TY - JOUR A1 - Liaskos, C. A1 - Rhoderick, G. A1 - Hodges, J. A1 - Possolo, A. A1 - Wilke, Olaf T1 - Pilot comparison CCQM-P177 - monoterpenes in nitrogen at 2.5 nmol/mol - final report N2 - Growing awareness of the impact of monoterpenes on climate, atmospheric chemistry, and indoor air quality has necessitated the development of measurement standards to globally monitor and control their emissions. For National Metrology Institutes to develop such standards, it is essential that they demonstrate measurement equivalence for assigned values at the highest levels of accuracy. This report describes the results of a pilot comparison for 4 key monoterpene species: α-pinene, 3-carene, R-limonene and 1,8-cineole, at a nominal amount-of-substance fraction of 2.5 nmol mol-1. The objective of this comparison is to evaluate participant capabilities to measure trace-level monoterpenes using their own calibration techniques. KW - Pilot comparison KW - CCQM KW - Monoterpene KW - Accuracy PY - 2020 DO - https://doi.org/10.1088/0026-1394/57/1A/08018 SN - 0026-1394 SN - 1681-7575 VL - 57 IS - 1A SP - 08018-1 EP - 08018-21 PB - IOP Science AN - OPUS4-51111 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Hildebrandt, L. A1 - von der Au, Marcus A1 - Zimmermann, T. A1 - Reese, A. A1 - Ludwig, J. A1 - Pröfrock, D. T1 - A metrologically traceable protocol for the quantification of trace metals in different types of microplastic N2 - The presence of microplastic (MP) particles in aquatic environments raised concern About possible enrichment of organic and inorganic pollutants due to their specific surface and chemical properties. In particular the role of metals within this context is still poorly understood. Therefore, the aim of this work was to develop a fully validated acid digestion protocol for metal analysis in different polymers, which is a prerequisite to study such interactions. The proposed digestion protocol was validated using six different certified reference materials in the microplastic size range consisting of polyethylene, polypropylene, acrylonitrile butadiene styrene and polyvinyl chloride. As ICP-MS/MS enabled time-efficient, sensitive and robust analysis of 56 metals in one measurement, the method was suitable to provide mass fractions for a multitude of other elements beside the certified ones (As, Cd, Cr, Hg, Pb, Sb, Sn and Zn). Three different microwaves, different acid mixtures as well as different temperatures in combination with different hold times were tested for optimization purposes. With the exception of Cr in acrylonitrile butadiene styrene, recovery rates obtained using the optimized protocol for all six certified reference materials fell within a range from 95.9% ± 2.7% to 112% ± 7%. Subsequent optimization further enhanced both precision and recoveries ranging from 103% ± 5% to 107 ± 4% (U; k = 2 (n = 3)) for all certified metals (incl. Cr) in acrylonitrile butadiene styrene. The results clearly show the analytical challenges that come along with metal analysis in chemically resistant plastics. Addressing specific analysis Tools for different sorption scenarios and processes as well as the underlying kinetics was beyond this study’s scope. However, the future application of the two recommended thoroughly validated total acid digestion protocols as a first step in the direction of harmonization of metal analysis in/on MP will enhance the significance and comparability of the generated data. It will contribute to a better understanding of the role of MP as vector for trace metals in the environment. KW - Microplatic KW - Digestion KW - Analytical Chemistry PY - 2020 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-510727 DO - https://doi.org/10.1371/journal.pone.0236120 VL - 15 IS - 7 SP - e0236120 AN - OPUS4-51072 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 - Steglich, P. A1 - Bondarenko, S. A1 - Mai, C. A1 - Paul, Martin A1 - Weller, Michael G. A1 - Mai, A. T1 - CMOS-Compatible Silicon Photonic Sensor for Refractive Index Sensing Using Local Back-Side Release N2 - Silicon photonic sensors are promising candidates for lab-on-a-chip solutions with versatile applications and scalable production prospects using complementary metal-oxide semiconductor (CMOS) fabrication methods. However, the widespread use has been hindered because the sensing area adjoins optical and electrical components making packaging and sensor handling challenging. In this work, a local back-side release of the photonic sensor is employed, enabling a separation of the sensing area from the rest of the chip. This approach allows preserving the compatibility of photonic integrated circuits in the front-end of line and metal interconnects in the back-end of line. The sensor is based on a micro-ring resonator and is fabricated on wafer-level using a CMOS technology. We revealed a ring resonator sensitivity for homogeneous sensing of 106 nm/RIU. KW - Photonic biosensor KW - Lab-on-a-chip KW - Ring resonator KW - Resonance wavelength shift KW - PIC technology KW - Back-side integration PY - 2020 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-517139 DO - https://doi.org/10.1109/LPT.2020.3019114 VL - 32 IS - 19 SP - 1241 EP - 1244 PB - IEEE AN - OPUS4-51713 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 - TY - JOUR A1 - Keller, S. A1 - Borde, T. A1 - Brangsch, J. A1 - Reimann, C. A1 - Kader, A. A1 - Schulze, D. A1 - Buchholz, R. A1 - Kaufmann, Jan Ole A1 - Karst, U. A1 - Schellenberger, E. A1 - Hamm, B. A1 - Makowski, M. R. T1 - Assessment of the hepatic tumor extracellular matrix using elastin‑specific molecular magnetic resonance imaging in an experimental rabbit cancer model N2 - To investigate the imaging performance of an elastin-specific molecular magnetic resonance imaging (MRI) probe with respect to the extracellular matrix (ECM) in an experimental hepatic cancer model. Twelve rabbits with hepatic VX2 tumors were examined using 3 T MRI 14, 21, and 28 days after tumor implantation for two subsequent days (gadobutrol, day 1; elastin-specific probe, day 2). The relative enhancement (RE) of segmented tumor regions (central and margin) and the peritumoral matrix was calculated using pre-contrast and delayed-phase T1w sequences. MRI measurements were correlated to histopathology and element-specific and spatially resolved mass spectrometry (MS). Mixed-model analysis was performed to assess the performance of the elastin-specific probe. In comparison to gadobutrol, the elastin probe showed significantly stronger RE, which was pronounced in the tumor margin (day 14–28: P ≤ 0.007). In addition, the elastin probe was superior in discriminating between tumor regions (χ2(4) = 65.87; P < 0.001). MRI-based measurements of the elastin probe significantly correlated with the ex vivo elastinstain (R = .84; P <0 .001) and absolute gadolinium concentrations (ICP-MS: R = .73, P <0 .01). LA-ICP-MS imaging confirmed the colocalization of the elastin-specific probe with elastic fibers. Elastin-specific molecular MRI is superior to non-specific gadolinium-based contrast agents in imaging the ECM of hepatic tumors and the peritumoral tissue. KW - Elastin-specific molecular agent KW - Extracellular matrix KW - Hepatocellular carcinoma KW - Inductively coupled plasma mass spectroscopy KW - Laser ablation-inductively coupled plasma-mass spectrometry KW - Magnetic resonance imaging KW - MR imaging KW - ESMA KW - Gadolinium PY - 2020 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-517360 DO - https://doi.org/10.1038/s41598-020-77624-8 VL - 10 IS - 1 SP - 20785 PB - Nature AN - OPUS4-51736 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 - Vogl, Jochen T1 - The triple-isotope calibration approach: a universal and standard-free calibration approach for obtaining absolute isotope ratios of multi-isotopic elements N2 - The theory of a new calibration approach for obtaining absolute isotope ratios of multi-isotopic elements without the use of any standard has been developed. The calibration approach basically uses the difference in the instrumental isotope fractionation of two different types of mass spectrometers, leading to two different fractionation lines in a three-isotope diagram. When measuring the same sample with both mass spectrometers, the different fractionation lines have one point in common: this is the ‘true’ logarithmized isotope ratio pair of the sample. Thus, the intersection of both fractionation lines provides us with the absolute isotope ratios of the sample. This theory has been tested in practice by measuring Cd and of Pb isotope ratios in the certified reference materials BAM-I012 and NIST SRM981 by thermal ionization mass spectrometry and by inductively coupled plasma mass spectrometry while varying the ionization conditions for both mass spectrometers. With this experiment, the theory could be verified, and absolute isotope ratios were obtained, which were metrologically compatible with the certified isotope ratios. The so-obtained absolute isotope ratios are biased by − 0.5% in average, which should be improved with further developments of the method. This calibration approach is universal, as it can be applied to all elements with three or more isotopes and it is not limited to the type of mass spectrometers applied; it can be applied as well to secondary ion mass spectrometry or others. Additionally, this approach provides information on the fractionation process itself via the triple-isotope fractionation exponent θ. KW - Triple isotope fractionation KW - Absolute isotope ratio KW - Mass spectrometry KW - Calibration KW - Uncertainty PY - 2020 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-516364 DO - https://doi.org/10.1007/s00216-020-03050-4 VL - 413 IS - 3 SP - 821 EP - 826 PB - Springer Verlag AN - OPUS4-51636 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Pramann, A. A1 - Vogl, Jochen A1 - Rienitz, O. T1 - The Uncertainty Paradox: Molar Mass of Enriched Versus Natural Silicon Used in the XRCD Method N2 - The X-ray crystal density method uses silicon spheres highly enriched in 28Si as a primary method for the dissemination of the SI base unit kilogram yielding smallest possible uncertainties associated with the mass m within a few parts in 10-8. This study compares different available and newly developed analytical methods and their results for the determination of the molar mass M of silicon highly enriched in 28Si (Me) and of silicon (Mx) with an almost natural isotopic distribution. While for Me relative uncertainties urel(Me) in the lower 10-9 range are obtained routinely, it was not possible to fall below a value of urel(Mx) < 4 x 10-6 in the case of natural silicon, which is approximately three orders of magnitude larger. The application of the state-of the-art isotope ratio mass spectrometry accompanied with sophisticated thoroughly investigated methods suggests an intrinsic cause for the large uncertainty associated with the molar mass of natural silicon compared to the enriched material. KW - silicon KW - Molar mass KW - Isotope ratios KW - SI KW - Kilogram KW - Mole KW - XRCD method PY - 2020 DO - https://doi.org/10.1007/s12647-020-00408-y VL - 35 SP - 499 EP - 510 PB - Springer Verlag AN - OPUS4-51637 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Goedecke, Caroline A1 - Dittmann, Daniel A1 - Eisentraut, Paul A1 - Wiesner, Yosri A1 - Schartel, Bernhard A1 - Klack, Patrick A1 - Braun, Ulrike T1 - Evaluation of thermoanalytical methods equipped with evolved gas analysis for the detection of microplastic in environmental samples N2 - Microplastic particles are currently detected in almost all environmental compartments. The results of detection vary widely, as a multitude of very different methods are used with very different requirements for analytical validity. In this work four thermoanalytical methods are compared and their advantages and limitations are discussed. One of them is thermal extraction-desorption gas chromatography mass spectrometry (TED-GC/MS), an analysis method for microplastic detection that has become established in recent years. In addition, thermogravimetric analysis coupled with Fourier-transform infrared spectroscopy (TGA-FTIR) and mass spectrometry (TGA-MS) were applied, two methods that are less common in this field but are still used in other research areas. Finally, microscale combustion calorimeter (MCC) was applied, a method not yet used for microplastic detection. The presented results are taken from a recently published interlaboratory comparison test by Becker et al. (2020). Here a reference material consisting of suspended matter and specified added polymer masses was examined, and only the results of the recoveries were presented. In the present paper, however, the results for the individual polymers are discussed in detail and individual perspectives for all instruments are shown. It was found that TED-GC/MS is the most suitable method for samples with unknown matrix and unknown, variable kinds and contents of microplastic. TGA-FTIR is a robust method for samples with known matrix and with defined kinds of microplastic. TGA-MS may offer a solution for the detection of PVC particles in the future. MCC can be used as a very fast and simple screening method for the identification of a potential microplastic load of standard polymers in unknown samples. KW - Microplastic KW - TED-GC/MS KW - TGA-MS KW - TGA-FTIR KW - MCC KW - Thermal analysis PY - 2020 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-516687 DO - https://doi.org/10.1016/j.jaap.2020.104961 VL - 152 SP - 104961 PB - Elsevier B.V. AN - OPUS4-51668 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - von der Au, Marcus A1 - Karbach, H. A1 - Bell, A. M. A1 - Bauer, O. B. A1 - Karst, U. A1 - Meermann, Björn T1 - Determination of metal uptake in single organisms, Corophiumvolutator, via complementary electrothermal vaporization/inductively coupled plasma mass spectrometry and laserablation/inductively coupled plasma mass spectrometry N2 - Rationale: (Eco-)toxicological effects are mostly derived empirically and are notcorrelated with metal uptake. Furthermore, if the metal content is determined,mostly bulk analysis of the whole organism population is conducted; thus, biologicalvariability is completely disregarded, and this may lead to misleading results. Toovercome this issue, we compared two different solid sampling techniques for theanalysis of single organisms.Methods: In this study, complementary electrothermal vaporization/inductivelycoupled plasma mass spectrometry (ETV/ICP-MS) , laser ablation/inductivelycoupled plasma mass spectrometry (LA/ICP-MS)-based methods for the analysisof individual organisms were developed and the results obtained were comparedwith the concentrations obtained after digestion and measured using ICP-MS.For this purpose, a common (eco-)toxicological test organism, the mud shrimpCorophium volutator, was selected. As proof-of-concept application, these organismswere incubated with environmentally relevant metals from galvanic anodes, whichare often used for protection against metal corrosion in, for example, offshorewind farms.Results: The bulk analysis revealed that large quantities of the incubated elementswere detectable. Using the ETV/ICP-MS method, we could identify a highbiovariability within the population of organisms tested. Using the LA/ICP-MSmethod, it could be determined that the large quantities of the elements detectedwere due to adsorption of the metals and not due to uptake, which correlates wellwith the absence of (eco-)toxicological effects.Conclusions: The results obtained imply the efficiency of complementary methods toexplain the absence or presence of (eco-)toxicological effects. In particular, methodsthat allow for single-organism analysis or provide even a spatial resolution supportthe interpretation of ecotoxicological findings. KW - ICP-MS KW - Metal toxicity KW - Metal uptake KW - Corophium volutator KW - Seawater PY - 2021 DO - https://doi.org/10.1002/rcm.8953 VL - 35 IS - 2 SP - e8953 AN - OPUS4-52077 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Gornushkin, Igor B. A1 - Pignatelli, Giuseppe A1 - Straße, Anne T1 - Optical detection of defects during laser metal deposition: Simulations and experiment N2 - Laser metal deposition is a rapidly evolving method for additive manufacturing that combines high performance and simplified production routine. Quality of production depends on instrumental design and operational parameters that require constant control during the process. In this work, feasibility of using optical spectroscopy as a control method is studied via modeling and experimentally. A simplified thermal model is developed based on the time-dependent diffusion-conduction heat equation and geometrical light collection into detection optics. Intense light emitted by a laser-heated spot moving across a sample surface is collected and processed to yield the temperature and other temperature-related parameters. In a presence of surface defects the temperature field is distorted in a specific manner that depends on a shape and size of the defect. Optical signals produced by such the distorted temperature fields are simulated and verified experimentally using a 3D metal printer and a sample with artificially carved defects. Three quantities are tested as possible metrics for process monitoring: temperature, integral intensity, and correlation coefficient. The shapes of the simulated signals qualitatively agree with the experimental signals; this allows a cautious inference that optical spectroscopy is capable of detecting a defect and, possibly, predicting its character, e.g. inner or protruding. KW - Additive manufacturing KW - Laser metal deposition (LMD) KW - Thermal model KW - Optical sensor KW - Process control PY - 2021 DO - https://doi.org/10.1016/j.apsusc.2021.151214 SN - 0169-4332 VL - 570 SP - 1 EP - 13 PB - Elsevier CY - Amsterdam AN - OPUS4-53292 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Solovyev, N. A1 - El-Khatib, Ahmed A1 - Costas-Rodrigues, M. A1 - Schwab, K. A1 - Griffin, E. A1 - Raab, A. A1 - Platt, B. A1 - Theuring, F. A1 - Vogl, Jochen A1 - Vanhaecke, F. T1 - Cu, Fe and Zn isotope ratios in murine Alzheimer's disease models suggest specific signatures of amyloidogenesis and tauopathy N2 - Alzheimer’s disease (AD) is characterized by accumulation of tau and amyloid-beta in the brain, and recent evidence suggests a correlation between associated protein aggregates and trace elements, such as copper, iron and zinc. In AD, distorted brain redox homeostasis and complexation by amyloid-beta and hyperphosphorylated tau May alter the isotopic composition of essential mineral elements. Therefore, high-precision isotopic analysis may reveal changes in the homeostasis of these elements. We used inductively coupled plasma-mass spectrometry (ICP-MS)-based techniques to determine the total Cu, Fe and Zn contents in the brain, as well as their isotopic compositions in both mouse brain and serum. Results for male transgenic tau (Line 66, L66) and amyloid/presenilin (5xFAD) mice were compared to those for the corresponding age- and gendermatched wild-type control mice (WT). Our data show that L66 brains showed significantly higher Fe levels than the corresponding WT. Significantly less Cu, but more Zn was found in 5xFAD brains. We observed significantly lighter isotopic compositions of Fe (enrichment in the lighter isotopes) in the brain, and in serum of L66 mice compared to WT. For 5xFAD mice, Zn exhibited a trend towards a lighter isotopic composition in brain and a heavier isotopic composition in serum compared to WT. Neither mouse model yielded differences in the isotopic composition of Cu. Our findings indicate significant pathology-specific alterations of Fe and Zn brain homeostasis in mouse models of AD. The associated changes in isotopic composition May serve as a marker for proteinopathies Underlying AD and other types of dementia. KW - Alzheimer’s disease KW - Tau KW - Amyloid-beta KW - Copper KW - Iron KW - Zinc KW - Multi-collector inductively coupled plasma-mass spectrometry (ICP-MS) KW - Brain KW - Serum KW - Isotopic analysis KW - Total element determination PY - 2021 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-520214 DO - https://doi.org/10.1016/j.jbc.2021.100292 VL - 296 SP - 100292 PB - Elsevier Inc. CY - Amsterdam AN - OPUS4-52021 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kader, A. A1 - Brangsch, J. A1 - Kaufmann, Jan Ole A1 - Zhao, J. A1 - Mangarova, D. B. A1 - Moeckel, J. A1 - Adams, L. C. A1 - Sack, I. A1 - Taupitz, M. A1 - Hamm, B. A1 - Makowski, M. R. T1 - Molecular MR Imaging of Prostate Cancer N2 - This review summarizes recent developments regarding molecular imaging markers for magnetic resonance imaging (MRI) of prostate cancer (PCa). Currently, the clinical standard includes MR imaging using unspecific gadolinium-based contrast agents. Specific molecular probes for the diagnosis of PCa could improve the molecular characterization of the tumor in a non-invasive examination. Furthermore, molecular probes could enable targeted therapies to suppress tumor growth or reduce the tumor size. KW - Prostate cancer KW - Magnetic resonance imaging KW - Molecular imaging KW - Imaging KW - Molecular marker KW - Screening KW - MRI KW - Diagnosis PY - 2021 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-519503 DO - https://doi.org/10.3390/biomedicines9010001 VL - 9 IS - 1 SP - 1 EP - 17 PB - MDPI CY - Basel AN - OPUS4-51950 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Albarrán Martínez, M. J. A1 - Ghigo, Tea T1 - The practice of writing inside an Egyptian monastic settlement N2 - Over the last few years, the Federal Institute for material research (BAM, Berlin) together with the Centre for the Study of Manuscript Cultures (CSMC, University of Hamburg) have initiated a systematic material investigation of black inks produced from Late Antiquity to the Middle Ages (ca. fourth century CE–fourteenth/fifteenth centuries CE), aimed primarily at extending and complementing findings from previous sporadic studies. Part of this systematic investigation has focused on Egyptian Coptic manuscripts, and the present preliminary study is one of its outputs. It centres on a corpus of 45 Coptic manuscripts—43 papyri and 2 ostraca—preserved at the Palau-Ribes and Roca-Puig collections in Barcelona. The manuscripts come from the Monastery of Apa Apollo at Bawit, one of the largest monastic settlements in Egypt between the Late Antiquity and the Early Islamic Period (sixth–eighth centuries CE). The composition of their black inks was investigated in situ using near-infrared reflectography (NIRR) and X-ray fluorescence (XRF). The analyses determined that the manuscripts were written using different types of ink: pure carbon ink; carbon ink containing iron; mixed inks containing carbon, polyphenols and metallic elements; and iron-gall ink. The variety of inks used for the documentary texts seems to reflect the articulate administrative system of the monastery of Bawit. This study reveals that, in contrast to the documents, written mostly with carbon-based inks, literary biblical texts were written with iron-gall ink. The frequent reuse of papyrus paper for certain categories of documents may suggest that carbon-based inks were used for ephemeral manuscripts, since they were easy to erase by abrasion. KW - Papyrus KW - Ink analysis KW - Coptic manuscripts KW - Bawit KW - Mixed ink KW - Near-infrared refectography KW - X-ray fuorescence PY - 2021 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-528833 DO - https://doi.org/10.1186/s40494-021-00541-0 SN - 2050-7445 VL - 9 IS - 1 SP - 1 EP - 15 PB - Springer Open CY - Rome, Italy AN - OPUS4-52883 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Thinnes, A. A1 - Westenberger, M. A1 - Piechotta, Christian A1 - Letho, L. A1 - Wirth, F. A1 - Lau, H. A1 - Klein, J. T1 - Cholinergic and metabolic effects of metformin in mouse brain N2 - Metformin is widely used as a first-line treatment for type 2 diabetes, but central effects of metformin have received little attention. When metformin (200 mg/kg i.p.) was administered to C57Bl6 mice, metformin concentration in cerebrospinal fluid peaked at 29 μM after 30 min but dropped quickly and was low at 90 min. In mouse hypothalamus sampled by microdialysis, systemically administered metformin caused minor and transient increases of acetylcholine, glucose and lactate while choline levels decreased. When metformin (0.2−10 mM) was locally infused via retrodialysis, there was a short-lasting increase of acetylcholine in the hypothalamus. Extracellular lactate levels in hypothalamus showed a massive increase upon metformin infusion while glucose levels decreased. In isolated mitochondria of mouse brain, metformin inhibited oxygen consumption and the activity of complex I. Inhibition of mitochondrial respiration likely explains lactate formation in the brain during metformin infusion which may cause lactic acidosis during metformin intoxication. The changes of cholinergic activity in the hypothalamus may be associated with appetite suppression observed during metformin treatment. KW - Metformin KW - Blood-brain barrier KW - Lactate KW - Glucose KW - Microdialysis KW - Hypothalamus PY - 2021 DO - https://doi.org/10.1016/j.brainresbull.2021.02.018 SN - 0361-9230 VL - 170 SP - 211 EP - 217 PB - Elsevier CY - Amsterdam, Niederlande AN - OPUS4-52189 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Ponader, Marco A1 - Röder, Bettina A1 - Paul, Martin A1 - Weller, Michael G. T1 - Sintered glass monoliths as supports for affinity columns N2 - A novel stationary phase for affinity separations is presented. This material is based on sintered borosilicate glass readily available as semi-finished filter plates with defined porosity and surface area. The material shows fast binding kinetics and excellent long-term stability under real application conditions due to lacking macropores and high mechanical rigidity. The glass surface can be easily modified with standard organosilane chemistry to immobilize selective binders or other molecules used for biointeraction. In this paper, the manufacturing of the columns and their respective column holders by 3D printing is shown in detail. The model system protein A/IgG was chosen as an example to examine the properties of such monolithic columns under realistic application conditions. Several specifications, such as (dynamic) IgG capacity, pressure stability, long-term performance, productivity, non-specific binding, and peak shape, are presented. It could be shown that due to the very high separation speed, 250 mg antibody per hour and column can be collected, which surpasses the productivity of most standard columns of the same size. The total IgG capacity of the shown columns is around 4 mg (5.5 mg/mL), which is sufficient for most tasks in research laboratories. The cycle time of an IgG separation can be less than 1 min. Due to the glass material’s excellent pressure resistance, these columns are compatible with standard HPLC systems. This is usually not the case with standard affinity columns, limited to manual use or application in low-pressure systems. The use of a standard HPLC system also improves the ability for automation, which enables the purification of hundreds of cell supernatants in one day. The sharp peak shape of the elution leads to an enrichment effect, which might increase the concentration of IgG by a factor of 3. The final concentration of IgG can be around 7.5 mg/mL without the need for an additional nano-filtration step. The purity of the IgG was > 95% in one step and nearly 99% with a second polishing run. KW - Affinity Chromatography KW - Affinity Extraction KW - Affinity Separation KW - Protein Purification KW - Down Stream Processing KW - Antibody Purification KW - Diagnostic Antibodies KW - Therapeutic Antibodies KW - Automated Purification KW - HPLC KW - FPLC KW - IgG determination KW - Concentration step KW - Monoclonal Antibodies KW - Polyclonal Antibodies KW - Human Plasma KW - Glass Support KW - Borosilicate Glass KW - Monolith KW - Sintered Material KW - Additive Manufacturing KW - Column holder KW - Construction KW - Open Science KW - Citizen Science KW - Protein A KW - Regeneration KW - High-Speed Separations KW - Robustness PY - 2021 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-527581 DO - https://doi.org/10.3390/separations8050056 SN - 2297-8739 N1 - Geburtsname von Ponader, Marco: Wilke, M. - Birth name of Ponader, Marco: Wilke, M. VL - 8 IS - 5 SP - 1 EP - 16 PB - MDPI CY - Basel AN - OPUS4-52758 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Even, Morgane A1 - Juritsch, Elevtheria A1 - Richter, Matthias T1 - Measurement of very volatile organic compounds (VVOCs) in indoor air by sorbent-based active sampling: Identifying the gaps towards standardisation N2 - The ISO 16000-6 standard describes a method for the determination of volatile organic compounds (VOCs) in indoor and test chamber air by sorbent-based active sampling, thermal desorption and gas chromatography coupled with mass spectrometry (GC/MS). It also gives directions to adapt this methodology to very volatile organic compounds (VVOCs). Indeed, toxicologically based guideline values are being implemented for these compounds and it becomes necessary to measure them. But a comprehensive and robust measurement method is lacking. This work highlights the points that still need to be explored towards the standardisation of a suitable procedure: investigations on sorbent combinations, the suitability of chromatography columns and the use of gaseous standards are required. The biggest challenge remains in the fact that strong sorbents adsorb water together with VVOCs. Water may impair the analysis and the optimal approach to eliminate it is still to be found and integrated into the sampling strategy. KW - Solvents KW - Air analysis KW - VOC KW - Thermal desorption KW - Gas chromatography KW - ISO 16000-6 PY - 2021 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-523919 DO - https://doi.org/10.1016/j.trac.2021.116265 VL - 140 SP - 116265 PB - Elsevier B.V. AN - OPUS4-52391 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Lange, M. A. A1 - Khan, I. A1 - Opitz, P. A1 - Hartmann, J: A1 - Ashraf, M. A1 - Qurashi, A. A1 - Prädel, L. A1 - Panthöfer, M. A1 - Cossmer, Antje A1 - Pfeifer, Jens A1 - Simon, Fabian A1 - von der Au, Marcus A1 - Meermann, Björn A1 - Mondeshki, M. A1 - Tahir, M. N. A1 - Tremel, W. T1 - A Generalized Method for High-Speed Fluorination of Metal Oxides by Spark Plasma Sintering Yields Ta3O7F and TaO2F with High Photocatalytic Activity for Oxygen Evolution from Water N2 - A general method to carry out the fluorination of metal oxides with poly(tetrafluoroethylene) (PTFE, Teflon) waste by spark plasma sintering (SPS) on a minute scale with Teflon is reported. The potential of this new approach is highlighted by the following results. i) The tantalum oxyfluorides Ta3O7F and TaO2F are obtained from plastic scrap without using toxic or caustic chemicals for fluorination. ii) Short reaction times (minutes rather than days) reduce the process time the energy costs by almost three orders of magnitude. iii) The oxyfluorides Ta3O7F and TaO2F are produced in gram amounts of nanoparticles. Their synthesis can be upscaled to the kg range with industrial sintering equipment. iv) SPS processing changes the catalytic properties: while conventionally prepared Ta3O7F and TaO2F show little catalytic activity, SPS-prepared Ta3O7F and TaO2F exhibit high activity for photocatalytic oxygen evolution, reaching photoconversion efficiencies up to 24.7% and applied bias to photoconversion values of 0.86%. This study shows that the materials properties are dictated by the processing which poses new challenges to understand and predict the underlying factors. KW - Fluorination KW - Oxygen evolution reaction KW - Photocatalysis KW - Spark plasma sintering KW - Tantalum oxyfluorides PY - 2021 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-524329 DO - https://doi.org/10.1002/adma.202007434 VL - 23 IS - 20 SP - 7434 PB - Wiley‐VCH GmbH AN - OPUS4-52432 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Weber, K. A1 - Weber, M. A1 - Menneken, M. A1 - Kral, A. G. A1 - Mertz-Kraus, R. A1 - Geisler, T. A1 - Vogl, Jochen A1 - Tütken, T. T1 - Diagenetic stability of non-traditional stable isotope systems (Ca, Sr, Mg, Zn) in teeth – An in-vitro alteration experiment of biogenic apatite in isotopically enriched tracer solution N2 - Stable isotope ratios and trace element concentrations of fossil bones and teeth are important geochemical proxies for the reconstruction of diet and past environment in archaeology and palaeontology. However, since diagenesis can significantly alter primary diet-related isotope signatures and elemental compositions, it is important to understand and quantify alteration processes. Here, we present the results of in-vitro Alteration experiments of dental tissues from a modern African elephant molar reacted in aqueous solutions at 30 °C and 90 °C for 4 to 63 days. Dental cubes with ≈ 3 mm edge length, comprising both enamel and dentin, were placed into 2 mL of acidic aqueous solution enriched in different isotopes (25Mg, 44Ca, 67Zn, 86Sr, initial pH 1). Element and isotope distribution profiles across the reacted cubes were measured with LA-(MC-)ICP-MS and EMPA, while potential effects on the bioapatite crystal structure were characterised by Raman spectroscopy. In all experiments isotope ratios measured by LA-(MC-)ICP-MS revealed an alteration of the enamel in the outer ≈ 200–300 μm. In contrast, dentin was fully altered (≈ 1.4 mm) after one week at 90 °C while the alteration did not exceed a depth of 150–200 μm during the 30 °C experiments. Then, the tracer solution started also to penetrate through the enamel-dentin junction into the innermost enamel, however, leaving the central part of the enamel unaltered, even after three months. The Raman spectra suggest an initial demineralisation in the acidic environment while organic matter (i.e. collagen) is still preserved. In the 90 °C experiment, Raman spectra of the v1 PO4) band of the dentin shift over time towards synthetic hydroxylapatite patterns and the Ca (and Sr) concentrations in the respective solutions decrease. This indicates precipitation of newly formed apatite. Isotope and element concentration profiles across the dental tissues reveal different exchange mechanisms for different isotope systems. Magnesium is leached from enamel and dentin, while Zn is incorporated into the apatite crystal structure. However, the distribution of both elements is not affected in the innermost enamel where their concentrations do not change over the whole duration of the experiments. We found no correlation of reaction depth in the cubes and experimental duration, which might be caused by natural variability of the dental material already at the beginning of the experiment. Our alteration experiments in a closed system at high temperatures ≤90 °C and low initial pH demonstrate that at least the central part of mm-thick mammalian enamel apatite seems to be resistant against alteration preserving its pristine bioapatite mineral structure as well as its in-vivo elemental and isotopic composition. The experiments assess diagenetic alteration in a novel multi-proxy approach using in-situ analyses in high spatial resolution. It is demonstrated that the isotopes of Ca, Sr, Zn and Mg in the dentin are prone for diagenetic alteration, while enamel is more resistant against alteration and could be used for dietary and physiological reconstructions in fossil teeth. KW - Bioapatite KW - Isotopes KW - Raman spectroscopy KW - Diagenesis KW - LA-(MC-)ICP-MS KW - EPMA PY - 2021 DO - https://doi.org/10.1016/j.chemgeo.2021.120196 VL - 572 SP - 120196 PB - Elsevier B.V. CY - Amsterdam AN - OPUS4-52447 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Brauckmann, C. A1 - Pramann, A. A1 - Rienitz, O. A1 - Schulze, A. A1 - Phukphatthanachai, Pranee A1 - Vogl, Jochen T1 - Combining Isotope Dilution and Standard Addition—Elemental Analysis in Complex Samples N2 - A new method combining isotope dilution mass spectrometry (IDMS) and standard addition has been developed to determine the mass fractions w of different elements in complex matrices: (a) silicon in aqueous tetramethylammonium hydroxide (TMAH), (b) sulfur in biodiesel fuel, and (c) iron bound to transferrin in human serum. All measurements were carried out using inductively coupled plasma mass spectrometry (ICP–MS). The method requires the gravimetric preparation of several blends (bi)—each consisting of roughly the same masses (mx,i) of the sample solution (x) and my,i of a spike solution (y) plus different masses (mz,i) of a reference solution (z). Only these masses and the isotope ratios (Rb,i) in the blends and reference and spike solutions have to be measured. The derivation of the underlying equations based on linear regression is presented and compared to a related concept reported by Pagliano and Meija. The uncertainties achievable, e.g., in the case of the Si blank in extremely pure TMAH of urel (w(Si)) = 90% (linear regression method, this work) and urel (w(Si)) = 150% (the method reported by Pagliano and Meija) seem to suggest better applicability of the new method in practical use due to the higher robustness of regression analysis. KW - Isotope dilution mass spectrometry KW - tandard addition KW - ICP-MS KW - lank characterization KW - Silicon KW - Sulfur KW - Transferrin KW - Tetramethylammonium hydroxide KW - Biodiesel fuel KW - Human serum PY - 2021 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-526376 DO - https://doi.org/10.3390/molecules26092649 VL - 26 IS - 9 SP - 2649 PB - MDPI CY - Basel AN - OPUS4-52637 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Wiesner, Yosri A1 - Altmann, Korinna A1 - Braun, U. T1 - Determination of Microplastic Mass Content by Thermal Extraction Desorption Gas Chromatography– Mass Spectrometry N2 - The scientific and practical challenge of detecting microplastics (MPs) in the environment in a targeted and rapid manner is solved by innovative coupling of thermogravimetric analysis with mass spectrometric methods. Fast identification and quantitative determination of most thermoplastic polymers and elastomers is possible by using thermal extraction Desorption gas chromatography–mass spectrometry (TED-GC–MS). KW - Microplastics KW - Mikroplastik KW - TED-GC/MS KW - Microplastics analytic KW - Mikroplastik Massegehalt PY - 2021 VL - 17 IS - 3 SP - 2 EP - 7 PB - MultiMedia (UK) LLC CY - Cranbury AN - OPUS4-52570 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Faßbender, Sebastian A1 - von der Au, Marcus A1 - Koenig, Maren A1 - Pelzer, J. A1 - Piechotta, Christian A1 - Vogl, Jochen A1 - Meermann, Björn T1 - Species-specific isotope dilution analysis of monomethylmercury in sediment using GC/ICP-ToF-MS and comparison with ICP-Q-MS and ICP-SF-MS N2 - A recently introduced inductively coupled plasma-time-of-flight-mass spectrometer (ICP-ToF-MS) shows enhanced sensitivity compared to previous developments and superior isotope ratio precision compared to other ToF and commonly used single-collector ICP-MS instruments. Following this fact, an improvement for isotope dilution ICP-MS using the new instrumentation has been reported. This study aimed at investigating whether this improvement also meets the requirements of species-specific isotope dilution using GC/ICP-MS, where short transient signals are recorded. The results of the analysis of monomethylmercury (MMHg) of a sediment reference material show that isotope ratio precision of ICP-MS instruments equipped with quadrupole, sector-field, and time-of-flight mass analyzers is similar within a broad range of peak signal-to-noise ratio when analyzing one isotopic system. The procedural limit of quantification (LOQ) for MMHg, expressed as mass fraction of Hg being present as MMHg, w(Hg)MMHg, was similar as well for all investigated instruments and ranged between 0.003 and 0.016 μg/kg. Due to the simultaneous detection capability, the ICP-ToF-MS might, however, be more favorable when several isotopic systems are analyzed within one measurement. In a case study, the GC/ICP-ToF-MS coupling was applied for analysis of MMHg in sediments of Finow Canal, a historic German canal heavily polluted with mercury. Mass fractions between 0.180 and 41 μg/kg (w(Hg)MMHg) for MMHg, and 0.056 and 126 mg/kg (w(Hg)total) for total mercury were found in sediment samples taken from the canal upstream and downstream of a former chemical plant. KW - Methylmercury KW - Legacy pollution KW - Finow Canal KW - Isotope dilution KW - Mercury speciation PY - 2021 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-529967 DO - https://doi.org/10.1007/s00216-021-03497-z SN - 1618-2642 VL - 413 IS - 21 SP - 5279 EP - 5289 PB - Springer CY - Berlin AN - OPUS4-52996 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Backes, A. T. A1 - Reinmuth-Selzle, K. A1 - Leifke, A. L. A1 - Ziegler, K. A1 - Krevert, C. S. A1 - Tscheuschner, Georg A1 - Lucas, K. A1 - Weller, Michael G. A1 - Berkemeier, T. A1 - Pöschl, U. A1 - Fröhlich-Nowoisky, J. T1 - Oligomerization and Nitration of the Grass Pollen Allergen Phl p 5 by Ozone, Nitrogen Dioxide, and Peroxynitrite: Reaction Products, Kinetics, and Health Effects N2 - The allergenic and inflammatory potential of proteins can be enhanced by chemical modification upon exposure to atmospheric or physiological oxidants. The molecular mechanisms and kinetics of such modifications, however, have not yet been fully resolved. We investigated the oligomerization and nitration of the grass pollen allergen Phl p 5 by ozone (O3), nitrogen dioxide (NO2), and peroxynitrite (ONOO–). Within several hours of exposure to atmospherically relevant concentration levels of O3 and NO2, up to 50% of Phl p 5 were converted into protein oligomers, likely by formation of dityrosine cross-links. Assuming that tyrosine residues are the preferential site of nitration, up to 10% of the 12 tyrosine residues per protein monomer were nitrated. For the reaction with peroxynitrite, the largest oligomer mass fractions (up to 50%) were found for equimolar concentrations of peroxynitrite over tyrosine residues. With excess peroxynitrite, the nitration degrees increased up to 40% whereas the oligomer mass fractions decreased to 20%. Our results suggest that protein oligomerization and nitration are competing processes, which is consistent with a two-step mechanism involving a reactive oxygen intermediate (ROI), as observed for other proteins. The modified proteins can promote pro-inflammatory cellular signaling that may contribute to chronic inflammation and allergies in response to air pollution. KW - Protein KW - Nitrotyrosine KW - Dityrosine KW - Allergy KW - Hay fever KW - Diesel exhaust KW - Combustion KW - Exhaust PY - 2021 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-529729 DO - https://doi.org/10.3390/ijms22147616 VL - 22 IS - 14 PB - MDPI CY - Basel AN - OPUS4-52972 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Haeckel, A. A1 - Ascher, Lena A1 - Beindorff, N. A1 - Prasad, S. A1 - Garczynska, K. A1 - Guo, J. A1 - Schellenberger, E. T1 - Long‑circulating XTEN864‑annexin A5 fusion protein for phosphatidylserine‑related therapeutic applications N2 - Annexin A5 (anxA5) is a marker for apoptosis, but has also therapeutic potential in cardiovascular diseases, cancer, and, due to apoptotic mimicry, against dangerous viruses, which is limited by the short blood circulation. An 864-amino-acid XTEN polypeptide was fused to anxA5. XTEN864-anxA5 was expressed in Escherichia coli and purified using XTEN as tag. XTEN864-anxA5 was coupled with DTPA and indium-111. After intravenous or subcutaneous injection of 111In-XTEN864-anxA5, mouse blood samples were collected for blood half-life determination and organ samples for biodistribution using a gamma counter. XTEN864-anxA5 was labeled with 6S-IDCC to confirm binding to apoptotic cells using flow cytometry. To demonstrate targeting of atherosclerotic plaques, XTEN864-anxA5 was labeled with MeCAT(Ho) and administered intravenously to atherosclerotic ApoE−/−mice. MeCAT(Ho)-XTEN864-anxA5 was detected together with MeCAT(Tm)-MAC-2 macrophage antibodies by imaging mass cytometry (CyTOF) of aortic root sections. The ability of anxA5 to bind apoptotic cells was not affected by XTEN864. The blood half-life of XTEN864-anxA5 was 13 h in mice after IV injection, markedly longer than the 7-min half-life of anxA5. 96 h after injection, highest amounts of XTEN864-anxA5 were found in liver, spleen, and kidney. XTEN864-anxA5 was found to target the adventitia adjacent to atherosclerotic plaques. XTEN864-anxA5 is a long-circulating fusion protein that can be efficiently produced in E. coli and potentially circulates in humans for several days, making it a promising therapeutic drug. KW - Programmed cell death KW - LA/ICP-MS Imaging KW - Medicinal application PY - 2021 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-533811 DO - https://doi.org/10.1007/s10495-021-01686-w VL - 26 IS - 9-10 SP - 534 EP - 547 PB - Springer AN - OPUS4-53381 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Meermann, Björn T1 - The future of elemental analytical chemistry – the sixth special issue dedicated to young analytical scientists N2 - Editorial for a special issue KW - Editorial KW - Special issue, young analytical scientists KW - Elemental analysis PY - 2021 DO - https://doi.org/10.1039/d1ja90038b VL - 36 IS - 9 SP - 1794 EP - 1796 PB - RSC AN - OPUS4-53086 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Ogrinc, N. A1 - Rossi, A. M. A1 - Durbiano, F. A1 - Becker, Roland A1 - Milavec, M. A1 - Bogozalec Kosir, A. A1 - Kakoulides, E. A1 - Ozer, H. A1 - Akcadag, F. A1 - Goenaga-Infante, H. A1 - Quaglia, M. A1 - Mallia, S. A1 - Umbricht, G. A1 - O'Connor, G. A1 - Guettler, B. T1 - Support for a European metrology network on food safety Food-MetNet N2 - This paper describes Food-MetNet, a coordinated preparatory initiative to establish the European Metrology Network on Food Safety (EMN-FS). Food-MetNet aims to establish a long-term ongoing dialogue between the metrology community and relevant stakeholders, in particular, European Union Reference Laboratories (EURLs), National Reference Laboratories (NRLs) and the Joint Research Centre (JRC). This dialogue is meant to support the collection of needs from stakeholders, the take-up of metrological research output and the development of the roadmaps needed to navigate future research. KW - Network KW - Metrology KW - Food KW - Safety KW - Stakeholders PY - 2021 DO - https://doi.org/10.1016/j.measen.2021.100285 VL - 18 SP - 1 EP - 4 PB - Elsevier AN - OPUS4-53740 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Becker, Roland A1 - Heyn, L. A1 - Jung, Christian T1 - Indoor exposure to airborne polycyclic aromatic hydrocarbons: A comparison of stir bar sorptive extraction and pump sampling N2 - Stir bar sorptive extraction (SBSE) was compared with standardized pump sampling regarding the prospects to assess airborne levels of polycyclic aromatic hydrocarbons (PAHs) in indoor environments. A historic railway water tower, which will be preserved as a technical monument for museum purposes, was sampled with both approaches because the built-in insulationmaterial was suspected to release PAHs to the indoor air. The 16 PAHs on the US EPA list were quantified using gas chromatography with mass spectrometric detection in filters from pump sampling after solvent extraction and on SBSE devices after thermal desorption. SBSEwas seen to sample detectable PAHmasseswith excellent repeatability and a congener pattern largely similar to that observed with pump sampling. Congener patterns were however significantly different from that in the PAH source because release from the insulation material is largely triggered by the respective congener vapor pressures. Absolute masses in the ng range sampled by SBSE corresponded to airborne concentrations in the ng L−1 range determined by pump sampling. Principle differences between SBSE and pump sampling as well as prospects of SBSE as cost-effective and versatile complement of pump sampling are discussed. KW - Polycyclic aromatic hydrocarbons KW - Adsorption KW - Extraction KW - Indoor air PY - 2021 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-537427 DO - https://doi.org/10.1002/eng2.12419 VL - 3 IS - 12 SP - 1 EP - 10 PB - John Wiley & Sons Ltd. AN - OPUS4-53742 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Ecke, Alexander A1 - Westphalen, Tanja A1 - Hornung, J. A1 - Voetz, M. A1 - Schneider, Rudolf T1 - A rapid magnetic bead-based immunoassay for sensitive determination of diclofenac N2 - Increasing contamination of environmental waters with pharmaceuticals represents an emerging threat for the drinking water quality and safety. In this regard, fast and reliable analytical methods are required to allow quick countermeasures in case of contamination. Here, we report the development of a magnetic bead-based immunoassay (MBBA) for the fast and cost-effective determination of the analgesic diclofenac (DCF) in water samples, based on diclofenac-coupled magnetic beads and a robust monoclonal anti-DCF antibody. A novel synthetic strategy for preparation of the beads resulted in an assay that enabled for the determination of diclofenac with a significantly lower limit of detection (400 ng/L) than the respective enzyme-linked immunosorbent assay (ELISA). With shorter incubation times and only one manual washing step required, the assay demands for remarkably shorter time to result (< 45 min) and less equipment than ELISA. Evaluation of assay precision and accuracy with a series of spiked water samples yielded results with low to moderate intra- and inter-assay variations and in good agreement with LC–MS/MS reference analysis. The assay principle can be transferred to other, e.g., microfluidic, formats, as well as applied to other analytes and may replace ELISA as the standard immunochemical method. KW - Immunoassay KW - Magnetic beads KW - Diclofenac KW - Water analysis KW - LC-MS/MS PY - 2021 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-542346 DO - https://doi.org/10.1007/s00216-021-03778-7 SN - 1618-2650 VL - 414 SP - 1563 EP - 1573 PB - Springer CY - Heidelberg AN - OPUS4-54234 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Lemke, Nora A1 - El-Khatib, Ahmed H. A1 - Tchipilov, Teodor A1 - Jakubowski, N. A1 - Weller, Michael G. A1 - Vogl, Jochen T1 - Procedure providing SI‑traceable results for the calibration of protein standards by sulfur determination and its application on tau N2 - Quantitative proteomics is a growing research area and one of the most important tools in the life sciences. Well-characterized and quantified protein standards are needed to achieve accurate and reliable results. However, only a limited number of sufficiently characterized protein standards are currently available. To fill this gap, a method for traceable protein quantification using sulfur isotope dilution inductively coupled plasma mass spectrometry (ICP-MS) was developed in this study. Gel filtration and membrane filtration were tested for the separation of non-protein-bound sulfur in the protein solution. Membrane filtration demonstrated a better performance due to the lower workload and the very low sulfur blanks of 11 ng, making it well suited for high-purity proteins such as NIST SRM 927, a bovine serum albumin (BSA). The method development was accomplished with NIST SRM 927e and a commercial avidin. The quantified mass fraction of NIST SRM 927e agreed very well with the certified value and showed similar uncertainties (3.6%) as established methods while requiring less sample preparation and no species-specific standards. Finally, the developed procedure was applied to the tau protein, which is a biomarker for a group of neurodegenerative diseases denoted “tauopathies” including, e.g., Alzheimer’s disease and frontotemporal dementia. For the absolute quantification of tau in the brain of transgenic mice overexpressing human tau, a well-defined calibration standard was needed. Therefore, a pure tau solution was quantified, yielding a protein mass fraction of (0.328 ± 0.036) g/kg, which was confirmed by amino acid analysis. KW - Iinductively coupled plasma mass spectrometry KW - Isotope dilution KW - Quantitative protein analysis KW - Sulfur KW - SI traceability PY - 2022 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-545200 DO - https://doi.org/10.1007/s00216-022-03974-z VL - 414 SP - 4441 EP - 4455 PB - Springer Verlag AN - OPUS4-54520 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Dariz, P. A1 - Wortmann, U. G. A1 - Vogl, Jochen A1 - Schmid, Thomas T1 - Beautiful Pietàs in South Tyrol (Northern Italy): local or imported works of art? N2 - The study, dedicated to Beautiful Pietàs conserved in South Tyrol (Northern Italy), aims to establish, for the first time, a connection between Austroalpine raw materials and the high-fired gypsum mortars constituting the Gothic figure groups in question. The origin and chronology of this stylistically and qualitatively differing ensemble have been subject of art historical debate for nearly a century. The discourse is dominated by three main hypotheses: itinerary of an Austrian artist versus itinerary of the work of art created in an artist’s workshop in Austria versus itinerary of the stylistic vocabulary via graphical or three-dimensional models. The comparison of the δ34S values and the 87Sr/86Sr ratios of the gypsum mortars and Austroalpine sulphate deposits (in a compilation of own reference samples and literature data) points to the exploitation of sediments in the Salzkammergut and possibly also in the evaporite district of the Eastern Calcareous Alps, thus evidencing the import of the sculptures and not the activities of local South Tyrolean or itinerant artists. Two geochronological units are distinguishable: The Pietà in the Church St. Martin in Göflan can be assigned to Upper Permian raw material, whereas the metrologically consistent sculptures in the Church of Our Lady of the Benedictine Abbey Marienberg and in the Chapel St. Ann in Mölten correlate with deposits of the Early Triassic (or the Lower-Middle Triassic transition). The medieval gypsum mortars also differ in their mineralogical characteristics, i.e. in their geologically related minor components, as in the first case, characterised by a significant proportion of primary anhydrite, natural carbonate impurities mainly consist of calcite (partly converted to lime-lump-like aggregates), whereas in the second group dolomite (or rather its hydration products after pyrometamorphic decomposition) predominates, accompanied by celestine, quartz and potassium feldspar. The Pietà in the Cathedral Maria Himmelfahrt in Bozen turned out to be made of Breitenbrunn calcareous sandstone (Leitha Mountains, Burgenland, Austria), which is why the sample is not considered in the geochemical analysis. KW - High-fired gypsum mortar KW - Sulphur isotope KW - Strontium isotope KW - Polarised light microscopy KW - Raman microspectroscopy PY - 2022 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-545610 DO - https://doi.org/10.1186/s40494-022-00678-6 SN - 2050-7445 VL - 10 IS - 1 SP - 1 EP - 17 PB - Springer Nature AN - OPUS4-54561 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Casali, C. A1 - Feiler, Torvid A1 - Heilmann, Maria A1 - Braga, D. A1 - Emmerling, Franziska A1 - Grepioni, F. T1 - Too much water? Not enough? In situ monitoring of the mechanochemical reaction of copper salts with dicyandiamide N2 - n situ monitoring of mechanochemical reactions between dicyandiamide (DCD) and CuX2 salts (X = Cl−, NO3−), for the preparation of compounds of agrochemical interest, showed the appearance of a number of phases. It is demonstrated that milling conditions, such as the amount of water added in wet grinding and/or the milling frequency, may affect the course of the mechanochemical reactions, and drive the reaction towards the formation of different products. It has been possible to discover by in situ monitored experiments two novel crystalline forms, namely the neutral complexes [Cu(DCD)2(OH2)2(NO3)2] (2) and [Cu(DCD)2(OH2)Cl2]·H2O (4), in addition to the previously known molecular salt [Cu(DCD)2(OH2)2][NO3]2·2H2O (1, DIVWAG) and neutral complex [Cu(DCD)2(OH2)Cl2] (3, AQCYCU), for which no synthesis conditions were available. Compounds 2 and 4 were fully characterized via a combination of solid-state techniques, including X-ray diffraction, Raman spectroscopy and TGA. KW - Mechanochemistry KW - In situ PY - 2022 DO - https://doi.org/10.1039/d1ce01670a VL - 24 IS - 6 SP - 1292 EP - 1298 PB - RSC AN - OPUS4-54344 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Simon, Fabian A1 - Gehrenkemper, Lennart A1 - von der Au, Marcus A1 - Wittwer, Phillip A1 - Roesch, Philipp A1 - Pfeifer, Jens A1 - Cossmer, Antje A1 - Meermann, Björn T1 - A fast and simple PFAS extraction method utilizing HR–CS–GFMAS for soil samples N2 - Here, we describe an optimized fast and simple extraction method for the determination of per- and polyfluorinated alkyl substances (PFASs) in soils utilizing high resolution-continuum source-graphite furnace molecular absorption spectrometry (HR–CS–GFMAS). To omit the bias of the solid phase extraction (SPE) step commonly used during the analysis of extractable organically bound fluorine (EOF) we optimized a fast and simple SPE-free extraction method. The developed extraction method consists of a liquid-solid extraction using acidified methanol without any additional SPE. Four extraction steps were representative to determine a high proportion of the EOF (>80% of eight extractions). Comparison of the optimized method with and without an additional SPE clean-up step revealed a drastic underestimation of EOF concentrations using SPE. Differences of up to 94% were observed which were not explainable by coextracted inorganic fluoride. Therefore, not only a more accurate but also a more economic as well as ecologic method (bypassing of unnecessary SPE) was developed. The procedural limit of quantification (LOQ) of the developed method was 10.30 μg/kg which was sufficient for quantifying EOF concentrations in all tested samples. For future PFAS monitoring and potential regulative decisions the herein presented optimized extraction method can offer a valuable contribution. KW - Per- and polyfluorinated alkly substances (PFASs) KW - High resolution-continuum source-graphite furnace molecular absorption spectrometry (HR-CS-GFMAS) KW - Soils KW - Solid phase extraction (SPE) KW - Extractable organically bound fluorine (EOF) KW - Solid-liquid extraction PY - 2022 DO - https://doi.org/10.1016/j.chemosphere.2022.133922 VL - 295 SP - 1 EP - 9 PB - Elsevier Ltd. AN - OPUS4-54359 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Frisch, M. A1 - Raza, M. H. A1 - Ye, M.-Y. A1 - Sachse, René A1 - Paul, B. A1 - Gunder, R. A1 - Pinna, N. A1 - Kraehnert, R. T1 - ALD-coated mesoporous iridium-titanium mixed oxides: Maximizing iridium utilization for an outstanding OER performance N2 - With the increasing production of renewable energy and concomitant depletion of fossil resources, the demand for efficient water splitting electrocatalysts continues to grow. Iridium (Ir) and iridium oxides (IrOₓ) are currently the most promising candidates for an efficient oxygen evolution reaction (OER) in acidic medium, which remains the bottleneck in water electrolysis. Yet, the extremely high costs for Ir hamper a widespread production of hydrogen (H₂) on an industrial scale. Herein, the authors report a concept for the synthesis of electrode coatings with template-controlled mesoporosity surface-modified with highly active Ir species. The improved utilization of noble metal species relies on the synthesis of soft-templated metal oxide supports and a subsequent shape-conformal deposition of Ir species via atomic layer deposition (ALD) at two different reaction temperatures. The study reveals that a minimum Ir content in the mesoporous titania-based support is mandatory to provide a sufficient electrical bulk conductivity. After ALD, a significantly enhanced OER activity results in dependency of the ALD cycle number and temperature. The most active developed electrocatalyst film achieves an outstanding mass-specific activity of 2622 mA mg(Ir)⁻¹ at 1.60 V(RHE) in a rotating-disc electrode (RDE) setup at 25 °C using 0.5 m H₂SO₄ as a supporting electrolyte. KW - Acidic oxygen evolution reaction KW - Atomic layer deposition KW - Electrocatalysis KW - Iridium oxide KW - Soft-templated mesoporous films PY - 2022 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-542651 DO - https://doi.org/10.1002/admi.202102035 SN - 2196-7350 SP - 1 EP - 11 PB - Wiley-VCH CY - Weinheim AN - OPUS4-54265 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Xiao, J. A1 - Vogl, Jochen A1 - Rosner, M. A1 - Jin, Z. T1 - Boron isotope fractionation in soil-plant systems and its influence on biogeochemical cycling N2 - Boron (B) is an essential mineral nutrient for higher plants. Although B plant nutrition is well studied, the B isotope fractionation at the soil-plant interface, within plant metabolism, and its influence on biogeochemical cycling is not fully understood. Boron concentrations and isotope variations (δ11B) of the dicotyledonous plants of Chenopodium album and Brassica napus and their growing soils along a climatic gradient were analyzed to decipher these unresolved issues of the B behavior. The boron concentrations and δ11B values show an increasing trend from roots to leaves for both plants, while a decreasing trend from flower to shell and to seed for Brassica napus. A large boron isotope fractionation occurs within the plants with median Δ11Bleaf-root ≈ +20‰, which is related to different boron transporters and transportation ways. Formation of borate dimerized rhamnogalacturonan II in cell and B(OH)3 transportation in xylem lead to heavier δ11B values from root to stem and leaf while B(OH)4􀀀 transportation in phloem lead to lighter δ11B values from flower to shell and seed. Although samples cover a distinct transect with systematically different climatic conditions, Δδ11B within the individual plant compartments and between the bulk plants and the soil available B do not show any systematic variation. This suggests that B uptake from the soil into Chenopodium album and Brassica napus occurs without a distinct isotope fractionation at the soil-plant interface (median Δ11Bbulkplant-soil = 􀀀 0.2‰) and plants are able to regulate boron uptake. Both the observed large B fractionation within plant and low or absent B isotope fractionation at the soil-plant interface may have profound implications for the biological and geological B cycle. If this observed boron behavior also exists in other plants, their litters would be an important source for exporting 11B-rich biological material from continental ecosystems via rivers to the global oceans. This may be helpful for the explanation of ocean B cycle and the increasing δ11B values over the Cenozoic. KW - Boron isotopic composition KW - Boron isotope fractionation KW - Soil available boron KW - Biological boron recycling KW - Chenopodium album KW - Brassica napus PY - 2022 DO - https://doi.org/10.1016/j.chemgeo.2022.120972 SN - 0009-2541 VL - 606 SP - 1 EP - 8 PB - Elsevier B.V. CY - Amsterdam AN - OPUS4-55031 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - von der Au, Marcus A1 - Faßbender, Sebastian A1 - Chronakis, Michail A1 - Vogl, Jochen A1 - Meermann, Björn T1 - Size determination of nanoparticles by ICP-ToF-MS using isotope dilution in microdroplets N2 - Within this work, the combination of a microdroplet generator and an ICP-ToF-MS for nanoparticle analysis is presented. For the size determination of platinum nanoparticles an on-line isotope dilution analysis approach was developed. The 194Pt/195Pt isotopic ratio was used for the characterization of the particles, while the 182W/183W isotopic ratio was monitored simultaneously for mass bias correction. The on-line ID-MDG-sp-ICP-ToF-MS approach was deployed for the size determination of three platinum nanoparticle samples (50 nm, 63 nm, 70 nm); for validation, complementary size characterization techniques (sp-ICP-ToF-MS and TEM) were used. The robustness of this technique was evidenced, by using sodium chloride concentrations up to 100 mg L−1 as a matrix component. Our new on-line ID MDG-sp-ICP-ToF-MS approach is a promising tool for the fast and reliable determination of nanoparticles' size in severe matrix concentrations, e.g., environmental samples. KW - ICP-ToF-MS KW - Nanoparticles KW - Isotope Dilution PY - 2022 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-552727 DO - https://doi.org/10.1039/D2JA00072E SN - 0267-9477 VL - 37 IS - 6 SP - 1203 EP - 1207 PB - Royal Society of Chemistry AN - OPUS4-55272 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Spallanzani, Roberta A1 - Koga, K. A1 - Cichy, S. A1 - Wiedenbeck, M. A1 - Schmidt, B. A1 - Oelze, Marcus A1 - Wilke, M. T1 - Lithium and boron difusivity and isotopic fractionation in hydrated rhyolitic melts N2 - Lithium and boron are trace components of magmas, released during exsolution of a gas phase during volcanic activity. In this study, we determine the difusivity and isotopic fractionation of Li and B in hydrous silicate melts. Two glasses were synthesized with the same rhyolitic composition (4.2 wt% water), having diferent Li and B contents; these were studied in difusion-couple experiments that were performed using an internally heated pressure vessel, operated at 300 MPa in the temperature range 700–1250 °C for durations from 0 s to 24 h. From this we determined activation energies for Li and B difusion of 57±4 kJ/mol and 152±15 kJ/mol with pre-exponential factors of 1.53 × 10–7 m2/s and 3.80× 10–8 m2 /s, respectively. Lithium isotopic fractionation during difusion gave β values between 0.15 and 0.20, whereas B showed no clear isotopic fractionation. Our Li difusivities and isotopic fractionation results difer somewhat from earlier published values, but overall confrm that Li difusivity increases with water content. Our results on B difusion show that similarly to Li, B mobility increases in the presence of water. By applying the Eyring relation, we confrm that B difusivity is limited by viscous fow in silicate melts. Our results on Li and B difusion present a new tool for understanding degassing-related processes, ofering a potential geospeedometer to measure volcanic ascent rates. KW - Hydrated silicate melts KW - Stable isotopes KW - Diffusion KW - Isotopic fractionation PY - 2022 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-554496 DO - https://doi.org/10.1007/s00410-022-01937-2 VL - 177 IS - 8 SP - 1 EP - 17 PB - Springer AN - OPUS4-55449 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kittner, Maria A1 - Kerndorff, A. A1 - Ricking, M. A1 - Bednarz, M. A1 - Obermaier, N. A1 - Lukas, M. A1 - Asenova, M. A1 - Bordós, G. A1 - Eisentraut, Paul A1 - Hohenblum, P. A1 - Hudcova, H. A1 - Humer, F. A1 - István, T. G. A1 - Kirchner, M. A1 - Marushevska, O. A1 - Nemejcová, D. A1 - Oswald, P. A1 - Paunovic, M. A1 - Sengl, M. A1 - Slobodnik, J. A1 - Spanowsky, K. A1 - Tudorache, M. A1 - Wagensonner, H. A1 - Liska, I. A1 - Braun, U. A1 - Bannick, C. G. T1 - Microplastics in the Danube River Basin: A First Comprehensive Screening with a Harmonized Analytical Approach N2 - In this study, carried out within the Joint Danube Survey 4, a comprehensive microplastic screening in the water column within a large European river basin from its source to estuary, including major tributaries, was realized. The objective was to develop principles of a systematic and practicable microplastic monitoring strategy using sedimentation boxes for collection of suspended particulate matter followed by its subsequent analysis using thermal extraction desorption-gas chromatography/mass spectrometry. In total, 18 sampling sites in the Danube River Basin were investigated. The obtained suspended particulate matter samples were subdivided into the fractions of >100 μm and <100 μm and subsequently analyzed for microplastic mass contents. The results showed that microplastics were detected in all samples, with polyethylene being the predominant polymer with maximum contents of 22.24 μg/mg, 3.23 μg/mg for polystyrene, 1.03 μg/mg for styrene-butadiene-rubber, and 0.45 μg/mg for polypropylene. Further, polymers such as different sorts of polyester, polyacrylates, polylactide, and natural rubber were not detected or below the detection limit. Additional investigations on possible interference of polyethylene signals by algae-derived fatty acids were assessed. In the context of targeted monitoring, repeated measurements provide more certainty in the interpretation of the results for the individual sites. Nevertheless, it can be stated that the chosen approach using an integrative sampling and determination of total plastic content proved to be successful. KW - Thermal extraction desorption-gas chromatography/mass spectrometry (TED-GC/MS), monitoring KW - Microplastics KW - River KW - Suspended particulate matter (SPM) KW - Sedimentation box (SB) PY - 2022 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-551444 DO - https://doi.org/10.1021/acsestwater.1c00439 VL - 2 IS - 7 SP - 1174 EP - 1181 PB - ACS Publications AN - OPUS4-55144 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Reinmuth-Selzle, K. A1 - Tchipilov, Teodor A1 - Backes, A. T. A1 - Tscheuschner, Georg A1 - Tang, K. A1 - Ziegler, K. A1 - Lucas, K. A1 - Pöschl, U. A1 - Fröhlich-Nowoisky, J. A1 - Weller, Michael G. T1 - Determination of the protein content of complex samples by aromatic amino acid analysis, liquid chromatography-UV absorbance, and colorimetry N2 - Fast and accurate determination of the protein content of a sample is an important and non-trivial task of many biochemical, biomedical, food chemical, pharmaceutical, and environmental research activities. Different methods of total protein determination are used for a wide range of proteins with highly variable properties in complex matrices. These methods usually work reasonably well for proteins under controlled conditions, but the results for non-standard and complex samples are often questionable. Here, we compare new and well-established methods, including traditional amino acid analysis (AAA), aromatic amino acid analysis (AAAA) based on the amino acids phenylalanine and tyrosine, reversed-phase liquid chromatography of intact proteins with UV absorbance measurements at 220 and 280 nm (LC-220, LC-280), and colorimetric assays like Coomassie Blue G-250 dye-binding assay (Bradford) and bicinchoninic acid (BCA) assay. We investigated different samples, including proteins with challenging properties, chemical modifications, mixtures, and complex matrices like air particulate matter and pollen extracts. All methods yielded accurate and precise results for the protein and matrix used for calibration. AAA, AAAA with fluorescence detection, and the LC-220 method yielded robust results even under more challenging conditions (variable analytes and matrices). These methods turned out to be well-suited for reliable determination of the protein content in a wide range of samples, such as air particulate matter and pollen. KW - Air particulate matter KW - Aromatic amino acid analysis KW - Atmospheric aerosol KW - Chemical protein modification KW - Derivatization KW - Nitration KW - Nitrotyrosine KW - LC-UV absorbance KW - Pollen extract KW - Protein quantification KW - Protein test KW - Kjeldahl KW - Tyrosine KW - Phenylalanine KW - Hydrolysis KW - Bradford KW - BCA test KW - 280 nm KW - Air filter samples KW - Fluorescence KW - HPLC KW - Chromatography KW - Protein content KW - 150th anniversary of BAM KW - Topical collection: Analytical Methods and Applications in the Materials and Life Sciences PY - 2022 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-545924 UR - https://pubmed.ncbi.nlm.nih.gov/35320366/ DO - https://doi.org/10.1007/s00216-022-03910-1 SP - 1 EP - 14 PB - Springer Nature Limited CY - New York, Heidelberg AN - OPUS4-54592 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Zweigle, J. A1 - Capitain, C. A1 - Simon, Fabian Michael A1 - Roesch, Philipp A1 - Bugsel, B. A1 - Zwiener, C. T1 - Non-extractable PFAS in functional textiles − Characterization by complementary methods: oxidation, hydrolysis, and fluorine sum parameters N2 - Per- and polyfluoroalkyl substances (PFAS) are widely used for durable water-repellent finishing of different fabrics and textiles like outdoor clothing, carpets, medical textiles and more. Existing PFAS extraction techniques followed by target analysis are often insufficient in detecting widely used side-chain fluorinated polymers (SFPs) that are barely or non-extractable. SFPs are typically copolymers consisting of a non-fluorinated backbone with perfluoroalkyl side-chains to obtain desired properties. We compared the accessible analytical information and performance of complementary techniques based on oxidation (dTOP assay, PhotoTOP), hydrolysis (THP assay), standard extraction, extractable organic fluorine (EOF), and total fluorine (TF) with five functional textiles and characterized 7 further textiles only by PhotoTOP oxidation. The results show that when applied directly to textile samples, oxidation by dTOP and PhotoTOP and also hydrolysis by the THP are able to capture large fractions of the TF in form of perfluoroalkyl side-chains present in the textiles while methods relying on extracts (EOF, target and non-target analysis) were much lower (e.g., factor ~25-50 lower). The conversion of large fractions of the measured TF into PFCAs or FTOHs from fluorinated side chains is in contrast to previous studies. Concentrations ranged from