TY - CONF A1 - Schmitt, Johannes T1 - Data Acquisition System for Single Particle Inductively Coupled Plasma Mass Spectrometry (spICP-MS) with Nanosecond Time Resolution N2 - This study presents our data acquisition system prototype for spICP-MS with nanosecond time resolution (nanoDAQ) and a matching data processing approach for nanosecond resolved single particle spICP-MS data. The system continuously samples the secondary electron multiplier (SEM) detector signal with a dwell time of approximately 2 ns and enables the detection of gold nanoparticles (AuNP) as small as 7.5 nm[1] with a commercial single quadrupole ICP-MS instrument. The acquired transient data is processed based on the temporal distance between detector events and the event density. It was shown that the inverse logarithm of the distance between detector events is proportional to the particle size and that the number of detector events corresponding to a particle signal distribution can be used to calibrate and determine the particle number concentration (PNC) of a nanoparticle dispersion.[1] The high data acquisition frequency of the systems allows recording of a statistically significant number of data points in 60 s or less, which leads to the main time limitation for analyses being merely the sample uptake time and rinsing step between analyte solutions. T2 - 55th Annual Conference of the German Society for Mass Spectrometry CY - Freising, Germany DA - 10.03.2024 KW - Nanoparticles KW - Mass Spectrometry KW - Instrumentation KW - spICP-MS PY - 2024 AN - OPUS4-62315 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Heinelt, Manuel T1 - Capabilities of Surface-Assisted Flowing Atmospheric-Pressure Afterglow Mass Spectrometry (SA-FAPA-MS) for Direct Analysis of Polycyclic Aromatic Hydrocarbons (PAHs) N2 - Ambient desorption/ionization mass spectrometry (ADI-MS) is a growing area in the analytical chemistry of organic molecules. It requires only minimal sample preparation and can reduce analysis time compared to traditional methods.[1] One evolving method is the plasma-based pin-to-capillary Flowing Atmospheric-Pressure Afterglow (FAPA) source. Which is an improved version of the original pin-to-plate FAPA, resulting in significantly lower background signals and less oxidation of the analytes.[2] In our case, samples are probed directly from thin-layer chromatography (TLC) plates, which have shown promising results in improving signal response and performance in mass spectral imaging in previous studies. Especially, cyano (CN)-HPTLC and reversed-phase (RP2)-TLC plates were suited best for the analysis of different organic molecules.[3] In this work, FAPA is investigated as a method to determine polycyclic aromatic hydrocarbons (PAHs). Furthermore, its suitability for rapid screening of real samples was investigated. 30 pure PAH standard samples were analyzed on different TLC surfaces. Cyano (CN)-HPTLC and reversed-phase (RP2)-TLC plates proved to be the most suitable substrate for the analysis of PAH compounds. Linear ranges of up to four orders of magnitude could be achieved. Limits of detection (LOD) of anthracene, chrysene, and fluorene were in the µg/L range. However, these pure analytes differ from PAH samples collected in the environment, which may contain hundreds of different PAHs among other constituents. Therefore, PAH containing real samples were used to test the method and its screening capability on more complex samples. A standard reference material (diesel particulate extract, NIST SRM 1975) was analyzed for method validation. For sample preparation, 1 µL of the extract was spotted directly onto the TLC surface. It was possible to perform a triple determination in approx. 20 min. Therefore, SA-FAPA-MS has a huge potential to be established as a method for rapid qualitative screening of PAHs in real samples. T2 - 55th Annual Conference of the German Society for Mass Spectrometry (Deutsche Gesellschaft für Massenspektrometrie, DGMS). CY - Freising, Germany DA - 10.03.2024 KW - Mass Spectrometry KW - Massenspektrometrie KW - Instrumental Analytical Chemistry KW - Instrumentelle Analytische Chemie KW - Polycyclic Aromatic Hydrocarbons PY - 2024 AN - OPUS4-62316 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Vermeeren, Sarah A1 - Witzler, Markus A1 - Makarow, Ramona A1 - Engelhard, Carsten A1 - Kaul, Peter T1 - Multivariate evaluation method for the detection of pest infestations on plants via VOC analysis using gas chromatography mass spectrometry N2 - Volatile organic compounds (VOCs) play an important role in the defense against pest infestations on plants. The analysis of these VOCs using gas chromatography mass spectrometry (GC-MS) enables the detection of pests by analyzing the VOC composition (VOC profiles) for specific patterns and markers. The analysis of such complex datasets with high biovariability poses a particular challenge. For this reason, a multivariate evaluation method based on a self-written Python script, using principal component analysis (PCA) and linear discriminant analysis (LDA), was developed and tested for functionality using a dataset, which has been evaluated manually and has identified five specific markers (2,4-dimethyl-1-heptene, 3-carene, alpha-longipinene, cyclosativene, and copaene) for Anoplophora glabripennis (ALB) infestation on Acer trees. The results obtained in the present study did not only match the manually evaluated results, but lead to further insight into the dataset. Another sesquiterpene which is assumed to be alpha-zingiberene was identified as an ALB specific marker in addition to 2,4-dimethyl-1-heptene and 3-carene. Furthermore, the European native beetle species goat moth Cossus cossus (CC) and poplar long-horned beetle Saperda carcharias (SC) were also analyzed for their VOCs to differentiate ALB specific VOC from other pest infestations. This comparison lead to the conclusion that the compounds alpha-longipinene, cyclosativene, and copaene are not specific for ALB but for pest infestation in general. It was possible to identify not only specifically produced VOCs, but also differences in concentrations that arise specifically during ALB infestation. Therefore, the evaluation method for the detection of plant pests presented in this study represents a time-saving alternative to conventional non computing methods, which in addition provides more detailed results. KW - Mass Spectrometry KW - Gas Chromatography KW - Volatile organic compounds KW - Pest infestation PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-639526 DO - https://doi.org/10.1038/s41598-025-11607-5 SN - 2045-2322 VL - 15 IS - 1 SP - 1 EP - 10 PB - Springer Science and Business Media LLC AN - OPUS4-63952 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Braun, Jennifer A1 - Engelhard, Carsten A1 - Kaul, Peter T1 - Optimized fast gas chromatography coupled with proton-transfer-reaction time-of-flight mass spectrometry for the selective near real-time analysis of herbivore-induced plant volatiles N2 - The analysis of herbivore-induced plant volatiles (HIPVs) is essential for understanding plant-environment interactions and defense strategies against herbivores. Proton transfer reaction time-of-flight mass spectrometry (PTR–TOF–MS) is a powerful analytical tool that enables real-time monitoring and quantification of diverse groups of HIPVs. However, the PTR–TOF–MS technique is constrained in its ability to effectively differentiate between isomers. When analyzing complex mixtures of HIPVs, the separation of isomers becomes crucial as major compound classes such as terpenes comprise thousands of isomers. In this study, we present an optimized fast gas chromatography (fastGC) based on a modified version of the commercially available fastGC add-on integrated into a mobile PTR–TOF. The system was optimized for the analysis of emissions from enclosed trunks of Acer platanoides infested by Anoplophora glabripennis (Motschulsky), commonly known as Asian longhorned beetle (ALB). The development of fastGC was primarily focused on the sesquiterpenes α-longipinene, cyclosativene and α-copaene, which serve as strong indicators of ALB infestation. These sesquiterpenes were separated in less than three minutes, with intra-day retention time RSD < 0.6 % and resolutions of 2.6 ± 0.3 and 1.3 ± 0.2. In comparison to the original system, the optimized fastGC demonstrates more than tripled sesquiterpene resolution, twice the sensitivity relative to direct inlet mode, and an approximately 10 % reduction in total analysis time. The optimized fastGC–PTR–TOF allows for near real-time analysis of complex mixtures of biogenic VOCs, making it a powerful tool for environmental monitoring, integrated pest management, and forest protection. KW - Mass Spectrometry KW - PTR-TOF-MS KW - Gas Chromatography KW - Herbivore-induced plant volatiles KW - Sesquiterpenes PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-639513 DO - https://doi.org/10.1016/j.chroma.2025.466236 SN - 0021-9673 VL - 1759 SP - 1 EP - 16 PB - Elsevier B.V. AN - OPUS4-63951 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Escobar-Carranza, Cristian C. T1 - On the Detection of Microplastics by Flowing Atmospheric-Pressure Afterglow Mass Spectrometry (FAPA-MS) N2 - Microplastics (MPs) are widespread pollutant particles that can be analyzed using Raman and FTIR spectroscopy combined with optical microscopy. Additionally, pyrolysis (Py) or thermal extraction and desorption (TED) coupled with gas chromatography-mass spectrometry (GC-MS) are used for the characterization of MPs.[1] However, sample throughput is limited due to GC separation. This work presents a feasibility study for the direct, rapid analysis of MPs using high-resolution mass spectrometry and a plasma-based ambient desorption/ionization source (FAPA, flowing atmospheric-pressure afterglow).[2] In earlier work, an in-house built ambient ionization source (modelled after the pin-to-capillary (p2c) FAPA design by Shelley et al. [3]) was coupled to HR-Orbitrap MS and used to characterize different MPs produced in-house from plastic materials including polystyrene (PS), polypropylene (PP), low-density polyethylene (LDPE), and polycarbonate (PC). Simultaneous detection of characteristic ions and particle imaging on a sampling mesh was feasible, with detection limits (LOD) for PS MPs at 311 µm in size and 1.3 mg in mass. Principal component analysis (PCA) was used for particle differentiation. This work presents an improved desorption/ionization approach using higher temperatures for desorption enhancement (approximately 500 °C, achieved with economical and commercially available parts) and a tailored source housing combined with a halo-shaped (h-FAPA) source configuration.[4] The scope was expanded to include MPs from poly(ethylene terephthalate) (PET), poly(methyl methacrylate) (PMMA), and poly(vinyl chloride) (PVC), sized 125–250 µm. Data visualization and interpretation were performed using Kendrick mass defect plots and other multivariate analysis tools. Compared to earlier results, h-FAPA-MS yielded at least 65% higher ion signals for selected ions in all MPs. These ions were detected mainly as protonated species [M+H]+. Higher thermal desorption temperatures aided in detecting all MPs, as the presence of higher molecular weight fragments added specificity to the analysis. Notably, experiments with the h-FAPA source demonstrated lower mass-based LODs for MPs than the p2c-FAPA source (e.g., 14 µg vs 1.3 mg for PS, respectively). T2 - ANAKON 2025 CY - Leipzig, Germany DA - 10.03.2025 KW - Mass Spectrometry KW - Plasma KW - FAPA-MS KW - Microplastics PY - 2025 AN - OPUS4-63604 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schütz, Désirée A.-M. T1 - Feasibility Study on the Adsorption of Environmental Contaminants onto Fresh and Aged Microplastics N2 - Microplastics (MPs) refer to plastic particles, fibers, or beads with sizes ranging from 100 nm to 5 mm in size. Their pervasive distribution as environmental contaminants have escalated into a significant global concern. Primary MPs are intentionally produced particles for industrial and commercial applications, such as exfoliants in personal care and cosmetic formulations. In contrast, secondary MPs are generated through the fragmentation and degradation of larger plastic materials, due to environmental weathering processes. [1] Due to their high surface area-to-volume ratio and hydrophobic nature, MPs have the potential to serve as vectors for the accumulation and transport of diverse organic contaminants, including polycyclic aromatic hydrocarbons (PAHs), perfluoroalkyl substances (PFAS), pharmaceuticals and personal care products (PPCPs), as well as trace metals such as silver, cadmium, chromium, and copper. In the environmental, MPs are subject to aging processes driven by factors such as temperature, ultraviolet radiation, oxygen, and chemical interactions with environmental toxins. This aging can induce significant alterations in their physicochemical properties, which, in turn, can affect the adsorption behavior. [2] Classical and alternative analytical methods such as high-performance liquid chromatography (HPLC) and ambient desorption/ionization high-resolution mass spectrometry (ADI-HR-MS) can help to study the adsorption potential. ADI-HR-MS allows rapid sample analysis with minimal preparation, providing results in under a minute, much faster than traditional chromatographic techniques. [3] This study aims to investigate the influence of aging and particle size on the ability of microplastics to act as vectors for environmental contaminants. Microplastics were prepared in-house and subjected to controlled aging conditions for 12, 24, 36, and 48 hours. Subsequently, the aged MPs were exposed in plastic-free containers to model solutions to simulate co-contaminants in the environment. Adsorption onto synthesized secondary microplastics, varying in size and aging status, was investigated at different time intervals with ambient MS and time-of-flight secondary ion mass spectrometry. T2 - ANAKON 2025 CY - Leipzig, Germany DA - 10.03.2025 KW - Mass Spectrometry KW - FAPA-MS KW - Microplastics KW - TOF-SIMS KW - Surface Analysis PY - 2025 AN - OPUS4-63606 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Heinelt, Manuel T1 - Feasibility Study on the Direct Detection of Per- and Polyfluoroalkyl Substances (PFAS) with Surface-Assisted Flowing Atmospheric-Pressure Afterglow Mass Spectrometry (SA-FAPA-MS) N2 - Per- and polyfluoroalkyl substances (PFAS) are a large class of thousands of synthetic chemicals that are used worldwide. However, growing environmental and human health concerns in the last two decades have led to more stringent regulatory requirements and the development of quantitative analytical methods for PFAS detection. Today, standardized and powerful methods exist, e.g., for the determination of PFAS in water, sludge, compost, soil, and drinking water (DIN 38407-42, DIN 38414-14, ISO 21675, and DIN EN 17892). While liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS) is often used, blank levels, sample preparation, and total analysis times can be challenging. [1] Here, ambient desorption/ionization mass spectrometry (ADI-MS) is considered interesting because it requires only minimal sample preparation and was able to reduce total analysis time in other types of applications. [2] Previously, we used a plasma-based pin-to-capillary flowing atmospheric-pressure afterglow source (FAPA) [3] to probe samples directly from thin-layer chromatography (TLC) plates and to perform quantitative analysis and mass spectral imaging [4]. In this work, a feasibility study for the direct detection of PFAS with FAPA-MS is reported. Selected PFAS samples were directly probed on functionalized TLC surfaces (normal-phase silica, reversed-phase-modified silica, cyano [CN]-modified silica, and dimethyl [RP2]-modified silica, diol modified silica, and amino [NH2]-modified silica). The suitability of the surfaces was evaluated and the compatibility of different solvents with the surfaces was studied. CN-HPTLC and RP2-TLC surfaces showed the best performance for direct PFAS detection with FAPA-MS. In addition, direct analysis of PFAS mixtures and selected matrices was performed with little sample preparation and short analysis time. T2 - ANAKON 2025 CY - Leipzig, Germany DA - 10.03.2025 KW - Mass Spectrometry KW - FAPA-MS KW - Instrumentation KW - PFAS KW - Surface Analysis PY - 2025 AN - OPUS4-63605 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Heinelt, Manuel T1 - Feasibility Study on the Direct Detection of Per- and Polyfluoroalkyl Substances (PFAS) with Surface-Assisted Flowing Atmospheric-Pressure Afterglow Mass Spectrometry (SA-FAPA-MS) N2 - Per- and polyfluoroalkyl substances (PFAS) are a large class of thousands of synthetic chemicals that are used worldwide. However, growing environmental and human health concerns in the last two decades have led to more stringent regulatory requirements and the development of quantitative analytical methods for PFAS detection. Today, standardized and powerful methods exist, e.g., for the determination of PFAS in water, sludge, compost, soil, and drinking water (DIN 38407-42, DIN 38414-14, ISO 21675, and DIN EN 17892). While liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS) is often used, blank levels, sample preparation, and total analysis times can be challenging. [1] Here, ambient desorption/ionization mass spectrometry (ADI-MS) is considered interesting because it requires only minimal sample preparation and was able to reduce total analysis time in other types of applications. [2] Previously, we used a plasma-based pin-to-capillary flowing atmospheric-pressure afterglow source (FAPA) [3] to probe samples directly from thin-layer chromatography (TLC) plates and to perform quantitative analysis and mass spectral imaging [4]. In this work, a feasibility study for the direct detection of PFAS with FAPA-MS is reported. Selected PFAS samples were directly probed on functionalized TLC surfaces (normal-phase silica, reversed-phase-modified silica, cyano [CN]-modified silica, and dimethyl [RP2]-modified silica, diol modified silica, and amino [NH2]-modified silica). The suitability of the surfaces was evaluated and the compatibility of different solvents with the surfaces was studied. CN-HPTLC and RP2-TLC surfaces showed the best performance for direct PFAS detection with FAPA-MS. In addition, direct analysis of PFAS mixtures and selected matrices was performed with little sample preparation and short analysis time. T2 - 56th Annual Conference of the DGMS CY - Göttingen, Germany DA - 04.03.2025 KW - FAPA-MS KW - Instrumentation KW - Mass Spectrometry KW - PFAS KW - Surface Analysis PY - 2025 AN - OPUS4-63643 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schütz, Désirée A.-M. T1 - Feasibility Study on the Adsorption of Environmental Contaminants onto Fresh and Aged Microplastics N2 - Microplastics (MPs) refer to plastic particles, fibers, or beads with sizes ranging from 100 nm to 5 mm in size. Their pervasive distribution as environmental contaminants have escalated into a significant global concern. Primary MPs are intentionally produced particles for industrial and commercial applications, such as exfoliants in personal care and cosmetic formulations. In contrast, secondary MPs are generated through the fragmentation and degradation of larger plastic materials, due to environmental weathering processes. [1] Due to their high surface area-to-volume ratio and hydrophobic nature, MPs have the potential to serve as vectors for the accumulation and transport of diverse organic contaminants, including polycyclic aromatic hydrocarbons (PAHs), perfluoroalkyl substances (PFAS), pharmaceuticals and personal care products (PPCPs), as well as trace metals such as silver, cadmium, chromium, and copper. In the environmental, MPs are subject to aging processes driven by factors such as temperature, ultraviolet radiation, oxygen, and chemical interactions with environmental toxins. This aging can induce significant alterations in their physicochemical properties, which, in turn, can affect the adsorption behavior. [2] Classical and alternative analytical methods such as high-performance liquid chromatography (HPLC) and ambient desorption/ionization high-resolution mass spectrometry (ADI-HR-MS) can help to study the adsorption potential. ADI-HR-MS allows rapid sample analysis with minimal preparation, providing results in under a minute, much faster than traditional chromatographic techniques. [3] This study aims to investigate the influence of aging and particle size on the ability of microplastics to act as vectors for environmental contaminants. Microplastics were prepared in-house and subjected to controlled aging conditions for 12, 24, 36, and 48 hours. Subsequently, the aged MPs were exposed in plastic-free containers to model solutions to simulate co-contaminants in the environment. Adsorption onto synthesized secondary microplastics, varying in size and aging status, was investigated at different time intervals with ambient MS and time-of-flight secondary ion mass spectrometry. T2 - 56th Annual Conference of the DGMS CY - Göttingen, Germany DA - 04.03.2025 KW - FAPA-MS KW - Mass Spectrometry KW - Microplastics KW - Surface Analysis KW - TOF-SIMS PY - 2025 AN - OPUS4-63644 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schardt, Annika T1 - Fast screening method for nanoparticles in surface waters via nanosecond spICP-MS and a tailored automated ion cloud recognition algorithm N2 - Single particle inductively coupled plasma mass spectrometry (spICP-MS) is a powerful technique for nanoparticle (NP) analysis in aqueous samples, which provides essential information on size distribution and particle number concentration (PNC) of nanometer-sized particles in various water samples for risk assessment and toxicity tests. In contrast to spectroscopic particle analysis methods, this mass spectrometry-based tool can provide chemical information on the elemental composition of NPs after minimal sample preparation. We recently presented a novel spICP-MS instrumentation and tailored software that acquires data with nanosecond time resolution, lowering the particle size detection limit to 7 nm for gold NP (1). The system directly samples the output signal of the electron multiplier and records the detection of individual ions with a time resolution of only a few nanoseconds. With nanosecond time resolution, we were able to visualize profiles of ion clouds that were produced from ionization of nanoparticles in the ICP on a single-ion basis and to use the temporal gap between those ions for particle sizing. Our latest improvement of the data acquisition system (nanoDAQ) features ca. 2 ns integration time and a matching processing software prototype, which automatically recognizes and counts ion clouds in the transient data. With this combination we achieved an experimentally determined size detection limit of ca. 5 nm for gold nanoparticles. A feasibility study shows that the nanoDAQ in combination with the ion cloud recognition algorithm succeeds in fast detection and counting of NP containing Ag, Ce, or Zr in waste water and surface water samples from the area of Siegen. PNCs ranged from ca. 7 x 106–2 x 108 particles/L, which is in good agreement with concentrations reported for similar water samples in the literature. T2 - 56th Annual Conference of the German Society for Mass Spectrometry (DGMS) CY - Göttingen, Germany DA - 04.03.2025 KW - Instrumentation KW - Mass Spectrometry KW - Nanoparticles KW - spICP-MS PY - 2025 AN - OPUS4-63662 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Escobar-Carranza, Cristian C. T1 - On the Detection of Microplastics by Flowing Atmospheric-Pressure Afterglow Mass Spectrometry (FAPA-MS) N2 - Microplastics (MPs) are widespread pollutant particles analyzed using Raman and FTIR spectroscopy combined with optical microscopy. Pyrolysis (Py) or thermal extraction and desorption (TED) coupled with gas chromatography-mass spectrometry (GC-MS) are used for the characterization of MPs, though GC limits sample throughput. This work explores direct, rapid MP analysis using high-resolution (HR) MS and a plasma-based ambient desorption/ionization source (FAPA, flowing atmospheric-pressure afterglow). Previously, an in-house pin-to-capillary (p2c) FAPA source coupled to HRMS characterized MPs made in-house from polystyrene (PS), polypropylene (PP), low-density polyethylene (LDPE), and polycarbonate (PC). Simultaneous detection of characteristic ions and particle imaging on a sampling mesh was feasible, with detection limits (LOD) for PS MPs at 311 µm in size and 1.3 mg in mass. Principal component analysis (PCA) was used for particle differentiation. This work introduces a high-temperature desorption method (~500 °C) with economical and commercially available parts and a tailored housing combined with a halo-shaped (h-FAPA) source configuration. The study expands to include poly(ethylene terephthalate) (PET), poly(methyl methacrylate) (PMMA), and poly(vinyl chloride) (PVC) MPs (125–250 µm). Data visualization and interpretation were performed using Kendrick mass defect plots and other multivariate analysis tools. Compared to earlier results, h-FAPA-MS yielded at least 65% higher ion signals for selected ions in all MPs. These ions were detected mainly as protonated species [M+H]+. Higher thermal desorption temperatures aided in detecting all MPs, as the presence of higher molecular weight fragments added specificity to the analysis. Notably, experiments with the h-FAPA source demonstrated lower mass-based LODs for MPs than the p2c-FAPA source (e.g., 14 µg vs 1.3 mg for PS, respectively). T2 - 56th Annual Conference of the German Society for Mass Spectrometry (DGMS) CY - Göttingen, Germany DA - 04.03.2025 KW - Instrumentation KW - Mass Spectrometry KW - FAPA-MS KW - Microplastics PY - 2025 AN - OPUS4-63663 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 - Onyenso, Gabriel A1 - AI-Zawity, Jiwar A1 - Farahbakhsh, Nastaran A1 - Schardt, Annika A1 - Yadigarli, Aydan A1 - Vakamulla Raghu, Swathi Naidu A1 - Engelhard, Carsten A1 - Müller, Mareike A1 - Schönherr, Holger A1 - Killian, Manuela S. T1 - Novel Ag-modified zirconia nanomaterials with antibacterial activity N2 - The outcome of an implant procedure largely depends on the implant's surface properties. Biomaterials are now designed to have surfaces with multifunctionality, such as favorable tissue integration and the ability to combat bacterial adhesion and colonization. Herein, we report on a simple approach to improve the antibacterial properties of zirconia nanotubes (ZrNTs) coatings by decorating with silver nanoparticles (AgNP), achieved through electrochemical anodization of a zirconium–silver alloy (Zr–Ag). The AgNPs were shown to partially consist of Ag2O, potentially enhancing the availability of Ag+ ions for antibacterial activity. The modified ZrNTs were characterized using SEM, EDS, ToF-SIMS, and XPS to determine their structural morphology and chemical composition, and were further subjected to antibacterial testing. The silver and zirconium ion release behavior was monitored via ICP-MS. ZrNTs decorated with AgNP exhibit strong antimicrobial activity (>99% bacterial killing) against both S. aureus and E. coli. Antimicrobial tests indicate that the antibacterial activity against the Gram-positive pathogen S. aureus was improved by a factor of 100 compared to unmodified ZrNTs, while unmodified ZrNTs already showed a comparable reduction of viable Gram-negative E. coli. This strategy illustrates a straightforward and effective modification that optimizes the interface between the host environment and the biomaterial surface to meet the very important criteria of biocompatibility and active antibacterial response. KW - Mass Spectrometry KW - Nanoparticles KW - Advanced Materials KW - ICP-MS KW - Antimicrobial material KW - ToF-SIMS PY - 2026 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-653990 DO - https://doi.org/10.1039/d5ra07099f SN - 2046-2069 VL - 16 IS - 3 SP - 2286 EP - 2297 PB - Royal Society of Chemistry (RSC) AN - OPUS4-65399 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Engelhard, Carsten T1 - Advances in Analytical Chemistry and Mass Spectrometry to Support a Sustainable and Circular Economy N2 - Recent advances in analytical chemistry have significantly supported efforts to realize a sustainable circular economy and circular chemistry. By enabling rapid materials analysis and characterization of materials transformation throughout their life cycle, analytical methods are playing a key role in supporting waste reduction, resource recovery, pollution monitoring, and sustainable manufacturing. In this presentation, recent developments in analytical chemistry and analytical instrumentation to support a sustainable and circular economy will be reviewed and selected contributions from our laboratories will be discussed. For example, high-resolution mass spectrometry combined with chromatography is an indispensable tool for the identification and characterization of plastics. To support the transition from linear to circular chemistry, whichs prioritizes reuse, recycling, and resource efficiency, accurate and detailed chemical information about plastic materials is essential. Here, targeted and non-targeted screening approaches help to characterize, for example, the quality and safety of recycled plastics. In addition, green analytical chemistry has emerged as a topic of interest, emphasizing the use of solvent-free and low-energy methods to minimized environmental impact during analysis. Here, ambient desorption/ionization high-resoluton mass spectrometry (ADI-MS) is considered a very attractive tool because it dos not require chromatography or large amounts of solvent, reduces sample preparation time, and produces virtually no chemical waste. Here, a solvent-free, plasma-based ADI-MS method is presented, which was carefuly developed for the direct identification and fast screening of per- and polyfluoroalkyl substances (PFAS). PFAS are a large class of thousands of synthetic chemicals that are used worldwide. However, growing environmental and human health concerns in the last two decades have led to more stringent regulatory requirements and the development of quantitative analytical methods for PFAS detection. Today, standardized and powerful methods exist, e.g., for the determination PFAS in water, sludge, compost, soil, and drinking water. While liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS) is often used, sample preparation, solvent consumption, and total analysis times can be challenging. Here, ADI-MS is considered interesting, because it requires only minimal sample preparation and little solvent consumption. In this work, a plasma-based pin-to-capillary flowing atmospheric-pressure afterglow source (FAPA) is used for the direct desorption/ionization of PFAS from thin-layer chromatography (TLC) plates. Selected PFAS samples were directly probed on functionalized TLC surfaces without a preceding planar chromatography step. In addition, direct analysis of PFAS mixtures and selected matrices was performed with little solvent consumption, no sample preparation and short analysis time. T2 - XXII European Conference on Analytical Chemistry (EUROANALYSIS) CY - Barcelona, Spain DA - 31.08.2025 KW - Mass Spectrometry KW - Extractables & Leachables KW - Non-Targeted Analysis KW - PFAS KW - FAPA-MS PY - 2025 AN - OPUS4-65275 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -