TY - JOUR A1 - Recknagel, Sebastian A1 - Richter, Silke A1 - Hoppe, Marion A1 - Meckelburg, Angela A1 - Prinz, Carsten A1 - Roik, Janina A1 - Abad Andrade, Carlos Enrique T1 - Powering precision: development of a certified reference material for elemental composition analysis of lithium nickel manganese cobalt oxide (Li-NMC) cathode material for lithium-ion batteries N2 - This work presents the development and certification of the world’s first certified reference material (CRM), BAM-S014, for a lithium nickel manganese cobalt oxide (LiNi0.33Mn0.33Co0.33O2 or Li-NMC 111) cathode material—an integral component in high-energy-density lithium-ion batteries that power electric vehicles (EVs), portable electronics, and stationary energy storage systems. By providing certified mass fractions for 11 elements, this CRM addresses a critical need for accurate and traceable elemental analysis, supporting quality control and regulatory compliance in the global battery industry. Ensuring reliable and harmonized measurements supports the efficient use of resources, including the reuse of recycled materials, and ultimately helps maintain product performance and safety. The values were assigned through an interlaboratory comparison involving 16 participating laboratories and various analytical techniques such as inductively coupled plasma optical emission spectrometry (ICP-OES), inductively coupled plasma mass spectrometry (ICP-MS), X-ray fluorescence (XRF) spectrometry, and combustion analysis. In addition to chemical characterization, the certification process includes homogeneity and stability testing of the candidate material. Details are provided on the analytical methods used for chemical characterization and the calculation of the uncertainties of the certified mass fractions. In addition to detailing the development of the CRMs, this work provides an overview of ongoing standardization activities in Li-component analysis, thereby guiding the calibration of analytical methods and contributing to the establishment of globally accepted standards for evaluating energy storage materials and advancing sustainable mobility and clean energy solutions. KW - Certified reference material KW - Lithium nickel manganese cobalt oxide KW - LNMC KW - Lithium-ion battery KW - Cathode material PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-643763 DO - https://doi.org/10.1007/s00216-025-05766-7 SN - 1618-2642 VL - 417 IS - 12 SP - 2643 EP - 2653 PB - Springer Nature AN - OPUS4-64376 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Zaki, Mohammad A1 - Prinz, Carsten A1 - Ruehle, Bastian T1 - A Self-Driving Lab for Nano- and Advanced Materials Synthesis N2 - The recent emergence of self-driving laboratories (SDL) and material acceleration platforms (MAPs) demonstrates the ability of these systems to change the way chemistry and material syntheses will be performed in the future. Especially in conjunction with nano- and advanced materials which are generally recognized for their great potential in solving current material science challenges, such systems can make disrupting contributions. Here, we describe in detail MINERVA, an SDL specifically built and designed for the synthesis, purification, and in line characterization of nano- and advanced materials. By fully automating these three process steps for seven different materials from five representative, completely different classes of nano- and advanced materials (metal, metal oxide, silica, metal organic framework, and core–shell particles) that follow different reaction mechanisms, we demonstrate the great versatility and flexibility of the platform. We further study the reproducibility and particle size distributions of these seven representative materials in depth and show the excellent performance of the platform when synthesizing these material classes. Lastly, we discuss the design considerations as well as the hardware and software components that went into building the platform and make all of the components publicly available. KW - Self-driving laboratories KW - Materials acceleration platforms KW - Nanomaterials KW - Advanced materials KW - Automation KW - Robotics KW - In-line characterization PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-627361 DO - https://doi.org/10.1021/acsnano.4c17504 SN - 1936-086X VL - 19 IS - 9 SP - 9029 EP - 9041 PB - ACS Publications CY - Washington, DC AN - OPUS4-62736 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kossatz, Philipp A1 - Mezhov, Alexander A1 - Andresen, Elina A1 - Prinz, Carsten A1 - Schmidt, Wolfram A1 - Resch-Genger, Ute T1 - Assessing the Applicability of Lanthanide-Based Upconverting Nanoparticles for Optically Monitoring Cement Hydration and Tagging Building Materials N2 - Chemically stable, lanthanide-based photon upconversion micro- and nanoparticles (UCNPs) with their characteristic multicolor emission bands in the ultraviolet (UV), visible (vis), near-infrared (NIR), and short-wave infrared (SWIR) arepromising optical reporters and barcoding tags. To assess the applicability of UCNPs for the monitoring of early stage cement hydration processes and as authentication tags for cementitious materials, we screened the evolution of the luminescence of Selfmade core-only NaYF4:Yb,Er UCNPs and commercial μm-sized Y2O2S:Yb,Er particles during the first stages of cement hydration, which largely determines the future properties of the hardened material. Parameters explored from the UCNP side included particle size, morphology, surface chemistry or coating, luminescence properties, and concentration in different cement mixtures. From the cement side, the influence of the mineral composition of the cement matrix was representatively examined for ordinary Portland cement (OPC) and its constituents tricalcium aluminate (C3A), tricalcium silicate (C3S), and gypsum at different water to cement ratios. Based on reflection and luminescence measurements, enabling online monitoring, which were complemented by XRD and isothermal heat-flow calorimetric measurements to determine whether the incorporation of these particles could impair cement hydration processes, well suited lanthanide particle reporters could be identified as well as application conditions. In addition, thereby the reporter influence on cement hydration kinetics could be minimized while still preserving a high level of information content. The best performance for the luminescence probing of changes during early stage cement hydration processes was observed for 25 nm-sized oleate (OA)-coated UCNPs added in a concentration of 0.1 wt %. Higher UCNP amounts of 1.0 wt % delayed cement hydration processes size- and surface coatingspecifically in the first 24 h. Subsequent luminescence stability screening studies performed over a period of about one year support the applicability of UCNPs as optical authentication tags for construction materials. KW - Quality assurance KW - Fluorescence KW - Nano KW - Particle KW - Synthesis KW - Quantum yield KW - NIR KW - Mechanism KW - Characterization KW - XRD KW - Calorimetry KW - Advanced material KW - Cement KW - Monitoring KW - Surface KW - Size KW - Lifetime KW - Barcode KW - Lanthanide KW - Upconversion KW - Encoding KW - Method PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-638318 DO - https://doi.org/10.1021/acsomega.5c02236 SN - 2470-1343 VL - 10 IS - 29 SP - 31587 EP - 31599 PB - ACS Publications CY - Washington, DC AN - OPUS4-63831 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Obenlüneschloß, Jorit A1 - Boysen, Nils A1 - Rönnby, Karl A1 - Muriqi, Arbresha A1 - Hoffmann, Volker A1 - Abad Andrade, Carlos Enrique A1 - Rogalla, Detlef A1 - Brokmann, Ulrike A1 - Rädlein, Edda A1 - Nolan, Michael A1 - Devi, Anjana T1 - Ein seltener mononuklearer Lithium‐Carben‐Komplex für die Atomlagenabscheidung von lithiumhaltigen Dünnschichten N2 - KurzfassungLithium ist das zentrale Element moderner Batterietechnologien, und die Herstellung von lithiumhaltigen Materialien mittels Atomlagenabscheidung (engl. Atomic Layer Deposition, ALD) bietet erhebliche Vorteile bei der Kontrolle der Schichtdicke und ‐zusammensetzung. In dieser Studie wird ein neuer mononuklearer, durch ein N‐heterocyclisches Carben (NHC) stabilisierter Lithiumkomplex, [Li(tBuNHC)(hmds)], als vielversprechender Präkursor für die ALD von lithiumhaltigen Dünnschichten vorgestellt. Die strukturelle Charakterisierung erfolgt durch den Vergleich von Dichtefunktionaltheorie (DFT) und Einkristall‐Röntgenbeugung (engl. Single‐Crystal X‐ray Diffraction, SC‐XRD), wobei die seltene mononukleare Struktur bestätigt wird. Thermogravimetrische Analysen (TGA) zeigen vorteilhafte thermische Eigenschaften für ALD‐Anwendungen. Die Verbindung weist einen niedrigen Schmelzpunkt, saubere Verdampfung und ermutigende Volatilitätsparameter im Vergleich zu anderen Lithium‐Präkursoren auf. ALD‐Experimente mit [Li(tBuNHC)(hmds)] und Ozon zeigen dessen Effektivität bei der Abscheidung von LiSixOy‐Filmen. Der ALD‐Prozess zeigt ein gesättigtes Wachstum pro Zyklus (engl. Growth per Cycle, GPC) von 0,95 Å. Die Zusammensetzung, analysiert mittels Rutherford‐Rückstreu‐Spektrometrie/Kernreaktionsanalyse (engl. Rutherford Backscattering Spectrometry/Nuclear Reaction Analysis, RBS/NRA), Röntgenphotoelektronenspektroskopie (engl. X‐ray Photoelectron Spectroscopy, XPS) und Glimmentladungsspektroskopie (engl. Glow Discharge Optical Emission Spectrometry, GD‐OES), bestätigt das Vorhandensein von Lithium und Silizium in den erwarteten Verhältnissen. Diese Arbeit stellt nicht nur einen neuen ALD‐Präkursor vor, sondern trägt auch zum Verständnis der Lithiumchemie bei und bietet Einblicke in die faszinierende Koordinationschemie und das thermische Verhalten von durch NHC‐Liganden stabilisierten Lithiumkomplexen. KW - Atomlagenabscheidung KW - N-heterozyklischer-Carben-(NHC)-stabilisierter Lithium-Präkursor KW - Mononuklearer Li–Carben-Komplex KW - Lithiumsilicat-Dünnfilme KW - Filmanalytik/-Charakterisierung PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-644045 DO - https://doi.org/10.1002/ange.202513066 SN - 0044-8249 N1 - Es gibt eine parallele Sprachausgabe (englisch), ein Link befindet sich im Feld zugehöriger Identifikator - There is a parallel language edition (English), a link is in the field related identifier SP - 1 EP - 12 PB - Wiley-VCH CY - Weinheim AN - OPUS4-64404 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Braymer, Joseph J. A1 - Knauer, Lukas A1 - Crack, Jason C. A1 - Oltmanns, Jonathan A1 - Heghmanns, Melanie A1 - Soares, Jéssica C. A1 - Le Brun, Nick E. A1 - Schünemann, Volker A1 - Kasanmascheff, Müge T1 - Yeast [FeFe]-hydrogenase-like protein Nar1 binds a [2Fe–2S] cluster N2 - Nar1 is an essential eukaryotic protein proposed to function as an iron–sulphur (Fe/S) cluster trafficking factor in the cytosolic iron–sulphur protein assembly (CIA) machinery. However, such a role has remained unclear due to difficulties in purifying adequate amounts of cofactor-bound protein. The [FeFe]-hydrogenase-like protein has two conserved binding sites for [4Fe–4S] clusters but does not show hydrogenase activity in vivo due to the lack of an active site [2Fe]H cofactor. Here, we report a new preparation procedure for Nar1 that facilitated studies by UV-vis, EPR, and Mössbauer spectroscopies, along with native mass spectrometry. Nar1 recombinantly produced in E. coli contained a [4Fe–4S] cluster, bound presumably at site 1, along with an unexpected [2Fe–2S] cluster bound at an unknown site. Fe/S reconstitution reactions installed a second [4Fe–4S] cluster at site 2, leading to protein with up to three Fe/S cofactors. It is proposed that the [2Fe–2S] cluster occupies a cavity in Nar1 that is filled by the [2Fe]H cofactor in [FeFe]-hydrogenases. Strikingly, two of the Fe/S clusters were rapidly destroyed by molecular oxygen, linking Nar1 oxygen sensitivity in vitro to phenotypes observed previously in vivo. Our biochemical results, therefore, validate a direct link between cellular oxygen concentrations and the functioning of the CIA pathway. These advances also now allow for the pursuit of in vitro Fe/S cluster transfer assays, which will shed light on Fe/S trafficking and insertion by CIA components. KW - Biocorrosion KW - Hydrogenases KW - Metalloprotein KW - Yeast PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-649463 DO - https://doi.org/10.1039/D5SC04860E SN - 2041-6520 VL - 17 IS - 1 SP - 373 EP - 380 PB - Royal Society of Chemistry (RSC) AN - OPUS4-64946 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Bayat, Mehmet Emin A1 - Kipphardt, Heinrich A1 - Tiebe, Carlo A1 - Tuma, Dirk A1 - Engelhard, Carsten T1 - Trace-Level Ammonia–Water Interactions in Hydrogen: Challenges in Gas Purity Analysis Using Optical-Feedback Cavity-Enhanced Absorption Spectroscopy (OF-CEAS) N2 - Ammonia is a critical impurity in hydrogen fuel due to its irreversible poisoning effect on proton exchange membrane fuel cells. Therefore, international standards (e.g., ISO 14687) set a stringent threshold of 100 nmol/mol. Furthermore, with the growing potential use of ammonia as a hydrogen carrier, its accurate quantification is becoming increasingly important. However, the presence of trace humidity poses analytical challenges, as ammonia may interact with water or interfaces, thereby affecting its detectability. Therefore, the goal of this work is to enable accurate trace ammonia quantification for hydrogen purity measurements through fundamental studies of the methodological challenges. Here, low-pressure sampling (ultra)long-path Optical-Feedback Cavity-Enhanced Absorption Spectroscopy (OF-CEAS) was applied with an effective optical path length of approximately 6.17 km. We studied three average amounts of ammonia: (38.2 ± 0.8) nmol/mol, (74.8 ± 0.7) nmol/mol, and (112.1 ± 1.2) nmol/mol. Furthermore, these amounts were investigated at trace-humidity levels ranging from 0.8 to 8.5 ppmV. We observed a systematic, nonlinear, and humidity-dependent positive measurement bias of up to + (1.0 ± 0.2) nmol/mol at the maximum investigated trace-humidity volume fraction of 8.5 ppmV. This bias was not caused by spectral interference but rather by water-induced accumulation of ammonia within the optical cavity. Moreover, time-resolved measurements in the presence of trace ammonia showed that water desorption follows first-order kinetics, whereas water adsorption followed mixed-order kinetics with an apparent reaction order of 1.57 ± 0.03. Distinct hydration states of surface-bound ammonia were identified, whereas under dry conditions and with increasing amounts of ammonia, enhanced surface adhesion through intermolecular clustering was observed. In addition, the presence of ammonium species within the sorption layer was indirectly confirmed by our experiments. In conclusion, we provide a deeper insight into trace-level ammonia–water interactions and establish a framework for optimizing methodologies, particularly for (ultra)long-path optical gas measurement systems. KW - Ammonia KW - Hydrogen KW - OF-CEAS KW - Humidity KW - Surface Interactions KW - Adsorption PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-643627 DO - https://doi.org/10.1021/acsmeasuresciau.5c00105 SN - 2694-250X SP - 1 EP - 15 PB - American Chemical Society (ACS) AN - OPUS4-64362 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Rua-Ibarz, Ana A1 - Nakadi, Flávio V. A1 - Bolea-Fernandez, Eduardo A1 - Bazo, Antonio A1 - Battistella, Beatrice A1 - Matiushkina, Anna A1 - Resch-Genger, Ute A1 - Abad Andrade, Carlos Enrique A1 - Resano, Martín T1 - Discrete entity analysis via microwave-induced nitrogen plasma–mass spectrometry in single-event mode N2 - In this work, single-event microwave-induced nitrogen plasma–mass spectrometry (single-event MINP-MS) was evaluated for the first time for the analysis of discrete entities such as nanoparticles, biological cells, and microplastics. Nitrogen (N2) effectively overcomes Ar-based polyatomic interferences, enabling (ultra)trace element determination of Fe and Se using their most abundant isotopes, 56Fe (91.66%) and 80Se (49.82%). Iron oxide nanoparticles (Fe2O3 NPs) ranging from 20 to 70 nm were accurately characterized, with excellent agreement with established sizing techniques, such as transmission electron microscopy (TEM) and dynamic light scattering (DLS). A limit of detection (LoD) of 8.6 ag for Fe─equivalent to an LoDsize of 19 nm for Fe2O3─was achieved, which is significantly lower than recent values reported for high-end quadrupole-based ICP-MS. Selenium nanoparticles (SeNPs) of 150 and 250 nm were also accurately characterized, without the N2-based plasma experiencing issues handling relatively large metallic NPs (linearity, R2 = 0.9994). Se-enriched yeast cells (SELM-1 certified reference material) were successfully analyzed via single-cell MINP-MS using external calibration based on SeNPs and a transport efficiency-independent approach. In addition, 2–3 μm polystyrene (PS) and polytetrafluoroethylene (PTFE) were accurately sized by monitoring 12C+, confirming the method’s suitability for handling micrometer-sized polymeric materials (microplastics). The average duration of individual events (680 ± 160 μs) suggests that the digestion of individual entities in N2-based plasmas is comparable to that in Ar-based plasmas. These results open new avenues for this instrumentation as an alternative to ICP ionization sources, also in the context of discrete entity analysis. KW - Microwave-Induced Nitrogen Plasma KW - Discrete entity analysis KW - Particle/droplet event counting KW - Comparison to SP-ICP-MS methodologies KW - Nitrogen plasma vs. argon ICP trade-offs KW - Trace elemental quantification at the single-entity level KW - Time-resolved mass spectrometry for discrete entities PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-643825 DO - https://doi.org/10.1021/acs.analchem.5c04341 SN - 0003-2700 SP - 1 EP - 8 PB - American Chemical Society (ACS) AN - OPUS4-64382 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Morcillo, Dalia A1 - Winckelmann, Alexander A1 - Oelze, Marcus A1 - Leonhardt, Robert A1 - Schmidt, Anita A1 - Richter, Silke A1 - Recknagel, Sebastian A1 - Vogl, Jochen A1 - Panne, Ulrich A1 - Abad Andrade, Carlos Enrique T1 - Exploring Age-Induced Lithium Isotope Fractionation in Lithium-Ion Batteries using Microwave-Induced Cold Nitrogen Plasma Mass Spectrometry N2 - This study explores Microwave-Inductively Coupled Atmospheric-pressure Plasma Mass Spectrometry (MICAP-MS) as a cost-effective alternative to Multi-Collector Inductively Coupled Plasma Mass Spectrometry (MC-ICP-MS) for analyzing lithium isotopic composition in lithium-ion batteries (LIBs). We investigate the performance of MICAP-MS in measuring Li isotope ratios in new and aged commercial lithium cobalt oxide (LCO) batteries. Our results show that MICAP-MS, operating under cold plasma conditions at 800 W with an 8 mm torch position, achieves results metrologically compatible with MC-ICP-MS, with a precision ranging from 0.6‰ to 3.4‰ for δ7Li values. MICAP-MS benefits from a dielectric resonator for uniform plasma, better ion velocity control, and higher energy efficiency. Optimal settings were identified with dwell times of 10 ms for 6Li and 1 ms for 7Li. The study of LIBs revealed that 6Li migrates towards the anode over multiple charge–discharge cycles, causing 7Li to accumulate in the cathode, a fractionation effect that becomes more pronounced with prolonged cycling. MICAP-MS provides a cost-effective, precise alternative to MC-ICP-MS, with lower operational costs and enhanced portability, advancing the study of isotopic fractionation and aging in lithium-ion batteries. KW - MICAP-MS KW - Lithium KW - Battery aging KW - Lithium isotopes KW - Nitrogen plasma KW - Isotope fractionation KW - lithium cobalt oxide KW - LCO PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-643777 DO - https://doi.org/10.1039/d4ja00324a SN - 0267-9477 SP - 1 EP - 11 PB - Royal Society of Chemistry (RSC) AN - OPUS4-64377 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Abad Andrade, Carlos Enrique A1 - Jegielka, Dennis A1 - Aloysius, Allen A1 - Recknagel, Sebastian T1 - SI-traceable total analysis of nitrate and nitrite by isotope dilution optical spectroscopy and its application to Berlin surface waters N2 - Accurate nitrate and nitrite data support water-quality regulation, yet routine methods rely on external calibration and rarely achieve SI traceability. We report a calibration-free determination of nitrate and nitrite by combining isotope dilution with high-resolution continuum-source graphite furnace molecular absorption spectrometry (ID-HR-CS-GF-MAS). A 15N-enriched nitrate spike (its concentration verified by reverse isotope dilution against the standard reference material NIST 3185) provides the SI link, and it is gravimetrically added to samples; nitrate and residual nitrite are converted in situ to nitric oxide (NO), whose 215 nm band is recorded at a pixel resolution of λ/Δλ ≈ 140 000. The 0.2127 nm shift between 14NO and 15NO electronic spectra is resolved, and a three-latent-variable partial least squares regression model yields the 15N/14N ratio with 0.3% precision. Instrumental LoD values of 4.8 ng (14N) and 3.2 ng (15N) translate to a method LoD of 4.8 ng of nitrogen (equivalent to 1.05 mg L−1 NO3− for a 20 μL aliquot). The furnace program allows for successive drying/pyrolysis loops, so additional 20 μL aliquots can be layered onto the graphite platform. Alternatively, a 10 mL anion-exchange solid-phase extraction step concentrates nitrate and nitrite fivefold, allowing for the analysis of even lower sample concentrations. Results for four certified reference materials (2.9 to 1000 mg L−1 NO3−) agreed with certified values, giving relative expanded uncertainties of 2 to 4%. Analysis of twenty Berlin surface-water samples revealed concentrations ranging from 0.10 to 7.3 mg L−1 NO3−, indicating that the Panke River and Teltow Canal are the primary sources of nitrogen. ID-HR-CS-GF-MAS thus delivers ID-MS-level accuracy in a few minutes per run with bench-top optics, and, with optional on-platform or SPE pre-concentration, extends SI-traceable nitrate/nitrite monitoring into the low-ng regime. KW - Isotope dilution KW - Nitrate and nitrite determination KW - SI-traceable quantification KW - Calibration-free analysis KW - Water quality KW - Berlin surface waters KW - NO molecular absorption bands PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-643785 DO - https://doi.org/10.1039/D5JA00252D SN - 0267-9477 VL - 40 IS - 10 SP - 2692 EP - 2701 PB - Royal Society of Chemistry (RSC) AN - OPUS4-64378 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Klinge, A A1 - Mönig, J A1 - Ziegert, C A1 - Richter, Matthias A1 - Kalbe, Ute A1 - Horn, Wolfgang A1 - Röhlen, U A1 - Rauscher, S A1 - Roswag-Klinge, E T1 - upMIN 100 – upcycling of mineral construction and demolition waste to substitute natural aggregates in earthen building materials N2 - The construction sector is one of the most resource-intensive sectors in Germany and is responsible for 40 % of CO2 emissions. Around 517 million tons of mineral raw materials are required annually for the construction of buildings in Germany. At the same time, mineral construction waste was the largest material flow at 229.3 million tons (2020). The rates of construction and demolition waste (CDW) recycling have increased since 2000, especially for mineral waste. Nevertheless, the majority of recycled aggregates are used in technically largely unregulated applications (e.g. road construction). This downcycling leads to a loss of valuable resources for technically and economically valuable applications. The upMIN 100 research project is investigating the question of whether and to what extent recycled CDW is suitable as an additive an binder in earthen building materials. The focus is placed on grain sizes of < 2 mm, which are currently predominantly landfilled, as there are at present no regulations for their use in building products. The soil matrix of earthen building materials however, naturally contains of different grain sizes, whith < 2mm – 0,063 for aggregates and < 0.063 mm as a binder. Therefore, the focused grain sizes (sand, clay and silt) could have a high usage potential. In order to enable the use of CDW, the technical feasibility must be ensured, quality requirements for source materials (e.g. threshold values for pollutants in terms of health and environmental compatibility and hazardous substances) and permissible proportions of recycled aggregates must be defined. Two different building material developments (earth blocks and -plaster)were used to assess both, the technical feasibility as well the pollutant content of the recycled aggregate and its final emissions into the indoor air. For both materials two mixtures could be established, that also meet the mechanical specifications according to the DIN standard, such as the compressive strength. A method was developed to design material mixtures with a high amount of CDW that comply with the defined limit values. The mixtures reached a recycling rate of 28 % with high mechanical properties and 70 % with minimum strength requirements. KW - Mineral waste KW - Upcycling KW - Earthen building product KW - Circular construction PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-652831 DO - https://doi.org/10.1088/1755-1315/1554/1/012084 SN - 1755-1307 VL - 1554 IS - 1 SP - 1 EP - 9 PB - IOP Publishing AN - OPUS4-65283 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Tavernaro, Isabella A1 - Rajotte, Isabelle A1 - Thibeault, Marie-Pier A1 - Sander, Philipp C. A1 - Kodra, Oltion A1 - Lopinski, Gregory A1 - Radnik, Jörg A1 - Johnston, Linda J. A1 - Brinkmann, Andreas A1 - Resch-Genger, Ute T1 - Quantifying surface groups on aminated silica nanoparticles of different size, surface chemistry, and porosity with solution NMR, XPS, optical assays, and potentiometric titration N2 - We assessed the quantification of surface amino functional groups (FGs) for a large set of commercial and custom-made aminated silica nanoparticles (SiO2 NPs) with sizes of 20–100 nm, prepared with different sol–gel routes, different amounts of surface amino FGs, and different porosity with four methods providing different, yet connected measurands in a bilateral study of two laboratories, BAM and NRC, with the overall aim to develop standardizable measurements for surface FG quantification. Special emphasis was dedicated to traceable quantitative magnetic resonance spectroscopy (qNMR) performed with dissolved SiO2 NPs. For the cost efficient and automatable screening of the amount of surface amino FGs done in a first step of this study, the optical fluorescamine assay and a potentiometric titration method were utilized by one partner, i.e., BAM, yielding the amount of primary amino FGs accessible for the reaction with a dye precursor and the total amount of (de)protonatable FGs. These measurements, which give estimates of the minimum and maximum number of surface amino FGs, laid the basis for quantifying the amount of amino silane molecules with chemo-selective qNMR with stepwise fine-tuned workflows, involving centrifugation, drying, weighting, dissolution, measurement, and data evaluation steps jointly performed by BAM and NRC. Data comparability and relative standard deviations (RSDs) obtained by both labs were used as quality measures for method optimization and as prerequisites to identify method-inherent limitations to be later considered for standardized measurement protocols. Additionally, the nitrogen (N) to silicon (Si) ratio in the near-surface region of the SiO2 NPs was determined by both labs using X-ray photoelectron spectroscopy (XPS), a well established surface sensitive analytical method increasingly utilized for microparticles and nano-objects which is currently also in the focus of international standardization activities. Overall, our results underline the importance of multi-method characterization studies for quantifying FGs on NMs involving at least two expert laboratories for effectively identifying sources of uncertainty, validating analytical methods, and deriving NM structure–property relationships. KW - Advanced Materials KW - Amino Groups KW - Calibration KW - Characterization KW - Functional groups KW - Method Comparison KW - Nano Particle KW - Validation KW - XPS KW - Optical Assay KW - Quantification KW - Surface Analysis KW - Reference Materials KW - Synthesis KW - Fluorescence PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-649992 DO - https://doi.org/10.1039/d5na00794a VL - 7 IS - 21 SP - 6888 EP - 6900 PB - Royal Society of Chemistry AN - OPUS4-64999 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Schusterbauer, Robert A1 - Schünemann, Pia A1 - Nickl, Philip A1 - Er, Jasmin A1 - Kämmer, Victoria A1 - Junge, Florian A1 - Fazzani, Salim A1 - Mrkwitschka, Paul A1 - Meermann, Björn A1 - Haag, Rainer A1 - Donskyi, Ievgen T1 - Bifunctional Reduced Graphene Oxide Derivatives for PFOA Adsorption N2 - Innovative materials are crucial for removing persistent pollutants per‐ and polyfluorinated alkyl substances (PFAS) from water. Here, a novel bifunctional reduced graphene oxide (TRGO) adsorbent is developed and characterized by advanced surface sensitive methods. Compared to pristine TRGO, the functionalized TRGO shows markedly improved PFAS removal efficiency and demonstrates strong potential for water purification applications. KW - Adsorber KW - PFAS KW - HR-CS-GFMAS PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-651238 DO - https://doi.org/10.1002/ceur.202500240 SN - 2751-4765 SP - 1 EP - 7 PB - Wiley VHC-Verlag AN - OPUS4-65123 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Mangarova, Dilyana B. A1 - Kaufmann, Jan Ole A1 - Brangsch, Julia A1 - Kader, Avan A1 - Möckel, Jana A1 - Heyl, Jennifer L. A1 - Verlemann, Christine A1 - Adams, Lisa C. A1 - Ludwig, Antje A1 - Reimann, Carolin A1 - Poller, Wolfram C. A1 - Niehaus, Peter A1 - Karst, Uwe A1 - Taupitz, Matthias A1 - Hamm, Bernd A1 - Weller, Michael G. A1 - Makowski, Marcus R. T1 - ADAMTS4-Specific MR Peptide Probe for the Assessment of Atherosclerotic Plaque Burden in a Mouse Model N2 - Introduction Atherosclerosis is the underlying cause of multiple cardiovascular pathologies. The present-day clinical imaging modalities do not offer sufficient information on plaque composition or rupture risk. A disintegrin and metalloproteinase with thrombospondin motifs 4 (ADAMTS4) is a strongly upregulated proteoglycan-cleaving enzyme that is specific to cardiovascular diseases, inter alia, atherosclerosis. Materials and Methods Male apolipoprotein E-deficient mice received a high-fat diet for 2 (n = 11) or 4 months (n = 11). Additionally, a group (n = 11) receiving pravastatin by drinking water for 4 months alongside the high-fat diet was examined. The control group (n = 10) consisted of C57BL/6J mice on standard chow. Molecular magnetic resonance imaging was performed prior to and after administration of the gadolinium (Gd)-based ADAMTS4-specific probe, followed by ex vivo analyses of the aortic arch, brachiocephalic arteries, and carotid arteries. A P value <0.05 was considered to indicate a statistically significant difference. Results With advancing atherosclerosis, a significant increase in the contrast-to-noise ratio was measured after intravenous application of the probe (mean precontrast = 2.25; mean postcontrast = 11.47, P < 0.001 in the 4-month group). The pravastatin group presented decreased ADAMTS4 expression. A strong correlation between ADAMTS4 content measured via immunofluorescence staining and an increase in the contrast-to-noise ratio was detected (R2 = 0.69). Microdissection analysis revealed that ADAMTS4 gene expression in the plaque area was significantly greater than that in the arterial wall of a control mouse (P < 0.001). Laser ablation–inductively coupled plasma–mass spectrometry confirmed strong colocalization of areas positive for ADAMTS4 and Gd. Conclusions Magnetic resonance imaging using an ADAMTS4-specific agent is a promising method for characterizing atherosclerotic plaques and could improve plaque assessment in the diagnosis and treatment of atherosclerosis. N2 - Einleitung Atherosklerose ist die Ursache für zahlreiche Herz-Kreislauf-Erkrankungen. Die derzeitigen klinischen Bildgebungsverfahren liefern keine ausreichenden Informationen über die Zusammensetzung von Plaques oder das Risiko einer Ruptur. A Disintegrin and Metalloproteinase with Thrombospondin Motifs 4 (ADAMTS4) ist ein stark hochreguliertes Proteoglykan-spaltendes Enzym, das unter anderem bei Herz-Kreislauf-Erkrankungen wie Atherosklerose spezifisch auftritt. Materialien und Methoden Männliche Apolipoprotein-E-defiziente Mäuse erhielten 2 (n = 11) oder 4 Monate lang (n = 11) eine fettreiche Ernährung. Zusätzlich wurde eine Gruppe (n = 11) untersucht, die 4 Monate lang neben der fettreichen Ernährung Pravastatin über das Trinkwasser erhielt. Die Kontrollgruppe (n = 10) bestand aus C57BL/6J-Mäusen, die mit Standardfutter ernährt wurden. Vor und nach der Verabreichung der gadolinium (Gd)-basierten ADAMTS4-spezifischen Sonde wurde eine molekulare Magnetresonanztomographie durchgeführt, gefolgt von Ex-vivo-Analysen des Aortenbogens, der Arteria brachiocephalica und der Arteria carotis. Ein P-Wert < 0,05 wurde als statistisch signifikanter Unterschied gewertet. Ergebnisse Mit fortschreitender Atherosklerose wurde nach intravenöser Anwendung der Sonde ein signifikanter Anstieg des Kontrast-Rausch-Verhältnisses gemessen (Mittelwert vor Kontrastmittelgabe = 2,25; Mittelwert nach Kontrastmittelgabe = 11,47, P < 0,001 in der 4-Monats-Gruppe). Die Pravastatin-Gruppe zeigte eine verminderte ADAMTS4-Expression. Es wurde eine starke Korrelation zwischen dem mittels Immunfluoreszenzfärbung gemessenen ADAMTS4-Gehalt und einem Anstieg des Kontrast-Rausch-Verhältnisses festgestellt (R2 = 0,69). Die Mikrodissektionsanalyse ergab, dass die ADAMTS4-Genexpression im Plaque-Bereich signifikant höher war als in der Arterienwand einer Kontrollmaus (P < 0,001). Laserablation-induktiv gekoppelte Plasma-Massenspektrometrie bestätigte eine starke Kolokalisierung von ADAMTS4- und Gd-positiven Bereichen. Schlussfolgerungen Die Magnetresonanztomographie mit einem ADAMTS4-spezifischen Kontrastmittel ist eine vielversprechende Methode zur Charakterisierung atherosklerotischer Plaques und könnte die Plaquebewertung in der Diagnose und Behandlung von Atherosklerose verbessern. KW - Peptide Aptamer KW - MRI Probe KW - Magnetic resonance imaging (MRI) KW - Peptide libraries KW - Laser ablation–inductively coupled plasma–mass spectrometry KW - ICP MS KW - Imaging PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-635832 DO - https://doi.org/10.1097/RLI.0000000000001152 SN - 1536-0210 VL - 60 IS - 8 SP - 499 EP - 507 PB - Ovid Technologies (Wolters Kluwer Health) CY - Philadelphia, Pennsylvania, USA AN - OPUS4-63583 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Döring, Sarah A1 - Konthur, Zoltán A1 - Weller, Michael G. A1 - Jaeger, Carsten A1 - Reinders, Yvonne T1 - Challenges and Insights in Absolute Quantification of Recombinant Therapeutic Antibodies by Mass Spectrometry: An Introductory Review N2 - This review describes mass spectrometry (MS)-based approaches for the absolute quantification of therapeutic monoclonal antibodies (mAbs), focusing on technical challenges in sample treatment and calibration. Therapeutic mAbs are crucial for treating cancer and inflammatory, infectious, and autoimmune diseases. We trace their development from hybridoma technology and the first murine mAbs in 1975 to today’s chimeric and fully human mAbs. With increasing commercial relevance, the absolute quantification of mAbs, traceable to an international standard system of units (SI units), has attracted attention from science, industry, and national metrology institutes (NMIs). Quantification of proteotypic peptides after enzymatic digestion using high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) has emerged as the most viable strategy, though methods targeting intact mAbs are still being explored. We review peptide-based quantification, focusing on critical experimental steps like denaturation, reduction, alkylation, choice of digestion enzyme, and selection of signature peptides. Challenges in amino acid analysis (AAA) for quantifying pure mAbs and peptide calibrators, along with software tools for targeted MS data analysis, are also discussed. Short explanations within each chapter provide newcomers with an overview of the field’s challenges. We conclude that, despite recent progress, further efforts are needed to overcome the many technical hurdles along the quantification workflow and discuss the prospects of developing standardized protocols and certified reference materials (CRMs) for this goal. We also suggest future applications of newer technologies for absolute mAb quantification. KW - Monoclonal antibody KW - Therapeutic antibodies KW - Mass spectrometry KW - Liquid chromatography KW - Absolute quantification KW - Metrology KW - Traceability KW - Certified reference material PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-623707 DO - https://doi.org/10.3390/antib14010003 SN - 2073-4468 VL - 14 IS - 1 SP - 1 EP - 26 PB - MDPI CY - Basel, Schweiz AN - OPUS4-62370 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Bosc-Bierne, Gaby A1 - Weller, Michael G. T1 - Investigation of impurities in peptide pools T1 - Untersuchung von Verunreinigungen in Peptidpools N2 - Peptide pools are important research tools in different biomedical fields. They consist of a complex mixture of defined peptides, which places high demands on the production and quality control of these products. Previously it has been shown that the combination of UHPLC with high-resolution mass-spectrometry (HRMS) is a fast and powerful method to confirm the relative concentration and the structural identity of all peptides expected to be in the pool. In this work, the additional information contained in the UV chromatograms and mass spectra is used to search for impurities due to synthesis by-products and degradation during storage and transportation and to identify possible analytical artifacts. It was shown that most impurities are only present in trace amounts and can be considered uncritical for most applications. The most frequent and perhaps unexpected impurities were homo- and heterodimers caused by the free cysteines contained in these peptide pools. Furthermore, pyroglutamate and aspartimide formation, deamidation, methionine oxidation, and amino acid deletions could be found. This list is not intended to be comprehensive, but rather a brief guide to quickly identify impurities and, in the long term, to suggest possible changes in the composition of the peptide pools to avoid such impurities by design or by special precautions. N2 - Peptidpools sind wichtige Forschungsinstrumente in verschiedenen biomedizinischen Bereichen. Sie bestehen aus einer komplexen Mischung definierter Peptide, was hohe Anforderungen an die Herstellung und Qualitätskontrolle dieser Produkte stellt. In der Vergangenheit wurde gezeigt, dass die Kombination von UHPLC mit hochauflösender Massenspektrometrie (HRMS) eine schnelle und leistungsfähige Methode zur Bestätigung der relativen Konzentration und der strukturellen Identität aller Peptide ist, die in dem Pool erwartet werden. In dieser Arbeit werden die zusätzlichen Informationen, die in den UV-Chromatogrammen und Massenspektren enthalten sind, genutzt, um nach Verunreinigungen zu suchen, die auf Nebenprodukte der Synthese und den Abbau während der Lagerung und des Transports zurückzuführen sind, und um mögliche analytische Artefakte zu identifizieren. Es hat sich gezeigt, dass die meisten Verunreinigungen nur in Spuren vorhanden sind und für die meisten Anwendungen als unkritisch angesehen werden können. Die häufigsten und vielleicht unerwartetsten Verunreinigungen waren Homo- und Heterodimere, die durch die in diesen Peptidpools enthaltenen freien Cysteine verursacht werden. Außerdem wurden Pyroglutamat- und Aspartimidbildung, Deamidierung, Methioninoxidation und Aminosäuredeletionen festgestellt. Diese Liste erhebt keinen Anspruch auf Vollständigkeit, sondern ist eher ein kurzer Leitfaden, um Verunreinigungen schnell zu identifizieren und langfristig mögliche Änderungen in der Zusammensetzung der Peptidpools vorzuschlagen, um solche Verunreinigungen durch Design oder besondere Vorsichtsmaßnahmen zu vermeiden. KW - Synthetic peptides KW - Degradation KW - Synthetic artifacts KW - Peptide losses KW - Stability of peptides KW - Disulfide dimers KW - Cysteine dimers KW - Isomers KW - Cysteine alkylation PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-626987 DO - https://doi.org/10.3390/separations12020036 SN - 2297-8739 VL - 12 IS - 2 SP - 1 EP - 18 PB - MDPI AG CY - Basel AN - OPUS4-62698 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Döring, Sarah A1 - Tscheuschner, Georg A1 - Flemig, Sabine A1 - Weller, Michael G. A1 - Konthur, Zoltán T1 - Cost-Effective Method for Full-Length Sequencing of Monoclonal Antibodies from Hybridoma Cells N2 - Background: Monoclonal antibodies play an important role in therapeutic and analytical applications. For recombinant expression, the coding sequences of the variable regions of the heavy and light chains are required. In addition, cloning antibody sequences, including constant regions, reduces the impact of hybridoma cell loss and ensures preservation of the naturally occurring full antibody sequence. Method: We combined amplification of IgG antibody variable regions from hybridoma mRNA with an advanced method for fulllength cloning of monoclonal antibodies in a simple two-step workflow. Following Sanger sequencing and evaluation of consensus sequences, the best matching variable, diversity, and joining (V-(D-)J) gene segments were identified according to identity scores from IgBLAST reference sequences. Simultaneously, the mouse IgG subclass was determined at the DNA level based on isotype-specific sequence patterns in the CH1 domain. Knowing the DNA sequence of V-(D-)J recombination responsible for the complementary determining region 3 (CDR 3), variable region-specific primers were designed and used to amplify the corresponding antibody constant regions. Results: To verify the approach, we applied it to the hybridoma clone BAM-CCMV-29-81 and obtained identical full-length antibody sequences as with RNA Illumina sequencing. Further validation at the protein level using an established MALDI-TOF MS-fingerprinting protocol showed that five out of six genetically encoded CDR domains of the monoclonal antibody BAM-CCMV-29-81 could be efficiently correlated. Conclusion: This simple, streamlined method enables the cost-effective determination of the full-length sequence of monoclonal antibodies from hybridoma cell lines, with the added benefit of obtaining the DNA sequence of the antibody ready for recombinant expression. KW - Full-length antibody sequencing KW - Hybridoma cell loss KW - MALDI-TOF MS KW - Immunoglobulin isotyping KW - RNA Illumina sequencing PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-639599 DO - https://doi.org/10.3390/antib14030072 SN - 2073-4468 VL - 14 IS - 3 SP - 1 EP - 17 PB - MDPI CY - Basel AN - OPUS4-63959 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - GEN A1 - Döring, Sarah T1 - Corundum Particles as Trypsin Carrier for Efficient Protein Digestion N2 - This dataset contains raw LC–MS/MS files of trypsin-digested NISTmAb acquired on a SCIEX TripleTOF 6600 mass spectrometer in DIA (SWATH) mode for antibody quantification. In addition, it includes MALDI-TOF MS peptide mass fingerprints of trypsin-digested Herceptin as well as reference spectra that can be used for antibody identification using the open-source software ABID 2.0 (https://bam.de/ABID). The data were generated within a study demonstrating the applicability of corundum-immobilized trypsin for antibody digestion and its suitability for peptide-based LC–MS/MS quantification and MALDI-TOF MS fingerprinting–based antibody identification. KW - NISTmAb KW - Herceptin KW - MALDI-TOF MS peptide mass fingerprint KW - ABID 2.0 PY - 2025 DO - https://doi.org/10.5281/zenodo.17416536 PB - Zenodo CY - Geneva AN - OPUS4-65365 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Starkholm, A. A1 - Al-Sabbagh, Dominik A1 - Sarisozen, S A1 - von Reppert, A A1 - Rössle, M A1 - Ostermann, Markus A1 - Unger, E A1 - Emmerling, Franziska A1 - Kloo, L A1 - Svensson, P A1 - Lang, F A1 - Maslyanchuk, O. T1 - Green Fabrication of Sulfonium-Containing Bismuth Materials for High-Sensitivity X-Ray Detection N2 - Organic–inorganic hybrid materials based on lead and bismuth have recently been proposed as novel X- and gamma-ray detectors for medical imaging, non-destructive testing, and security, due to their high atomic numbers and facile preparation compared to traditional materials like amorphous selenium and Cd(Zn)Te. However, challenges related to device operation, excessively high dark currents, and long-term stability have delayed commercialization. Here, two novel semiconductors incorporating stable sulfonium cations are presented, [(CH3CH2)3S]6Bi8I30 and [(CH3CH2)3S]AgBiI5, synthesized via solvent-free ball milling and fabricated into dense polycrystalline pellets using cold isostatic compression, two techniques that can easily be upscaled, for X-ray detection application. The fabricated detectors exhibit exceptional sensitivities (14 100–15 190 µC Gyair−1 cm−2) and low detection limits (90 nGyair s−1 for [(CH3CH2)3S]6Bi8I30 and 78 nGyair s−1 for [(CH3CH2)3S]AgBiI5), far surpassing current commercial detectors. Notably, they maintain performance after 9 months of ambient storage. The findings highlight [(CH3CH2)3S]6Bi8I30 and [(CH3CH2)3S]AgBiI5 as scalable, cost-effective and highly stable alternatives to traditional semiconductor materials, offering great potential as X-ray detectors in medical and security applications. KW - Mechanochemistry KW - X-ray detectors PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-630306 DO - https://doi.org/10.1002/adma.202418626 SP - 1 EP - 10 PB - Wiley VHC-Verlag AN - OPUS4-63030 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Temgoua, Ranil C.T. A1 - Dontsi, Fabiola T. A1 - Lebègue, Estelle A1 - Thobie-Gautier, Christine A1 - Tonlé, Ignas K. A1 - Boujtita, Mohammed T1 - Understanding the behavior of phenylurazole-tyrosine-click electrochemical reaction using hybrid electroanalytical techniques N2 - In this work, the electrochemical behavior of 4-phenylurazole (Ph-Ur) was studied and the latter was used as a molecular anchor for the electrochemical bioconjugation of tyrosine (Y). Cyclic voltammetry (CV) and controlled potential coulometry (CPC) allowed the in-situ generation of the PTAD (4-phenyl-3 H-1,2,4-triazole-3,5(4 H)-dione) species from phenylurazole on demand for tyrosine electrolabeling. The chemoselectivity of the reaction was studied with another amino acid (lysine, Lys) and no changes in Lys were observed. To evaluate the performance of tyrosine electrolabeling, coulometric analyses at controlled potentials were performed on solutions of phenylurazole and the phenylurazole-tyrosine mixture in different proportions (2:1, 1:1, and 1:2). The electrolysis of the phenylurazole-tyrosine mixture in the ratio (1:2) produced a charge of 2.07 C, very close to the theoretical value (1.93 C), with high reaction kinetics, a result obtained here for the first time. The products obtained were identified and characterized by liquid chromatography coupled to high-resolution electrospray ionization mass spectrometry (LC-HRMS and LC- HRMS2). Two products were formed from the click reactions, one of which was the majority. Another part of this work was to study the electrochemical degradation of the molecular anchor 4-phenylazole (Ph-Ur). Four stable degradation products of phenylurazole were identified (C7H9N2O, C6H8N, C6H8NO, C14H13N4O2) based on chromatographic profiles and mass spectrometry results. The charge generated during the electrolysis of phenylurazole (two-electron process) (2.85 C) is inconsistent with the theoretical or calculated charge (1.93 C), indicating that secondary/parasitic reactions occurred during the electrolysis of the latter. In conclusion, the electrochemically promoted click phenylurazole-tyrosine reactions give rise to click products with high reaction kinetics and yields in the (1:2) phenylurazole-tyrosine ratios, and the presence of side reactions is likely to affect the yield of the click phenylurazole-tyrosine reaction. KW - Clinical Biochemistry KW - Spectroscopy KW - Drug Discovery KW - Pharmaceutical Science KW - Analytical Chemistry PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-599267 DO - https://doi.org/10.1016/j.jpba.2024.116147 VL - 245 SP - 1 EP - 8 PB - Elsevier BV AN - OPUS4-59926 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - von Törne, Wipert Jannik A1 - Steinhäuser, Lorin A1 - Klyk-Seitz, Urszula-Anna A1 - Piechotta, Christian T1 - High-resolution mass spectrometric elucidation of electron ionization induced fragmentation pathways of methylated warfarin and selected hydroxylated species N2 - The plant secondary metabolite families of coumarin and 4-hydroxy coumarin have a broad pharmacological spectrum ranging from antibacterial to anticancer properties. One prominent member of this substance class is the synthetic but naturally inspired anticoagulant drug and rodenticide warfarin (coumadin). A vast number of publications focus on the identification of warfarin and its major cytochrome P450-mediated phase I metabolites by liquid chromatography (LC) with mass spectrometry (MS) and tandem mass spectrometric (MS/MS) detection techniques. For the first time, electron ionization (EI) induced high-resolution quadrupole time-of-flight mass spectrometric (HR-qToF-MS) data of in-liner derivatized warfarin and selected hydroxylated species is provided in this study as an alternative to LC-MS/MS approaches. Furthermore, the characteristic fragments and fragmentation pathways of the analyzed methyl ethers are concluded. The obtained data of analytical standards, specific deuterated and 13C-labeled compounds prove inductive cleavage of the acyl or acetonyl side chain, methyl migration, and H-migration, along with consequential inductive cleavage as predominant fragmentation routes. Based on the HR-spectral data, commonalities and differences between the analyzed compounds and fragment groups were evaluated with future applicability in structure elucidation and spectra prediction of related compounds. KW - High-resolution mass spectrometry KW - Warfarin KW - Hydroxy warfarin KW - Fragmentation pathway PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-596025 DO - https://doi.org/10.1016/j.ijms.2024.117220 SN - 1387-3806 VL - 499 SP - 1 EP - 7 PB - Elsevier B.V. AN - OPUS4-59602 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - von Törne, Wipert Jannik A1 - Klyk-Seitz, Urszula-Anna A1 - Piechotta, Christian T1 - Developing a GC-EI-MS/MS method for quantifying warfarin and five hydroxylated metabolites generated by the Fenton reaction N2 - AbstractSince the 1950s, Warfarin has been used globally as both a prescription drug and a rodenticide. Research has shown that warfarin and other rodenticides are present in the environment and food chain. However, emerging contaminants are subject to degradation by biotic and abiotic processes and advanced oxidation processes. In some cases, detecting the parent compound may not be possible due to the formation of structurally changed species. This approach aims to identify hydroxylated transformation products of warfarin in a laboratory setting, even after the parent compound has undergone degradation. Therefore, the Fenton reaction is utilized to insert hydroxylation into the parent compound, warfarin, by hydroxyl and hydroperoxyl radicals generated by Fe2+/Fe3+ redox reaction with hydrogen peroxide. Using multiple reaction monitoring, a GC–MS/MS method, incorporating isotopically labeled reference compounds, is used to quantify the expected derivatized species. The analytes are derivatized using trimethyl-3-trifluoromethyl phenyl ammonium hydroxide, and the derivatization yield of warfarin is determined by using isotopically labeled reference compounds. The method has a linear working range of 30 to 1800 ng/mL, with detection limits ranging from 18.7 to 67.0 ng/mL. The analytes are enriched using a C18-SPE step, and the recovery for each compound is calculated. The Fenton reaction generates all preselected hydroxylated transformation products of warfarin. The method successfully identifies that 4′-Me-O-WAR forms preferentially under the specified experimental conditions. By further optimizing the SPE clean-up procedures, this GC–MS-based method will be suitable for detecting transformation products in more complex matrices, such as environmental water samples. Overall, this study provides a better understanding of warfarin’s degradation and offers a robust analytical tool for investigating its transformation products. KW - Health, Toxicology and Mutagenesis KW - Pollution KW - Environmental Chemistry KW - General Medicine PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-595737 DO - https://doi.org/10.1007/s11356-024-32133-3 SN - 0944-1344 VL - 31 SP - 16986 EP - 16994 PB - Springer Science and Business Media LLC AN - OPUS4-59573 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kornev, Roman A1 - Gornushkin, Igor B. A1 - Shabarova, Lubov A1 - Kadomtseva, Alena A1 - Mochalov, Georgy A1 - Rekunov, Nikita A1 - Romanov, Sergey A1 - Medov, Vitaly A1 - Belousova, Darya A1 - Maleev, Nikita T1 - Plasma-Chemical Disposal of Silicon and Germanium Tetrachlorides Waste by Hydrogen Reduction N2 - The processes of hydrogen reduction of silicon and germanium chlorides under the conditions of high-frequency (40.68 MHz) counteracted arc discharge stabilized between two rod electrodes are investigated. The main gas-phase and solid products of plasma-chemical transformations are determined. Thermodynamic analysis of SiCl4 + H2 and GeCl4 + H2 systems for optimal process parameters was carried out. Using the example of hydrogen reduction of SiCl4 by the method of numerical modeling, gas-dynamic and thermal processes for this type of discharge are investigated. The impurity composition of gas-phase and solid reaction products is investigated. The possibility of single-stage production of high-purity Si and Ge mainly in the form of compact ingots, as well as high-purity chlorosilanes and trichlorogermane, is shown. KW - High-frequency arc discharge KW - Hydrogen reduction KW - Silicon chlorides KW - Germanium chlorides PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-594454 DO - https://doi.org/10.3390/sci6010001 VL - 6 IS - 1 SP - 1 EP - 12 PB - MDPI AG AN - OPUS4-59445 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Flierl, Lukas A1 - Rienitz, Olaf A1 - Vogl, Jochen A1 - Pramann, Axel T1 - An advancement of the gravimetric isotope mixture method rendering the knowledge of the spike purity superfluous N2 - The gravimetric isotope mixture method is the primary method to determine absolute isotope ratios. This method, however, depends on the existence of suitable spike materials and knowledge of their purities. Determining the purity of the spikes can be tedious and labour-intensive. In this publication, an advancement of the gravimetric isotope mixture method, rendering the determination of the purity of the spike materials unnecessary, is presented. The advancement combines mass spectrometry and ion chromatography leading to an approach being independent of the purity of the spike materials. In the manuscript the mathematical background and the basic idea of the novel approach are described using a two-isotope system like copper or lithium. KW - Isotope amount ratios KW - Metrology KW - Mass spectrometry KW - Ion chromatography PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-608726 DO - https://doi.org/10.1007/s00216-024-05465-9 SP - 5325 EP - 5333 PB - Springer Science and Business Media LLC AN - OPUS4-60872 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Wegner, Karl David A1 - Hildebrandt, N. T1 - Near infrared quantum dots for biosensing and bioimaging N2 - Quantum dots (QDs) possess unique optoelectronic properties, which make them very attractive to be used as optical probes in biosensing and bioimaging applications. The strong absorbance and light scattering of biological compounds like tissue and blood in the visible range pose a problem. However, if optical probes emitting in the near-infrared (NIR) range are used, scattering, absorption, and autofluorescence of biological components are strongly reduced. This allows for an increased light penetration depth and higher spatial and temporal resolution for the investigation of biological processes. The synthesis and application of NIR emitting QDs is a fast-growing research field and the benefits of using QDs were demonstrated for a variety of applications, such as photoelectrochemical biosensor, in vivo vascular imaging, and fluorescence-guided surgery. This article reviews the state-of-the-art developments in the preparation of NIR/IR QDs and highlights the latest research about their utilization in biosensing and bioimaging applications. KW - Quantum dots KW - Near-infrared KW - Biosensing KW - Bioimaging KW - NIR-II / SWIR KW - Advanced nanomaterials PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-609708 SN - 0165-9936 DO - https://doi.org/10.1016/j.trac.2024.117922 VL - 180 SP - 1 EP - 19 PB - Elsevier B.V. AN - OPUS4-60970 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Chronakis, Michail Ioannis A1 - Meermann, Björn A1 - von der Au, Marcus T1 - The evolution of data treatment tools in single-particle and single-cell ICP-MS analytics N2 - Single-particle inductively coupled plasma-mass spectrometry (sp-ICP-MS) is one of the most powerful tools in the thriving field of nanomaterial analysis. Along the same lines, single-cell ICP-MS (sc-ICP-MS) has become an invaluable tool in the study of the variances of cell populations down to a per-cell basis. Their importance and application fields have been listed numerous times, across various reports and reviews. However, not enough attention has been paid to the immense and ongoing development of the tools that are currently available to the analytical community for the acquisition, and more importantly, the treatment of single-particle and single-cell-related data. Due to the ever-increasing demands of modern research, the efficient and dependable treatment of the data has become more important than ever. In addition, the field of single-particle and single-cell analysis suffers due to a large number of approaches for the generated data—with varying levels of specificity and applicability. As a result, finding the appropriate tool or approach, or even comparing results, can be challenging. This article will attempt to bridge these gaps, by covering the evolution and current state of the tools at the disposal of sp-ICP-MS users. Graphical Abstract KW - Trend Article KW - spICP-MS KW - Data Tools KW - scICP-MS PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-610539 DO - https://doi.org/10.1007/s00216-024-05513-4 SP - 1 EP - 7 PB - Springer Science and Business Media LLC AN - OPUS4-61053 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Breuninger, Esther S. A1 - Tolu, Julie A1 - Aemisegger, Franziska A1 - Thurnherr, Iris A1 - Bouchet, Sylvain A1 - Mestrot, Adrien A1 - Ossola, Rachele A1 - McNeill, Kristopher A1 - Tukhmetova, Dariya A1 - Vogl, Jochen A1 - Meermann, Björn A1 - Sonke, Jeroen E. A1 - Winkel, Lenny H. E. T1 - Marine and terrestrial contributions to atmospheric deposition fluxes of methylated arsenic species N2 - Arsenic, a toxic element from both anthropogenic and natural sources, reaches surface environments through atmospheric cycling and dry and wet deposition. Biomethylation volatilizes arsenic into the atmosphere and deposition cycles it back to the surface, affecting soil-plant systems. Chemical speciation of deposited arsenic is important for understanding further processing in soils and bioavailability. However, the range of atmospheric transport and source signature of arsenic species remain understudied. Here we report significant levels ofmethylated arsenic in precipitation, cloudwater and aerosols collected under free tropospheric conditions at Pic du Midi Observatory (France) indicating long-range transport, which is crucial for atmospheric budgets. Through chemical analyses andmoisture source diagnostics, we identify terrestrial and marine sources for distinct arsenic species. Estimated atmospheric deposition fluxes of methylated arsenic are similar to reported methylation rates in soils, highlighting atmospheric deposition as a significant, overlooked source of potentially bioavailable methylated arsenic species impacting plant uptake in soils. KW - Arsenic KW - Speciation KW - Fluxes KW - Marine KW - Terrestrial KW - Sulfur isotopes PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-615551 DO - https://doi.org/10.1038/s41467-024-53974-z SN - 2041-1723 VL - 15 IS - 1 SP - 1 EP - 13 PB - Springer Science and Business Media LLC AN - OPUS4-61555 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Zweigle, J. A1 - Schmidt, A. A1 - Bugsel, B. A1 - Vogel, Christian A1 - Simon, Fabian A1 - Zwiener, C. T1 - Perfluoroalkyl acid precursor or weakly fluorinated organic compound? A proof of concept for oxidative fractionation of PFAS and organofluorines N2 - Organofluorine mass balance approaches are increasingly applied to investigate the occurrence of per- and polyfluoroalkyl substances (PFAS) and other organofluorines in environmental samples more comprehensively. Usually, complex samples prevent the identification and quantification of every fluorine-containing molecule. Consequently, large unidentified fractions between fluorine sum parameters such as extractable organic fluorine (EOF) and the sum of quantified analytes are frequently reported. We propose using oxidative conversion to separate (unidentified) weakly fluorinated compounds (e.g., pesticides, pharmaceuticals) from PFAA-precursors (perfluoroalkyl chain lengths ≥ C6). We show with three organofluorine model substances (flufenamic acid, diflufenican, pantoprazole) that CF3-groups or aromatic fluorine can be quantitatively converted to inorganic fluoride and trifluoroacetic acid (TFA) by applying PhotoTOP oxidation (UV/TiO2). The principle of fluorine separation in mixtures is demonstrated by the oxidation of the three weakly fluorinated compounds together with the PFAA-precursor 6:2/6:2 fluorotelomer mercaptoalkyl phosphate diester (FTMAP). After oxidation, the products F− and TFA were separated from PFCAs ( C4) by SPE, and the fractions were analyzed individually. Closed mass balances both with and without the addition of organic matrix were achieved. Eventually, the fluorine balance was verified by total fluorine measurements with combustion ion chromatography (CIC). The proposed methods should be considered a proof of concept to potentially explain unidentified fractions of the EOF, especially if compounds with low fluorine content such as pesticides, pharmaceuticals, and their transformation products contribute largely to the EOF. Future studies are needed to show the applicability to the complexity of environmental samples. Graphical Abstract KW - Combustion Ion Chromatography KW - Per- and Polyfluoroalkyl substances (PFAS) PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-613429 DO - https://doi.org/10.1007/s00216-024-05590-5 SP - 1 EP - 10 PB - Springer Science and Business Media LLC AN - OPUS4-61342 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - D'Agostino, Giancarlo A1 - Oelze, Marcus A1 - Vogl, Jochen A1 - Ghestem, Jean-Philippe A1 - Lafaurie, Nicolas A1 - Klein, Ole A1 - Pröfrock, Daniel A1 - Di Luzio, Marco A1 - Bergamaschi, Luigi A1 - Jaćimović, Radojko A1 - Oster, Caroline A1 - Irrgeher, Johanna A1 - Lancaster, Shaun T. A1 - Walch, Anna A1 - Röthke, Anita A1 - Michaliszyn, Lena A1 - Pramann, Axel A1 - Rienitz, Olaf A1 - Sara-Aho, Timo A1 - Cankur, Oktay A1 - Kutan, Derya A1 - Noireaux, Johanna T1 - Development and application of reference and routine analytical methods providing SI-traceable results for the determination of technology-critical elements in PCB from WEEE N2 - The recovery and reprocessing of technology-critical elements (TCE) present in printed circuit boards (PCB) from electrical and electronic waste is essential both for recycling valuable materials subject to supply risk and for reducing the environmental impact. Although the quantitative knowledge of TCE amounts in endof- life PCB plays a key role, there are neither matrix certified reference materials nor harmonized analytical methods available to establish the traceability of the results to the International System of Units. To fill these gaps, we developed and applied five reference analytical methods based on ICP-MS standard addition calibrations and INAA k0- and relative calibrations suitable to certify reference materials. In addition, we developed and tested six analytical methods based on more commonly used ICP-MS external standard calibrations to provide industry with routine analysis methods. Twenty TCE (Ag, Au, Co, Cu, Dy, Ga, Gd, Ge, In, La, Li, Nd, Ni, Pd, Pr, Pt, Rh, Sm, Ta and Ti) were selected as target analytes and a batch of powdered PCB was used as measurement material. An overall mutual agreement was observed among data collected by reference methods at a few percent relative uncertainty levels. Moreover, all but one of the methods developed for routine analysis demonstrated their suitability in industrial applications by producing data within ± 20% of the values established with reference methods. KW - Technology critical elements KW - Electronic waste KW - Printed circuit boards KW - Traceability KW - Uncertainty PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-612416 DO - https://doi.org/10.1039/d4ja00235k SN - 1364-5544 VL - 39 IS - 11 SP - 2809 EP - 2823 PB - Royal Society of Chemistry (RSC) AN - OPUS4-61241 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Lancaster, Shaun T. A1 - Sahlin, Eskil A1 - Oelze, Marcus A1 - Ostermann, Markus A1 - Vogl, Jochen A1 - Laperche, Valérie A1 - Touze, Solène A1 - Ghestem, Jean-Philippe A1 - Dalencourt, Claire A1 - Gendre, Régine A1 - Stammeier, Jessica A1 - Klein, Ole A1 - Pröfrock, Daniel A1 - Košarac, Gala A1 - Jotanovic, Aida A1 - Bergamaschi, Luigi A1 - Di Luzio, Marco A1 - D’Agostino, Giancarlo A1 - Jaćimović, Radojko A1 - Eberhard, Melissa A1 - Feiner, Laura A1 - Trimmel, Simone A1 - Rachetti, Alessandra A1 - Sara-Aho, Timo A1 - Roethke, Anita A1 - Michaliszyn, Lena A1 - Pramann, Axel A1 - Rienitz, Olaf A1 - Irrgeher, Johanna T1 - Evaluation of X-ray fluorescence for analysing critical elements in three electronic waste matrices: A comprehensive comparison of analytical techniques N2 - As the drive towards recycling electronic waste increases, demand for rapid and reliable analytical methodology to analyse the metal content of the waste is increasing, e.g. to assess the value of the waste and to decide the correct recycling routes. Here, we comprehensively assess the suitability of different x-ray fluorescence spectroscopy (XRF)-based techniques as rapid analytical tools for the determination of critical raw materials, such as Al, Ti, Mn, Fe, Co, Ni, Cu, Zn, Nb, Pd and Au, in three electronic waste matrices: printed circuit boards (PCB), light emitting diodes (LED), and lithium (Li)-ion batteries. As validated reference methods and materials to establish metrological traceability are lacking, several laboratories measured test samples of each matrix using XRF as well as other independent complementary techniques (instrumental neutron activation analysis (INAA), inductively coupled plasma mass spectrometry (ICP-MS) and ICP optical emission spectrometry (OES)) as an inter-laboratory comparison (ILC). Results highlighted key aspects of sample preparation, limits of detection, and spectral interferences that affect the reliability of XRF, while additionally highlighting that XRF can provide more reliable data for certain elements compared to digestion-based approaches followed by ICP-MS analysis (e.g. group 4 and 5 metals). A clear distinction was observed in data processing methodologies for wavelength dispersive XRF, highlighting that considering the metals present as elements (rather than oxides) induces overestimations of the mass fractions when compared to other techniques. Eventually, the effect of sample particle size was studied and indicated that smaller particle size (<200 μm) is essential for reliable determinations. KW - XRF KW - WEEE KW - PCB KW - Battery KW - LED KW - Recycling PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-614060 DO - https://doi.org/10.1016/j.wasman.2024.10.015 VL - 190 SP - 496 EP - 505 PB - Elsevier B.V. AN - OPUS4-61406 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Gregório, Bruno J.R. A1 - Ramos, Inês I. A1 - Marques, Sara S. A1 - Barreiros, Luísa A1 - Magalhães, Luís M. A1 - Schneider, Rudolf A1 - Segundo, Marcela A. T1 - Microcarrier-based fluorescent yeast estrogen screen assay for fast determination of endocrine disrupting compounds N2 - The presence of endocrine-disrupting compounds (EDCs) in water poses a significant threat to human and animal health, as recognized by regulatory agencies throughout the world. The Yeast Estrogen Screen (YES) assay is an excellent method to evaluate the presence of these compounds in water due to its simplicity and capacity to assess the bioaccessible forms/fractions of these compounds. In the presence of a compound with estrogenic activity, Saccharomyces cerevisiae cells, containing a lacZ reporter gene encoding the enzyme β-galactosidase, are induced, the enzyme is synthesised, and released to the extracellular medium. In this work, a YES-based approach encompassing the use of a lacZ reporter gene modified strain of S. cerevisiae, microcarriers as solid support, and a fluorescent substrate, fluorescein di-β-D-galactopyranoside, is proposed, allowing for the assessment of EDCs’ presence after only 2 h of incubation. The proposed method provided an EC50 of 0.17 ± 0.03 nM and an LLOQ of 0.03 nM, expressed as 17β-estradiol. The assessment of different EDCs provided EC50 values between 0.16 and 1.2 × 103 nM. After application to wastewaters, similar results were obtained for EDCs screening, much faster, compared to the conventional 45 h spectrophotometric procedure using a commercial kit, showing potential for onsite high-throughput screening of environmental contamination. KW - Biosensoren KW - YES assay KW - Endokrine Disruptoren PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-602315 DO - https://doi.org/10.1016/j.talanta.2024.125665 VL - 271 SP - 1 EP - 7 PB - Elsevier B.V. CY - Amsterdam AN - OPUS4-60231 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Braymer, Joseph J. A1 - Stehling, Oliver A1 - Stümpfig, Martin A1 - Rösser, Ralf A1 - Spantgar, Farah A1 - Blinn, Catharina M. A1 - Mühlenhoff, Ulrich A1 - Pierik, Antonio J. A1 - Lill, Roland T1 - Requirements for the biogenesis of [2Fe-2S] proteins in the human and yeast cytosol N2 - The biogenesis of iron–sulfur (Fe/S) proteins entails the synthesis and trafficking of Fe/S clusters, followed by their insertion into target apoproteins. In eukaryotes, the multiple steps of biogenesis are accomplished by complex protein machineries in both mitochondria and cytosol. The underlying biochemical pathways have been elucidated over the past decades, yet the mechanisms of cytosolic [2Fe-2S] protein assembly have remained ill-defined. Similarly, the precise site of glutathione (GSH) requirement in cytosolic and nuclear Fe/S protein biogenesis is unclear, as is the molecular role of the GSH-dependent cytosolic monothiol glutaredoxins (cGrxs). Here, we investigated these questions in human and yeast cells by various in vivo approaches. [2Fe-2S] cluster assembly of cytosolic target apoproteins required the mitochondrial ISC machinery, the mitochondrial transporter Atm1/ABCB7 and GSH, yet occurred independently of both the CIA system and cGrxs. This mechanism was strikingly different from the ISC-, Atm1/ABCB7-, GSH-, and CIA-dependent assembly of cytosolic–nuclear [4Fe-4S] proteins. One notable exception to this cytosolic [2Fe-2S] protein maturation pathway defined here was yeast Apd1 which used the CIA system via binding to the CIA targeting complex through its C-terminal tryptophan. cGrxs, although attributed as [2Fe-2S] cluster chaperones or trafficking proteins, were not essential in vivo for delivering [2Fe-2S] clusters to either CIA components or target apoproteins. Finally, the most critical GSH requirement was assigned to Atm1-dependent export, i.e. a step before GSH-dependent cGrxs function. Our findings extend the general model of eukaryotic Fe/S protein biogenesis by adding the molecular requirements for cytosolic [2Fe-2S] protein maturation. KW - Biokorrosion KW - Hydrogenasen KW - Microbially Induced Corrosion PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-602328 DO - https://doi.org/10.1073/pnas.2400740121 SN - 0027-8424 VL - 121 IS - 21 SP - 1 EP - 12 PB - Proceedings of the National Academy of Sciences CY - Washington D.C. AN - OPUS4-60232 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Groschke, Matthias A1 - Becker, Roland T1 - Comparison of carrier gases for the separation and quantification of mineral oil hydrocarbon (MOH) fractions using online coupled high performance liquid chromatography-gas chromatography-flame ionisation detection N2 - On-line coupled high performance liquid chromatography-gas chromatography-flame ionisation detection (HPLC-GC-FID) was used to compare the effect of hydrogen, helium and nitrogen as carrier gases on the chromatographic characteristics for the quantification of mineral oil hydrocarbon (MOH) traces in food related matrices. After optimisation of chromatographic parameters nitrogen carrier gas exhibited characteristics equivalent to hydrogen and helium regarding requirements set by current guidelines and standardisation such as linear range, quantification limit and carry over. Though nitrogen expectedly led to greater peak widths, all required separations of standard compounds were sufficient and humps of saturated mineral oil hydrocarbons (MOSH) and aromatic mineral oil hydrocarbons (MOAH) were appropriate to enable quantitation similar to situations where hydrogen or helium had been used. Slightly increased peak widths of individual hump components did not affect shapes and widths of the MOSH and MOAH humps were not significantly affected by the use of nitrogen as carrier gas. Notably, nitrogen carrier gas led to less solvent peak tailing and smaller baseline offset. Overall, nitrogen may be regarded as viable alternative to hydrogen or helium and may even extend the range of quantifiable compounds to highly volatile hydrocarbon eluting directly after the solvent peak. KW - Mineral oil hydrocarobons KW - Food KW - Liquid chromatography KW - Gas chromatography KW - MOSH/MOAH PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-601450 DO - https://doi.org/10.1016/j.chroma.2024.464946 SN - 0021-9673 VL - 1726 SP - 1 EP - 7 PB - Elsevier CY - New York, NY AN - OPUS4-60145 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Schmidt, Stephan A1 - Hoffmann, Holger A1 - Garbe, Leif-Alexander A1 - Harrer, Andrea A1 - Steiner, Markus A1 - Himly, Martin A1 - Schneider, Rudolf T1 - Re-assessment of monoclonal antibodies against diclofenac for their application in the analysis of environmental waters N2 - The non-steroidal anti-inflammatory drug (NSAID) diclofenac (DCF) is an important environmental contaminant occurring in surface waters all over the world, because, after excretion, it is not adequately removed from wastewater in sewage treatment plants. To be able to monitor this pollutant, highly efficient analytical methods are needed, including immunoassays. In a medical research project, monoclonal antibodies against diclofenac and its metabolites had been produced. Based on this monoclonal anti-DCF antibody, a new indirect competitive enzyme-linked immunosorbent assay (ELISA) was developed and applied for environmental samples. The introduction of a spacer between diclofenac and the carrier protein in the coating conjugate led to higher sensitivity. With a test midpoint of 3 mg L−1 and a measurement range of 1–30 mg L−1, the system is not sensitive enough for direct analysis of surface water. However, this assay is quite robust against matrix influences and can be used for wastewater. Without adjustment of the calibration, organic solvents up to 5%, natural organic matter (NOM) up to 10 mg L−1, humic acids up to 2.5 mg L−1, and salt concentrations up to 6 g L−1 NaCl and 75 mg L−1 CaCl2 are tolerated. The antibody is also stable in a pH range from 3 to 12. Cross-reactivity (CR) of 1% or less was determined for the metabolites 40-hydroxydiclofenac (40-OH-DCF), 5-hydroxydiclofenac (5-OH-DCF), DCF lactam, and other NSAIDs. Relevant cross-reactivity occurred only with an amide derivative of DCF, 6-aminohexanoic acid (DCF-Ahx), aceclofenac (ACF) and DCF methyl ester (DCF-Me) with 150%, 61% and 44%, respectively. These substances, however, have not been found in samples. Only DCF-acyl glucuronide with a cross-reactivity of 57% is of some relevance. For the first time, photodegradation products were tested for cross-reactivity. With the ELISA based on this antibody, water samples were analysed. In sewage treatment plant effluents, concentrations in the range of 1.9–5.2 mg L−1 were determined directly, with recoveries compared to HPLC-MS/MS averaging 136%. Concentrations in lakes ranged from 3 to 4.4 ng L−1 and were, after pre-concentration, determined with an average recovery of 100% KW - Antikörper KW - Immunoassay KW - Wasser PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-602280 DO - https://doi.org/10.1039/d3ay01333b VL - 16 IS - 21 SP - 3349 EP - 3363 PB - Royal Society of Chemistry (RSC) CY - London AN - OPUS4-60228 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Tatzel, Michael A1 - Oelze, Marcus A1 - Frick, Daniel A. A1 - Di Rocco, Tommaso A1 - Liesegang, Moritz A1 - Stuff, Maria A1 - Wiedenbeck, Michael T1 - Silicon and oxygen isotope fractionation in a silicified carbonate rock N2 - Silicon isotope fractionation during silicification is poorly understood and impedes our ability to decipher paleoenvironmental conditions from Si isotopes in ancient cherts. To investigate isotope fractionation during silica-for-carbonate replacement we analyzed the microscale Si and O isotope composition in different silica phases in a silicified zebra dolostone as well as their bulk δ18O and Δ’17O compositions. The subsequent replacement of carbonate layers is mimicked by decreasing δ18O and δ30Si. The textural relationship and magnitude of Si and O isotope fractionation is best explained by near-quantitative silica precipitation in an open system with finite Si. A Rayleigh model for silicification suggests positive Ɛ30/28Si during silicification, conforming with predictions for isotope distribution at chemical equilibrium from ab-initio models. Application of the modelled Ɛ30Si-T relationship yields silicification temperatures of approx. 50°C. To reconcile the δ18Ochert composition with these temperatures, the δ18O of the fluid must have been between -2.5 and -4 ‰, compositions for which the quartz phases fall close to the oxygen equilibrium fractionation line in three-isotope space. Diagenetic silica replacement appears to occur in O and Si isotopic equilibrium allowing reconstructions of temperatures of silicification from Si isotopes and derive the δ18O composition of the fluid – a highly desired value needed for accurate reconstructions of the temperature- and δ18O histories of the oceans. KW - Silicon isotopes PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-603430 DO - https://doi.org/10.1016/j.chemgeo.2024.122120 SN - 0009-2541 VL - 658 SP - 1 EP - 13 PB - Elsevier B.V. AN - OPUS4-60343 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Tukhmetova, Dariya A1 - Langhammer, Nicole A1 - Vogl, Jochen A1 - Meermann, Björn T1 - Online Isotope Analysis of Sulfur in Proteins via Capillary Electrophoresis Coupled With Multicollector ICP‐MS (CE/MC‐ICP‐MS): A Proof of Concept Study N2 - Isotope ratio analysis of sulfur in biological samples using inductively coupled plasma-mass spectrometry (ICP-MS) has gained significant interest for applications in quantitative proteomics. Advancements like coupling separation techniques with multicollector ICP-MS (MC-ICP-MS) enhance the throughput of species-specific sulfur isotope ratio measurements, fostering new avenues for studying sulfur metabolism in complex biological matrices. This proof-of-concept study investigates the feasibility of online CE/MC-ICP-MS for directly analyzing sulfur isotope ratios in proteins (albumin). Leveraging our previous work on the applicability of CE/ICP-MS for quantifying sulfur-containing biological molecules, we explore its potential for sulfur isotope analysis. Our results demonstrate that direct analysis of sulfur isotopes in albumin protein using online capillary electrophoresis MC-ICP-MS (CE/MC-ICP-MS) eliminates the need for laborious pretreatment steps, while yielding isotope ratios comparable to the reference values. Although initial precision can be improved through further system optimization and protein injection techniques, this approach paves the way for future analysis of mixtures of various biological compounds in, for example, clinical diagnosis studies. KW - Isotope analysis KW - Sulfur KW - CE/MC-ICP-MS PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-612439 DO - https://doi.org/10.1002/elps.202400128 SN - 0173-0835 SP - 1 EP - 6 PB - Wiley-Blackwell CY - Weinheim AN - OPUS4-61243 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Mugani, R. A1 - El Khalloufi, F. A1 - Kasada, M. A1 - Redouane, E. M. A1 - Haida, M. A1 - Aba, R. P. A1 - Essadki, Y. A1 - Zerrifi, S. E. A. A1 - Herter, Sven-Oliver A1 - Hejjaj, A. A1 - Aziz, F. A1 - Ouazzani, N. A1 - Azevedo, J. A1 - Campos, A. A1 - Putschew, A. A1 - Grossart, H.-P. A1 - Mandi, L. A1 - Vasconcelos, V. A1 - Oudra, B. T1 - Monitoring of toxic cyanobacterial blooms in Lalla Takerkoust reservoir by satellite imagery and microcystin transfer to surrounding farms N2 - Cyanobacterial harmful algal blooms (CyanoHABs) threaten public health and freshwater ecosystems worldwide. In this study, our main goal was to explore the dynamics of cyanobacterial blooms and how microcystins (MCs) move from the Lalla Takerkoust reservoir to the nearby farms. We used Landsat imagery, molecular analysis, collecting and analyzing physicochemical data, and assessing toxins using HPLC. Our investigation identified two cyanobacterial species responsible for the blooms: Microcystis sp. and Synechococcus sp. Our Microcystis strain produced three MC variants (MC-RR, MC-YR, and MC-LR), with MC-RR exhibiting the highest concentrations in dissolved and intracellular toxins. In contrast, our Synechococcus strain did not produce any detectable toxins. To validate our Normalized Difference Vegetation Index (NDVI) results, we utilized limnological data, including algal cell counts, and quantified MCs in freeze-dried Microcystis bloom samples collected from the reservoir. Our study revealed patterns and trends in cyanobacterial proliferation in the reservoir over 30 years and presented a historical map of the area of cyanobacterial infestation using the NDVI method. The study found that MC-LR accumulates near the water surface due to the buoyancy of Microcystis. The maximum concentration of MC-LR in the reservoir water was 160 μg/L. In contrast, 4 km downstream of the reservoir, the concentration decreased by a factor of 5.39 to 29.63 μg/L, indicating a decrease in MC-LR concentration with increasing distance from the bloom source. Similarly, the MC-YR concentration decreased by a factor of 2.98 for the same distance. Interestingly, the MC distribution varied with depth, with MC-LR dominating at the water surface and MC-YR at the reservoir outlet at a water depth of 10 m. Our findings highlight the impact of nutrient concentrations, environmental factors, and transfer processes on bloom dynamics and MC distribution. We emphasize the need for effective management strategies to minimize toxin transfer and ensure public health and safety. KW - Cyanotoxin KW - HPLC-MS/MS KW - Surface water PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-623672 DO - https://doi.org/10.1016/j.hal.2024.102631 SN - 1568-9883 VL - 135 SP - 1 EP - 14 PB - Elsevier CY - Amsterdam AN - OPUS4-62367 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Schardt, Annika A1 - Schmitt, Johannes A1 - Engelhard, Carsten T1 - Single particle inductively coupled plasma mass spectrometry with nanosecond time resolution N2 - In this proof-of-principle study, we present our contribution to single particle inductively coupled plasma mass spectrometry (spICP-MS) developments with a novel in-house built data acquisition system with nanosecond time resolution (nanoDAQ) and a matching data processing approach. The new system can continuously sample the secondary electron multiplier (SEM) detector signal and enables the detection of gold nanoparticles (AuNP) as small as 7.5 nm with the commercial single quadrupole ICP-MS instrument used in this study. Recording of the SEM signal by the nanoDAQ is performed with a dwell time of approximately 4 ns. A tailored method was developed to process this type of transient data, which is based on determining the temporal distance between detector events that is denoted as event gap (EG). We found that the inverse logarithm of EG is proportional to the particle size and that the number of detector events corresponding to a particle signal distribution can be used to calibrate and determine the particle number concentration (PNC) of a nanoparticle dispersion. Due to the high data acquisition frequency, a statistically significant number of data points can be obtained in 60 s or less and the main time limitation for analyses is merely the sample uptake time and rinsing step between analyte solutions. At this stage, the data processing method provides average information on complete data sets only and will be adapted to enable particle-by-particle analysis with future hardware/software revision. KW - ICP-MS KW - Nanoparticles KW - Nanosecond time resolution KW - Single particle detection PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-612706 DO - https://doi.org/10.1039/d3ja00373f SN - 1364-5544 SN - 0267-9477 VL - 39 IS - 2 SP - 389 EP - 400 PB - Royal Society of Chemistry (RSC) CY - Cambridge AN - OPUS4-61270 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Vogel, Christian A1 - Roesch, Philipp A1 - Wittwer, Philipp A1 - Sommerfeld, Thomas A1 - Riedel, Maren A1 - Leube, Peter A1 - Kalbe, Ute A1 - Schoknecht, Ute A1 - Simon, Franz-Georg T1 - Per- and Polyfluoroalkyl Substances (PFAS) in Ski Waxes and Snow from Cross-Country Skiing in Germany - Comparative study of Sum Parameter and Target Analysis N2 - Per- and polyfluoroalkyl substances (PFAS) are often environmentally exposed via discharge through human consumer products, such as ski waxes. In our study we analyzed various ski waxes from the 1980s and 2020s, to determine both the sum parameter values total fluorine (TF), extractable organically bound fluorine (EOF), hydrolysable organically bound fluorine (HOF) as well as targeted PFAS analysis. This showed that modern high-performance waxes contain up to 6 % TF, but also PFAS-free labelled ski waxes contain traces of PFAS with EOF/HOF values in the low mg kg-1 range. With the ban of all fluorine-based waxes with the start of the 2023/2024 winter season this will probably change soon. Moreover, we applied our analysis methods to snow samples from a frequently used cross country ski trail (Kammloipe) in the Ore Mountain region in Germany, assessing the potential PFAS entry/discharge through ski waxes. Melted snow samples from different spots were analyzed by the adsorbable organically bound fluorine (AOF) sum parameter and PFAS target analysis and confirmed the abrasion of the ski waxes into the snow. Moreover, on a PFAS hotspot also soil samples were analyzed, which indicate that PFAS from the ski waxes adsorb after snow melting into the soil. KW - Combustion Ion Chromatography KW - Per- and Polyfluoroalkyl substances (PFAS) KW - Consumer Products PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-612760 DO - https://doi.org/10.1016/j.hazadv.2024.100484 VL - 16 SP - 1 EP - 5 PB - Elsevier B.V. AN - OPUS4-61276 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Roesch, Philipp A1 - Schinnen, Andrea A1 - Riedel, Maren A1 - Sommerfeld, Thomas A1 - Sawal, G. A1 - Bandow, N. A1 - Vogel, Christian A1 - Kalbe, Ute A1 - Simon, Franz-Georg T1 - Investigation of pH-dependent extraction methods for PFAS in (fluoropolymer-based) consumer products: A comparative study between targeted and sum parameter analysis N2 - Here, we report a comparative study of different sum parameter analysis methods for the extraction of per- and polyfluoroalkyl substances (PFAS) from manufactured consumer products, which can be measured by combustion ion chromatography (CIC). Therefore, a hydrolysis-based extraction method was further developed, which accounts for the addition of hydrolyzable covalently bound polyfluoroalkylated side-chain polymers (SFPs) to the extractable organic fluorine portion of the mass balance proposed as "hydrolyzable organically bound fluorine" (HOF). To test this hypothesis, the method was applied to 39 different consumer products containing fluoropolymers or monomeric PFAS taken from four different categories: outdoor textiles, paper packaging, carpeting, and permanent baking sheets. We also evaluated the method's efficiency by extracting four synthesized fluorotelomer polyacrylate reference compounds. The total fluorine (TF) and extractable organically bound fluorine (EOF) values were measured through CIC using established protocols. The TF values ranged from sub-ppb to %-levels, depending on the compound class. All samples showed results for hydrolyzed organofluorine (HOF) between 0.03 and 76.3 μg/g, while most EOF values were lower (fragmentation and de novo methods N2 - Non‐targeted screenings (NTS) are essential tools in different fields, such as forensics, health and environmental sciences. NTSs often employ mass spectrometry (MS) methods due to their high throughput and sensitivity in comparison to, for example, nuclear magnetic resonance–based methods. As the identification of mass spectral signals, called annotation, is labour intensive, it has been used for developing supporting tools based on machine learning (ML). However, both the diversity of mass spectral signals and the sheer quantity of different ML tools developed for compound annotation present a challenge for researchers in maintaining a comprehensive overview of the field.In this work, we illustrate which ML‐based methods are available for compound annotation in non‐targeted MS experiments and provide a nuanced comparison of the ML models used in MS data analysis, unravelling their unique features and performance metrics. Through this overview we support researchers to judiciously apply these tools in their daily research. This review also offers a detailed exploration of methods and datasets to show gaps in current methods, and promising target areas, offering a starting point for developers intending to improve existing methodologies. KW - Mass Spectrometry KW - Spectra annotation KW - Machine learning PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-608732 DO - https://doi.org/10.1002/rcm.9876 VL - 38 IS - 20 SP - 1 EP - 15 PB - Wiley AN - OPUS4-60873 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Peter, Elisa K. A1 - Jaeger, Carsten A1 - Lisec, Jan A1 - Peters, R. Sven A1 - Mourot, Rey A1 - Rossel, Pamela E. A1 - Tranter, Martyn A1 - Anesio, Alexandre M. A1 - Benning, Liane G. T1 - Endometabolic profiling of pigmented glacier ice algae: the impact of sample processing N2 - Introduction Glacier ice algae, mainly Ancylonema alaskanum and Ancylonema nordenskiöldi, bloom on Greenland Ice Sheet bare ice surfaces. They significantly decrease surface albedo due to their purple-brown pigmentation, thus increasing melt. Little is known about their metabolic adaptation and factors controlling algal growth dynamics and pigment formation. A challenge in obtaining such data is the necessity of melting samples, which delays preservation and introduces bias to metabolomic analysis. There is a need to evaluate the physiological response of algae to melting and establish consistent sample processing strategies for metabolomics of ice microbial communities. Objectives To address the impact of sample melting procedure on metabolic characterization and establish a processing and analytical workflow for endometabolic profiling of glacier ice algae. Methods We employed untargeted, high-resolution mass spectrometry and tested the effect of sample melt temperature (10, 15, 20 °C) and processing delay (up to 49 h) on the metabolome and lipidome, and complemented this approach with cell counts (FlowCam), photophysiological analysis (PAM) and diversity characterization. Results and Conclusion We putatively identified 804 metabolites, with glycerolipids, glycerophospholipids and fatty acyls being the most prominent superclasses ( 50% of identified metabolites). Among the polar metabolome, carbohydrates and amino acid-derivatives were the most abundant. We show that 8% of the metabolome is affected by melt duration, with a pronounced decrease in betaine membrane lipids and pigment precursors, and an increase in phospholipids. Controlled fast melting at 10 °C resulted in the highest consistency, and is our recommendation for future supraglacial metabolomics studies. KW - Metabolic profiling KW - Mass Spectrometry KW - Ice algae PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-607921 DO - https://doi.org/10.1007/s11306-024-02147-6 VL - 20 IS - 5 SP - 1 EP - 15 PB - Springer Science and Business Media LLC AN - OPUS4-60792 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Tobias, Charlie A1 - López-Puertollano, Daniel A1 - Abad-Somovilla, Antonio A1 - Mercader, J. V. A1 - Abad-Fuentes, A. A1 - Rurack, Knut T1 - Development of Simple and Rapid Bead-Based Cytometric Immunoassays Using Superparamagnetic Hybrid Core−Shell Microparticles N2 - Flow cytometry-based immunoassays are valuable in biomedical research and clinical applications due to their high throughput and multianalyte capability, but their adoption in areas such as food safety and environmental monitoring is limited by long assay times and complex workflows. Rapid, simplified bead-based cytometric immunoassays are needed to make these methods viable for point-of-need applications, especially with the increasing accessibility of miniaturized cytometers. This work introduces superparamagnetic hybrid polystyrene-silica core−shell microparticles as promising alternatives to conventional polymer beads in competitive cytometric immunoassays. These beads, featuring high specificity, sensitivity, and excellent handling capabilities via magnetic separation, were evaluated with three different antibodies and binding methods, showing variations in signal intensity based on the antibody and its attachment method. The optimal performance was achieved through a secondary antibody binding approach, providing strong and consistent signals with minimal uncertainty. The optimized protocol made it possible to achieve a detection limit of 0.025 nM in a total assay time of only 15 min and was successfully used to detect ochratoxin A (OTA) in raw flour samples. This work highlights the potential of these beads as versatile tools for flow cytometry-based immunoassays, with significant implications for food safety, animal health, environmental monitoring, and clinical diagnostics. KW - Immunoassays KW - Bead-based KW - Core-shell particles KW - Cytometry KW - Mycotoxins PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-610593 DO - https://doi.org/10.1021/acsmeasuresciau.4c00038 SP - 1 EP - 11 PB - American Chemical Society CY - Washington, D.C. AN - OPUS4-61059 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Mansurova, Maria A1 - Johann, Sergej A1 - Kohlhoff, Harald A1 - Rurack, Knut A1 - Bartholmai, Matthias A1 - Bell, Jérémy T1 - On-Site Analytical Tool Based on Crude Oil Fluorescence and Chemometrics for the Rapid Determination of the Nature and Essential Properties of Oil Spills N2 - With the reduction of large oil spills because of stricter regulations and safety measures, the question of how to manage smaller oil spills arises. Few on-site analytical tools are available for first responders or other law enforcement personnel to rapidly test for crude oil in the early management of localized polluted areas. The approach reported here relies on well-described computer-assisted multivariate data analysis of the intrinsic fluorescence fingerprints of crude oils to build a multivariate model for the rapid classification of crude oils and the prediction of their properties. Thanks to a dedicated robust portable reader, the method allowed classification and accurate prediction of various properties of crude oil samples like density (according to API, the American Petroleum Institute and viscosity as well as composition parameters such as volume fractions of paraffins or aromatics. In this way, autonomous operation in on-site or in-the-field applications becomes possible based on the direct (undiluted and untreated) measurement of samples and a rapid, tablet-operated readout system to yield a robust and simple analytical test with superior performance. Testing in real-life scenarios allowed the successful classification and prediction of a number of oil spill samples as well as weathered samples that closely resemble samples collected by first responders. KW - Oil spills KW - Fluorescence KW - PCA KW - Petroleum KW - Rapid test KW - Portable PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-595442 DO - https://doi.org/10.1021/acsestwater.3c00648 VL - 4 IS - 2 SP - 621 EP - 627 PB - American Chemical Society (ACS) AN - OPUS4-59544 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Tukhmetova, Dariya A1 - Lisec, Jan A1 - Vogl, Jochen A1 - Meermann, Björn T1 - Development of an Online Isotope Dilution CE/ICP–MS Method for the Quantification of Sulfur in Biological Compounds N2 - We report an analytical methodology for the quantification of sulfur in biological molecules via a speciesunspecific postcolumn isotope dilution (online ID) approach using capillary electrophoresis (CE) coupled online with inductively coupled plasma−mass spectrometry (online ID CE/ICP−MS). The method was optimized using a mixture of standard compounds including sulfate, methionine, cysteine, cystine, and albumin, yielding compound recoveries between 98 and 105%. The quantity of sulfur is further converted to the quantity of the compounds owing to the prior knowledge of the sulfur content in the molecules. The limit of detection and limit of quantification of sulfur in the compounds were 1.3−2.6 and 4.1−8.4 mg L−1, respectively, with a correlation coefficient of 0.99 within the concentration range of sulfur of 5−100 mg L−1. The capability of the method was extended to quantify albumin in its native matrix (i.e., in serum) using experimentally prepared serum spiked with a pure albumin standard for validation. The relative expanded uncertainty of the method for the quantification of albumin was 6.7% (k = 2). Finally, we tested the applicability of the method on real samples by the analysis of albumin in bovine and human sera. For automated data assessment, a software application (IsoCor) which was developed by us in a previous work was developed further for handling of online ID data. The method has several improvements compared to previously published setups: (i) reduced adsorption of proteins onto the capillary wall owing to a special capillary-coating procedure, (ii) baseline separation of the compounds in less than 30 min via CE, (iii) quantification of several sulfur species within one run by means of the online setup, (iv) SI traceability of the quantification results through online ID, and (v) facilitated data processing of the transient signals using the IsoCor application. Our method can be used as an accurate approach for quantification of proteins and other biological molecules via sulfur analysis in complex matrices for various fields, such as environmental, biological, and pharmaceutical studies as well as clinical diagnosis. Sulfur is an essential element in living organisms, where it plays important roles in various biological processes, such as protein synthesis, enzyme activity, and antioxidant defense. However, the biological effects of different sulfur species can vary widely, and imbalances in sulfur speciation have been observed in a range of diseases, including cancer, Alzheimer’s disease, and diabetes.1−3 The accurate quantification of sulfur and its species in biological samples requires sensitive and selective analytical techniques. In recent years, separation techniques coupled online with inductively coupled plasma−mass spectrometry (ICP−MS) have emerged as powerful online analytical tools complementary to molecular spectrometric methods for speciation analysis of biological compounds. External calibration4−9 and isotope dilution (ID)10−15 are common calibration approaches applied for online quantification of sulfur species in complex samples. The ID analysis is advantageous over. KW - Analytical Chemistry KW - CE/MC-ICP-MS KW - species-specific isotope information PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-594736 DO - https://doi.org/10.1021/acs.analchem.3c03553 SN - 0003-2700 SP - 1 EP - 8 PB - American Chemical Society (ACS) AN - OPUS4-59473 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Chen, Xinyue A1 - Dong, Ximan A1 - Zhang, Chuyan A1 - Zhu, Meng A1 - Ahmed, Essraa A1 - Krishnamurthy, Giridharan A1 - Rouzbahani, Rozita A1 - Pobedinskas, Paulius A1 - Gauquelin, Nicolas A1 - Jannis, Daen A1 - Kaur, Kawaljit A1 - Hafez, Aly Mohamed Elsayed A1 - Thiel, Felix A1 - Bornemann, Rainer A1 - Engelhard, Carsten A1 - Schönherr, Holger A1 - Verbeeck, Johan A1 - Haenen, Ken A1 - Jiang, Xin A1 - Yang, Nianjun T1 - Interlayer Affected Diamond Electrochemistry N2 - Diamond electrochemistry is primarily influenced by quantities of sp3‐carbon, surface terminations, and crystalline structure. In this work, a new dimension is introduced by investigating the effect of using substrate‐interlayers for diamond growth. Boron and nitrogen co‐doped nanocrystalline diamond (BNDD) films are grown on Si substrate without and with Ti and Ta as interlayers, named BNDD/Si, BNDD/Ti/Si, and BNDD/Ta/Ti/Si, respectively. After detailed characterization using microscopies, spectroscopies, electrochemical techniques, and density functional theory simulations, the relationship of composition, interfacial structure, charge transport, and electrochemical properties of the interface between diamond and metal is investigated. The BNDD/Ta/Ti/Si electrodes exhibit faster electron transfer processes than the other two diamond electrodes. The interlayer thus determines the intrinsic activity and reaction kinetics. The reduction in their barrier widths can be attributed to the formation of TaC, which facilitates carrier tunneling, and simultaneously increases the concentration of electrically active defects. As a case study, the BNDD/Ta/Ti/Si electrode is further employed to assemble a redox‐electrolyte‐based supercapacitor device with enhanced performance. In summary, the study not only sheds light on the intricate relationship between interlayer composition, charge transfer, and electrochemical performance but also demonstrates the potential of tailored interlayer design to unlock new capabilities in diamond‐based electrochemical devices. KW - Nanocrystalline diamond KW - Interfaces KW - Electrochemistry KW - TOF-SIMS KW - SEM PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-621576 DO - https://doi.org/10.1002/smtd.202301774 SN - 2366-9608 VL - 9 IS - 2 SP - 1 EP - 10 PB - Wiley VHC-Verlag CY - Weinheim AN - OPUS4-62157 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Chan, George C.-Y. A1 - Hieftje, Gary M. A1 - Omenetto, Nicoló A1 - Axner, Ove A1 - Bengtson, Arne A1 - Bings, Nicolas H. A1 - Blades, Michael W. A1 - Bogaerts, Annemie A1 - Bolshov, Mikhail A. A1 - Broekaert, José A.C. A1 - Chan, WingTat A1 - Costa-Fernández, José M. A1 - Crouch, Stanley R. A1 - De Giacomo, Alessandro A1 - D’Ulivo, Alessandro A1 - Engelhard, Carsten A1 - Falk, Heinz A1 - Farnsworth, Paul B. A1 - Florek, Stefan A1 - Gamez, Gerardo A1 - Gornushkin, Igor B. A1 - Günther, Detlef A1 - Hahn, David W. A1 - Hang, Wei A1 - Hoffmann, Volker A1 - Jakubowski, Norbert A1 - Karanassios, Vassili A1 - Koppenaal, David W. A1 - Kenneth Marcus, R. A1 - Noll, Reinhard A1 - Olesik, John W. A1 - Palleschi, Vincenzo A1 - Panne, Ulrich A1 - Pisonero, Jorge A1 - Ray, Steven J. A1 - Resano, Martín A1 - Russo, Richard E. A1 - Scheeline, Alexander A1 - Smith, Benjamin W. A1 - Sturgeon, Ralph E. A1 - Todolí, José-Luis A1 - Tognoni, Elisabetta A1 - Vanhaecke, Frank A1 - Webb, Michael R. A1 - Winefordner, James D. A1 - Yang, Lu A1 - Yu, Jin A1 - Zhang, Zhanxia T1 - Landmark Publications in Analytical Atomic Spectrometry: Fundamentals and Instrumentation Development N2 - The almost-two-centuries history of spectrochemical analysis has generated a body of literature so vast that it has become nearly intractable for experts, much less for those wishing to enter the field. Authoritative, focused reviews help to address this problem but become so granular that the overall directions of the field are lost. This broader perspective can be provided partially by general overviews but then the thinking, experimental details, theoretical underpinnings and instrumental innovations of the original work must be sacrificed. In the present compilation, this dilemma is overcome by assembling the most impactful publications in the area of analytical atomic spectrometry. Each entry was proposed by at least one current expert in the field and supported by a narrative that justifies its inclusion. The entries were then assembled into a coherent sequence and returned to contributors for a round-robin review. KW - Analytical atomic spectrometry KW - Spectroscopy KW - Instrumental analysis PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-621588 DO - https://doi.org/10.1177/00037028241263567 SN - 1943-3530 VL - 78 SP - 1 EP - 456 PB - Sage CY - London AN - OPUS4-62158 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Plouffe, A. A1 - Lee, R. G. A1 - Byrne, K. A1 - Kjarsgaard, I. M. A1 - Petts, D. C. A1 - Wilton, D.H.C. A1 - Ferbey, T. A1 - Oelze, Marcus T1 - Tracing Detrital Epidote Derived from Alteration Halos to Porphyry Cu Deposits in Glaciated Terrains: The Search for Covered Mineralization N2 - Distal alteration related to porphyry Cu mineralization is typically characterized by an abundance of green minerals, such as epidote, tremolite, and chlorite, within the propylitic and sodic-calcic alteration zones and extends far outside (>1 km) the mineralized zone(s). Glacial erosion and dispersal derived from rocks affected by propylitic and sodic-calcic alteration have resulted in the development of extensive dispersal trains of epidote in till (glacial sediment) that can reach 8 to 330 km2 as observed at four porphyry Cu study sites in the Quesnel terrane of south-central British Columbia: Highland Valley Copper, Gibraltar, Mount Polley, and Woodjam deposits. At each of these sites, epidote is more abundant in heavy mineral concentrates of till collected directly over and down-ice from mineralization and associated alteration. Epidote grains in till with >0.6 ppm Sb and >8 ppm As (as determined by laser ablation-inductively coupled plasma-mass spectrometry) are attributed to a porphyry alteration provenance. There is a greater abundance of epidote grains with high concentrations of trace elements (>12 ppm Cu, >2,700 ppm Mn, >7 ppm Zn, and >37 ppm Pb) in each porphyry district com� pared to background regions. This trace element signature recorded in till epidote grains is heterogeneously distributed in these districts and is interpreted to reflect varying degrees of metal enrichment from a porphyry fluid source. Tracing the source of the epidote in the till (i.e., geochemically tying it to porphyry-related propy� litic and/or sodic-calcic alteration), coupled with porphyry vectoring tools in bedrock, will aid in the detection of concealed porphyry Cu mineralization in glaciated terrains. KW - Indicator minerals KW - Porphyry Cu deposits KW - Epidote KW - Glaciated terrains KW - Propylitic alteration PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-635209 DO - https://doi.org/10.5382/econgeo.5049 SN - 1554-0774 VL - 119 IS - 2 SP - 305 EP - 329 PB - Society of Economic Geologists, Inc. AN - OPUS4-63520 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Potopnyk, M. A1 - Mech-Piskorz, J. A1 - Angulo, G. A1 - Ceborska, M. A1 - Luboradzki, R. A1 - Andresen, Elina A1 - Gajek, A. A1 - Wisniewska, A. A1 - Resch-Genger, Ute T1 - Aggregation/Crystallization-Induced Emission in Naphthyridine-Based Carbazolyl-Modified Donor-Acceptor Boron Dyes Tunable by Fluorine Atoms N2 - Four donor-acceptor boron difluoride complexes based on the carbazole electron donor and the [1,3,5,2]oxadiazaborinino[3,4-a][1,8]naphthyridine acceptor were designed, synthesized, and systematically spectroscopically investigated in solutions, in the solid states, and dye-doped polymer films. The dyes exhibit an intense blue to red solid-state emission with photoluminescence quantum yields of up to 56% in pure dye samples and 86% in poly(methyl methacrylate) films. All boron complexes show aggregation-induced emission and reversible mechanofluorochromism. The optical properties of these dyes and their solid state luminescence can be tuned by substitution pattern, i.e., the substituents at the naphthyridine unit. Exchange of CH3- for CF3-groups does not only increase the intramolecular charge transfer character, but also provides a crystallization-induced emission enhancement. KW - Spectroscopy KW - Dye KW - Luminescence KW - Sensor KW - Fluorescence KW - Quantum yield KW - Lifetime KW - Quality assurance KW - Synthesis PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-597426 DO - https://doi.org/10.1002/chem.202400004 SN - 0947-6539 SP - 1 EP - 12 PB - Wiley VHC-Verlag AN - OPUS4-59742 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Wang, P. A1 - Morales-Marquez, R. A1 - Cervas, G. A1 - Hernandez Medel, A. A1 - Ogayar, M. P. A1 - Jimenez de Aberasturi, D. A1 - de Isidro-Gomez, A. I. A1 - Torres-Padro, A. A1 - Palomares, F. J. A1 - Garcia-Orrit, S. A1 - Sousa, C. T. A1 - Espinosa, A. A1 - Telle, H. H. A1 - Ortgies, D. H. A1 - Vega-Mayoral, V. A1 - Cabanillas-Gonzalez, J. A1 - Rodriguez, E. M. A1 - Resch-Genger, Ute A1 - Wegner, Karl David A1 - Juarez, B. H. T1 - The role of temperature in the photoluminescence quantum yield (PLQY) of Ag2S-based nanocrystals N2 - Highly emissive Ag2S nanocrystals (NCs) passivated with a gradated shell incorporating Se and Zn were synthesized in air, and the temperature dependence of their photoluminescence quantum yield (PLQY) was quantified in both organic and aqueous media at B1200 nm. The relevance of this parameter, measured at physiological temperatures, is highlighted for applications that rely on the near infrared (NIR) photoluminescence of NCs, such as deep NIR imaging or luminescence nanothermometry. Hyperspectral NIR imaging shows that Ag2S-based NCs with a PLQY in organic media of about 10% are inefficient for imaging at 40 8C through 20 mm thick tissue with low laser irradiation power densities. In contrast, water-transferred Ag2S-based NCs with an initial PLQY of 2% in water exhibit improved robustness against temperature changes, enabling improved imaging performance. KW - Quantum dots KW - Ag2S KW - Fluorescence KW - Nanomaterial design KW - Advanced nanomaterials KW - Shortwave infrared (SWIR) KW - Temperature sensing PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-613877 DO - https://doi.org/10.1039/D4MH01016G SP - 1 EP - 11 PB - Royal Society of Chemistry (RSC) AN - OPUS4-61387 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Geißler, Daniel A1 - Wegner, Karl David A1 - Fischer, C. A1 - Resch-Genger, Ute T1 - Exploring Simple Particle-Based Signal Amplification Strategies in a Heterogeneous Sandwich Immunoassay with Optical Detection N2 - Heterogeneous sandwich immunoassays are widely used for biomarker detection in bioanalysis and medical diagnostics. The high analyte sensitivity of the current “gold standard” enzyme-linked immunosorbent assay (ELISA) originates from the signal-generating enzymatic amplification step, yielding a high number of optically detectable reporter molecules. For future point-of-care testing (POCT) and point-of-need applications, there is an increasing interest in more simple detection strategies that circumvent time-consuming and temperature-dependent enzymatic reactions. A common concept to aim for detection limits comparable to those of enzymatic amplification reactions is the usage of polymer nanoparticles (NP) stained with a large number of chromophores. We explored different simple NP-based signal amplification strategies for heterogeneous sandwich immunoassays that rely on an extraction-triggered release step of different types of optically detectable reporters. Therefore, streptavidinfunctionalized polystyrene particles (PSP) are utilized as carriers for (i) the fluorescent dye coumarin 153 (C153) and (ii) hemin (hem) molecules catalyzing the luminol reaction enabling chemiluminescence (CL) detection. Additionally, (iii) NP labeling with hemin-based microperoxidase MP11 was assessed. For each amplification approach, the PSP was first systematically optimized regarding size, loading concentration, and surface chemistry. Then, for an immunoassay for the inflammation marker C- eactive protein (CRP), the analyte sensitivity achievable with optimized PSP ystems was compared with the established ELISA concept for photometric and CL detection. Careful optimization led to a limit of detection (LOD) of 0.1 ng/mL for MP11-labeled PSP and CL detection, performing similarly well to a photometric ELISA (0.13 ng/mL), which demonstrates the huge potential of our novel assay concept. KW - Nanoparticle KW - Fluorescence KW - Immunoassay KW - Quality assurance KW - Antibody KW - Polymer KW - Dye KW - Signal enhancement KW - CRP KW - Biosensing PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-597853 DO - https://doi.org/10.1021/acs.analchem.3c03691 SN - 1520-6882 VL - 96 IS - 13 SP - 5078 EP - 5085 PB - American Chemical Society CY - Columbus, Ohio AN - OPUS4-59785 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Herter, Sven-Oliver A1 - Koch, Matthias A1 - Haase, Hajo T1 - First Synthesis of Ergotamine-13CD3 and Ergotaminine-13CD3 from Unlabeled Ergotamine N2 - Ergot alkaloids (EAs) formed by Claviceps fungi are one of the most common food contaminants worldwide, affecting cereals such as rye, wheat, and barley. To accurately determine the level of contamination and to monitor EAs maximum levels set by the European Union, the six most common EAs (so-called priority EAs) and their corresponding epimers are quantified using high-performance liquid chromatography coupled with tandem mass spectrometry (HPLC-MS/MS). The quantification of EAs in complex food matrices without appropriate internal tandards is challenging but currently carried out in the standard method EN 7425:2021 due to their commercial unavailability. To address the need for isotopically labeled EAs, we focus on two semi-synthetic approaches for the synthesis of these reference standards. Therefore, we investigate the feasibility of the N6-demethylation of native ergotamine to yield norergotamine, which can subsequently be remethylated with an isotopically labeled methylating reagent, such as iodomethane (13CD3-I), to yield isotopically labeled ergotamine and its C8-epimer ergotaminine. Testing the isotopically labeled ergotamine/-inine against native ergotamine/-inine with HPLC coupled to high-resolution HR-MS/MS proved the structure of ergotamine-13CD3 and ergotaminine-13CD3. Thus, for the first time, we can describe their synthesis from unlabeled, native ergotamine. Furthermore, this approach is promising as a universal way to synthesize other isotopically labeled EAs. KW - Reference Material KW - HPLC-MS/MS KW - Mycotoxins KW - Standards KW - Organic Synthesis KW - Isotope PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-600167 DO - https://doi.org/10.3390/toxins16040199 VL - 16 IS - 4 SP - 1 EP - 12 PB - MDPI AN - OPUS4-60016 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Auxillos, J. A1 - Crouigneau, R. A1 - Li, Y.-F. A1 - Dai, Y. A1 - Stigliani, A. A1 - Tavernaro, Isabella A1 - Resch-Genger, Ute A1 - Sandelin, A. A1 - Marie, R. A1 - Pedersen, S. F. T1 - Spatially resolved analysis of microenvironmental gradient impact on cancer cell phenotypes N2 - Despite the physiological and pathophysiological significance of microenvironmental gradients, e.g., for diseases such as cancer, tools for generating such gradients and analyzing their impact are lacking. Here, we present an integrated microfluidic-based workflow that mimics extracellular pH gradients characteristic of solid tumors while enabling high-resolution live imaging of, e.g., cell motility and chemotaxis, and preserving the capacity to capture the spatial transcriptome. Our microfluidic device generates a pH gradient that can be rapidly controlled to mimic spatiotemporal microenvironmental changes over cancer cells embedded in a 3D matrix. The device can be reopened allowing immunofluorescence analysis of selected phenotypes, as well as the transfer of cells and matrix to a Visium slide for spatially resolved analysis of transcriptional changes across the pH gradient. This workflow is easily adaptable to other gradients and multiple cell types and can therefore prove invaluable for integrated analysis of roles of microenvironmental gradients in biology. KW - Bioimaging KW - Fluorescence KW - Cell KW - Cancer KW - Method KW - Microfluids KW - Model KW - Calibration KW - Sensor KW - Ph KW - Probe KW - Workflow PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-604631 DO - https://doi.org/10.1126/sciadv.adn3448 VL - 19 IS - 18 SP - 1 EP - 17 AN - OPUS4-60463 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Sun, Yijuan A1 - Gawlitza, Kornelia A1 - Valderrey, Virginia A1 - Bell, Jérémy A1 - Rurack, Knut T1 - Polymerizable BODIPY probe crosslinker for the molecularly imprinted polymer-based detection of organic carboxylates via fluorescence N2 - This contribution reports the development of a polymerizable BODIPY-type fluorescent probe targeting small-molecule carboxylates for incorporation into molecularly imprinted polymers (MIPs). The design of the probe crosslinker includes a urea recognition site p-conjugated to the 3-position of the BODIPY core and two methacrylate moieties. Titration experiments with a carboxylate-expressing antibiotic, levofloxacin (LEVO), showed a blue shift of the absorption band as well as a broadening and decrease in emission, attributed to hydrogen bonding between the probe’s urea group and the carboxylate group of the antibiotic. Using this probe crosslinker, core–shell particles with a silica core and a thin MIP shell were prepared for the detection of LEVO. The MIP exhibited highly selective recognition of LEVO, with an imprinting factor of 18.1 compared to the non-imprinted polymer. Transmission electron microscopy confirmed the core–shell structure and spectroscopic studies revealed that the receptor’s positioning leads to a unique perturbation of the polymethinic character of the BODIPY chromophore, entailing the favourable responses. These features are fully preserved in the MIP, whereas no such response was observed for competitors such as ampicillin. The sensory particles allowed to detect LEVO down to submicromolar concentrations in dioxane. We have developed here for the first time a BODIPY probe for organic carboxylates and incorporated it into polymers using the imprinting technique, paving the way for BODIPY-type fluorescent MIP sensors. KW - Fluorescence KW - BODIPY probe KW - Molecularly Imprinted Polymers KW - Sensor Materials KW - Dyes KW - Water analysis KW - Advanced materials PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-598629 DO - https://doi.org/10.1039/D3MA00476G SP - 1 EP - 11 PB - Royal Society of Chemistry (RSC) AN - OPUS4-59862 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Verhassel, Alejandra A1 - Kimani, Martha Wamaitha A1 - Gidwani, Kamlesh A1 - Sandholm, Jouko A1 - Gawlitza, Kornelia A1 - Rurack, Knut A1 - Härkönen, Pirkko T1 - Detection of Tn-antigen in breast and prostate cancer models by VVL-labeled red dye-doped nanoparticles N2 - Aim: Fluorescence detection of breast and prostate cancer cells expressing Tn-antigen, a tumor marker, with Vicia villosa lectin (VVL)-labeled nanoparticles. Materials & methods: Breast and prostate cancer cells engineered to express high levels of Tn-antigen and non-engineered controls were incubated with VVL-labeled or unlabeled red dye-doped silica-coated polystyrene nanoparticles. The binding to cells was studied with flow cytometry, confocal microscopy, and electron microscopy. Results: Flow cytometry showed that the binding of VVL-labeled nanoparticles was significantly higher to Tn-antigen-expressing cancer cells than controls. Confocal microscopy demonstrated that particles bound to the cell surface. According to the correlative light and electron microscopy the particles bound mostly as aggregates. Conclusion: VVL-labeled nanoparticles could provide a new tool for the detection of Tn-antigen-expressing breast and prostate cancer cells. KW - Breast cancer cells KW - Fluorescence detection KW - Lectin labeling KW - Prostate cancer cells KW - Silica-coated polystyrene nanoparticles KW - Tn-antigen KW - VVL PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-613451 DO - https://doi.org/10.1080/17435889.2024.2405454 SN - 1743-5889 VL - 19 SP - 2463 EP - 2478 PB - Taylor & Francis CY - London AN - OPUS4-61345 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Morcillo, Dalia A1 - Winckelmann, Alexander A1 - Frick, Daniel A. A1 - Jacobsen, Lars A1 - Seger, Tino A1 - Florek, Stefan A1 - Richter, Silke A1 - Vogl, Jochen A1 - Recknagel, Sebastian A1 - Panne, Ulrich A1 - Abad Andrade, Carlos Enrique T1 - Lithium isotope ratio analysis of geological samples using atomic absorption spectrometry with improved spectral resolution N2 - This study introduces an improved spectrometric method with enhanced precision to determine isotope ratios in geological samples without chromatographic separation. Firstly, the improvement is achieved by increasing the spectral resolution of the spectrometer applied in well-known high-resolution continuum source atomic absorption spectrometry (HR-CS-AAS). The resulting resolving power and linear dispersion of the upgraded setup, which is denoted in the following as HR+CS-AAS, is well adapted to the line widths of the Li isotope components we investigated. Secondly, our proposed method combines optical absorption spectrometry with machine learning data analysis using an extreme gradient boosting algorithm (XGBoost). This method was applied to analyze certified geological reference materials with δLSVEC(7Li/6Li) (hereafter δ7Li) values ranging from −0.5 ‰ to 4.5 ‰. With a pixel related optical resolving power of λ/∆λ ≈ 780 000, we obtain precisions in δ7Li measurements from 1.0 ‰ to 2.5 ‰. The method is validated by comparing the results with multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS), confirming its metrological compatibility. This work presents a fast, robust, and reliable method for δ7Li measurement in geological samples. KW - Isotope KW - High-resolution continuum source atomic absorption spectroscopy KW - Lithium KW - Machine learning KW - Echelle spectrometer PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-611807 DO - https://doi.org/10.1016/j.sab.2024.107013 VL - 220 SP - 1 EP - 5 PB - Elsevier BV AN - OPUS4-61180 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Yanbaeva, M. A1 - Soyka, J. A1 - Holthoff, J. M. A1 - Rietsch, P. A1 - Engelage, E. A1 - Ruff, A. A1 - Resch-Genger, Ute A1 - Weiss, R. A1 - Eigler, S. A1 - Huber, S. M. T1 - Dimethylene-Cyclopropanide Units as Building Blocks for Fluorescence Dyes N2 - Many organic dyes are fluorescent in solution. In the solid state, however, quenching processes often dominate, hampering material science applications such as light filters, light-emitting devices, or coding tags. We show that the dimethylene-cyclopropanides caffold can be used to form two structurally different types of chromophores, which feature fluorescence quantum yields up to 0.66 in dimethyl sulfoxide and 0.53 in solids. The increased fluorescence in the solid state for compounds bearing malonate substituents instead of dicyanomethide ones is rationalized by the induced twist between the planes of the cyclopropanide core and a pyridine ligand. KW - Fluorescence KW - Dye KW - Sensor KW - Quantum yield KW - Spectroscopy KW - Photophysics KW - Synthesis KW - Solvatochromism PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-614931 DO - https://doi.org/10.1002/chem.202402476 VL - 30 IS - 56 SP - 1 EP - 7 PB - Chemistry - A European Journal AN - OPUS4-61493 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Epping, Ruben A1 - Lisec, Jan A1 - Koch, Matthias T1 - Changes in Black Truffle (Tuber melanosporum) Aroma during Storage under Different Conditions N2 - The enticing aroma of truffles is a key factor for their culinary value. Although all truffle species tend to be pricy, the most intensely aromatic species are the most sought after. Research into the aroma of truffles encompasses various disciplines including chemistry, biology, and sensory science. This study focusses on the chemical composition of the aroma of black truffles (Tuber melanosporum) and the changes occurring under different storage conditions. For this, truffle samples were stored under different treatments, at different temperatures, and measured over a total storage time of 12 days. Measurements of the truffle aroma profiles were taken with SPME/GC–MS at regular intervals. To handle the ample data collected, a systematic approach utilizing multivariate data analysis techniques was taken. This approach led to a vast amount of data which we made publicly available for future exploration. Results reveal the complexity of aroma changes, with 695 compounds identified, highlighting the need for a comprehensive understanding. Principal component analyses offer initial insights into truffle composition, while individual compounds may serve as markers for age (formic acid, 1-methylpropyl ester), freshness (2-Methyl-1-propanal; 1-(methylthio)-propane), freezing (tetrahydrofuran), salt treatment (1-chloropentane), or heat exposure (4-hydroxy-3-methyl-2-butanone). This research suggests that heat treatment or salt contact significantly affects truffle aroma, while freezing and cutting have less pronounced effects in comparison. The enrichment of compounds showing significant changes during storage was investigated with a metabolomic pathway analysis. The involvement of some of the enriched compounds on the pyruvate/glycolysis and sulfur pathways was shown. KW - Mass Spectrometry KW - Metabolomics KW - Tuber melanosporum KW - Truffle Aroma PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-601731 DO - https://doi.org/10.3390/jof10050354 VL - 10 IS - 5 SP - 1 EP - 22 PB - MDPI AN - OPUS4-60173 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Wegner, Karl David A1 - Resch-Genger, Ute T1 - The 2023 Nobel Prize in Chemistry: Quantum dots N2 - The 2023 Nobel Prize in Chemistry was awarded to Aleksey I. Ekimov (prize share 1/3), Louis E. Brus (prize share 1/3), and Moungi G. Bawendi (prize share 1/3) for groundbreaking inventions in the field of nanotechnology, i.e., for the discovery and synthesis of semiconductor nanocrystals, also termed quantum dots, that exhibit size-dependent physicochemical properties enabled by quantum size effects. This feature article summarizes the main milestones of the discoveries and developments of quantum dots that paved the road to their versatile applications in solid-state lighting, display technology, energy conversion, medical diagnostics, bioimaging, and image-guided surgery. KW - Quantum dots KW - Semiconductor nanocrystals KW - Luminescence KW - Quantitative spectroscopy KW - Quantum yield KW - Advanced nanomaterials KW - Quality assurance KW - Energy transfer PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-597843 DO - https://doi.org/10.1007/s00216-024-05225-9 VL - 2024 SP - 1 EP - 11 PB - Springer CY - Cham AN - OPUS4-59784 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Fiedler, Saskia A1 - Frenzel, Florian A1 - Würth, Christian A1 - Tavernaro, Isabella A1 - Grüne, M. A1 - Schweizer, S. A1 - Engel, A. A1 - Resch-Genger, Ute T1 - Interlaboratory Comparison on Absolute Photoluminescence Quantum Yield Measurements of Solid Light Converting Phosphors with Three Commercial Integrating Sphere Setups N2 - Scattering luminescent materials dispersed in liquid and solid matrices and luminescent powders are increasingly relevant for fundamental research and industry. Examples are luminescent nano- and microparticles and phosphors of different compositions in various matrices or incorporated into ceramics with applications in energy conversion, solid-state lighting, medical diagnostics, and security barcoding. The key parameter to characterize the performance of these materials is the photoluminescence/fluorescence quantum yield (Φf), i.e., the number of emitted photons per number of absorbed photons. To identify and quantify the sources of uncertainty of absolute measurements of Φf of scattering samples, the first interlaboratory comparison (ILC) of three laboratories from academia and industry was performed by following identical measurement protocols. Thereby, two types ofcommercial stand-alone integrating sphere setups with different illumination and detection geometries were utilized for measuring the Φf of transparent and scattering dye solutions and solid phosphors, namely, YAG:Ce optoceramics of varying surface roughness, used as converter materials for blue light emitting diodes. Special emphasis was dedicated to the influence of the measurement geometry, the optical properties of the blank utilized to determine the number of photons of the incident excitation light absorbed by the sample, and the sample-specific surface roughness. While the Φf values of the liquid samples matched between instruments, Φf measurements of the optoceramics with different blanks revealed substantial differences. The ILC results underline the importance of the measurement geometry, sample position, and blank for reliable Φf data of scattering the YAG:Ce optoceramics, with the blank’s optical properties accounting for uncertainties exceeding 20%. KW - Nano KW - Fluorescence KW - Reference material KW - Luminescence KW - Quantitative spectroscopy KW - Particle KW - Quantum yield KW - Quality assurance KW - Phosphor KW - Converter material KW - Lifetime KW - Interlaboratory comparison KW - Method KW - Uncertainty PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-600945 DO - https://doi.org/10.1021/acs.analchem.4c00372 SN - 0003-2700 SP - 6730 EP - 6737 PB - ACS Publications AN - OPUS4-60094 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - López-Iglesias, C. A1 - Markovina, A. A1 - Nirmalananthan-Budau, N. A1 - Resch-Genger, Ute A1 - Klinger, D. T1 - Optically monitoring the microenvironment of a hydrophobic cargo in amphiphilic nanogels: influence of network composition on loading and release N2 - Amphiphilic nanogels (ANGs) are promising carriers for hydrophobic cargos such as drugs, dyes, and catalysts. Loading content and release kinetics of these compounds are controlled by type and number of hydrophobic groups in the amphiphilic copolymer network. Thus, understanding the interactions between cargo and colloidal carrier is mandatory for a tailor-made and cargo-specific ANG design. To systematically explore the influence of the network composition on these interactions, we prepared a set of ANGs of different amphiphilicity and loaded these ANGs with varying concentrations of the solvatochromic dye Nile Red (NR). Here, NR acts as a hydrophobic model cargo to optically probe the polarity of its microenvironment. Analysis of the NR emission spectra as well as measurements of the fluorescence quantum yields and decay kinetics revealed a decrease in the polarity of the NR microenvironment with increasing hydrophobicity of the hydrophobic groups in the ANG network and dye–dye interactions at higher loading concentrations. At low NR concentrations, the hydrophobic cargo NR is encapsulated in the hydrophobic domains. Increasing NR concentrations resulted in probe molecules located in a more hydrophilic environment, i.e., at the nanodomain border, and favored dye–dye interactions and NR aggregation. These results correlate well with release experiments, indicating first NR release from more hydrophilic network locations. Overall, our findings demonstrate the importance to understand carrier–drug interactions for efficient loading and controlled release profiles in amphiphilic nanogels. KW - Particle KW - Energy transfer KW - Limit of detection KW - Polymer KW - Luminescence KW - Quantitative spectroscopy KW - Nano KW - Quantum yield KW - Lifetime KW - Quality assurance KW - Dye KW - Probe KW - Sensor KW - Nile Red PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-601603 DO - https://doi.org/10.1039/d4nr00051j SN - 2040-3364 IS - 16 SP - 9525 EP - 9535 PB - The Royal Society of Chemistry AN - OPUS4-60160 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Deumer, J. A1 - Andresen, Elina A1 - Gollwitzer, C. A1 - Schürmann, R. A1 - Resch-Genger, Ute T1 - Adding More Shape to Nanoscale Reference Materials-LiYF4:Yb,Tm Bipyramids as Standards for Sizing Methods and Particle Number Concentration N2 - The increasing industrial use of nanomaterials calls for the reliable characterization of their physicochemical key properties like size, size distribution, shape, and surface chemistry, and test and reference materials (RMs) with sizes and shapes, closely matching real-world nonspheric nano-objects. An efficient strategy to minimize efforts in producing nanoscale RMs (nanoRMs) for establishing, validating, and standardizing methods for characterizing nanomaterials are multimethod nanoRMs. Ideal candidates are lanthanide-based, multicolor luminescent, and chemically inert nanoparticles (NPs) like upconversion nanoparticles (UCNPs), which can be prepared in different sizes, shapes, and chemical composition with various surface coatings. This makes UCNPs interesting candidates as standards not only for sizing methods, but also for element-analytical methods like laser ablation-inductively coupled plasma mass spectrometry (LA-ICP-MS), quantitative bioimaging methods like X-ray fluorescence computed tomography (XFCT), and luminescence methods and correlative measurements. Here, we explore the potential of two monodisperse LiYF4:Yb,Tm bipyramids with peak-to-peak distances of (43 ± 2) nm and (29 ± 2) nm as size standards for small-angle X-ray scattering (SAXS) and tools for establishing and validating the sophisticated simulations required for the analysis of SAXS data derived from dispersions of nonspheric nano-objects. These SAXS studies are supplemented by two-dimensional (2D)-transmission electron microscopy measurements of the UCNP bipyramids. Additionally, the particle number concentration of cyclohexane dispersions of these UCNP bipyramids is determined by absolute SAXS measurements, complemented by gravimetry, thermogravimetric analysis (TGA), and inductively coupled plasma optical emission spectrometry (ICP-OES). This approach enables traceable particle number concentration measurements of ligand-capped nonspheric particles with unknown chemical composition. KW - Fluorescence KW - Upconversion nanoparticles KW - SAXS KW - Particle number concentration KW - Reference material KW - Traceability KW - Quality assurance KW - Quantum yield KW - Spectroscopy KW - Synthesis KW - Quantification KW - NanoRM KW - Nano KW - Particle KW - Bipyramid KW - Reference data KW - Simulation PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-617940 DO - https://doi.org/10.1021/acs.analchem.4c03641 SP - 1 EP - 8 PB - ACS Publications AN - OPUS4-61794 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Wasternack, J. A1 - Schröder, H. V. A1 - Witte, J. F. A1 - Ilisson, M. A1 - Hupatz, H. A1 - Hille, J. F. A1 - Gaedke, M. A1 - Valkonen, A. M. A1 - Sobottka, S. A1 - Krappe, A. A1 - Schubert, M. A1 - Paulus, B. A1 - Rissanen, K. A1 - Sarkar, B. A1 - Eigler, S. A1 - Resch-Genger, Ute A1 - Schalley, C. A. T1 - Switchable protection and exposure of a sensitive squaraine dye within a redox active rotaxane N2 - In nature,molecular environments in proteins can sterically protect and stabilize reactive species such as organic radicals through non-covalent interactions.Here, wereport a near-infrared fluorescent rotaxane in which the stabilization of a chemically labile squaraine fluorophore by the coordination of a tetralactam macrocycle can be controlled chemically and electrochemically. The rotaxane can be switched between two co-conformations inwhich thewheel either stabilizes or exposes the fluorophore. Coordination by the wheel affects the squaraine’s stability across four redox states and renders the radical anion significantly more stable—by a factor of 6.7—than without protection by a mechanically bonded wheel. Furthermore, the fluorescence properties can be tuned by the redox reactions in a stepwise manner. Mechanically interlockedmolecules provide an excellent scaffold to stabilize and selectively expose reactive species in a co-conformational switching process controlled by external stimuli. KW - Fluorescence KW - Dye KW - Sensor KW - Quantum yield KW - Spectroscopy KW - Photophysics KW - Synthesis KW - Squaraine KW - Switch KW - Redox-active KW - Rotaxane PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-614959 DO - https://doi.org/10.1038/s42004-024-01312-1 VL - 7 SP - 1 EP - 11 AN - OPUS4-61495 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Li, Xunyu A1 - Riedel, Jens A1 - You, Yi T1 - Practical high-resolution spectroscopy with a spatial heterodyne spectrometer: Determination of instrumental function for lineshape recovery N2 - The spatial heterodyne spectrometer (SHS) is a well-recognized platform for its high resolving power in various use cases of spectroscopy. Same as other spectrometer topologies, the SHS, unfortunately, also suffers from classical challenges such as distorted lineshape due to the instrumental function. The goal of this work is to tackle this persisting issue through a simple numerical approach. With the inherent characteristics of an SHS interferogram, we report the direct extraction and determination of the instrumental function in its numerical representation from an SHS interferogram; this instrumental function was further used for spectral data processing that enables significant improvements in spectral resolution through deconvolution algorithms.Here, we systematically discuss the recognition of the embedded instrumental function among various ingredients within an interferogram. To verify the numerical approach, lithium was chosen as the model sample, resembling the use of SHS in an isotopic analysis application. Specifically, the resonance transition of lithium D-lines (2P1/2,3/2 ← 2S1/2) was selected to assess the performance of the spectral processing. With the spectral deconvolution, the spectral features that represent the 6Li and 7Li were nearly baseline-separated, allowing for the accurate measure of the isotopic abundance without external references or algorithm adjustments (e.g., curve fitting). KW - SHS KW - Isotopic analysis KW - High Resolution PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-613401 DO - https://doi.org/10.1016/j.sab.2024.107053 SN - 0584-8547 VL - 221 SP - 1 EP - 5 PB - Elsevier AN - OPUS4-61340 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - You, Yi A1 - Danischewski, Julia A1 - Molnar, Brian A1 - Riedel, Jens A1 - Shelley, Jacob T1 - Manipulation of Gaseous Ions with Acoustic Fields at Atmospheric Pressure N2 - The ability to controllably move gaseous ions is an essential aspect of ion-based spectrometry (e.g., mass spectrometry and ion mobility spectrometry) as well as materials processing. At higher pressures, ion motion is largely governed by diffusion and multiple collisions with neutral gas molecules. Thus, high-pressure ion optics based on electrostatics require large fields, radio frequency drives, complicated geometries, and/or partially transmissive grids that become contaminated. Here, we demonstrate that low-power standing acoustic waves can be used to guide, block, focus, and separate beams of ions akin to electrostatic ion optics. Ions preferentially travel through the static-pressure regions (“nodes”) while neutral gas does not appear to be impacted by the acoustic field structure and continues along a straight trajectory. This acoustic ion manipulation (AIM) approach has broad implications for ion manipulation techniques at high pressure, while expanding our fundamental understanding of the behavior of ions in gases. KW - Ion mobility spectrometry KW - Acoustic KW - Mass spectrometry PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-600704 DO - https://doi.org/10.1021/jacs.4c01224 SP - 1 EP - 6 PB - ACS Publications AN - OPUS4-60070 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Xue, Boyang A1 - Wang, Zhangjun A1 - Zhu, Tao A1 - Gu, Yezhen A1 - Sun, Weihong A1 - Chen, Chao A1 - Li, Zhigang A1 - Riedel, Jens A1 - You, Yi T1 - High repetition-rate laser-induced breakdown spectroscopy combined with two-dimensional correlation method for analysis of sea-salt aerosols N2 - Laser-induced breakdown spectroscopy (LIBS) offers a tantalizing glimpse into real-time, on-the-spot aerosol analysis. Yet, the reliance on traditional lasers, with their limitations in energy and frequency, hampers optimal sample handling, dissociation, and excitation. To address those challenges, we propose a novel tactic: utilize a high repetition-rate (rep.-rate) laser with low pulse energy in combination with the two-dimensional correlation (2D-corr.) technique for sea-salt aerosols analyses. By examining the emission patterns from both the laser pulse train and individual pulses, we recognize distinctive analyte-specific rep.-rate responses, which allowed spectral reconstruction of analytes, avoiding background interferences. This discovery enabled the rep.-rate modulation for a 2D-corr. spectroscopy workflow. Consequently, we successfully differentiated between particle-related and air-species-related spectral components, obviating expensive spectrometers or intensified image detectors. For instance, the Na I at 589 nm stemming from aerosols exhibited an entirely different correlation contribution compared to O I at 777 nm, resulting in reconstructed clean aerosol-spectra without spectral peaks originated from air species. This 2D-corr. aerosol LIBS approach shows promising analytical potential streamlining aerosol particle analysis. KW - LIBS KW - Aerosol PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-613392 DO - https://doi.org/10.1016/j.sab.2024.107048 SN - 0584-8547 VL - 221 SP - 1 EP - 8 PB - Elsevier AN - OPUS4-61339 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Wittwer, Philipp A1 - Roesch, Philipp A1 - Vogel, Christian A1 - Simon, Fabian A1 - Gehrenkemper, Lennart A1 - Feldmann, Ines A1 - Simon, Franz-Georg T1 - Less Is More: Influence of Cross-Linking Agent Concentration on PFOS Adsorption in Chitosan N2 - As a result of the continuous use of persistent per- and polyfluoroalkyl substances (PFAS), e.g., in aviation firefighting foams, contamination with PFAS has been found in soil, groundwater, and surface water around thousands of industrial and military installations. Due to their harmful (environmental) potential, further dispersion in the environment needs to be stopped, which can be achieved by appropriate absorption materials. In this work, the influence of the cross-linking agent epichlorohydrin (ECH) concentration on the perfluorooctanesulfonic acid (PFOS) adsorption capacity of chitosan gel was investigated. It was found that higher ECH concentration during the cross-linking step decreases the PFOS adsorption capacity of the cross-linked chitosan gel from 0% to 4% ECH solution by about 15%. Using a concentration of 1%, ECH resulted still in an acid-stable material, and a maximum PFOS loading capacity of 4.04 mmol/g was obtained, one of the highest described in the literature. Furthermore, we used a rapid small-scale column test to compare the PFOS adsorption capacity of chitosan and activated carbon, each in both milled and unmilled form. Unmilled chitosan showed the highest PFOS adsorption capacity considering adsorption material dry masses (>0.9 and <0.4 mmol/g for both types of chitosan and activated carbon, respectively). Milled activated carbon proved to be the better adsorption material, considering the fixed volume of the adsorber (>99.9% PFOS adsorbed). Overall, the cross-linking agent concentration in chitosan is a crucial factor influencing its PFOS absorption potential. Our results feature cross-linked chitosan as an effective economic and ecologic alternative for PFOS adsorption in aqueous solutions. KW - Combustion Ion Chromatography KW - Per- and Polyfluoroalkyl substances (PFAS) KW - Remediation PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-618406 DO - https://doi.org/10.3390/app142311145 VL - 14 IS - 23 SP - 1 EP - 13 PB - MDPI AN - OPUS4-61840 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Wen, Keqing A1 - Gorbushina, Anna A1 - Schwibbert, Karin A1 - Bell, Jérémy T1 - Microfluidic platform with precisely controlled hydrodynamic parameters and integrated features for generation of microvortices to accurately form and monitor biofilms in flow N2 - Microorganisms often live in habitats characterized by fluid flow, and their adhesion to surfaces in industrial systems or clinical settings may lead to pipe clogging, microbially influenced corrosion, material deterioration, food spoilage, infections, and human illness. Here, a novel microfluidic platform was developed to investigate biofilm formation under precisely controlled (i) cell concentration, (ii) temperature, and (iii) flow conditions. The developed platform central unit is a single-channel microfluidic flow cell designed to ensure ultrahomogeneous flow and condition in its central area, where features, e.g., with trapping properties, can be incorporated. In comparison to static and macroflow chamber assays for biofilm studies, microfluidic chips allow in situ monitoring of biofilm formation under various flow regimes and have better environment control and smaller sample requirements. Flow simulations and experiments with fluorescent particles were used to simulate bacteria flow in the platform cell for calculating flow velocity and direction at the microscale level. The combination of flow analysis and fluorescent strain injection in the cell showed that microtraps placed at the center of the channel were efficient in capturing bacteria at determined positions and to study how flow conditions, especially microvortices, can affect biofilm formation. The microfluidic platform exhibited improved performances in terms of homogeneity and robustness for in vitro biofilm formation. We anticipate the presented platform to be suitable for broad, versatile, and high-throughput biofilm studies at the microscale level. KW - Topographical pattern KW - E. coli KW - Fluorescence KW - Bacteria trapping KW - Particle velocimetry PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-610450 DO - https://doi.org/10.1021/acsbiomaterials.4c00101 SN - 2373-9878 VL - 10 IS - 7 SP - 4626 EP - 4634 PB - ACS Publ. CY - Washington, DC AN - OPUS4-61045 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Wetzel, Annica A1 - Morell, Daniel A1 - von der Au, Marcus A1 - Wittstock, Gunther A1 - Özcan Sandikcioglu, Özlem A1 - Witt, Julia T1 - Transpassive Metal Dissolution vs. Oxygen Evolution Reaction: Implication for Alloy Stability and Electrocatalysis T1 - Transpassive Metallauflösung vs. Sauerstoffentwicklung: Auswirkungen auf Legierungsstabilität und Elektrokatalyse N2 - Multi-principal element alloys (MPEAs) are gaining interest in corrosion and electrocatalysis research due to their electrochemical stability across a broad pH range and the design flexibility they offer. Using the equimolar CrCoNi alloy, we observe significant metal dissolution in a corrosive electrolyte (0.1 M NaCl, pH 2) concurrently with the oxygen evolution reaction (OER) in the transpassive region despite the absence of hysteresis in polarization curves or other obvious corrosion indicators. We present a characterization scheme to delineate the contribution of OER and alloy dissolution, using scanning electrochemical microscopy (SECM) for OER-onset detection, and quantitative chemical analysis with inductively coupled-mass spectrometry (ICP-MS) and ultraviolet visible light (UV-Vis) spectroscopy to elucidate metal dissolution processes. In-situ electrochemical atomic force microscopy (EC-AFM) revealed that the transpassive metal dissolution on CrCoNi is dominated by intergranular corrosion. These results have significant implications for the stability of MPEAs in corrosion systems, emphasizing the necessity of analytically determining metal ions released from MPEA electrodes into the electrolyte when evaluating Faradaic efficiencies of OER catalysts. The release of transition metal ions not only reduces the Faradaic efficiency of electrolyzers but may also cause poisoning and degradation of membranes in electrochemical reactors. N2 - Multi-Hauptelement-Legierungen (MPEAs) gewinnen in der Korrosions- und Elektrokatalyseforschung aufgrund ihrer elektrochemischen Stabilität über einen breiten pH-Bereich und der Vielfalt der möglichen chemischen Zusammensetzungen zunehmend an Interesse. In unseren Untersuchungen mit der äquimolaren CrCoNi-Legierung in einem sauren Elektrolyten (0.1 M NaCl, pH 2) beobachteten wir eine signifikante Metallauflösung, die mit der Sauerstoffentwicklungsreaktion (OER) im transpassiven Bereich einhergeht, obwohl in zyklischen Polarisationskurven keine Hysterese auftrat oder andere offensichtliche Korrosionsindikatoren vorlagen. In diesem Artikel wird ein Charakterisierungskonzept eingeführt, dass die Beiträge der OER und der Legierungsauflösung differenziert. Hierfür kommt die elektrochemische Rastermikroskopie (SECM) zum Nachweis des Beginns der OER und die quantitative chemische Analyse mit induktiv gekoppelter Massenspektrometrie (ICP-MS) und UV/Vis-Spektrometrie zur Aufklärung der Metallauflösungsprozesse zum Einsatz. Die elektrochemische In situ-Atomkraftmikroskopie (EC-AFM) zeigte, dass die intergranulare Korrosion der dominierende Mechanismus der transpassive Metallauflösung von CrCoNi ist. Diese Ergebnisse besitzen erhebliche Auswirkungen für die Beurteilung der Stabilität von MPEAs in Korrosionssystemen und der Stromausbeute von OER-Katalysatoren auf der Basis von MPEAs. Die Daten unterstreichen die Notwendigkeit der analytischen Bestimmung von Metallionen, die von MPEA-Elektroden freigesetzt werden. Die Freisetzung von Übergangsmetallionen verringert nicht nur die Stromausbeute von Elektrolyseuren, sondern kann zu einer Schädigung von Membranen in elektrochemischen Reaktoren führen. KW - Transpassive dissolution KW - Corrosion KW - Multi-prinicpal element alloys (MPEAs) KW - Passivation PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-597045 DO - https://doi.org/10.1002/anie.202317058 SP - 1 EP - 8 PB - Wiley VHC-Verlag AN - OPUS4-59704 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Grimmer, Christoph A1 - Richter, Matthias A1 - Neuhaus, T. A1 - Prinz, Carsten A1 - Strzelczyk, Rebecca Skadi A1 - Colakoglu, Irem A1 - Horn, Wolfgang T1 - Towards a multi-VOC emission reference material with temporally constant emission profile for QA/QC of materials emission testing procedures N2 - Emission reference materials (ERMs) are sought after to further control and improve indoor air quality. The impregnation of porous materials with volatile organic compounds (VOCs) is a promising approach to produce ERMs. Different VOCs were used to impregnate various porous materials (mainly zeolites, activated carbons and a metal organic framework). The influence of different methodological parameters and material properties were studied to optimize the impregnation procedure and to find the best material/VOC combination. The impregnation procedure remains quite irreproducible, nevertheless, very good ERM candidates were identified. Two materials (zeolite 4 and AC 1 impregnated with n-hexadecane) showed a very stable emission over 14 days (<10 % change). Another material (AC 1 impregnated with toluene) showed a declining emission profile but with a very good in-batch reproducibility and a storage stability of up to 12 months. KW - Emission reference material KW - Porous materials KW - Indoor air quality KW - Emission test chamber KW - CO2 assisted impregnation KW - EN 16516 PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-612238 DO - https://doi.org/10.1016/j.chemosphere.2024.143437 SN - 1879-1298 VL - 366 SP - 1 EP - 8 PB - Elsevier AN - OPUS4-61223 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Scholl, Juliane A1 - Lisec, Jan A1 - Haase, Hajo A1 - Koch, Matthias T1 - Identification of transformation products from fluorinated lithium-ion battery additives TPFPB and TPFPP: forever chemicals of tomorrow? N2 - AbstractFluorinated organic compounds (FOCs) represent a class of synthetic chemicals distinguished by their resilient carbon–fluorine bonds, which demonstrate an ability to withstand environmental degradation over an extended period. The integration of FOCs into cutting-edge applications, including lithium-ion batteries (LiBs), presents considerable potential for environmental harm that has not yet been sufficiently addressed. This study focuses on the environmental fate of two fluorinated aromatics, tris(pentafluorophenyl)borane (TPFPB) and tris(pentafluorophenyl)phosphine (TPFPP), given their important role in improving the performance of LiBs. To achieve this, laboratory simulation methods including total oxidizable precursor assay, electrochemistry (EC), Fenton reaction, UV-C irradiation, and hydrolysis were employed. Liquid chromatography and gas chromatography coupled with high-resolution mass spectrometry were used for identification of transformation products (TPs) and prediction of their molecular formulae. Despite the structural similarity between TPFPB and TPFPP, distinct differences in electrochemical behavior and degradation pathways were observed. TPFPB readily underwent hydroxylation and hydrolysis, resulting in a wide range of 49 TPs. A total of 28 TPs were newly identified, including oligomers and highly toxic dioxins. In contrast, TPFPP degraded exclusively under harsh conditions, requiring the development of innovative conditioning protocols for EC. In total, the simulation experiments yielded nine structurally different compounds, including seven previously undescribed, partially defluorinated TPs. This study highlights the potential risks associated with the use of FOCs in LiBs and provides insight into the complex environmental behavior of FOCs. KW - Mass Spectrometry KW - LiBs KW - POPs KW - Transformation products KW - Electrochemistry PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-611339 DO - https://doi.org/10.1007/s00216-024-05526-z SP - 1 EP - 15 PB - Springer Science and Business Media LLC AN - OPUS4-61133 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Wetzel, Annica A1 - Morell, Daniel A1 - von der Au, Marcus A1 - Witt, Julia A1 - Özcan Sandikcioglu, Özlem T1 - Transpassive Behavior of Equimolar CrMnFeCoNi and CrCoNi Multi‐Principal Element Alloys in an Alkaline NaCl Electrolyte N2 - AbstractWe investigated the corrosion properties and transpassive behavior of CrMnFeCoNi and CrCoNi multi‐principal element alloys (MPEAs) in a 0.1 M NaCl electrolyte at pH 12. By using SECM‐based tip substrate voltammetry (TSV) in combination with the chemical analysis of the electrolyte, we were able to differentiate between anodic metal dissolution and oxygen evolution in the transpassive range. Our investigations have shown that CrCoNi has a significantly higher corrosion resistance compared to CrMnFeCoNi. In the studied alkaline environment, a transpassive oxide film is formed on the surface of CrCoNi during secondary passivation. This transpassive oxide film appears to play a significant role in oxygen evolution, as the increase in TSV currents at the microelectrode coincides with the corresponding current density plateau of the voltametric current trace. The formation of the transpassive oxide film was not observed in previous studies conducted in acidic environments. Moreover, the alkaline electrolyte induced a positive hysteresis and mild pitting corrosion, in addition to intergranular corrosion, which was the sole corrosion process observed at acidic pH levels. These findings enhance the understanding of the processes governing the transpassivity of CrMnFeCoNi and CrCoNi MPEAs in alkaline environments and have potential implications for the development of application‐tailored corrosion‐resistant MPEAs. KW - Multi-principal element alloys KW - MPEA KW - Corrosion KW - Oxygen evolution reaction KW - Transpassive region PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-611594 DO - https://doi.org/10.1002/celc.202400346 SN - 2196-0216 SP - 1 EP - 9 PB - Wiley AN - OPUS4-61159 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Hülagü, Deniz A1 - Tobias, Charlie A1 - Dao, Radek A1 - Komarov, Pavel A1 - Rurack, Knut A1 - Hodoroaba, Vasile-Dan T1 - Towards 3D determination of the surface roughness of core–shell microparticles as a routine quality control procedure by scanning electron microscopy N2 - AbstractRecently, we have developed an algorithm to quantitatively evaluate the roughness of spherical microparticles using scanning electron microscopy (SEM) images. The algorithm calculates the root-mean-squared profile roughness (RMS-RQ) of a single particle by analyzing the particle’s boundary. The information extracted from a single SEM image yields however only two-dimensional (2D) profile roughness data from the horizontal plane of a particle. The present study offers a practical procedure and the necessary software tools to gain quasi three-dimensional (3D) information from 2D particle contours recorded at different particle inclinations by tilting the sample (stage). This new approach was tested on a set of polystyrene core-iron oxide shell-silica shell particles as few micrometer-sized beads with different (tailored) surface roughness, providing the proof of principle that validates the applicability of the proposed method. SEM images of these particles were analyzed by the latest version of the developed algorithm, which allows to determine the analysis of particles in terms of roughness both within a batch and across the batches as a routine quality control procedure. A separate set of particles has been analyzed by atomic force microscopy (AFM) as a powerful complementary surface analysis technique integrated into SEM, and the roughness results have been compared. KW - Core–shell particles KW - Image analysis KW - Roughness KW - Scanning electron microscopy KW - Atomic force microscopy KW - Tilting KW - Batch analysis PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-607590 DO - https://doi.org/10.1038/s41598-024-68797-7 SN - 2045-2322 VL - 14 IS - 1 SP - 1 EP - 13 PB - Springer Science and Business Media LLC AN - OPUS4-60759 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Mrkwitschka, Paul A1 - Rühle, Bastian A1 - Kuchenbecker, Petra A1 - Löhmann, Oliver A1 - Lindemann, Franziska A1 - Hodoroaba, Vasile-Dan T1 - Embedding and cross-sectioning as a sample preparation procedure for accurate and representative size and shape measurement of nanopowders N2 - Reliable measurement of the size of polydisperse, complex-shaped commercial nanopowders is a difficult but necessary task, e.g., for regulatory requirements and toxicity risk assessment. Suitable methods exist for the accurate characterization of the size of non-aggregated, stabilized, spherical and monodisperse nanoparticles. In contrast, industrial nanoscale powders usually require dedicated sample preparation procedures developed for the analysis method of choice. These nano-powders tend to agglomerate and/or aggregate, a behavior which in combination with an innate broad particle size distribution and irregular shape often significantly alters the achievable accuracy of the measured size parameters. The present study systematically tests two commercially available nanoscale powders using different sample preparation methods for correlative analysis by scanning electron microscopy, dynamic light scattering, Brunauer–Emmet–Teller method and differential mobility analysis. One focus was set on the sample preparation by embedding nanoparticles in carbon-based hot-mounting resin. Literature on this topic is scarce and the accuracy of the data extracted from cross sections of these particles is unclearly stated. In this paper systematic simulations on the deviation of the size parameters of well-defined series of nanoparticles with different shapes from the nominal value were carried out and the contributing factors are discussed. KW - Nanopowder KW - Electron microscopy KW - Sample preparation KW - Cross-sectioning KW - Cerium oxide KW - Zinc oxide PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-593289 DO - https://doi.org/10.1038/s41598-023-51094-0 SN - 2045-2322 VL - 14 SP - 1 EP - 10 PB - Springer Nature CY - London AN - OPUS4-59328 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Zhang, Kun A1 - Carrod, Andrew J. A1 - Del Giorgio, Elena A1 - Hughes, Joseph A1 - Rurack, Knut A1 - Bennet, Francesca A1 - Hodoroaba, Vasile-Dan A1 - Harrad, Stuart A1 - Pikramenou, Zoe T1 - Luminescence Lifetime-Based Sensing Platform Based on Cyclometalated Iridium(III) Complexes for the Detection of Perfluorooctanoic Acid in Aqueous Samples N2 - Luminescence lifetimes are an attractive analytical method for detection due to its high sensitivity and stability. Iridium probes exhibit luminescence with long excited-state lifetimes, which are sensitive to the local environment. Perfluorooctanoic acid (PFOA) is listed as a chemical of high concern regarding its toxicity and is classified as a “forever chemical”. In addition to strict limits on the presence of PFOA in drinking water, environmental contamination from industrial effluent or chemical spills requires rapid, simple, accurate, and cost-effective analysis in order to aid containment. Herein, we report the fabrication and function of a novel and facile luminescence sensor for PFOA based on iridium modified on gold surfaces. These surfaces were modified with lipophilic iridium complexes bearing alkyl chains, namely, IrC6 and IrC12, and Zonyl-FSA surfactant. Upon addition of PFOA, the modified surfaces IrC6-FSA@Au and IrC12-FSA @Au show the largest change in the red luminescence signal with changes in the luminescence lifetime that allow monitoring of PFOA concentrations in aqueous solutions. The platform was tested for the measurement of PFOA in aqueous samples spiked with known concentrations of PFOA and demonstrated the capacity to determine PFOA at concentrations >100 μg/L (240 nM). KW - Perfluorooctanoic Acid (PFOA) KW - Cyclometalated iridium (III) complexes KW - Luminescent lifetime KW - Optically active surfaces KW - ToF-SIMS PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-594535 UR - https://pubs.acs.org/doi/10.1021/acs.analchem.3c04289 DO - https://doi.org/10.1021/acs.analchem.3c04289 VL - 96 IS - 4 SP - 1565 EP - 1575 PB - American Chemical Society (ACS) AN - OPUS4-59453 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Junge, Florian A1 - Wittwer, Philipp A1 - Sommerfeld, Thomas A1 - Gehrenkemper, Lennart A1 - Zoister, Christian A1 - Nickl, Philip A1 - Koch, Matthias A1 - Meermann, Björn A1 - Haag, Rainer T1 - Adsorber Charge Dominates over Hydrophobic or Fluorophilic Functionalization in Influencing Adsorption of PFCA onto Polystyrene Resins N2 - A systematic series of industrial-relevant polystyrene-based anion exchange resins that are functionalized with hydro- or fluorocarbon chains are compared regarding their adsorption behavior toward perfluorocarboxylic acids (PFCA) in respect to their charge, chain length, and type of chain. The results clearly show the dominance of electrostatic interactions in the adsorption process as uncharged adsorber materials showed no adsorption at all. In contrast, the charged adsorber materials showed in general a PFCA removal of 80% to 30% over the experiment depending on effluent fraction. Unexpectedly, for perfluorobutanoic acid (PFBA) the highest removal rate is found with consistently >90%. Despite observing significant benefits in the adsorption of PFCA for fluoroalkylated adsorbers in comparison to their non-fluorinated counterparts, this effect of fluoroalkylation is comparatively small and can not be clearly attributed to fluorophilic interactions between the fluoroalkyl chains. These findings help clarifying that the introduction of fluorocarbon moieties in adsorber materials is not necessary in order to remove fluorocarbon molecules from the environment. KW - PFAS KW - Remediation KW - Adsorption KW - Fluorophilic interactions PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-601883 DO - https://doi.org/10.1002/admi.202400199 SN - 2196-7350 SP - 1 EP - 10 PB - John Wiley & Sons CY - Hoboken, New Jersey, USA AN - OPUS4-60188 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Miliūtė, Aistė A1 - Bustamante, Joana A1 - Karafiludis, Stephanos A1 - Zöllner, Moritz A1 - Eddah, Mustapha A1 - Emmerling, Franziska A1 - Mieller, Björn A1 - George, Janine A1 - Stawski, Tomasz M. T1 - Synthesis and phase purity of the negative thermal expansion material ZrV2O7 N2 - Synthesis of pure, homogeneous, and reproducible materials is key for the comprehensive understanding, design, and tailoring of material properties. In this study, we focus on the synthesis of ZrV2O7, a material known for its negative thermal expansion properties. We investigate the influence of solid-state and wet chemistry synthesis methods on the purity and homogeneity of ZrV2O7 samples. Our findings indicate that different synthesis methods significantly impact the material's characteristics. The solid-state reaction provided high-purity material through extended milling time and repeated calcination cycles, while the sol-gel reaction enabled a “near-atomic” level of mixing and, therefore, homogenous phase-pure ZrV2O7. We confirmed purity via X-ray diffraction and Raman spectroscopy, highlighting differences between phase-pure and multiphase ceramics. These analytical techniques allowed us to distinguish subtle differences in the structure of the material. Based on ab initio simulated phonon data, we were able to interpret the Raman spectra and visualise Raman active atom vibrations. We show that phase purity enables the unbiased characterisation of material properties such as negative thermal expansion. KW - NTE KW - Sol-gel KW - Solid-state KW - Ab-initio KW - XRD KW - Raman PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-624013 DO - https://doi.org/10.1039/d4tc04095c SN - 2050-7534 SP - 1 EP - 13 PB - Royal Society of Chemistry (RSC) AN - OPUS4-62401 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Bosc-Bierne, Gaby A1 - Ewald, Shireen A1 - Kreuzer, Oliver J. A1 - Weller, Michael G. T1 - Efficient Quality Control of Peptide Pools by UHPLC and Simultaneous UV and HRMS Detection N2 - Peptide pools consist of short amino acid sequences and have proven to be versatile tools in various research areas in immunology and clinical applications. They are commercially available in many different compositions and variants. However, unlike other reagents that consist of only one or a few compounds, peptide pools are highly complex products which makes their quality control a major challenge. Quantitative peptide analysis usually requires sophisticated methods, in most cases isotope-labeled standards and reference materials. Usually, this would be prohibitively laborious and expensive. Therefore, an approach is needed to provide a practical and feasible method for quality control of peptide pools. With insufficient quality control, the use of such products could lead to incorrect experimental results, worsening the well-known reproducibility crisis in the biomedical sciences. Here we propose the use of ultra-high performance liquid chromatography (UHPLC) with two detectors, a standard UV detector at 214 nm for quantitative analysis and a high-resolution mass spectrometer (HRMS) for identity confirmation. To be cost-efficient and fast, quantification and identification are performed in one chromatographic run. An optimized protocol is shown, and different peak integration methods are compared and discussed. This work was performed using a peptide pool known as CEF advanced, which consists of 32 peptides derived from cytomegalovirus (CMV), Epstein–Barr virus (EBV) and influenza virus, ranging from 8 to 12 amino acids in length. N2 - Peptidpools bestehen aus kurzen Aminosäuresequenzen und haben sich als vielseitige Werkzeuge in verschiedenen Forschungsbereichen der Immunologie und bei klinischen Anwendungen erwiesen. Sie sind in vielen verschiedenen Zusammensetzungen und Varianten im Handel erhältlich. Im Gegensatz zu anderen Reagenzien, die nur aus einer oder wenigen Verbindungen bestehen, sind Peptidpools jedoch hochkomplexe Produkte, was ihre Qualitätskontrolle zu einer großen Herausforderung macht. Die quantitative Peptidanalyse erfordert in der Regel ausgefeilte Methoden, in den meisten Fällen isotopenmarkierte Standards und Referenzmaterialien. Dies ist in der Regel sehr aufwändig und teuer. Daher wird ein Ansatz benötigt, der eine praktische und praktikable Methode zur Qualitätskontrolle von Peptidpools bietet. Bei unzureichender Qualitätskontrolle könnte die Verwendung solcher Produkte zu falschen Versuchsergebnissen führen, was das bekannte Problem der Reproduzierbarkeit in den biomedizinischen Wissenschaften noch verschärfen würde. Hier schlagen wir die Verwendung der Ultrahochleistungs-Flüssigkeitschromatographie (UHPLC) mit zwei Detektoren vor, einem Standard-UV-Detektor bei 214 nm für die quantitative Analyse und einem hochauflösenden Massenspektrometer (HRMS) für die Identitätsbestätigung. Um kosteneffizient und schnell zu sein, werden Quantifizierung und Identifizierung in einem einzigen chromatographischen Lauf durchgeführt. Es wird ein optimiertes Protokoll gezeigt, und es werden verschiedene Peak-Integrationsmethoden verglichen und diskutiert. Für diese Arbeit wurde ein Peptidpool verwendet, der als CEF advanced bekannt ist und aus 32 Peptiden besteht, die vom Cytomegalovirus (CMV), Epstein-Barr-Virus (EBV) und Influenzavirus stammen und zwischen 8 und 12 Aminosäuren lang sind. KW - Synthetic peptides KW - Quality control KW - Impurites KW - Byproducts KW - Degradation KW - Mass spectrometry KW - Orbitrap PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-602299 DO - https://doi.org/10.3390/separations11050156 SN - 2297-8739 VL - 11 IS - 5 SP - 1 EP - 18 PB - MDPI CY - Basel AN - OPUS4-60229 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Weller, Michael G. T1 - The mystery of homochirality on earth N2 - Homochirality is an obvious feature of life on Earth. On the other hand, extraterrestrial samples contain largely racemic compounds. The same is true for any common organic synthesis. Therefore, it has been a perplexing puzzle for decades how these racemates could have formed enantiomerically enriched fractions as a basis for the origin of homochiral life forms. Numerous hypotheses have been put forward as to how preferentially homochiral molecules could have formed and accumulated on Earth. In this article, it is shown that homochirality of the abiotic organic pool at the time of formation of the first self-replicating molecules is not necessary and not even probable. It is proposed to abandon the notion of a molecular ensemble and to focus on the level of individual molecules. Although the formation of the first self-replicating, most likely homochiral molecule, is a seemingly improbable event, on a closer look, it is almost inevitable that some homochiral molecules have formed simply on a statistical basis. In this case, the non-selective leap to homochirality would be one of the first steps in chemical evolution directly out of a racemic “ocean”. Moreover, most studies focus on the chirality of the primordial monomers with respect to an asymmetric carbon atom. However, any polymer with a minimal size that allows folding to a secondary structure would spontaneously lead to asymmetric higher structures (conformations). Most of the functions of these polymers would be influenced by this inherently asymmetric folding. Furthermore, a concept of physical compartmentalization based on rock nanopores in analogy to nanocavities of digital immunoassays is introduced to suggest that complex cell walls or membranes were also not required for the first steps of chemical evolution. To summarize, simple and universal mechanisms may have led to homochiral self-replicating systems in the context of chemical evolution. A homochiral monomer pool is deemed unnecessary and probably never existed on primordial Earth. N2 - Homochiralität ist ein offensichtliches Merkmal des Lebens auf der Erde. Andererseits enthalten extraterrestrische Proben überwiegend racemische Verbindungen. Dasselbe gilt für jede gängige organische Synthese. Daher war es jahrzehntelang ein Rätsel, wie diese Racemate enantiomeren-angereicherte Fraktionen als Grundlage für den Ursprung homochiraler Lebensformen bilden konnten. Zahlreiche Hypothesen wurden aufgestellt, wie sich bevorzugt homochirale Moleküle auf der Erde gebildet und angereichert haben könnten. In diesem Artikel wird gezeigt, dass Homochiralität des abiotischen organischen Pools zum Zeitpunkt der Bildung der ersten selbstreplizierenden Moleküle nicht notwendig und nicht einmal wahrscheinlich ist. Es wird vorgeschlagen, die Vorstellung eines molekularen Ensembles aufzugeben und sich auf die Ebene der einzelnen Moleküle zu konzentrieren. Obwohl die Bildung des ersten selbstreplizierenden, höchstwahrscheinlich homochiralen Moleküls ein scheinbar unwahrscheinliches Ereignis ist, ist es bei näherer Betrachtung fast unvermeidlich, dass sich einige homochirale Moleküle einfach auf statistischer Basis gebildet haben. In diesem Fall wäre der nichtselektive Sprung zur Homochiralität einer der ersten Schritte der chemischen Evolution direkt aus einem racemischen "Ozean". Darüber hinaus konzentrieren sich die meisten Studien auf die Chiralität der ursprünglichen Monomere in Bezug auf ein asymmetrisches Kohlenstoffatom. Jedes Polymer mit einer Mindestgröße, die eine Faltung zu einer Sekundärstruktur erlaubt, würde jedoch spontan zu asymmetrischen höheren Strukturen (Konformationen) führen. Die meisten Funktionen dieser Polymere würden durch diese inhärent asymmetrische Faltung beeinflusst. Darüber hinaus wird ein Konzept der physikalischen Kompartimentierung auf der Basis von Gesteinsnanoporen in Analogie zu den Nanokavitäten digitaler Immunoassays vorgestellt, das darauf hindeutet, dass auch für die ersten Schritte der chemischen Evolution keine komplexen Zellwände oder Membranen notwendig waren. Zusammenfassend lässt sich sagen, dass einfache und universelle Mechanismen zu homochiralen selbstreplizierenden Systemen im Rahmen der chemischen Evolution geführt haben könnten. Ein homochiraler Monomerpool wird als unnötig angesehen, welcher auf der Urerde wahrscheinlich nie existiert hat. KW - Chemical evolution KW - Enantiomeric excess ee KW - Chirality KW - Racemate KW - Folding chirality KW - Self-assembly KW - self-replication KW - Single molecule KW - Prebiotic chemistry KW - Protein folding KW - Peptide folding KW - Proteinoid KW - Conformation KW - Segregation KW - Compartmentalization KW - Digital immunoassay KW - Porous rock KW - Miller and Urey KW - Primordial soup KW - Murchison meteorite KW - Micrometeorites KW - Tholins PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-598349 DO - https://doi.org/10.3390/life14030341 SN - 2075-1729 VL - 14 IS - 3 SP - 1 EP - 13 PB - MDPI CY - Basel AN - OPUS4-59834 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Gugin, Nikita A1 - Yusenko, Kirill A1 - King, Andrew A1 - Meyer, Klas A1 - Al-Sabbagh, Dominik A1 - Villajos Collado, José Antonio A1 - Emmerling, Franziska T1 - Lighting up industrial mechanochemistry: Real-time in situ monitoring of reactive extrusion using energy-dispersive X-ray diffraction N2 - Mechanochemistry is an environmentally friendly synthetic approach that enables the sustainable production of a wide range of chemicals while reducing or eliminating the need for solvents. Reactive extrusion aims to move mechanochemistry from its conventional gram-scale batch reactions, typically performed in laboratory ball mills, to a continuous, large-scale process. Meeting this challenge requires in situ monitoring techniques to gain insights into reactive extrusion and its underlying processes. While the effectiveness of in situ Raman spectroscopy in providing molecular-level information has been demonstrated, our study uses energy-dispersive X-ray diffraction to monitor reactive extrusion in real time at the crystalline level. Our results provide previously unavailable control over the reactive extrusion process, promoting its perception as an industrially feasible green alternative to traditional solvent-based syntheses. KW - Mechanochemistry KW - Reactive extrusion KW - Green chemistry KW - In situ studies KW - Time-resolved in situ KW - TRIS KW - Synchrotron radiation KW - Scalable synthesis KW - Solid-state reactions KW - Reaction mechanisms PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-613969 DO - https://doi.org/10.1016/j.chempr.2024.07.033 VL - 10 IS - 11 SP - 1 EP - 16 PB - Elsevier B.V. AN - OPUS4-61396 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kader, A. A1 - Snellings, J. A1 - Adams, L. C. A1 - Gottheil, P. A1 - Mangarova, D. B. A1 - Heyl, J. L. A1 - Kaufmann, Jan Ole A1 - Moeckel, J. A1 - Brangsch, J. A1 - Auer, T. A. A1 - Collettini, F. A1 - Sauer, F. A1 - Hamm, B. A1 - Käs, J. A1 - Sack, I. A1 - Makowski, M. R. A1 - Braun, J. T1 - Sensitivity of magnetic resonance elastography to extracellular matrix and cell motility in human prostate cancer cell line-derived xenograft models N2 - Prostate cancer (PCa) is a significant health problem in the male population of the Western world. Magnetic resonance elastography (MRE), an emerging medical imaging technique sensitive to mechanical properties of biological tissues, detects PCa based on abnormally high stiffness and viscosity values. Yet, the origin of these changes in tissue properties and how they correlate with histopathological markers and tumor aggressiveness are largely unknown, hindering the use of tumor biomechanical properties for establishing a noninvasive PCa staging system. To infer the contributions of extracellular matrix (ECM) components and cell motility, we investigated fresh tissue specimens from two PCa xenograft mouse models, PC3 and LNCaP, using magnetic resonance elastography (MRE), diffusion-weighted imaging (DWI), quantitative histology, and nuclear shape analysis. Increased tumor stiffness and impaired water diffusion were observed to be associated with collagen and elastin accumulation and decreased cell motility. Overall, LNCaP, while more representative of clinical PCa than PC3, accumulated fewer ECM components, induced less restriction of water diffusion, and exhibited increased cell motility, resulting in overall softer and less viscous properties. Taken together, our results suggest that prostate tumor stiffness increases with ECM accumulation and cell adhesion - characteristics that influence critical biological processes of cancer development. MRE paired with DWI provides a powerful set of imaging markers that can potentially predict prostate tumor development from benign masses to aggressive malignancies in patients. Statement of significance: Xenograft models of human prostate tumor cell lines, allowing correlation of microstructure-sensitive biophysical imaging parameters with quantitative histological methods, can be investigated to identify hallmarks of cancer. KW - Magnetic resonance elastography KW - Quantitative histology KW - Prostate cancer KW - Stiffness KW - Fluidity KW - Apparent diffusion coefficient KW - Collagen KW - Elastin KW - Nuclear shape PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-618361 DO - https://doi.org/10.1016/j.bioadv.2024.213884 SN - 2772-9508 VL - 161 SP - 1 EP - 12 PB - Elsevier CY - Amsterdam AN - OPUS4-61836 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Mangarova, Dilyana Branimirova A1 - Reimann, Carolin A1 - Kaufmann, Jan Ole A1 - Möckel, Jana A1 - Kader, Avan A1 - Adams, Lisa Christine A1 - Ludwig, Antje A1 - Onthank, David A1 - Robinson, Simon A1 - Karst, Uwe A1 - Helmer, Rebecca A1 - Botnar, Rene A1 - Hamm, Bernd A1 - Makowski, Marcus Richard A1 - Brangsch, Julia T1 - Elastin-specific MR probe for visualization and evaluation of an interleukin-1β targeted therapy for atherosclerosis N2 - Atherosclerosis is a chronic inflammatory condition of the arteries and represents the primary cause of various cardiovascular diseases. Despite ongoing progress, finding effective anti-inflammatory therapeutic strategies for atherosclerosis remains a challenge. Here, we assessed the potential of molecular magnetic resonance imaging (MRI) to visualize the effects of 01BSUR, an anti-interleukin-1β monoclonal antibody, for treating atherosclerosis in a murine model. Male apolipoprotein E-deficient mice were divided into a therapy group (01BSUR, 2 × 0.3 mg/kg subcutaneously, n = 10) and control group (no treatment, n = 10) and received a high-fat diet for eight weeks. The plaque burden was assessed using an elastin-targeted gadolinium-based contrast probe (0.2 mmol/kg intravenously) on a 3 T MRI scanner. T1-weighted imaging showed a significantly lower contrast-to-noise (CNR) ratio in the 01BSUR group (pre: 3.93042664; post: 8.4007067) compared to the control group (pre: 3.70679168; post: 13.2982156) following administration of the elastin-specific MRI probe (p < 0.05). Histological examinations demonstrated a significant reduction in plaque size (p < 0.05) and a significant decrease in plaque elastin content (p < 0.05) in the treatment group compared to control animals. This study demonstrated that 01BSUR hinders the progression of atherosclerosis in a mouse model. Using an elastin-targeted MRI probe, we could quantify these therapeutic effects in MRI. N2 - Atherosklerose ist eine chronische entzündliche Erkrankung der Arterien und die Hauptursache für verschiedene Herz-Kreislauf-Erkrankungen. Trotz kontinuierlicher Fortschritte ist es nach wie vor schwierig, wirksame entzündungshemmende Therapiestrategien für Atherosklerose zu finden. In dieser Studie haben wir das Potenzial der molekularen Magnetresonanztomographie (MRT) zur Visualisierung der Wirkung von 01BSUR, einem monoklonalen Anti-Interleukin-1β-Antikörper, zur Behandlung von Atherosklerose in einem Mausmodell untersucht. Männliche Apolipoprotein-E-defiziente Mäuse wurden in eine Therapiegruppe (01BSUR, 2 × 0,3 mg/kg subkutan, n = 10) und eine Kontrollgruppe (keine Behandlung, n = 10) aufgeteilt und erhielten acht Wochen lang eine fettreiche Diät. Die Plaquebelastung wurde mit einer auf Elastin ausgerichteten Kontrastmittelsonde auf Gadoliniumbasis (0,2 mmol/kg intravenös) auf einem 3-T-MRT-Scanner untersucht. Die T1-gewichtete Bildgebung zeigte ein signifikant niedrigeres Kontrast-Rausch-Verhältnis (CNR) in der 01BSUR-Gruppe (vorher: 3,93042664; nachher: 8,4007067) im Vergleich zur Kontrollgruppe (vorher: 3,70679168; nachher: 13,2982156) nach Verabreichung der Elastin-spezifischen MRT-Sonde (p < 0,05). Histologische Untersuchungen zeigten eine signifikante Verringerung der Plaque-Größe (p < 0,05) und eine signifikante Abnahme des Plaque-Elastin-Gehalts (p < 0,05) in der Behandlungsgruppe im Vergleich zu den Kontrolltieren. Diese Studie zeigte, dass 01BSUR das Fortschreiten der Atherosklerose in einem Mausmodell hemmt. Mit einer auf Elastin ausgerichteten MRT-Sonde konnten wir diese therapeutischen Effekte in der MRT quantifizieren. KW - Atherosclerosis KW - Molecular imaging KW - Elastin KW - Plaque KW - Interleukin-1beta PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-610858 DO - https://doi.org/10.1038/s41598-024-71716-5 VL - 14 IS - 1 SP - 1 EP - 11 PB - Springer Science and Business Media LLC AN - OPUS4-61085 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Nerger, Tino A1 - Neumann, Patrick P. A1 - Weller, Michael G. T1 - Drone-Based Localization of Hazardous Chemicals by Passive Smart Dust N2 - The distribution of tiny sensors over a specific area was first proposed in the late 1990s as a concept known as smart dust. Several efforts focused primarily on computing and networking capabilities, but quickly ran into problems related to power supply, cost, data transmission, and environmental pollution. To overcome these limitations, we propose using paper-based (confetti-like) chemosensors that exploit the inherent selectivity of chemical reagents, such as colorimetric indicators. In this work, cheap and biodegradable passive sensors made from cellulose could successfully indicate the presence of hazardous chemicals, e.g., strong acids, by a significant color change. A conventional color digital camera attached to a drone could easily detect this from a safe distance. The collected data were processed to define the hazardous area. Our work presents a combination of the smart dust concept, chemosensing, paper-based sensor technology, and low-cost drones for flexible, sensitive, economical, and rapid detection of hazardous chemicals in high-risk scenarios. KW - Cellulose KW - Passive Smart Dust KW - Drohne KW - Kolorimetrische Sensoren PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-614641 DO - https://doi.org/10.3390/s24196195 VL - 24 IS - 19 SP - 1 EP - 16 PB - MDPI AN - OPUS4-61464 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Fischer, Janina A1 - Kaufmann, Jan Ole A1 - Weller, Michael G. T1 - Simple Determination of Affinity Constants of Antibodies by Competitive Immunoassays N2 - The affinity constant, also known as the equilibrium constant, binding constant, equilibrium association constant, or the reciprocal value, the equilibrium dissociation constant (Kd), can be considered as one of the most important characteristics for any antibody–antigen pair. Many methods based on different technologies have been proposed and used to determine this value. However, since a very large number of publications and commercial datasheets do not include this information, significant obstacles in performing such measurements seem to exist. In other cases where such data are reported, the results have often proved to be unreliable. This situation may indicate that most of the technologies available today require a high level of expertise and effort that does not seem to be available in many laboratories. In this paper, we present a simple approach based on standard immunoassay technology that is easy and quick to perform. It relies on the effect that the molar IC50 approaches the Kd value in the case of infinitely small concentrations of the reagents. A two-dimensional dilution of the reagents leads to an asymptotic convergence to Kd. The approach has some similarity to the well-known checkerboard titration used for the optimization of immunoassays. A well-known antibody against the FLAG peptide, clone M2, was used as a model system and the results were compared with other methods. This approach could be used in any case where a competitive assay is available or can be developed. The determination of an affinity constant should belong to the crucial parameters in any quality control of antibody-related products and assays and should be mandatory in papers using immunochemical protocols. N2 - Die Affinitätskonstante, auch bekannt als Gleichgewichtskonstante, Bindungskonstante, Gleichgewichtsassoziationskonstante oder der reziproke Wert, die Gleichgewichtsdissoziationskonstante (Kd), kann als eine der wichtigsten Eigenschaften für jedes Antikörper-Antigen-Paar angesehen werden. Zur Bestimmung dieses Wertes wurden zahlreiche Methoden auf der Grundlage verschiedener Technologien vorgeschlagen und verwendet. Da jedoch eine sehr große Anzahl von Veröffentlichungen und kommerziellen Datenblätter diese Information nicht enthalten, scheint es erhebliche Hindernisse bei der Durchführung solcher Messungen zu geben. In anderen Fällen, in denen solche Daten angegeben werden, haben sich die Ergebnisse häufig als unzuverlässig erwiesen. Diese Situation könnte darauf hindeuten, dass die meisten der heute verfügbaren Technologien ein hohes Maß an Fachwissen und Aufwand erfordern, das in vielen Labors nicht vorhanden zu sein scheint. In diesem Beitrag stellen wir einen einfachen Ansatz vor, der auf der Standard-Immunoassay-Technologie basiert und einfach und schnell durchführbar ist. Er beruht auf dem Effekt, dass sich der molare IC50 bei unendlich kleinen Reagenz-Konzentrationen dem Kd-Wert annähert. Eine zweidimensionale Verdünnung der Reagenzien führt zu einer asymptotischen Konvergenz zu Kd. Der Ansatz hat eine gewisse Ähnlichkeit mit der bekannten Checkerboard-Titration, die zur Optimierung von Immunoassays verwendet wird. Ein bekannter Antikörper gegen das FLAG-Peptid, Klon M2, wurde als Modellsystem verwendet, und die Ergebnisse wurden mit anderen Methoden verglichen. Dieser Ansatz kann überall dort angewendet werden, wo ein kompetitiver Assay verfügbar ist oder entwickelt werden kann. Die Bestimmung einer Affinitätskonstante sollte zu den entscheidenden Parametern bei der Qualitätskontrolle von Antikörperprodukten und -assays gehören und in Arbeiten, die immunchemische Protokolle verwenden, obligatorisch sein. KW - ELISA KW - Competitive immunoassay KW - IC50 KW - Test midpoint KW - Point of inflection KW - Equilibrium constant KW - Dissociation constant KW - Binding strength KW - Antibody antigen complex KW - Bio-interaction KW - SPR KW - Surface-plasmon resonance KW - FLAG peptide KW - Clone M2 KW - Antibody quality PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-605607 DO - https://doi.org/10.3390/mps7030049 SN - 2409-9279 VL - 7 IS - 3 SP - 1 EP - 11 PB - MDPI CY - Basel AN - OPUS4-60560 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Raysyan, Anna A1 - Zwigart, S. A1 - Eremin, S. A. A1 - Schneider, Rudolf T1 - BPA Endocrine Disruptor Detection at the Cutting Edge: FPIA and ELISA Immunoassays N2 - BPA is a chemical commonly used in the production of polymer-based materials that can have detrimental effects on the thyroid gland and impact human reproductive health. Various expensive methods, such as liquid and gas chromatography, have been suggested for detecting BPA. The fluorescence polarization immunoassay (FPIA) is an inexpensive and efficient homogeneous mix-and-read method that allows for high-throughput screening. FPIA offers high specificity and sensitivity and can be carried out in a single phase within a timeframe of 20–30 min. In this study, new tracer molecules were designed that linked the fluorescein fluorophore with and without a spacer to the bisphenol A moiety. To assess the influence of the C6 spacer on the sensitivity of an assay based on the respective antibody, hapten–protein conjugates were synthesized and assessed for performance in an ELISA setup, and this resulted in a highly sensitive assay with a detection limit of 0.05 µg/L. The lowest limit of detection was reached by employing the spacer derivate in the FPIA and was 1.0 µg/L, working range from 2 to 155 µg/L. The validation of the methods was conducted using actual samples compared to LC–MS/MS, which served as the reference method. The FPIA and ELISA both demonstrated satisfactory concordance. KW - Fluorescence Polarization KW - Enzyme-Linked Immunosorbent Assay KW - Endokriner Disruptor KW - Bisphenol A KW - Freisetzung PY - 2023 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-579497 DO - https://doi.org/10.3390/bios13060664 VL - 13 IS - 6 SP - 1 EP - 12 PB - MDPI CY - Basel AN - OPUS4-57949 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Stratulat, C. A1 - Ginghina, R. E. A1 - Bratu, A. E. A1 - Isleyen, A. A1 - Tunc, M. A1 - Hafner-Vuk, K. A1 - Frey, A. M. A1 - Kjeldsen, H. A1 - Vogl, Jochen T1 - Development- and Validation-Improved Metrological Methods for the Determination of Inorganic Impurities and Ash Content from Biofuels N2 - In this study, five laboratories, namely, BRML (Romania), TUBITAK UME (Turkey), IMBIH (Bosnia and Herzegovina), BAM (Germany), and DTI (Denmark), developed and validated analytical procedures by ICP-MS, ICP-OES, MWP-AES, WD-XRF, and ID-MS for the determination of inorganic impurities in solid and liquid biofuels, established the budget of uncertainties, and developed the method for determining the amount of ash in the measurement range 0–1.2% with absolute repeatability less than 0.1% and absolute reproducibility of 0.2% (according to EN ISO 18122). In order to create homogeneous certified reference materials, improved methodologies for the measurement and characterization of solid and liquid biofuels were developed. Thus, information regarding the precision, accuracy, and bias of the method, and identifying the factors that intervened in the measurement of uncertainty were experimentally determined, supplementing the information from the existing standards in the field. KW - Development KW - Validate method KW - Biodiesel KW - ICP-MS KW - ICP-OES KW - MW-AES KW - WD-XRF KW - ID-MS KW - Inorganic impurities KW - Ash content KW - Wood chips PY - 2023 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-578743 DO - https://doi.org/10.3390/en16135221 VL - 16 IS - 13 SP - 1 EP - 14 PB - MDPI AN - OPUS4-57874 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Menero-Valdés, P. A1 - Chronakis, Michail Ioannis A1 - Fernández, B. A1 - Quarles Jr., C. D. A1 - González-Iglesias, H. A1 - Meermann, Björn A1 - Pereiro, R. T1 - Single Cell–ICP–ToF-MS for the Multiplexed Determination of Proteins: Evaluation of the Cellular Stress Response N2 - An automated and straightforward detection and data treatment strategy for the determination of the protein relative concentration in individual human cells by single cell–inductively coupled plasma–time-of-flight mass spectrometry (sc-ICP-ToF-MS) is proposed. Metal nanocluster (NC)-labeled specific antibodies for the target proteins were employed, and ruthenium red (RR) staining, which binds to the cells surface, was used to determine the number of cell events as well as to evaluate the relative volume of the cells. As a proof of concept, the expression of hepcidin, metallothionein-2, and ferroportin employing specific antibodies labeled with IrNCs, PtNCs, and AuNCs, respectively, was investigated by sc-ICP-ToF-MS in human ARPE-19 cells. Taking into account that ARPE-19 cells are spherical in suspension and RR binds to the surface of the cells, the Ru intensity was related to the cell volume (i.e., the cell volume is directly proportional to (Ru intensity)3/2), making it possible to determine not only the mass of the target proteins in each individual cell but also the relative concentration. The proposed approach is of particular interest in comparing cell cultures subjected to different supplementations. ARPE-19 cell cultures under two stress conditions were compared: a hyperglycemic model and an oxidative stress model. The comparison of the control with treated cells shows not only the mass of analyzed species but also the relative changes in the cell volume and concentration of target proteins, clearly allowing the identification of subpopulations under the respective treatment. KW - Peptides and Proteins KW - Immunology KW - Metals PY - 2023 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-581630 DO - https://doi.org/10.1021/acs.analchem.3c02558 VL - 95 IS - 35 SP - 13322 EP - 13329 PB - ACS Publications AN - OPUS4-58163 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Martusevich, A. A1 - Kornev, R. A1 - Ermakov, A. A1 - Gornushkin, Igor B. A1 - Nazarov, V. A1 - Shabarova, L. A1 - Shkrunin, V. T1 - Spectroscopy of Laser-Induced Dielectric Breakdown Plasma in Mixtures of Air with Inert Gases Ar, He, Kr, and Xe N2 - The generation of ozone and nitrogen oxides by laser-induced dielectric breakdown (LIDB) in mixtures of air with noble gases Ar, He, Kr, and Xe is investigated using OES and IR spectroscopy, mass spectrometry, and absorption spectrophotometry. It is shown that the formation of NO and NO2 noticeably depends on the type of inert gas; the more complex electronic configuration and the lower ionization potential of the inert gas led to increased production of NO and NO2. The formation of ozone occurs mainly due to the photolytic reaction outside the gas discharge zone. Equilibrium thermodynamic analysis showed that the formation of NO in mixtures of air with inert gases does not depend on the choice of an inert gas, while the equilibrium concentration of the NO+ ion decreases with increasing complexity of the electronic configuration of an inert gas. KW - Laser-induced dielectric breakdown (LIDB) KW - Nitrogen monoxide KW - Nitrogen dioxide KW - Ozone KW - Emission spectroscopy KW - Inert gases KW - Thermodynamic analysis PY - 2023 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-568258 DO - https://doi.org/10.3390/s23020932 SN - 1424-8220 VL - 23 IS - 2 SP - 1 EP - 13 PB - MDPI CY - Basel, Switzerland AN - OPUS4-56825 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -