TY - JOUR
A1 - Dittmar, Stefan
A1 - Weyrauch, Steffen
A1 - Reemtsma, Thorsten
A1 - Eisentraut, Paul
A1 - Altmann, Korinna
A1 - Ruhl, Aki S.
A1 - Jekel, Martin
T1 - Settling Velocities of Tire and Road Wear Particles: Analyzing Finely Graded Density Fractions of Samples from a Road Simulator and a Highway Tunnel
N2 - The terminal settling velocity is considered the most critical parameter determining the transport of tire and road wear particles (TRWP) in aquatic environments. Nonetheless, no respective empirical data has been reported so far. In this study, particle samples from a road simulator and a highway tunnel were investigated with a validated imaging method. Different density and size fractions of both samples were measured separately, acquiring sizes and settling velocities of more than 30,000 individual particles. In addition, tire marker polymers were analyzed for each fraction via thermal extraction desorption-gas chromatography/mass spectrometry. Finally, the acquired particle data was combined according to the fractions’ estimated tire contents in order to deduce detailed probability distributions of particle size and settling velocity for the actual TRWP from both samples. Weighted by TRWP-incorporated tire mass, median diameters of 54 and 44 μm as well as median settling velocities of 0.65 and 0.22 mm/s were found for TRWP from the road simulator and highway tunnel, respectively. This study thus provides the first ever empirical data on TRWP settling velocities in water, which can be highly valuable input for modeling the environmental transport of TRWP and for dimensioning TRWP retention systems.
KW - Microplastics
KW - TED-GC/MS
KW - Sinking velocities
KW - Transport
PY - 2025
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-635449
DO - https://doi.org/10.1021/acs.est.5c04165
SN - 0013-936X
VL - 59
IS - 26
SP - 13434
EP - 13446
PB - American Chemical Society (ACS)
AN - OPUS4-63544
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Das, Prasenjit
A1 - Chakraborty, Gouri
A1 - Yang, Jin
A1 - Roeser, Jérôme
A1 - Küçükkeçeci, Hüseyin
A1 - Nguyen, Anh Dung
A1 - Schwarze, Michael
A1 - Gabriel, Jose
A1 - Penschke, Christopher
A1 - Du, Shengjun
A1 - Weigelt, Vincent
A1 - Khalil, Islam E.
A1 - Schmidt, Johannes
A1 - Saalfrank, Peter
A1 - Oschatz, Martin
A1 - Rabeah, Jabor
A1 - Schomäcker, Reinhard
A1 - Emmerling, Franziska
A1 - Thomas, Arne
T1 - The Effect of Pore Functionality in Multicomponent Covalent Organic Frameworks on Stable Long‐Term Photocatalytic H2 Production
N2 - AbstractIn nature, organic molecules play a vital role in light harvesting and photosynthesis. However, regarding artificial water splitting, the research focus is primarily on inorganic semiconductors. Although organic photocatalysts have high structural variability, they tend to exhibit lower quantum efficiencies for water splitting than their inorganic counterparts. Multicomponent reactions (MCRs) offer an attractive route to introduce different functional units into covalent organic frameworks (COFs) and enable semiconducting properties and high chemical stability, creating promising materials for long‐term photocatalytic applications, such as H2 production. Herein, five highly crystalline donor‐acceptor based, 4‐substituted quinoline‐linked MCR‐COFs are presented that are prepared via the three‐component Povarov reaction. The pore functionality is varied by applying different vinyl derivatives (e.g., styrene, 2‐vinyl pyridine, 4‐vinylpyridine, 4‐vinyl imidazole, 2,3,4,5,6‐pentafluorostyrene), which has a strong influence on the obtained photocatalytic activity. Especially an imidazole‐functionalized COF displays promising photocatalytic performance due to its high surface area, crystallinity, and wettability. These properties enable it to maintain its photocatalytic activity even in a membrane support. Furthermore, such MCR‐COFs display dramatically enhanced (photo)chemical stability even after long‐term solar light irradiation and exhibit a high and steady H2 evolution for at least 15 days.
KW - Sstability
KW - Covalent organic frameworks
KW - Pore functionality
KW - Long-term H2 production
KW - Multicomponent reactions
PY - 2025
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-639787
DO - https://doi.org/10.1002/aenm.202501193
SN - 1614-6832
SP - 1
EP - 10
PB - Wiley VHC-Verlag
AN - OPUS4-63978
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Visileanu, Emilia
A1 - Altmann, Korinna
A1 - Stepa, Raluca
A1 - Haiducu, Maria
A1 - Miclea, Paul Tiberiu
A1 - Vladu, Alina
A1 - Dondea, Felicia
A1 - Grosu, Marian Catalin
A1 - Scarlat, Razvan
T1 - Comparative Analysis of Airborne Particle Concentrations in Textile Industry Environments Throughout the Workday
N2 - This paper addresses the growing concern surrounding microplastic pollution, particularly within the textile industry, and the associated potential health risks linked to the inhalation and ingestion of microplastic particles. Microplastics, defined as plastic particles smaller than five millimeters, are increasingly found not only in aquatic environments, but also in soils, air, and food. Although research on the health impacts of microplastics is still emerging, early studies indicate that these particles could contribute to health issues, including oxidative stress, inflammation, and cardiovascular diseases. Notably, individuals with higher concentrations of plastics in arterial plaques are more susceptible to heart attacks and strokes. In the textile industry, synthetic fibers such as polyester, nylon, and acrylic release microplastics into the air during production. The paper discusses a study conducted in a textile company that processes polyester yarns, where airborne microplastic concentrations were measured at various locations throughout the day. Particle sizes ranging from 0.3 nm to 10 nm were analyzed, revealing the presence of polyester polymers in the particulate matter. These findings underscore the widespread nature of microplastic pollution, particularly in industrial settings, and raise concerns about the health risks associated with prolonged exposure to airborne microplastics. While further research is necessary to fully understand the extent of these health impacts, preliminary data suggest a troubling link between microplastic inhalation and cardiovascular conditions.
KW - Microplastics
KW - Textiles
KW - Airborne particles
PY - 2025
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-635269
DO - https://doi.org/10.3390/microplastics4020034
SN - 2673-8929
VL - 4
IS - 2
SP - 1
EP - 17
PB - MDPI AG
AN - OPUS4-63526
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Rodríguez-Sánchez, Noelia
A1 - Domínguez-Santos, J. Enrique
A1 - Bhattacharya, Biswajit
A1 - Prinz, Carsten
A1 - Canosa, Inés
A1 - Flores, Amando
A1 - Jiménez-Rodríguez, Antonia
A1 - Ruiz-Salvador, A. Rabdel
A1 - Emmerling, Franziska
A1 - Ballesteros, Menta
T1 - Mechanochemical synthesis of multivariate UPO-3 (Cu-ZIF-9-ica) MOF for inactivation of antibiotic-resistant bacteria and irrigation-quality water production via heterogeneous photo-Fenton catalysis
N2 - Water scarcity and pollution are critical global challenges, particularly in agriculture, the largest consumer of water. The development of sustainable, effective, and environmentally friendly disinfection methods is essential to address the risks posed by antibiotic-resistant bacteria and to ensure safe reuse of water for irrigation. In this study, we report the synthesis of the metal-organic framework (MOF) Universidad Pablo de Olavide-3 (UPO-3) via a mechanochemical approach, a scalable and sustainable method compared to traditional solvothermal synthesis. The resulting UPO-3/H2O2 system exhibits robust photocatalytic properties under visible light, achieving effective and broad-spectrum antibacterial activity. The disinfection efficiency of the catalyst was evaluated against Escherichia coli as a model of microbial pathogen in two saline matrices, considering the key parameters of the heterogeneous photo-Fenton process, including catalyst dosage, initial H2O2 concentration, and light irradiation. Notably, it inactivated two important virulent and antibiotic-resistant bacterial pathogens (Staphylococcus aureus and Pseudomonas aeruginosa). Furthermore, UPO-3 shows exceptional performance under real-world conditions, such as river water disinfection, achieving >5-log reduction of E. coli, fulfilling a critical criterion for Class A water reuse under Regulation (EU) 2020/741. These results highlight UPO-3 as a versatile and sustainable solution for water reuse, addressing water scarcity and advancing efforts to achieve United Nations Sustainable Development Goal 6.
KW - Water reuse
KW - Antibiotic-resistant bacteria
KW - Water disinfection
KW - Mechanochemical synthesis
KW - Metal organic framework
PY - 2025
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-639766
DO - https://doi.org/10.1016/j.chemosphere.2025.144610
SN - 0045-6535
VL - 386
SP - 1
EP - 11
PB - Elsevier Ltd.
AN - OPUS4-63976
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Go, Eun Sul
A1 - Hong, Eun Ji
A1 - Lee, Ji Yeong
A1 - Stolar, Tomislav
A1 - Peterson, Gregory I.
A1 - Emmerling, Franziska
A1 - Kim, Kyoungsoo
A1 - Kim, Jeung Gon
T1 - Insights into Mechanochemical Solid-State Ball-Milling Reaction: Monitoring Transition from Heterogeneous to Homogeneous Conditions
N2 - As mechanochemical synthesis has advanced significantly, there has been intense interest in understanding the underlying mechanisms of these reactions. Given that many mechanochemical processes are conducted in the solid-state without solvation yet sometimes yield faster reactions than those in solution, we sought to address the following question: Are mechanochemical reactions homo- or heterogeneous? To investigate, we employed a model system involving the mixing and copolymerization of l-lactide (LLA) and d-lactide (DLA), monitored through powder X-ray diffraction (PXRD), nuclear magnetic resonance, and differential scanning calorimetry. In situ and ex situ PXRD analyses of the mixture of LLA and DLA showed that vibratory ball milling rapidly transformed the initially heterogeneous lactide mixture into a homogeneous phase within one min due to collisions between the balls and the jar. By varying the milling conditions, we were able to regulate the level of mixing, which subsequently influenced the copolymerization outcomes. In the solid-state ball-milling copolymerization of LLA and DLA in the presence of a catalyst and initiator, multiblock copolymers of poly(l-lactic acid) and poly(d-lactic acid) were formed within one min during the early stage of the reaction, when incomplete mixing of the monomers led to a process governed by phase heterogeneity. In contrast, prolonged polymerization promoted conditions approaching homogeneity, ultimately yielding atactic poly(lactic acid). This transition from heterogeneous to homogeneous reactions is a distinctive feature compared to conventional homogeneous reactions, potentially leading to mechano-exclusive reaction designs.
KW - Mechanochemistry
KW - Ball-milling
KW - Homogeneous reaction
KW - Heterogeneous reaction
PY - 2025
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-638008
DO - https://doi.org/10.1021/jacsau.5c00322
SN - 2691-3704
VL - 5
IS - 6
SP - 2720
EP - 2727
PB - American Chemical Society (ACS)
AN - OPUS4-63800
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Feiler, Torvid
A1 - Emmerling, Franziska
A1 - Bhattacharya, Biswajit
T1 - Sustainable mechanochemical approach for the selective synthesis of multicomponent organic solids: real-time in situ insights
N2 - Crystalline multicomponent organic solids (MOSs) such as cocrystals and ionic cocrystals hold immense potential in diverse functional applications, ranging from pharmaceuticals to optoelectronics. However, conventional solution-based crystallization methods often result in polymorphic mixtures and lack precise control over product composition. Herein, we report a comparative investigation of solution crystallization versus mechanochemical synthesis for constructing MOSs from 9-anthracenecarboxylic acid (ACA) and 4,4 '-bipyridine (BPY). Solution-based approaches consistently yielded concomitant formation of neutral cocrystal (CC) and ionic cocrystal (ICC) forms, regardless of the solvent used. The resulting multicomponent solids were comprehensively characterized using a combination of single crystal X-ray diffraction, powder X-ray diffraction, Fourier-transform infrared spectroscopy, differential thermal analysis, and thermogravimetric analysis. In contrast, mechanochemical methods, including neat grinding (without solvent) and liquid-assisted grinding (with minimum solvent), enabled selective formation of either a phase pure CC or ICC form. Less polar and nonpolar organic solvents favor the kinetic CC, while polar water promotes formation of the thermodynamically stable ICC. Time-resolved in situ powder X-ray diffraction (TRIS-PXRD) captures the dynamic evolution of solid-state phases and reveals the complete transformation of the CC into ICC under neat grinding or water-assisted conditions. This study highlights the powerful role of mechanochemistry and in situ monitoring in steering solid-state reactivity and offers a sustainable pathway for the targeted and scalable synthesis of pure multicomponent organic materials.
KW - Cocrystal
KW - Synchrotron X-ray powder diffraction
KW - Time-resolved in situ investigation
PY - 2025
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-641409
DO - https://doi.org/10.1039/D5CE00663E
SN - 1466-8033
SP - 1
EP - 9
PB - Royal Society of Chemistry (RSC)
CY - Cambridge
AN - OPUS4-64140
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Karafiludis, Stephanos
A1 - Scoppola, E.
A1 - Wolf, S.E.
A1 - Kochovski, Z.
A1 - Matzdorff, D.
A1 - Van Driessche, A. E. S.
A1 - Hövelmann, J.
A1 - Emmerling, Franziska
A1 - Stawski, Tomasz M.
T1 - Evidence for liquid-liquid phase separation during the early stages of Mg-struvite formation
N2 - The precipitation of struvite, a magnesium ammonium phosphate hexahydrate (MgNH₄PO₄ · 6H₂O) mineral, from wastewater is a promising method for recovering phosphorous. While this process is commonly used in engineered environments, our understanding of the underlying mechanisms responsible for the formation of struvite crystals remains limited. Specifically, indirect evidence suggests the involvement of an amorphous precursor and the occurrence of multi-step processes in struvite formation, which would indicate non-classical paths of nucleation and crystallization. In this study, we use synchrotron-based in situ x-ray scattering complemented by cryogenic transmission electron microscopy to obtain new insights from the earliest stages of struvite formation. The holistic scattering data captured the structure of an entire assembly in a time-resolved manner. The structural features comprise the aqueous medium, the growing struvite crystals, and any potential heterogeneities or complex entities. By analysing the scattering data, we found that the onset of crystallization causes a perturbation in the structure of the surrounding aqueous medium. This perturbation is characterized by the occurrence and evolution of Ornstein-Zernike fluctuations on a scale of about 1 nm, suggesting a non-classical nature of the system. We interpret this phenomenon as a liquid-liquid phase separation, which gives rise to the formation of the amorphous precursor phase preceding actual crystal growth of struvite. Our microscopy results confirm that the formation of Mg-struvite includes a short-lived amorphous phase, lasting >10 s.
KW - Physical and theoretical chemistry
KW - Non-classical crystallization
KW - Struvite
KW - Liquid-liquid-phase-separation
KW - Nucleation
KW - Crystallization
KW - In-situ scattering
PY - 2023
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-584766
DO - https://doi.org/10.1063/5.0166278
SN - 1089-7690
VL - 159
IS - 13
SP - 1
EP - 12
PB - AIP Publishing
CY - Woodbury, NY
AN - OPUS4-58476
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Stawski, Tomasz
A1 - Karafiludis, Stephanos
A1 - Pimentel, Carlos
A1 - Montes-Hernández, German
A1 - Kochovski, Zdravko
A1 - Bienert, Ralf
A1 - Weimann, Karin
A1 - Emmerling, Franziska
A1 - Scoppola, Ernesto
A1 - Van Driessche, Alexander E.S.
T1 - Solution-driven processing of calcium sulfate: The mechanism of the reversible transformation of gypsum to bassanite in brines
N2 - Here, we show that calcium sulfate dihydrate (gypsum) can be directly, rapidly and reversibly converted to calcium sulfate hemihydrate (bassanite) in high salinity solutions (brines). The optimum conditions for the efficient production of bassanite in a short time (<5 min) involve the use of brines with c(NaCl) > 4 M and maintaining a temperature, T > 80 °C. When the solution containing bassanite crystals is cooled down to around room temperature, eventually gypsum is formed. When the temperature is raised again to T > 80 °C, bassanite is rapidly re-precipitated. This contrasts with the better-known behaviour of the bassanite phase in low-salt environments. In low-salinity aqueous solutions, bassanite is considered to be metastable with respect to gypsum and anhydrite, and therefore gypsum-to-bassanite conversion does not occur in pure water. Interestingly, the high-salinity transformation of gypsum-to-bassanite has been reported by many authors and used in practice for several decades, although its very occurrence actually contradicts numerical thermodynamic predictions regarding solubility of calcium sulfate phases. By following the evolution of crystalline phases with in situ and time-resolved X-ray diffraction/scattering and Raman spectroscopy, we demonstrated that the phase stability in brines at elevated temperatures was inaccurately represented in the thermodynamic databases. Most notably for c(NaCl) > 4 M, and T > 80 °C gypsum becomes readily more soluble than bassanite, which induces the direct precipitation of the latter from gypsum. The fact that these transformations are controlled by the solution provides extensive opportunities for precise manipulation of crystal formation. Our experiments confirmed that bassanite remained the sole crystalline phase for many hours before reverting into gypsum. This property is extremely advantageous for practical processing and efficient crystal extraction in industrial scenarios.
KW - Industrial and Manufacturing Engineering
KW - Strategy and Management
KW - General Environmental Science
KW - Renewable Energy, Sustainability and the Environment
KW - Building and Construction
KW - Calcium sulfate
KW - Gypsum
KW - Bassanite
KW - Scattering
KW - Raman
KW - In situ
KW - Synchrotron
KW - BESSY
KW - MySpot
PY - 2024
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-594698
UR - https://www.sciencedirect.com/science/article/pii/S0959652624004591#appsec1
DO - https://doi.org/10.1016/j.jclepro.2024.141012
SN - 0959-6526
VL - 440
SP - 1
EP - 12
PB - Elsevier B.V.
AN - OPUS4-59469
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Edzards, Joshua
A1 - Saßnick, Holger-Dietrich
A1 - de Oliveira Guilherme Buzanich, Ana
A1 - Valencia, Ana M.
A1 - Emmerling, Franziska
A1 - Beyer, Sebastian
A1 - Cocchi, Caterina
T1 - Effects of Ligand Substituents on the Character of Zn-Coordination in Zeolitic Imidazolate Frameworks
N2 - Due to their favorable properties and high porosity, zeolitic imidazolate frameworks (ZIFs) have recently received much limelight for key technologies such as energy storage, optoelectronics, sensorics, and catalysis. Despite widespread interest in these materials, fundamental questions regarding the zinc coordination environment remain poorly understood. By focusing on zinc(II)2-methylimidazolate (ZIF-8) and its tetrahedrally coordinated analogues with Br-, Cl-, and H-substitution in the 2-ring position, we aim to clarify how variations in the local environment of Zn impact the charge distribution and the electronic properties of these materials. Our results from densityfunctional theory confirm the presence of a Zn coordinative bond with a large polarization that is quantitatively affected by different substituents on the organic ligand. Moreover, our findings suggest that the variations in the Zn coordination induced by the functionalization have a negligible effect on the electronic structure of the considered compounds. On the other hand, halogen terminations of the ligands lead to distinct electronic contributions in the vicinity of the frontier region which ultimately reduce the band gap size by a few hundred millielectron volts. Experimental results obtained from X-ray absorption spectroscopy (Zn K-edge) confirm the trends predicted by theory and, together with them, contribute to a better understanding of the structure−property relationships that are needed to tailor ZIFs for target applications.
KW - Surfaces
KW - Physical and Theoretical Chemistry
KW - General Energy
KW - Electronic
KW - Coatings and Films
KW - Optical and Magnetic Materials
PY - 2023
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-589117
DO - https://doi.org/10.1021/acs.jpcc.3c06054
SN - 1932-7447
VL - 127
IS - 43
SP - 21456
EP - 21464
PB - American Chemical Society (ACS)
AN - OPUS4-58911
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Zuffa, Caterina
A1 - Cappuccino, Chiara
A1 - Casali, Lucia
A1 - Emmerling, Franziska
A1 - Maini, Lucia
T1 - Liquid reagents are not enough for liquid assisted grinding in the synthesis of [(AgBr)(n-pica)]n
N2 - This study investigates the mechanochemical reactions between AgBr 3-picolylamine and 4-picolylamine. The use of different stoichiometry ratios of the reagents allows [(AgBr)(n-pica)]n and [(AgBr)2(n-pica)]n to be obtained, and we report the new structures of [(AgBr)2(3-pica)]n and [(AgBr)2(4-pica)]n which are characterized by the presence of the following: (a) infinite inorganic chains, (b) silver atom coordinated only by bromide atoms and (c) argentophilic interactions. Furthermore, we studied the interconversion of [(AgBr)(n-pica)]n/[(AgBr)2(n-pica)]n by mechanochemical and thermal properties. The in situ experiments suggest that [(AgBr)(3-pica)]n is kinetically favoured while [(AgBr)2(3-pica)]n is converted into [(AgBr)(3-pica)]n only with a high excess of the ligand. Finally, the liquid nature of the ligands is not sufficient to assist the grinding process, and the complete reaction is observed with the addition of a small quantity of acetonitrile.
KW - Mechanochemistry
KW - Complex
PY - 2024
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-594755
DO - https://doi.org/10.1039/d3cp04791a
SN - 1463-9076
SP - 1
EP - 10
PB - Royal Society of Chemistry (RSC)
AN - OPUS4-59475
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Villajos Collado, José Antonio
A1 - Bienert, M.
A1 - Gugin, Nikita
A1 - Emmerling, Franziska
A1 - Maiwald, Michael
T1 - A database to select affordable MOFs for volumetric hydrogen cryoadsorption considering the cost of their linkers
N2 - Physical adsorption at cryogenic temperature (cryoadsorption) is a reversible mechanism that can reduce the pressure of conventional compressed gas storage systems. Metal–organic framework (MOF) materials are remarkable candidates due to the combination of high specific surface area and density which, in some cases, provide a high volumetric storage capacity. However, such extensive use of MOFs for this application requires the selection of affordable structures, easy to produce and made from feasible metallic and organic components. Herein, we introduce a MOF database detailing the crystallographic and porous properties of 3600 existing MOFs made from industrially relevant metals and their organic composition. The comparison of the available minimum costs of linkers allowed the creation of a database to select affordable structures with high potential for volumetric hydrogen storage by cryoadsorption, considering their composition based on individual or mixed building blocks. A user inter� face, available online, facilitates the selection of MOFs based on the properties or names of structures and linkers.
KW - MOF´s
PY - 2023
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-583619
DO - https://doi.org/10.1039/d3ma00315a
VL - 4
IS - 18
SP - 4226
EP - 4237
PB - Royal Society of Chemistry (RSC)
AN - OPUS4-58361
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Scheurrell, Kerstin
A1 - B. Martins, Inês C.
A1 - Murray, Claire
A1 - Emmerling, Franziska
T1 - Exploring the role of solvent polarity in mechanochemical Knoevenagel condensation: in situ investigation and isolation of reaction intermediates
N2 - Mechanochemistry has proven to be a highly effective method for the synthesis of organic compounds. We studied the kinetics of the catalyst-free Knoevenagel reaction between 4-nitrobenzaldehyde and malononitrile, activated and driven by ball milling. The reaction was investigated in the absence of solvents (neat grinding) and in the presence of solvents with different polarities (liquid-assisted grinding). The reaction was monitored using time-resolved in situ Raman spectroscopy and powder X-ray diffraction (PXRD). Our results indicate a direct relationship between solvent polarity and reaction kinetics, with higher solvent polarity leading to faster product (2-(4-nitrobenzylidone)malononitrile) formation. For the first time, we were able to isolate and determine the structure of an intermediate 2-(hydroxy(4-nitrophenyl)methyl)malononitrile based on PXRD data.
KW - Physical and Theoretical Chemistry
KW - General Physics and Astronomy
PY - 2023
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-588071
DO - https://doi.org/10.1039/D3CP02883F
SN - 1463-9076
VL - 25
IS - 35
SP - 23637
EP - 23644
PB - Royal Society of Chemistry (RSC)
AN - OPUS4-58807
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Peters, Stefan
A1 - Kunkel, Benny
A1 - Cakir, Cafer Tufan
A1 - Kabelitz, Anke
A1 - Witte, Steffen
A1 - Bernstein, Thomas
A1 - Bartling, Stephan
A1 - Radtke, Martin
A1 - Emmerling, Franziska
A1 - Abdel-Mageed, Ali Mohamed
A1 - Wohlrab, Sebastian
A1 - de Oliveira Guilherme Buzanich, Ana
T1 - Time-, space- and energy-resolved in situ characterization of catalysts by X-ray absorption spectroscopy
N2 - A novel setup for dispersive X-ray absorption spectroscopy (XAS) with simultaneous resolution of space, time and energy for in situ characterization of solid materials is demonstrated.
KW - Dispersive XAS
KW - Catalysis
KW - In situ
KW - Structure analysis
PY - 2023
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-584924
DO - https://doi.org/10.1039/d3cc03277a
SN - 1359-7345
SP - 1
EP - 4
PB - Royal Society of Chemistry (RSC)
AN - OPUS4-58492
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Wiesner, Yosri
A1 - Bednarz, Marius
A1 - Braun, Ulrike
A1 - Bannick, Claus Gerhard
A1 - Ricking, Mathias
A1 - Altmann, Korinna
T1 - A promising approach to monitor microplastic masses in composts
N2 - Inputs of plastic impurities into the environment via the application of fertilizers are regulated in Germany and the EU by means of ordinances. Robust and fast analytical methods are the basis of legal regulations. Currently, only macro- and large microplastic contents (>1 mm) are measured. Microplastics (1–1,000 µm), are not yet monitored. Thermal analytical methods are suitable for this purpose, which can determine the mass content and can also be operated fully automatically in routine mode. Thermal extraction desorption-gas chromatography/mass spectrometry (TED-GC/MS) allows the identification of polymers and the determination of mass contents in solid samples from natural environments. In accordance with the German or European Commission (EC) Fertiliser Ordinance, composting plants should be monitored for microplastic particles with this method in the future. In this context a compost plant was sampled. At the end of the rotting process, the compost was sieved and separated in a coarse (>1 mm) and a fine fraction (<1 mm). The fine fraction was processed using density separation comparing NaCl and NaI as possible salt alternative and screened for microplastic masses by TED-GC/MS with additional validation and quality assurance experiments. With TED-GC/MS total microplastics mass contents of 1.1–3.0 μg/mg in finished compost could be detected with polyethylene mainly. What differs much to the total mass of plastics in the coarse fraction with up to 60 μg/mg, which were visually searched, identified via ATR-FTIR and gravimetrically weighted.
KW - Microplastics
KW - TED-GC/MS
KW - Compost
KW - Monitoring
KW - Soil
PY - 2023
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-586688
DO - https://doi.org/10.3389/fenvc.2023.1281558
SN - 2673-4486
VL - 4
SP - 1
EP - 12
PB - Frontiers Media
CY - Lausanne
AN - OPUS4-58668
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Heinekamp, Christian
A1 - Kneiske, Sönke
A1 - de Oliveira Guilherme Buzanich, Ana
A1 - Ahrens, Mike
A1 - Braun, Thomas
A1 - Emmerling, Franziska
T1 - A fluorolytic sol-gel route to access an amorphous Zr fluoride catalyst: A useful tool for C-F bond activation
N2 - A route to a ZrF4 catalyst active in room temperature Friedel–Crafts and dehydrofluorination reactions was developed via a fluorolytic sol–gel route, which was followed by a postfluorination step using a stream of CHClF2. The behaviour of different Zr(IV) precursors in a sol–gel reaction with anhydrous isopropanol/HF solution was investigated. The subsequent post-fluorination step was optimised in its temperature ramp and confirmed the necessity of a fluorination of the generated xerogels to obtain catalytic activity. The process is discussed in the context of the analysis of the materials using Brunauer–Emmett–Teller analysis (BET), powder X-ray diffraction (XRD), infrared spectroscopy (IR), thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The local structure of the amorphous catalyst was elucidated by extended X-ray absorption fine structure spectroscopy (EXAFS).
KW - Catalysis
KW - Heterogeneous catalysis
KW - C-F bond activation
KW - Postfluorination
PY - 2024
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-593433
DO - https://doi.org/10.1039/D3CY01439H
SN - 2044-4761
SP - 1
EP - 8
PB - Royal Society of Chemistry (RSC)
AN - OPUS4-59343
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Paul, Martin
A1 - Tscheuschner, Georg
A1 - Herrmann, Stefan
A1 - Weller, Michael G.
T1 - Fast Detection of 2,4,6-Trinitrotoluene (TNT) at ppt Level by a Laser-Induced Immunofluorometric Biosensor
N2 - The illegal use of explosives by terrorists and other criminals is an increasing issue in public spaces, such as airports, railway stations, highways, sports venues, theaters, and other large buildings. Security in these environments can be achieved by different means, including the installation of scanners and other analytical devices to detect ultra-small traces of explosives in a very short time-frame to be able to take action as early as possible to prevent the detonation of such devices. Unfortunately, an ideal explosive detection system still does not exist, which means that a compromise is needed in practice. Most detection devices lack the extreme analytical sensitivity, which is nevertheless necessary due to the low vapor pressure of nearly all explosives. In addition, the rate of false positives needs to be virtually zero, which is also very difficult to achieve. Here we present an immunosensor system based on kinetic competition, which is known to be very fast and may even overcome affinity limitation, which impairs the performance of many traditional competitive assays. This immunosensor consists of a monolithic glass column with a vast excess of immobilized hapten, which traps the fluorescently labeled antibody as long as no explosive is present. In the case of the explosive 2,4,6-trinitrotoluene (TNT), some binding sites of the antibody will be blocked, which leads to an immediate breakthrough of the labeled protein, detectable by highly sensitive laser-induced fluorescence with the help of a Peltier-cooled complementary metal-oxide-semiconductor (CMOS) camera. Liquid handling is performed with high-precision syringe pumps and chip-based mixing-devices and flow-cells. The system achieved limits of detection of 1 pM (1 ppt) of the fluorescent label and around 100 pM (20 ppt) of TNT. The total assay time is less than 8 min. A cross-reactivity test with 5000 pM solutions showed no signal by pentaerythritol tetranitrate (PETN), 1,3,5-trinitroperhydro-1,3,5-triazine (RDX), and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX). This immunosensor belongs to the most sensitive and fastest detectors for TNT with no significant cross-reactivity by non-related compounds. The consumption of the labeled antibody is surprisingly low: 1 mg of the reagent would be sufficient for more than one year of continuous biosensor operation.
KW - Airport
KW - Aviation
KW - Bombs
KW - Terrorism
KW - Biosensing
KW - Continuous Sensor
KW - High-Speed
KW - Ultrasensitive
PY - 2020
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-511245
DO - https://doi.org/10.3390/bios10080089
VL - 10
IS - 8
SP - 89
PB - MDPI
CY - Basel
AN - OPUS4-51124
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Costa, Elena
A1 - Climent Terol, Estela
A1 - Gawlitza, Kornelia
A1 - Wan, Wei
A1 - Weller, Michael G.
A1 - Rurack, Knut
T1 - Optimization of analytical assay performance of antibody-gated indicator-releasing mesoporous silica particles
N2 - Antibody-gated indicator delivery (gAID) systems based on mesoporous silica nano- and microparticle scaffolds are a promising class of materials for the sensitive chemical detection of small-molecule analytes in simple test formats such as lateral flow assays (LFAs) or microfluidic chips. Their architecture is reminiscent of drug delivery systems, only that reporter molecules instead of drugs are stored in the voids of a porous host particle. In addition, the pores are closed with macromolecular “caps” through a tailored “gatekeeping” recognition chemistry so that the caps are opened when an analyte has reacted with a “gatekeeper”. The subsequent uncapping leads to a release of a large number of indicator molecules, endowing the system with signal amplification features. Particular benefits of such systems are their modularity and adaptability. With the example of the immunochemical detection of type-I pyrethroids by fluorescent dye-releasing gAID systems, the influence of several tuning modes on the optimisation of such hybrid sensory materials is introduced here. In particular, different mesoporous silica supports (from nano- and microparticles to platelets and short fibres), different functionalisation routes and different loading sequences were assessed. The materials’ performances were evaluated by studying their temporal response behaviour and detection sensitivity, including the tightness of pore closure (through the amount of blank release in the absence of analyte) and the release kinetics. Our results indicate that the better the paratope-accommodating Fab region of the antibody “cap” fits into the host material's pore opening, the better the closing/opening mechanism can be controlled. Because such materials are well-suited for LFAs, performance assessment included a test-strip format besides conventional assays in suspension. In combination with dyes as indicators and smartphones for read-out, simple analytical tests for use by untrained personnel directly at a point-of-need such as an aeroplane cabin can be devised, allowing for sensitivities down to the μg kg−1 range in <5 min with case-required selectivities.
KW - Antibody-gated indicator delivery
KW - Lateral flow assay
KW - SBA-15
KW - SBA-16
KW - Type-I pyrethroids
KW - Phenothrin
KW - Permethrin
KW - Etofenprox
KW - Amplification
KW - Biosensors
KW - Immunoassays
KW - Mesoporous particles
KW - Optical detection
PY - 2020
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-517053
DO - https://doi.org/10.1039/d0tb00371a
VL - 8
IS - 22
SP - 4950
EP - 4961
PB - Royal Society of Chemistry
AN - OPUS4-51705
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Tscheuschner, Georg
A1 - Schwaar, Timm
A1 - Weller, Michael G.
T1 - Fast Confirmation of Antibody Identity by MALDI-TOF MS Fingerprints
N2 - Thousands of antibodies for diagnostic and other analytical purposes are on the market. However, it is often difficult to identify duplicates, reagent changes, and to assign the correct original publications to an antibody. This slows down scientific progress and might even be a cause of irreproducible research and a waste of resources. Recently, activities were started to suggest the sole use of recombinant antibodies in combination with the open communication of their sequence. In this case, such uncertainties should be eliminated. Unfortunately, this approach seems to be rather a long-term vision since the development and manufacturing of recombinant antibodies remain quite expensive in the foreseeable future. Nearly all commercial antibody suppliers also may be reluctant to publish the sequence of their antibodies, since they fear counterfeiting. De novo sequencing of antibodies is also not feasible today for a reagent user without access to the hybridoma clone. Nevertheless, it seems to be crucial for any scientist to have the opportunity to identify an antibody undoubtedly to guarantee the traceability of any research activity using antibodies from a third party as a tool. For this purpose, we developed a method for the identification of antibodies based on a MALDI-TOF MS fingerprint. To circumvent lengthy denaturation, reduction, alkylation, and enzymatic digestion steps, the fragmentation was performed with a simple formic acid hydrolysis step. Eighty-nine unknown monoclonal antibodies were used for this study to examine the feasibility of this approach. Although the molecular assignment of peaks was rarely possible, antibodies could be easily recognized in a blinded test, simply from their mass-spectral fingerprint. A general protocol is given, which could be used without any optimization to generate fingerprints for a database. We want to propose that, in most scientific projects relying critically on antibody reagents, such a fingerprint should be established to prove and document the identity of the used antibodies, as well as to assign a specific reagent to a datasheet of a commercial supplier, public database record, or antibody ID.
KW - Reproducibility
KW - Quality Control
KW - Traceability
KW - Diagnostics
KW - Hybridoma
KW - Monoclonal Antibody
KW - Recombinant Antibody
PY - 2020
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-506611
DO - https://doi.org/10.3390/antib9020008
SN - 2073-4468
VL - 9
IS - 2
SP - 1
EP - 17
PB - MDPI
CY - Basel
AN - OPUS4-50661
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Ziegler, K.
A1 - Kunert, A. T.
A1 - Reinmuth-Selzle, K.
A1 - Leifke, A. L.
A1 - Widera, D.
A1 - Weller, Michael G.
A1 - Schuppan, D.
A1 - Fröhlich-Nowoisky, J.
A1 - Lucas, K.
A1 - Pöschl, U.
T1 - Chemical modification of pro-inflammatory proteins by peroxynitrite increases activation of TLR4 and NF-κB: Implications for the health effects of air pollution and oxidative stress
N2 - Environmental pollutants like fine particulate matter can cause adverse health effects through oxidative stress and inflammation. Reactive oxygen and nitrogen species (ROS/RNS) such as peroxynitrite can chemically modify proteins, but the effects of such modifications on the immune system and human health are not well understood. In the course of inflammatory processes, the Toll-like receptor 4 (TLR4) can sense damage-associated molecular patterns (DAMPs). Here, we investigate how the TLR4 response and pro-inflammatory potential of the proteinous DAMPs α-Synuclein (α-Syn), heat shock protein 60 (HSP60), and high-mobility-group box 1 protein (HMGB1), which are relevant in neurodegenerative and cardiovascular diseases, changes upon chemical modification with peroxynitrite.
For the peroxynitrite-modified proteins, we found a strongly enhanced activation of TLR4 and the pro-inflammatory transcription factor NF-κB in stable reporter cell lines as well as increased mRNA expression and secretion of the pro-inflammatory cytokines TNF-α, IL-1β, and IL-8 in human monocytes (THP-1). This enhanced activation of innate immunity via TLR4 is mediated by covalent chemical modifications of the studied DAMPs.
Our results show that proteinous DAMPs modified by peroxynitrite more potently amplify inflammation via TLR4 activation than the native DAMPs, and provide first evidence that such modifications can directly enhance innate immune responses via a defined receptor. These findings suggest that environmental pollutants and related ROS/RNS may play a role in promoting acute and chronic inflammatory disorders by structurally modifying the body's own DAMPs. This may have important consequences for chronic neurodegenerative, cardiovascular or gastrointestinal diseases that are prevalent in modern societies, and calls for action, to improve air quality and climate in the Anthropocene.
KW - Protein nitration
KW - Protein oligomerization
KW - Damage-associated molecular patterns (DAMPs)
KW - Pattern recognition receptor
KW - Anthropocene
KW - Environmental pollutants
PY - 2020
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-517128
DO - https://doi.org/10.1016/j.redox.2020.101581
VL - 37
SP - 101581
PB - Elsevier B.V.
AN - OPUS4-51712
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Brangsch, J.
A1 - Reimann, C.
A1 - Kaufmann, Jan Ole
A1 - Adams, L. C.
A1 - Onthank, D.
A1 - Thöne-Reineke, C.
A1 - Robinson, S.
A1 - Ponader, Marco
A1 - Weller, Michael G.
A1 - Buchholz, R.
A1 - Karst, U.
A1 - Botnar, R.
A1 - Hamm, B.
A1 - Makowski, M. R.
T1 - Molecular MR-Imaging for Noninvasive Quantification of the Anti-Inflammatory Effect of Targeting Interleukin-1β in a Mouse Model of Aortic Aneurysm
N2 - Background:
Molecular-MRI is a promising imaging modality for the assessment of abdominal aortic aneurysms (AAAs). Interleukin-1β (IL-1β) represents a new therapeutic tool for AAA-treatment, since pro-inflammatory cytokines are key-mediators of inflammation. This study investigates the potential of molecular-MRI to evaluate therapeutic effects of an anti-IL-1β-therapy on AAA-formation in a mouse-model.
Methods:
Osmotic-minipumps were implanted in apolipoprotein-deficient-mice (N = 27). One group (Ang-II+01BSUR group, n = 9) was infused with angiotensin-II (Ang-II) for 4 weeks and received an anti-murine IL-1β-antibody (01BSUR) 3 times. One group (Ang-II-group, n = 9) was infused with Ang-II for 4 weeks but received no treatment. Control-group (n = 9) was infused with saline and received no treatment. MR-imaging was performed using an elastin-specific gadolinium-based-probe (0.2 mmol/kg).
Results:
Mice of the Ang-II+01BSUR-group showed a lower aortic-diameter compared to mice of the Ang-II-group and control mice (p < 0.05). Using the elastin-specific-probe, a significant decrease in elastin-destruction was observed in mice of the Ang-II+01BSUR-group. In vivo MR-measurements correlated well with histopathology (y = 0.34x-13.81, R2 = 0.84, p < 0.05), ICP-MS (y = 0.02x+2.39; R2 = 0.81, p < 0.05) and LA-ICP-MS. Immunofluorescence and western-blotting confirmed a reduced IL-1β-expression.
Conclusions:
Molecular-MRI enables the early visualization and quantification of the anti-inflammatory-effects of an IL-1β-inhibitor in a mouse-model of AAAs. Responders and non-responders could be identified early after the initiation of the therapy using molecular-MRI.
KW - Cardiovascular
KW - Molecular-MRI
KW - Magnetic resonance imaging
KW - Gadolinium-based contrast agent
KW - Elastin-specific contrast agent ESMA
KW - Gadovist
KW - Gadofosveset
KW - MR Angiography
KW - Inductively Coupled Mass Spectroscopy
KW - Element Specific Bioimaging Using Laser Ablation
KW - Visualization
PY - 2020
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-517150
DO - https://doi.org/10.1177/1536012120961875
N1 - Geburtsname von Ponader, Marco: Wilke, M. - Birth name of Ponader, Marco: Wilke, M.
VL - 19
SP - 61875
PB - SAGE
AN - OPUS4-51715
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -