TY - JOUR A1 - Richter, Maria A1 - Güttler, Arne A1 - Pauli, Jutta A1 - Vogel, K. A1 - Homann, Christian A1 - Würth, Christian A1 - Resch-Genger, Ute T1 - Extending certified spectral fluorescence standards for the calibration and performance validation of fluorescence instruments to the NIR—closing the gap from 750 to 940 nm with two novel NIR dyes N2 - Fluorescence techniques such as fluorescence spectroscopy, microfluorometry, and fluorescence microscopy, providing spectral, intensity, polarization, and lifetime information, are amongst the most broadly utilized analytical methods in the life and materials sciences. However, the measured fluorescence data contain sample- and instrument-specific contributions, which hamper their comparability across instruments and laboratories. Comparable, instrument-independent fluorescence data require the determination of the fluorescence instrument’s wavelength-dependent spectral responsivity, also termed emission correction curve, for the same instrument settings as those used for the fluorescence measurements as a prerequisite for the subsequent correction of the measured instrument-specific data. Such a spectral correction is essential for the performance comparison of different fluorescent labels and reporters, quantitative fluorescence measurements, the determination of the fluorescence quantum yield, and the spectroscopic measure for the fluorescence efficiency of a fluorophore. Simple-to-use tools for obtaining emission correction curves are chromophore-based reference materials (RMs), referred to as fluorescence standards, with precisely known, preferably certified instrument-independent fluorescence spectra. However, for the increasingly used near-infrared (NIR) wavelength region >700 nm, at present, no spectral fluorescence standards are available. To close this gap, we developed two novel spectral fluorescence standards, BAM F007 and BAM-F009, with broad emission bands from about 580 to 940 nm in ethanolic solution. These liquid fluorescence standards currently under certification, which will be released in 2025, will expand the wavelength range of the already available certified Calibration Kit BAM F001b-F005b from about 300–730 to 940 nm. In this research article, we will detail the criteria utilized for dye and matrix selection and the homogeneity and stability tests accompanying dye certification as well as the calculation of the wavelength-dependent uncertainty budgets of the emission spectra BAM F007 and BAM-F009, determined with the traceably calibrated BAM reference spectrofluorometer. These fluorescence standards can provide the basis for comparable fluorescence measurements in the ultraviolet, visible, and NIR for the fluorescence community. KW - Quality assurance KW - Reference material KW - Fluorescence KW - Dye KW - Traceability KW - Metrology KW - Calibration KW - Reference data KW - Reference product KW - Digital certificate KW - NIR KW - Instrument performance validation PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-626317 DO - https://doi.org/10.1007/s00216-024-05723-w SN - 1618-2650 SP - 1 EP - 15 PB - Springer AN - OPUS4-62631 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Krappe, Alexander R. A1 - Mayer, Jacob C. A1 - Zhang, Wuai A1 - Filla, Lina M. A1 - Ligorio, Giovanni A1 - Hermerschmidt, Felix A1 - Eitelhuber, Larissa S. A1 - Güttler, Arne A1 - Weber, Manuela A1 - Paulus, Beate A1 - Resch-Genger, Ute A1 - List-Kratochvil, Emil J.W. A1 - Eigler, Siegfried T1 - Highly Emissive Hexa-peri-benzocoronene-fluoranthene Hybrid as Easily Processable and Stable OLED Material N2 - We report the synthesis of a fluorescent polycyclic aromatic hydrocarbon dye with a “symmetry-broken” core, derived from the related hexa-peri-benzocoronene (HBC) core with fluoranthene subunit. The fluorophore is composed of a pure Carbon skeleton without heteroatoms and exhibits remarkable photo luminescence properties with a photoluminescence Quantum yield (PLQY) of up to 67% in toluene, exceeding that of theparent HBC by a factor of 30. The single crystal X-ray structure reveals the distorted polycyclic aromatic hydrocarbon structure, which is responsible for the optoelectronic properties, as supported by density functional theory calculations. We show that the new fluorescent dye can be readily used for the fabrication of organic light-emitting diodes (OLED) without extensive optimization, whereby solubility in a variety of solvents and successful film formation are decisive. KW - Quantum Yield KW - OLED KW - Fluorescence KW - Synthesis PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-631298 DO - https://doi.org/10.1002/chem.202500742 SN - 1521-3765 SP - 1 EP - 7 PB - John Wiley & Sons, Inc AN - OPUS4-63129 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Frenzel, F. A1 - Fiedler, S. A1 - Bardan, A. A1 - Güttler, Arne A1 - Würth, Christian A1 - Resch-Genger, Ute T1 - Influence of Measurement Geometry and Blank on Absolute Measurements of Photoluminescence Quantum Yields of Scattering Luminescent Films N2 - For a series of 500 μm-thick polyurethane films containing different concentrations of luminescent and scattering YAG:Ce microparticles, we systematically explored and quantified pitfalls of absolute measurements of photoluminescence quantum yields (Φf) for often employed integrating sphere (IS) geometries, where the sample is placed either on a sample holder at the bottom of the IS surface or mounted in the IS center. Thereby, the influence of detection and illumination geometry and sample position was examined using blanks with various scattering properties for measuring the number of photons absorbed by the sample. Our results reveal that (i) setup configurations where the scattering sample is mounted in the IS center and (ii) transparent blanks can introduce systematic errors in absolute Φf measurements. For strongly scattering, luminescent samples, this can result in either an under- or overestimation of the absorbed photon flux and hence an under- or overestimation of Φf. The size of these uncertainties depends on the scattering properties of the sample and instrument parameters, such as sample position, IS size, wavelength-dependent reflectivity of the IS surface coating, and port configuration. For accurate and reliable absolute Φf measurements, we recommend (i) a blank with scattering properties closely matching those of the sample to realize similar distributions of the diffusely scattered excitation photons within the IS, and (ii) a sufficiently high sample absorption at the excitation wavelength. For IS setups with center-mounted samples, measurement geometries should be utilized that prevent the loss of excitation photons by reflections from the sample out of the IS. KW - Quality assurance KW - Fluorescence KW - Nano KW - Particle KW - Quantum yield KW - Characterization KW - Silica KW - Scattering KW - Uncertainty KW - Film KW - Pphosphor KW - YAG:Ce KW - LED KW - Converter material KW - Solid material KW - Polymer KW - Composite material KW - Advanced material PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-638304 DO - https://doi.org/10.1021/acs.analchem.4c06726 SN - 1520-6882 SP - 1 EP - 8 PB - ACS Publications AN - OPUS4-63830 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Tavernaro, Isabella A1 - Simon, Fabian A1 - Gehrenkemper, Lennart A1 - Tobias, Charlie A1 - Resch-Genger, Ute A1 - Meermann, Björn T1 - Quantification of the amount of surface groups of aminated silica nano- and microparticles utilizing a fluorine tag and HR-CS-GFMAS N2 - The performance, bioavailability, and safe use of engineered nanomaterials (NMs) depends not only on properties such as size, shape, and surface area, but largely on surface chemistry. While many sizing methods have been established, there is still a lack of validated screening methods for determining NM surface functional groups (FGs). In this context, we present a fast and simple method for FG quantification using high resolution-continuum source-graphite furnace molecular absorption spectrometry (HR-CS-GFMAS) and assess its applicability for the surface analysis of representatively chosen aminated silica nanoparticles (NPs) and microparticles (MPs) in conjunction with amino FG labeling with a fluorine tag. For this proof-of-concept study, first surface amino FG screening of the silica NPs and MPs was done with a potentiometric back titration method, providing the total amount of protonatable surface FGs, and two optical assays relying on reporter dyes with sizes and spatial requirements, i.e., surface binding areas smaller or larger than that of the fluorine tag to estimate the maximum and reporter-accessible number of amino FGs. Subsequently, the surface amino FGs were labeled with the fluorine tag 4-(trifluoromethyl)benzoic acid (TFMB) and the amount of fluorine originating from the bound TFMB molecules was quantified by HR-CS-GFMAS in two common organic solvents, i.e., dimethyl sulfoxide (DMSO) or ethanol (EtOH) to assess possible interferences from organic matrices. Our study revealed limits of detection (LODs) and quantification (LOQs) for fluorine of 1.0 µg/L and 3.5 µg/L in EtOH and 1.5 µg/L and 5.0 µg/L in DMSO, respectively. Overall, a quick and simple method for analyzing surface FGs on NPs and MPs was presented utilizing broadly available fluorine tags and HR-CS-GFMAS for fluorine quantification, which can be applied, e.g., for homogeneity, stability, and aging studies of surface-modified particles. This could contribute to ease the understanding of property-safety relationships for surface-functionalized NMs. KW - Fluorine Analysis KW - Nano- and microparticles KW - Surface group quantification PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-641965 DO - https://doi.org/10.1007/s00216-025-06107-4 SN - 1618-2642 SP - 1 EP - 11 PB - Springer Science and Business Media LLC CY - Berlin ; Heidelberg AN - OPUS4-64196 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Scharek, Vera M. A1 - Kröger, Tommy A1 - Keil, Karin A1 - Traub, Heike A1 - Meermann, Björn T1 - A new elemental analytical approach for microplastic sum parameter analysis—ETV/ICP-MS with CO2 N2 - Microplastics (MPs) are pervasive environmental pollutants and are considered one of the main challenges of our time. However, a fast and comprehensive analytical approach for MP analysis in complex matrices traceable to SI units is still lacking. In this context, we report a fast screening tool for the sum parameter analysis of MPs using electrothermal vaporization (ETV) coupled to inductively coupled plasma-mass spectrometry (ICP-MS). In our proof-of-concept study, we observed size-independent detection of MPs as peaks above the 13C+ signal background in the nano- to micrometer range without limitations regarding the polymer type. Quantification of the 13C+ MP signals was accomplished via an external gas calibration utilizing dynamic dilution of carbon dioxide with argon, yielding recovery rates of 80–96% for MP reference material (RM) of polymer types commonly found in the environment. The applicability to a soil sample was demonstrated through spiking experiments with a polyethylene (PE) MP RM in soil. The limit of detection (LOD) was estimated to be 0.13 µg C, equaling the detection of a single spherical low-density-PE particle of about 70 µm, and a limit of quantification (LOQ) of 0.42 µg C. KW - ETV/ICP-MS KW - Mikroplastik KW - Summenparameter PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-646418 DO - https://doi.org/10.1007/s00216-025-06146-x SN - 1618-2642 SP - 1 EP - 10 PB - Springer CY - Berlin ; Heidelberg AN - OPUS4-64641 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Bayerl, C. A1 - Shahryari, M. A1 - Reiter, R. A1 - Proß, V. A1 - Lehmann, K. A1 - Kühl, A. A. A1 - Becker, Dorit A1 - Schulz, Andreas A1 - Infante Duarte, C. A1 - Taupitz, M. A1 - Geisel, D. A1 - Tzschätzsch, H. A1 - Saatz, Jessica A1 - Traub, Heike A1 - Asbach, P. T1 - Quantitative Analysis of Gadolinium Deposits in Liver Tissue of Patients After Single or Multiple Gadolinium-based Contrast Agent Application N2 - Gadolinium-based contrast agents (GBCAs) are widely used in magnetic resonance imaging. Concerns exist regarding gadolinium deposition and its potential histopathologic tissue alterations, especially after repeated administrations of linear, less stable GBCAs. This study aimed to quantify gadolinium mass fractions in liver specimens of subjects exposed to GBCAs in correlation with histopathologic features. In this study, mass fractions of gadolinium in human liver specimens from 25 subjects who underwent liver tumor resection surgery and had received GBCA (1 to 9 times over 4 years), were quantitatively analyzed using inductively coupled plasma–mass spectrometry (ICP-MS). Histomorphology was assessed based on the nonalcoholic fatty liver disease activity score (NAS). Our results suggest that after intravenous administration of GBCA, a small fraction of gadolinium is retained in the liver over a time period of at least several weeks. A relationship was observed between Gadolinium retention and the number of GBCA administrations, but not with the cumulative dose and the degree of fatty liver disease. KW - ICP-MS KW - Contrast agent KW - Gadolinium KW - Liver PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-646608 DO - https://doi.org/10.1097/RLI.0000000000001254 SN - 1536-0210 SP - 1 EP - 10 PB - Lippincott Williams & Wilkins CY - Philadelphia, Pa. AN - OPUS4-64660 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Lozano-Martín, Daniel A1 - Tuma, Dirk A1 - Chamorro, César R. T1 - Evaluation of Reference Equations of State for Density Prediction in Regasified LNG Mixtures Using High-Precision Experimental Data N2 - This study evaluates the performance of three reference equations of state (EoS), AGA8-DC92, GERG-2008, and SGERG-88, in predicting the density of regasified liquefied natural gas (RLNG) mixtures. A synthetic nine-component RLNG mixture was gravimetrically prepared. High-precision density measurements were obtained using a single-sinker magnetic suspension densimeter over a temperature range of (250 to 350) K and pressures up to 20 MPa. The experimental data were compared with EoS predictions to evaluate their accuracy. AGA8-DC92 and GERG-2008 showed excellent agreement with the experimental data, with deviations within their stated uncertainty. In contrast, SGERG-88 exhibited significantly larger deviations for this RLNG mixture, particularly at low temperatures of (250 to 260) K, where discrepancies reached up to 3 %. Even at 300 K, deviations larger than 0.4 % were observed at high pressures, within the model’s uncertainty, but notably higher than those of the other two EoSs. The analysis was extended to three conventional 11-component natural gas mixtures (labeled G420 NG, G431 NG, and G432 NG), previously studied by our group using the same methodology. While SGERG-88 showed reduced accuracy for the RLNG mixture, it performed reasonably well for these three mixtures, despite two of them have a very similar composition to the RLNG. This discrepancy is attributed to the lower CO2 and N2 content typical in RLNG mixtures, demonstrating the sensitivity of EoS performance to minor differences in composition. These findings highlight the importance of selecting appropriate EoS models for accurate density prediction in RLNG applications. KW - Regasified LNG KW - Equation of state KW - Density KW - Gravimetric preparation PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-646506 DO - https://doi.org/10.1007/s10765-025-03669-4 SN - 0195-928X VL - 46 SP - 1 EP - 25 PB - Springer Science and Business Media LLC CY - Heidelberg AN - OPUS4-64650 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Heide, Maximilian A1 - Reifenrath, Jonas A1 - Herrmann, Alexander A1 - Engelhard, Carsten T1 - Fast and Sustainable Active Pharmaceutical Ingredient (API) Screening in Over-the-Counter and Prescription Drug Products by Surface-Assisted Plasma-Based Desorption/Ionization High-Resolution Mass Spectrometry N2 - Fast chemical analysis of pharmaceutical preparations is important for quality assurance, counterfeit drug detection, and consumer health. While quantitative methods such as high-performance liquid chromatography mass spectrometry (HPLC-MS) are powerful, there is a need for sustainable and environmentally friendly methods, which require less chemicals and produce less waste. Here, solvent-free ambient desorption/ionization (ADI) MS methods are attractive because they do not require time-consuming chromatography, produce little to no chemical waste, and, thus, contribute to green chemistry practice. In addition, sample throughput can be higher compared to HPLC-MS. In this study, a method for direct analysis of single- and multi agent drugs using a plasma-based ADI source (flowing atmospheric-pressure afterglow, FAPA) coupled to high-resolution (HR) MS was developed and optimized for best performance. The approach is rapid and only requires analytes to be in solution (only a few µL) before application onto thin-layer chromatography (TLC) surfaces, specifically dimethyl (RP2-) and cyano (CN-) modified silica, for surface-assisted (SA) FAPA-HRMS measurements. No chromatographic separation was required, and the TLC plates served only as sample carriers. A broad variety of 19 active pharmaceutical ingredients (APIs) was carefully selected to cover analgesics, anesthetics, antibiotics, antiepileptics, calcium channel blockers, diuretics, expectorants, opioids, peripheral vasodilators, stimulants, and sympathomimetics. Fast screening and identification of APIs was performed by SA-FAPA-HRMS. Typically, the protonated molecular ion ([M+H]+) was the most abundant species, while some compounds (codeine, metamizole, phenoxymethylpenicillin, and torasemide) did show some degree of fragmentation. As a proof-of-principle application, benzocaine was directly detected in saliva samples post-intake of a lozenge. Time-resolved semi-quantitative screening was performed. The limit of detection for benzocaine in saliva was 8 ng/mL (48.4 fmol) using internal standard calibration and CN-HPTLC plates. In addition, direct quantification of artificially spiked saliva was performed with minimal sample preparation. Here, SA-FAPA-HRMS with a CN-HPTLC sample substrate yielded best performance (20.02±0.52 µg/mL, RSD=2.6%, deviation of -1.9% from the theoretical value) compared to RP2-TLC (18.97±1.37 µg/mL, RSD=7.2%, -7.0%), and HPLC-UV (18.51±0.03 µg/mL, RSD=0.2%, -9.3%) results. In conclusion, SA FAPA HRMS is considered attractive for rapid and sustainable analysis of pharmaceuticals with potential in non-invasive patient monitoring. KW - Mass Spectrometry KW - Pharmaceuticals KW - Green Chemistry KW - Ambient Desorption/Ionization PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-640718 DO - https://doi.org/10.1039/D5AY01050K SN - 1759-9660 VL - 17 IS - 18 SP - 7799 EP - 7809 PB - Royal Society of Chemistry (RSC) AN - OPUS4-64071 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Homann, Christian A1 - Peeters, Régis A1 - Mirmajidi, Hana A1 - Berg, Jessica A1 - Fay, Michael A1 - Rodrigues, Lucas Carvalho Veloso A1 - Radicchi, Eros A1 - Jain, Akhil A1 - Speghini, Adolfo A1 - Hemmer, Eva T1 - Rapid microwave-assisted synthesis of morphology-controlled luminescent lanthanide-doped Gd2O2S nanostructures N2 - Gadolinium oxysulfide (Gd2O2S) is an attractive material of demonstrated suitability for a variety of imaging applications, leveraging its magnetic, scintillating, and luminescent properties, particularly when doped with optically active lanthanide ions (Ln3+). For many of these applications, control over size and morphology at the nanoscale is crucial. This study demonstrates the rapid microwave-assisted Synthesis of colloidal Ln2O2S (Ln = Gd and dopants Yb, Er, Tb) nanostructures in as little as 20 min. Structural characterization using X-ray diffraction analysis (XRD), Raman spectroscopy, as well as Transmission electron microscopy (TEM), including elemental mapping via energy dispersive X-ray spectroscopy (EDS), unveiled the key role of elemental sulphur (S8) in the reaction mixtures for materials growth. By systematically varying the Ln-to-S ratio from 1 : 0.5 to 1 : 15, controlled morphologies ranging from triangular nanoplatelets to berry- and flower-like shapes were achieved. Doping with Er3+/Yb3+ endowed the nano-triangles with upconverting and near-infrared emitting properties. Tb3+-doped Gd2O2S exhibited the characteristic green Tb3+ emission under UV excitation, while also showing X-ray excited optical luminescence (XEOL), rendering the material interesting as a potential nano-scintillator. KW - Upconversion KW - Microwave-assisted synthesis KW - Synthesis KW - Fluorescence KW - Nano KW - Particle KW - NIR KW - XRD KW - X-ray fluoressence KW - Morphology control KW - Raman PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-647907 DO - https://doi.org/10.1039/D5TC01646K SN - 2050-7526 VL - 13 IS - 35 SP - 18492 EP - 18507 PB - Royal Society of Chemistry (RSC) AN - OPUS4-64790 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Frenzel, Olivia A1 - Westphalen, Tanja A1 - Kaminski, Katja A1 - Kluge, Stephanie A1 - Bücker, Michael A1 - Piechotta, Christian T1 - Evaluation and Validation of an Accelerated Weathering Procedure to Characterise the Release of Bisphenol A from Polycarbonate Under Exposure to Simulated Environmental Conditions N2 - Bisphenol A (BPA) has been listed as a substance of very high concern (SVHC) due to its endocrine-disrupting properties according to REACH in 2017. European competent authorities have prepared a REACH restriction proposal to reduce BPA levels in the environment. The proposed limit for the concentration of free BPA and other bisphenols in articles is 10 mg kg−1. If exceeded, migration testing can demonstrate that no more than 0.04 mg L−1 is released from the product or material over its lifetime. German authorities are drafting a new restriction proposal after the original was temporarily withdrawn. The residual and migration limits mentioned above were key requirements from the previous restriction proposal. Numerous national and international standards exist for assessing how environmental factors affect the physical and chemical properties of products and materials—such as notch impact strength and tensile strength—but these standards do not cover the release of pollutants. A standardised procedure that covers all aspects of artificial weathering and monitors the subsequent release of pollutants is necessary, especially in the context of the regulation of these substances. An accelerated weathering procedure was established for non-protected samples. This material was not intended for outdoor applications. The testing procedure applied a typical weathering scenario that represents Central European climate conditions. The procedure was validated and applied to samples under distinct quality assurance aspects. Released BPA is quantified via an organic isotope dilution LC-MS/MS method. In parallel, identical samples were weathered outdoors on a weathering rack. Haze and yellowness index are measured to compare outdoor and weathering chamber results. KW - Artificial weathering KW - Polycarbonate KW - Bisphenol A KW - Simulated environmental conditions PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-645020 DO - https://doi.org/10.3390/app151910361 SN - 2076-3417 VL - 15 IS - 19 SP - 1 EP - 15 PB - MDPI AG AN - OPUS4-64502 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Matiushkina, Anna A1 - Abram, Sarah-Luise A1 - Tavernaro, Isabella A1 - Richstein, R. A1 - Reithofer, M. R. A1 - Andresen, Elina A1 - Michaelis, Matthias A1 - Koch, Matthias A1 - Resch-Genger, Ute T1 - Quantifying Citrate Surface Ligands on Iron Oxide Nanoparticles with TGA, CHN Analysis, NMR, and RP-HPLC with UV Detection N2 - Although citrate is frequently used as a surface ligand for nanomaterials (NMs) such as metal, metal oxide, and lanthanide-based NMs in hydrophilic environments due to its biocompatibility and simple replacement by other more strongly binding ligands in postsynthetic surface modification reactions, its quantification on NM surfaces has rarely been addressed. Here, we present a multimethod approach for citrate quantification on iron oxide nanoparticles (IONPs) broadly applied in the life and material sciences. Methods explored include thermogravimetric (TGA) and elemental (CHN) analysis, providing citrate-nonspecific information on the IONP coating, simple photometry, and citrate-selective reversed-phase high-performance liquid chromatography (RP-HPLC) with absorption (UV) detection and quantitative nuclear magnetic resonance spectroscopy (qNMR). Challenges originating from the strongly absorbing magnetic NM and paramagnetic iron species interfering with optical and NMR Methods were overcome by suitable sample preparation workflows. Our multimethod approach to citrate quantification highlights the advantages of combining specific and unspecific methods for characterizing NM Surface chemistry and method cross-validation. It also demonstrates that chemically nonselective measurements can favor an overestimation of the amount of a specific surface ligand by signal contributions from molecules remaining on the NM surface, e.g., from particle synthesis, such as initially employed ligands and/or surfactants. Our results emphasize the potential of underexplored selective RPHPLC for quantifying ligands on NMs, which does not require a multistep sample preparation workflow such as qNMR for many NMs and provides a higher sensitivity. These findings can pave the road to future applications of versatile HPLC methods in NM characterization. KW - Advanced material KW - Functional group KW - Iron oxide KW - Ligand KW - Nano KW - Particle KW - Quantification KW - Surface analysis PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-648632 DO - https://doi.org/10.1021/acs.analchem.5c03024 SN - 0003-2700 VL - 97 IS - 36 SP - 19627 EP - 19634 PB - American Chemical Society (ACS) CY - Washington, DC AN - OPUS4-64863 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Jaeger, Carsten A1 - Lintelmann, Jutta A1 - Franke, Raimo A1 - Artati, Anna A1 - Cecil, Alexander A1 - Broda, Frank A1 - Klawonn, Frank A1 - Erban, Alexander A1 - Kopka, Joachim A1 - Fuchs, Beate A1 - Sommer, Ulf A1 - Neumann-Schaal, Meina A1 - O'Connor, Gavin T1 - Analytical practices, use and needs of standard and reference materials in the German-speaking metabolomics community: results of an online survey N2 - Introduction Since the early 2000s, metabolomics has grown rapidly, becoming integral to fields like life sciences, health, and environmental research. This expansion has led to the formation of national and international societies, such as Germany’s DGMet, to tackle emerging challenges. One of DGMet’s goals is to improve measurement quality by assessing community needs for harmonization and standardization. A recent survey within the German-speaking community aimed to identify current practices and gaps in the use of chemical standards and reference materials, to guide future standardization efforts and collaborative initiatives. Methods An online survey was conducted between June 2023 and April 2024. The survey consisted of 38 key questions and was open to research institutions from Germany, Austria, and Switzerland. Results The survey was accessed by 68 laboratories, with 23 institutes providing complete or partial responses (34% response rate), which is comparable to rates reported in similar surveys within the metabolomics and lipidomics communities. Respondents were mainly experienced researchers from Germany, focusing mainly on health-related (“red”) metabolomics, as indicated by 78% of the respondents, followed by microbial (“grey”, 48%) and plant (“green”, 39%) metabolomics (multiple answers possible). The use of targeted methods was reported more frequently (91%) than that of non-targeted methods (78%), whereas metabolite fractions studied were equally split between polar, midpolar and lipid fractions (83% each). Human (74%), mouse (61%) and Arabidopsis (30%) were the most frequently studied organisms. Most participants used synthetic chemical standards for instrument qualification (83%), calibration (78%), and metabolite identification (74%), while matrix reference materials were mainly applied for quality control (52%) and method validation (44%). There was a strong demand for more standards, especially for metabolite identification and quantification, with cost being a major barrier, particularly for isotopically labelled standards and certified reference materials. Conclusions Valuable insights into the use of standards and reference materials within the German-speaking metabolomics community were obtained. Moving forward, the community should address critical gaps in metabolomics standardization. To achieve this, it must share its knowledge, articulate its needs clearly, and actively engage in joint efforts with national metrology institutes and international standardization initiatives. KW - Reference material KW - Chemical standard KW - Metabolomics KW - Mass spectrometry PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-647303 DO - https://doi.org/10.1007/s11306-025-02360-x VL - 21 IS - 6 SP - 1 EP - 11 PB - Springer-Nature CY - Heidelberg AN - OPUS4-64730 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Steinbeck, Christoph A1 - Jung, Nicole A1 - Bach, Felix A1 - Neumann, Steffen A1 - Herres-Pawlis, Sonja A1 - Liermann, Johannes A1 - Koepler, Oliver A1 - Bannwarth, Christoph A1 - Bender, Theo A1 - Bocklitz, Thomas A1 - Boehm, Franziska A1 - Bonatto Minella, Christian A1 - Biedermann, Frank A1 - Brack, Werner A1 - Cunha, Ricardo A1 - Czodrowski, Paul A1 - Eberl, Franziska A1 - Engel, Thomas A1 - Engstfeld, Albert A1 - Fischer, Tillmann G. A1 - Friedrich, Pascal A1 - Glorious, Frank A1 - Golub, Benjamin A1 - Grathwol, Christoph A1 - Haag, Rainer A1 - Hunold, Johannes A1 - Jacob, Christoph A1 - Johannsen, Jochen A1 - Jollife, John A1 - Kast, Stefan A1 - Kettner, Carsten A1 - Kuhn, Stefan A1 - Lanza, Giacomo A1 - Lisec, Jan A1 - Manolikakes, Georg A1 - Mata, Ricardo A1 - Meiler, Jens A1 - Müller, Matthias A1 - Müller-Pfefferkorn, Ralph A1 - Ortmeyer, Jochen A1 - Patterson, Wendy A1 - Pleiss, Jürgen A1 - Riedel, Annalisa A1 - Riedel, Jens A1 - Schatzschneider, Ulrich A1 - Schuster, Leonie A1 - Seeberger, Peter A1 - Seibert, Johann-Nikolaus A1 - Stadler, Peter A1 - Zeitler, Kirsten T1 - Proposal NFDI4Chem 2025-2030 In the National Research Data Infrastructure (NFDI) — Our Vision: All Chemists Publish FAIR Data N2 - The first funding period of NFDI4Chem established a robust foundation for research data management (RDM) in chemistry by promoting FAIR data principles and creating a cohesive infrastructure to capture well-annotated data early in the lab through electronic lab notebooks (ELNs) and making this data available in public repositories. Key achievements include standardised data formats and metadata, a federated repository environment, and improved data visibility and accessibility. Training programs and outreach have significantly increased awareness and adoption of best RDM practices. In the second funding period, the consortium aims to advance these achievements by consolidating this infrastructure, developing a model for its sustainable maintenance and operation, and fostering cultural change for its widespread adoption. Goals include ensuring seamless data workflows from laboratories to open repositories, enhancing interoperability, and supporting innovative research through AI-ready data. The work plan is organised into six task areas (TAs). TA1 (Management) provides leadership and supports all other TAs in achieving their objectives. TA2 (Smart Lab) aims to develop a fully digital research environment, including an ELN as a modular platform. This environment will support data collection, management, storage, analysis, and sharing. Integrating devices and external resources will enable seamless data transfer to repositories. TA3 (Repositories) will consolidate the repository ecosystem. The goal is to integrate repositories into a federated system for better accessibility and interoperability, ensuring long-term data availability and sustainability. TA4 (Metadata, Data Standards, and Publication Standards) focuses on developing and promoting new data and metadata standards in an international community process. This includes applying ontologies to create a semantic foundation for linking research data, making it machine-readable and enabling knowledge graphs. TA5 (Community and Training) is dedicated to fostering a cultural shift towards digital chemistry through continuous engagement, collecting requirements, and providing extensive training and support through workshops and open education resources. It will promote FAIR-compliant machine learning applications, embedding RDM into academic curricula to ensure future scientists are well-versed in these practices. TA6 (Synergies and Cross-Cutting Topics) aims to enhance collaboration across NFDI consortia and beyond. This includes developing ontologies, terminology services, the search service, and other cross-cutting solutions, integrating these developments into existing infrastructure, enabling interdisciplinary data harmonisation and fostering machine learning applications. KW - Research Data Management KW - FAIR KW - Chemistry PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-648540 DO - https://doi.org/10.3897/rio.11.e177037 SN - 2367-7163 VL - 11 SP - 1 EP - 100 PB - Pensoft Publishers AN - OPUS4-64854 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Li, Xunyu A1 - Riedel, Jens A1 - You, Yi T1 - Spectrally resolved lithium isotope quantification through high-resolution spatial heterodyne spectrometry N2 - Isotope ratio determination of lithium is increasingly important in fields ranging from geochemistry to battery diagnostics. While mass spectrometry remains the gold standard, it is costly, cumbersome, and incompatible with portable or inline implementations. Optical emission spectroscopy presents an appealing alternative. However, it is traditionally limited by insufficient spectral resolution or resolving power to separate lithium isotope emissions due to their generalized designs for a wide spectral range; this often requires overly complicated algorithms to overcome the instrumental drawbacks. (79) Results Here, we report a high-resolution optical method for lithium isotope quantification using a custom-built spatial heterodyne spectrometer (SHS) combined with a reduced-pressure glow discharge source. This configuration yielded a resolving power of 189,000 and enabled baseline resolution of lithium d-line emission features even without the need for preliminary data processing. Despite the inherent low sensitivity of SHS, a detection limit of 30 pmol was achieved using a standard industrial camera. To improve quantitative accuracy, we introduced a deconvolution-based spectral lineshape recovery technique alongside a bootstrapping-based error propagation strategy. These methods facilitated robust isotope ratio calibration using both peak-height and peak-area metrics. The SHS platform additionally enabled the determination of relative transition probabilities, suggesting the feasibility of calibration-free operation. This work demonstrates the practical viability of SHS for high-specificity, high-resolution lithium isotope analysis. The approach is compact, potentially field-deployable, and adaptable to other elements with optically resolvable isotope shifts, offering a route toward accessible and calibration-free optical isotopic analyses. KW - SHS KW - Isotope KW - High-resolution spectroscopy PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-635139 DO - https://doi.org/10.1016/j.aca.2025.344329 SN - 1873-4324 VL - 1368 SP - 1 EP - 8 PB - Elsevier B.V. AN - OPUS4-63513 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Mohan, M. A1 - Prochazka, D. A1 - You, Yi A1 - Riedel, Jens A1 - Gornushkin, Igor A1 - Rocnakova, I. A1 - Papula, M. A1 - Porízka, P. A1 - Kaizer, J. T1 - Investigating plasma morphology at material boundaries under varying ambient pressures N2 - Laser-Induced Breakdown Spectroscopy (LIBS) is a widely used technique for elemental analysis. The analysis of the obtained LIBS spectra generally assumes plasma homogeneity. However, using focused laser beams for interrogation, LIBS probes materials on the microscale and is, thus, prone to artefacts from sample heterogeneities on the micrometer scale. An ablation at a material boundary of two matrices may result in a significant inhomogeneity in the plasma plume, which can severely impact the accuracy of quantitative analysis. Since this propagation of the surface morphology into the plasma plume is driven by the plasma expansion, its final impact is strongly pressure dependent. This study examines the influence of varying ambient pressures (7–1000 mbar) on plasma morphology, spectral characteristics, and key plasma properties such as electron number density at a well-defined Cu–Sn boundary, in comparison with the results obtained using homogeneous alloys. Several approaches of plasma imaging with bandpass filters, spectroscopy, and Radon transform-based 3D reconstruction were employed to analyze elemental distribution, signal-to-noise (SNR) and signal-to-background (SBR) ratios, as well as electron number densities. The 3D reconstructions revealed a pronounced plasma asymmetry for the ablation at the material boundary, in contrast to the near-axial symmetry observed for the ablation of homogeneous alloys. At lower pressures, this distinct elemental separation in plasma persisted, while higher pressures led to an increased collisional mixing and homogenization. SNR and SBR were consistently lower for ablation at the boundary compared to homogeneous samples. These findings highlight how boundary ablation contributes to plasma inhomogeneities in LIBS analysis of heterogeneous materials and emphasize the need to account for these effects when using LIBS for elemental mapping of fine heterogeneous structures. KW - Laser-induced breakdown spectroscopy KW - Plasma inhomogeneity KW - Plasma tomography KW - Radon transform KW - Material boundaries KW - Ambient pressure effects PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-634777 DO - https://doi.org/10.1016/j.talanta.2025.128377 SN - 1873-3573 VL - 295 SP - 1 EP - 8 PB - Elsevier B.V. AN - OPUS4-63477 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kleinbub, Sherin A1 - Braymer, Joseph J A1 - Pfeiffer, Friedhelm A1 - Dyall-Smith, Mike A1 - Spirgath, Kristin A1 - Alfaro-Espinoza, Gabriela A1 - Koerdt, Andrea T1 - From Genes to Black Rust: Genomic insights into corrosive methanogens N2 - Within the past ten years, genetic evidence has been increasing for the direct role that microbes play in microbiologically influenced corrosion (MIC), also known as biocorrosion or biodeterioration. One prominent example is the correlation between the corrosion of metal and the presence of genes encoding an extracellular [NiFe]-hydrogenase (MIC hydrogenase) in the methanogenic archaeon, Methanococcus maripaludis. In this study, DNA sequencing and bioinformatic analysis were used to classify the MIC hydrogenase as belonging to a core set of genes, the MIC core, found so far in Methanococci and Methanobacteria classes of methanogens. Genetic evidence is provided for the mobilization of the MIC core via multiple mechanisms, including a horizontal gene transfer event from Methanobacteria to Methanococci and a newly described MIC-transposon. A detailed comparison of M. maripaludis genomes further pointed to the relevance that cell wall modifications involving N-glycosylation of S-layer proteins and the MIC hydrogenase likely play in methanogen-induced MIC (Mi-MIC). Microscopic analysis of corrosive methanogens encoding the MIC core indicated that Methanobacterium-affiliated strain IM1 can form extensive biofilms on the surface of corrosion products whereas individual cells of M. maripaludis Mic1c10 were only found localized to crevices in the corrosion layer. An updated model of Mi-MIC involving two modes of action is presented, which predicts that the propensity of cells to adhere to iron surfaces directly influences the rate of corrosion due to the localization of the MIC hydrogenase at the metal-microbe interface. KW - Biocorrosion KW - Hydrogenases KW - Metalloprotein KW - Microbes PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-649425 DO - https://doi.org/10.1093/femsmc/xtaf018 SN - 2633-6685 VL - 6 SP - 1 EP - 19 PB - Oxford University Press (OUP) AN - OPUS4-64942 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Richter, Matthias A1 - Schühle, Florian T1 - Experimental determination of 7-day uptake rates for diffusive sampling of 86 volatile and semi-volatile organic compounds relevant for indoor air monitoring and investigation on their sensitivity to exposure time and indoor climate N2 - This study aimed to experimentally determine uptake rates for 86 indoor relevant volatile and semi-volatile organic compounds (VOC, SVOC) for the passive sampler type Perkin Elmer/Markes™ with Tenax® TA as sorbent, which was used in the German Environmental Survey on Health (GerES VI) carried out by the German Environmental Agency (UBA) in the years 2023-2024. For this purpose, single reference gas atmospheres of 76 pure VOCs (liquid at room temperature) and a group of 10 SVOCs and VOCs (solid at room temperature) were generated using two generation procedures. By exposing the samplers to individual components, it was ruled out that interactions in a mixture have a influence on the uptake rate. Another aspect was to precisely describe the methodology and the resulting uncertainties, as there are gaps in the literature in this regard. The selection of the compounds was based on the findings of the preceding GerES V study for which data was missing or needed to be verified. In each experiment, a number of six passive samplers was exposed to the test gas atmospheres in dynamically operated exposure chambers for seven days. The sensitivity of the uptake rates of a group of 10 selected VOCs to variations in exposure time, ambient temperature, and air humidity in a multi-component reference gas atmosphere was investigated. Here, a decrease in the uptake rate with the exposure time could be observed stabilising from the fifth day of exposure onwards. A significant effect of temperature and humidity on the uptake rate was not apparent. The determined uptake rates exhibit uncertainties of < 20 % for 71 substances, and < 10 % for 51 substances which are also in good agreement with the literature, if already published elsewhere. The quantity of investigated substances, the detailed description of the methodology used to determine the uptake rates complemented by the respective uncertainties, as well as the compilation of comparative data, contribute to a better assessment of the quality and relevance of such data, which had not been published before. KW - Indoor air quality KW - Volatile organic compounds KW - Uptake rates KW - Passive sampling KW - Tenax TA PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-629913 DO - https://doi.org/10.1016/j.indenv.2025.100095 VL - 2 IS - 2 SP - 1 EP - 11 PB - Elsevier AN - OPUS4-62991 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Sun, Yijuan A1 - Pérez-Padilla, Víctor A1 - Valderrey, Virginia A1 - Bell, Jérémy A1 - Gawlitza, Kornelia A1 - Rurack, Knut T1 - Ratiometric detection of perfluoroalkyl carboxylic acids using dual fluorescent nanoparticles and a miniaturised microfluidic platform N2 - The widespread contamination of soil and water with perfluoroalkyl substances (PFAS) has caused considerable societal and scientific concern. Legislative measures and an increased need for remediation require effective on-site analytical methods for PFAS management. Here we report on the development of a green-fluorescent guanidine-BODIPY indicator monomer incorporated into a molecularly imprinted polymer (MIP) for the selective detection of perfluorooctanoic acid (PFOA). Complexation of PFOA by the indicator, which is mediated by concerted protonation-induced ion pairing-assisted hydrogen bonding, significantly enhances fluorescence in polar organic solvents. The MIP forms as a thin layer on silica nanoparticles doped with tris(bipyridine)ruthenium(II) chloride, which provides an orange emission signal as internal reference, resulting in low measurement uncertainties. Using a liquid-liquid extraction protocol, this assay enables the direct detection of PFOA in environmental water samples and achieves a detection limit of 0.11 µM. Integration into an opto-microfluidic system enables a compact and user-friendly system for detecting PFOA in less than 15 minutes. KW - PFAS KW - Molecular imprinting KW - Microfluidics KW - Fluorescence KW - Onsite assay PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-650270 DO - https://doi.org/10.1038/s41467-025-66872-9 SN - 2041-1723 VL - 16 IS - 1 SP - 1 EP - 16 PB - Springer Science and Business Media LLC AN - OPUS4-65027 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Oskoei, Párástu A1 - Afonso, Rúben A1 - Bastos, Verónica A1 - Nogueira, João A1 - Keller, Lisa-Marie A1 - Andresen, Elina A1 - Saleh, Maysoon I. A1 - Rühle, Bastian A1 - Resch-Genger, Ute A1 - Daniel-da-Silva, Ana L. A1 - Oliveira, Helena T1 - Upconversion Nanoparticles with Mesoporous Silica Coatings for Doxorubicin Targeted Delivery to Melanoma Cells N2 - Melanoma is one of the most aggressive skin cancers and requires innovative therapeutic strategies to overcome the limitations of conventional therapies. In this work, upconversion nanoparticles coated with mesoporous silica and functionalized with folic acid (UCNP@mSiO2-FA) were developed as a targeted nanocarrier system for the delivery of doxorubicin (DOX). The UCNPs were synthesized via thermal decomposition, coated with mesoporous silica shells, and functionalized with folic acid (FA) to enable receptor-mediated targeting. DOX was then loaded into the mesoporous silica coating by adsorption, yielding UCNP@mSiO2-FA-DOX. The different UCNPs were characterized for size, composition, colloidal stability, and loading and release of DOX. This comprehensive physicochemical characterization confirmed a high DOX loading efficiency and a slightly increased drug release under acidic conditions, mimicking the tumour microenvironment. In vitro assays using four melanoma cell lines (A375, B16-F10, MNT-1, and SK-MEL-28) revealed an excellent biocompatibility of UCNP@mSiO2-FA and a significantly higher cytotoxicity of UCNP@mSiO2-FA-DOX compared to unloaded UCNPs, in a dose-dependent manner. Cell cycle analysis demonstrated G2/M phase arrest after treatment with UCNP@mSiO2-FA-DOX, confirming its antiproliferative effect. Overall, UCNP@mSiO2-FA-DOX represents a promising nanoplatform for targeted melanoma therapy, combining active tumour targeting and enhanced anticancer efficacy. KW - Fluorescence KW - Synthesis KW - Nano KW - Particle KW - Silica KW - Cell KW - Uptake KW - Drug KW - Characterization KW - DOX KW - Imaging KW - Toxicity KW - Release KW - pH PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-653596 DO - https://doi.org/10.3390/molecules31010074 SN - 1420-3049 VL - 31 IS - 1 SP - 1 EP - 18 PB - MDPI AG AN - OPUS4-65359 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Ahmed, A. A. A. A1 - Alegret, N. A1 - Almeida, B. A1 - Alvarez-Puebla, R. A1 - Andrews, A. M. A1 - Ballerini, L. A1 - Barrios-Capuchino, J. J. A1 - Becker, C. A1 - Blick, R. H. A1 - Bonakdar, S. A1 - Chakraborty, I. A1 - Chen, X. A1 - Cheon, J. A1 - Chilla, G. A1 - Conceicao, A. L. C. A1 - Delehanty, J. A1 - Dulle, M. A1 - Efros, A. L. A1 - Epple, M. A1 - Fedyk, M. A1 - Feliu, N. A1 - Feng, M. A1 - Fernandez-Chacon, R. A1 - Fernandez-Cuesta, I. A1 - Fertig, N. A1 - Förster, S. A1 - Garrido, J. A. A1 - George, M. A1 - Guse, A. H. A1 - Hampp, N. A1 - Harberts, J. A1 - Han, J. A1 - Heekeren, H. R. A1 - Hofmann, U. G. A1 - Holzapfel, M. A1 - Hosseinkazemi, H. A1 - Huang, Y. A1 - Huber, P. A1 - Hyeon, T. A1 - Ingebrandt, S. A1 - Ienca, M. A1 - Iske, A. A1 - Kang, Y. A1 - Kasieczka, G. A1 - Kim, D.-H. A1 - Kostarelos, K. A1 - Lee, J.-H. A1 - Lin, K.-W. A1 - Liu, S. A1 - Liu, X. A1 - Liu, Y. A1 - Lohr, C. A1 - Mailänder, V. A1 - Maffongelli, L. A1 - Megahed, S. A1 - Mews, A. A1 - Mutas, M. A1 - Nack, L. A1 - Nakatsuka, N. A1 - Oertner, T. G. A1 - Offenhäusser, A. A1 - Oheim, M. A1 - Otange, B. A1 - Otto, F. A1 - Patrono, E. A1 - Peng, B. A1 - Picchiotti, A. A1 - Pierini, F. A1 - Pötter-Nerger, M. A1 - Pozzi, M. A1 - Pralle, A. A1 - Prato, M. A1 - Qi, B. A1 - Ramos-Cabrer, P. A1 - Resch-Genger, Ute A1 - Ritter, N. A1 - Rittner, M. A1 - Roy, S. A1 - Santoro, F. A1 - Schuck, N. W. A1 - Schulz, F. A1 - Seker, E. A1 - Skiba, M. A1 - Sosniok, M. A1 - Stephan, H. A1 - Wang, R. A1 - Wang, T. A1 - Wegner, Karl David A1 - Weiss, P. S. A1 - Xu, M. A1 - Yang, C. A1 - Zargarin, S. S. A1 - Zeng, Y. A1 - Zhou, Y. A1 - Zhu, D. A1 - Zierold, R. A1 - Parak, W. J. T1 - Interfacing with the Brain: How Nanotechnology Can Contribute N2 - Interfacing artificial devices with the human brain is the central goal of neurotechnology. Yet, our imaginations are often limited by currently available paradigms and technologies. Suggestions for brain−machine interfaces have changed over time, along with the available technology. Mechanical levers and cable winches were used to move parts of the brain during the mechanical age. Sophisticated electronic wiring and remote control have arisen during the electronic age, ultimately leading to plug-and-play computer interfaces. Nonetheless, our brains are so complex that these visions, until recently, largely remained unreachable dreams. The general problem, thus far, is that most of our technology is mechanically and/or electrically engineered, whereas the brain is a living, dynamic entity. As a result, these worlds are difficult to interface with one another. Nanotechnology, which encompasses engineered solid-state objects and integrated circuits, excels at small length scales of single to a few hundred nanometers and, thus, matches the sizes of biomolecules, biomolecular assemblies, and parts of cells. Consequently, we envision nanomaterials and nanotools as opportunities to interface with the brain in alternative ways. Here, we review the existing literature on the use of nanotechnology in brain−machine interfaces and look forward in discussing perspectives and limitations based on the authors’ expertise across a range of complementary disciplines from neuroscience, engineering, physics, and chemistry to biology and medicine, computer science and mathematics, and social science and jurisprudence. We focus on nanotechnology but also include information from related fields when useful and complementary. KW - Nanoneuro interface KW - Brain-on-a-chip KW - Nanostructured interface KW - Electrode arrays KW - Neuro-implants KW - Advanced nanomaterials KW - Quality assurance PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-634893 DO - https://doi.org/10.1021/acsnano.4c10525 SN - 1936-086X VL - 19 IS - 11 SP - 10630 EP - 10717 PB - ACS Publications AN - OPUS4-63489 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - El-Dahshan, O. A1 - Deniaud, A. A1 - Ling, W. L. A1 - Wegner, Karl David A1 - Proux, O. A1 - Veronesi, G. A1 - Reiss, P. T1 - Hydrothermal microwave synthesis of water soluble NIR-II emitting Ag2S quantum dots N2 - Hydrothermal-based synthetic methods of quantum dots allow for the exploration of reaction parameters normally inaccessible to typical aqueous-based batch reactions, such as elevated reaction temperatures (>100 °C) and reaction pressures above atmospheric pressure. Coupled with microwave heating, new instantaneously bio-compatible quantum dots (QDs) with enhanced opitcal properties can be yielded. As of today, aqueous-based synthetic methods often lag behind their organic analogues in terms of the photophysical properties of the QDs obtained and the ease of modulation of both the emission wavelength and crystallite size. Using a novel microwave-assisted hydrothermal approach, the synthesis of silver sulphide (Ag2S) QDs exhibiting NIR emission spanning the biological transparency windows via modulation of the reaction parameters has been developed. The intrinsic link between their optical and structural properties is explored via laboratory and synchrotron-based structural analysis techniques. Their toxicity towards a hepatic cell line was assessed, and related back to their structure and size. Overall this work aims to not only further develop the repertoire of synthetic methods for the synthesis of Ag2S QDs, but also paves the way for the development of safer QDs suitable for future clinical applications. KW - Quantum dots KW - Microwave synthesis KW - Quality assurance KW - NIR-II emission KW - PL quantum yield KW - Ag2S PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-634825 DO - https://doi.org/10.1039/d5nr00052a SN - 2040-3372 VL - 17 IS - 24 SP - 14637 EP - 14646 PB - RSC AN - OPUS4-63482 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Habibimarkani, Heydar A1 - Abram, Sarah-Luise A1 - de Oliveira Guilherme Buzanich, Ana A1 - Prinz, Carsten A1 - Sahre, Mario A1 - Hodoroaba, Vasile-Dan A1 - Radnik, Jörg T1 - In-depth analysis of FeNi-based nanoparticles for the oxygen evolution reaction N2 - This study investigates the effect of varying iron-to-nickel ratios on the catalytic performance of Fe-Ni oxide nanoparticles (NPs) for the oxygen evolution reaction (OER). Addressing the issue of high energy wastage due to large overpotentials in OER, we synthesized and characterized different NP catalysts with different Fe: Ni oxide ratios. Transmission Electron Microscopy (TEM), Energy Dispersive X-ray Spectroscopy (EDS), and X-ray Diffraction (XRD) were employed to determine the morphology, elemental and phase composition of the NPs. Furthermore, in-depth profiling with X-ray Photoelectron Spectroscopy (XPS) and Hard X-ray Photoelectron Spectroscopy (HAXPES) revealed that iron predominantly exists as oxide, while nickel exhibits both metallic and oxidic forms depending on the Fe content. XPS indicated an enrichment of iron at the NP surface, whereas HAXPES and EDS data agreed on the bulk stoichiometry. The assessment of the catalytic activity via cyclic voltammetry (CV) showed that the Fe: Ni ratio of 2:3 exhibited superior performance, characterized by lower overpotential and a smaller Tafel slope. KW - Fe-Ni oxide KW - Nanoparticles KW - OER KW - Catalytic performance KW - Cyclic voltammetry PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-626932 UR - https://www.nature.com/articles/s41598-025-92720-3 DO - https://doi.org/10.1038/s41598-025-92720-3 VL - 15 IS - 1 SP - 1 EP - 17 PB - Springer Nature AN - OPUS4-62693 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Meiers, Emelie A1 - Scholl, Juliane A1 - Droas, Morten A1 - Vogel, Christian A1 - Leube, Peter A1 - Sommerfeld, Thomas A1 - Bagheri, A. A1 - Adam, Christian A1 - Seubert, A. A1 - Koch, Matthias T1 - Development and evaluation of analytical strategies for the monitoring of per- and polyfluoroalkyl substances from lithium-ion battery recycling materials N2 - Per- and polyfluoroalkyl substances (PFAS) are well-known as “forever chemicals” and persistent pollutants released by different anthropogenic sources. The potential release of PFAS from accumulating electronic waste and lithium-ion battery (LIB) recycling activities has gained increasing attention in the past years. This creates a need for analytical methods tailored for the determination of PFAS out of environmental matrices related to the named activities or directly out of the concerned materials. In this work, analytical strategies for the monitoring of PFAS in LIB recycling materials were explored for a group of legacy perfluoro sulfonic- and carbonic acids (PFSA and PFCA) and of fluorinated sulfonylimides suspected to be LIB electrolyte ingredients. These analytical strategies comprehend PFAS target approaches with a herein optimized liquid chromatography tandem mass spectrometry (LC–MS/MS) method equipped with a HILIC (hydrophilic interaction liquid chromatography) column in combination with the TOP (total oxidizable precursor) assay and an adapted sample preparation method for high-matrix LIB recycling materials. The validated target method was applied to a set of LIB recycling materials: end-of-life batteries, black masses from hydrometallurgical recycling, and gas absorption solutions from thermal treatment of black masses as part of the recycling procedure. Investigation results show that the LIB industry can be connected to the release of both “LIB”-PFAS, such as the target sulfonylimides, and “already-legacy” PFAS, like the PFSA and PFCA. Especially, the presence of trifluoroacetic acid (TFA) as an emerging pollutant in every investigated LIB material type underlines the threat of PFAS emissions from LIB waste and recycling activities. KW - Per- and polyfluoroalkyl substances (PFAS) KW - Battery PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-647015 DO - https://doi.org/10.1007/s00216-025-06165-8 SN - 1618-2642 VL - 417 SP - 6567 EP - 6583 PB - Springer Science and Business Media LLC AN - OPUS4-64701 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - 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 -