acid, anhydride, lactone, phenol, carbonyl, and pyrone groups) on such a large number of ACs. The comparably economical TGA method was found to provide good surrogates for the PZC by pyrolytic mass loss up to 600 ◦C (ML600), for the oxygen content by ML1000 and for the carbon content by oxidation. Mass loss profles depict the AC’s chemistry like fngerprints. Furthermore, we found that SOG contents determined by TGA-FTIR covered a wide individual range and depended on the raw material and production process of the AC. TGA and TGA-FTIR might therefore be used to identify the suitability of a particular AC for a variety of target substances in diferent target waters. This can help practitioners to control AC use in waterworks or wastewater treatment plants.
KW - Adsorbtion
KW - Organic contaminants
KW - Temperature-programmed desorption
KW - Proximate analysis
KW - Principal component analysis
PY - 2022
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-555506
DO - https://doi.org/10.1007/s13201-022-01723-2
SN - 2190-5495
VL - 12
SP - 1
EP - 13
PB - Springer
CY - Berlin
AN - OPUS4-55550
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Mazzeo, P. P.
A1 - Prencipe, M.
A1 - Feiler, Torvid
A1 - Emmerling, Franziska
A1 - Bacchi, A.
T1 - On the mechanism of cocrystal mechanochemical reaction via low melting eutectic: A time-resolved in situ monitoring investigation
N2 - Mechanochemistry has become a sustainable and attractive cost-effective synthetic technique, largely used within the frame of crystal engineering. Cocrystals, namely, crystalline compounds made of different chemical entities within the same crystal structure, are typically synthesized in bulk via mechanochemistry; however, whereas the macroscopic aspects of grinding are becoming clear, the fundamental principles that underlie mechanochemical cocrystallization at the microscopic level remain poorly understood. Time-resolved in situ (TRIS) monitoring approaches have opened the door to exceptional detail regarding mechanochemical reactions. We here report a clear example of cocrystallization between two solid coformers that proceeds through the formation of a metastable low melting binary eutectic phase. The overall cocrystallization process has been monitored by time-resolved in situ (TRIS) synchrotron X-ray powder diffraction with a customized ball milling setup, currently available at μ Spot beamline at BESSY-II, Helmholtz-Zentrum Berlin. The binary system and the low melting eutectic phase were further characterized via DSC, HSM, and VT-XRPD.
KW - Mechanochemistry
KW - In situ
KW - Cocrystal
PY - 2022
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-552977
DO - https://doi.org/10.1021/acs.cgd.2c00262
SN - 1528-7505
VL - 22
IS - 7
SP - 4260
EP - 4267
PB - ACS Publ.
CY - Washington, DC
AN - OPUS4-55297
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Pakrashy, S.
A1 - Mandal, P. K.
A1 - Goswami, J. N.
A1 - Dey, S. K.
A1 - Choudhury, S. M.
A1 - Bhattacharya, Biswajit
A1 - Emmerling, Franziska
A1 - Alasmary, F. A.
A1 - Dolai, M.
T1 - Bioinformatics and Network Pharmacology of the First Crystal Structured Clerodin: Anticancer and Antioxidant Potential against Human Breast Carcinoma Cell
N2 - Clerodin was isolated from the medicinal plant Clerodendrum infortunatum, and CSD search showed the first crystal structure of clerodin by a single-crystal X-ray diffraction study. We checked its binding potential with target proteins by docking and conducted network pharmacology analysis, ADMET analysis, in silico pathway analysis, normal mode analysis (NMA), and cytotoxic activity studies to evaluate clerodin as a potential anticancer agent. The cell viability studies of clerodin on the human breast carcinoma cell line (MCF-7) showed toxicity on MCF-7 cells but no toxicity toward normal human lymphocyte cells (HLCs). The anticancer mechanism of clerodin was validated by its enhanced capacity to produce intracellular reactive oxygen species (ROS) and to lower the reduced glutathione content in MCF-7 cells.
KW - Anticancer
KW - Clerodin
PY - 2022
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-567600
DO - https://doi.org/10.1021/acsomega.2c07173
SN - 2470-1343
VL - 7
IS - 51
SP - 48572
EP - 48582
PB - ACS Publ.
CY - Washington, DC
AN - OPUS4-56760
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -