TY - CONF A1 - Tavernaro, Isabella T1 - Quantifying the Total and Accessible Number of Surface Functional Groups and Ligands on Engineered Nanomaterials Using a Multimodal Approach N2 - Functionalized nanomaterials (NM) with their unique size-dependent properties are of increasing relevance for current and future developments in various fields such as medical and pharmaceutical industry, computing, electronics or food and consumer products. For instance, NMs are used as drug carriers, fluorescent sensors, and multimodal labels in bio-analytical assays and imaging applications. The performance and safety of NMs are influenced by their intrinsic physicochemical properties. Among these, the surface chemistry of the particles, which is largely determined by the chemical nature and density of functional groups and ligands, plays a crucial role in enhancing the stability, and processability of NMs, as well as their interactions with the environment. Thus, particle standards with well-designed surfaces and methods for functional group quantification can foster the sustainable development of functional and safe(r) NM.[1] To develop simple, versatile, and multimodal tools for quantifying various bioanalytically relevant functional groups (FG) such as amine,[2,3] carboxy,[2] thiol, and aldehyde[4] functionalities, we explored and compared several analytical methods. These methods included electrochemical titration, dye-based optical assays, and other instrumental techniques like nuclear magnetic resonance, mass spectrometry, and thermal analysis. Our multimodal approach’s potential for FG quantification was demonstrated using both commercial and custom-made polymeric and silica particles with different densities of functional groups. T2 - ANAKON 2025 CY - Leipzig, Germany DA - 10.03.2025 KW - Quality Assurance KW - Nano Particle KW - qNMR KW - Potentiometry KW - Reference Material KW - Surface Analysis KW - Advance Materials KW - Functional Group KW - Silica KW - Synthesis KW - Optical Assays KW - Reference Data PY - 2025 AN - OPUS4-65000 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Stockmann, Jörg M. T1 - Reference material for the determination of the field of view of small-area X-ray photoelectron spectrometers N2 - Small-area/spot photoelectron spectroscopy (SAXPS) is a powerful tool for the investigation of small surface features like microstructures of electronic devices, sensors or other functional surfaces. For evaluating the quality of such microstructures, it is crucial to know whether a small signal in a spectrum is an unwanted contamination of the field of view (FoV), defined by the instrument settings, or it originated from outside. The aperture has a major influence on the signal-contribution from the outside. For the evaluation of the FoV, we determined the Au4f intensities measured with the center of the FoV aligned with the center of the spot and normalized to the Au4f intensity determined on the Au-film. With this test specimen, it was possible to characterize the FoV: The signal-contribution from the outside is reduceable down to lower than 50 %, when the aperture is 30 % of the structure dimension for our Kratos AXIS Ultra DLD system. T2 - Kratos User's Meeting 2020 CY - Online meeting DA - 21.09.2020 KW - Small-area XPS KW - Field of View KW - Imaging XPS KW - Reference Material PY - 2020 AN - OPUS4-51412 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Stockmann, Jörg M. T1 - New Test Specimen for the Determination of the Field of View of Small-Area XPS N2 - Small-area/spot photoelectron spectroscopy (SAXPS) is a powerful tool for the investigation of small surface features like microstructures of electronic devices, sensors or other functional surfaces. For evaluating the quality of such microstructures, it is crucial to know whether a small signal in a spectrum is an unwanted contamination of the field of view (FoV), defined by the instrument settings, or it originated from outside. The aperture has a major influence on the signal-contribution from the outside. For the evaluation of the FoV, we determined the Au4f intensities measured with the center of the FoV aligned with the center of the spot and normalized to the Au4f intensity determined on the Au-film. With this test specimen, it was possible to characterize the FoV: The signal-contribution from the outside is reduceable down to lower than 50 %, when the aperture is 30 % of the structure dimension for our Kratos AXIS Ultra DLD system. T2 - Kratos User's Meeting 2020 CY - Online meeting DA - 21.09.2020 KW - Small Area XPS KW - Reference Material KW - Imaging XPS KW - Field of View PY - 2020 AN - OPUS4-51413 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Sommerfeld, Thomas A1 - Riedel, Juliane A1 - Lisec, Jan A1 - Mauch, Tatjana A1 - Richter, Silke A1 - Koch, Matthias T1 - Development of a certified reference material for per- and polyfluoroalkyl substances (PFAS) in textiles N2 - Per- and polyfluoroalkyl substances (PFASs) are a large group of emerging organic pollutants that contaminate the environment, food, and consumer products. Textiles and other outdoor products are a major source of PFAS exposure due to their water-repellent impregnations. Determination of PFASs in textiles is increasingly important for enhancing their contribution to the circular economy. While maximum levels and restrictions exist for certain key compounds under the Stockholm Convention on Persistent Organic Pollutants and the REACH regulation, certified reference materials (CRMs) are not currently available. To address this issue, the first CRM for determining PFASs in outdoor textiles (BAM-B003) was developed. It fully complies with the requirements of ISO 17034 and ISO 33405. This work presents the entire process of CRM development process, including preparation, a homogeneity study, a stability study, and value assignment. Certification was based on an in-house study at BAM using liquid chromatography tandem mass spectrometry (LC–MS/MS) with stable isotope dilution analysis (SIDA). The certified mass fractions of 18 PFASs range widely from 0.46 to 69 µg/kg, with a prevalence of PFOA (69 µg/kg), PFOS (41 µg/kg) and PFHxA (35 µg/kg) exceeding legal limits. BAM-B003 is intended for analytical quality control and contributes to improving the chemical safety of textiles and strengthening the circular economy. KW - Reference Material KW - PFAS KW - Textiles PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-641040 DO - https://doi.org/10.1007/s00216-025-06098-2 SN - 1618-2642 SP - 1 EP - 9 PB - Springer Science and Business Media LLC AN - OPUS4-64104 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Schannor, Mathias A1 - Oelze, Marcus A1 - Traub, Heike A1 - He, Yubei A1 - Schmidt, Robin A1 - Heidemann, Luisa A1 - Savic, Lynn Jeanette A1 - Vogl, Jochen A1 - Meermann, Björn T1 - Advancing Biomarker Research: In Situ Cu Isotope Analysis in Liver Tumors by LA-MC-ICP-MS N2 - Stable metal isotopes have received increasing attention as medical biomarkers due to their potential to detect changes in metal metabolism related to diseases. In particular, copper stable isotopes are a powerful tool to identify isotopic variation between tumors and healthy tissue, suggesting application in cancer diagnosis. However, potential mechanisms causing isotope fractionation, such as redox- or bond-forming reactions and interactions of metals during transmembrane import and export, are less well understood. Here, we established an in situ method using laser ablation-multicollector-inductively coupled plasma-mass spectrometry (LA-MC-ICP-MS) to advance our understanding of the underlying processes responsible for isotope fractionation between normal and diseased tissues. Gelatin-based bracketing standards and quality control reference materials, crucial for laser ablation analysis, were developed to allow correction for instrumentally induced isotope fractionation during LA-MC-ICP-MS analysis. Using such matrix-matched standards, the method achieved intermediate precisions for delta values of better than 0.15 ‰ (2 s) for inorganic reference materials and of better than 0.17 ‰ (2 s) for biological reference materials. The developed routine was tested on rabbit VX2 liver tumor samples, a model system resembling human hepatocellular carcinoma (HCC) used to study liver cancer. In situ Cu isotope compositions between healthy (𝛿65/63NIST976(Cu) = −1.5 ‰ to 0.2 ‰) and tumorous (𝛿65/63NIST976(Cu) = 0.0 ‰ to 1.3 ‰) liver tissue show distinct differences in their isotope ratios. The observed isotopic dichotomy is consistent with previous solution-based MC-ICP-MS work, showing enrichment of heavy 65Cu in cancer biopsies relative to healthy tissue. KW - Biomarker KW - Laser Ablation KW - Reference Material PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-626865 DO - https://doi.org/10.1021/acs.analchem.4c05626 SN - 1520-6882 VL - 97 IS - 8 SP - 4425 EP - 4432 PB - American Chemical Society (ACS) AN - OPUS4-62686 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schannor, Mathias T1 - LA-MC-ICPMS analysis of Cu isotopes in biological material N2 - Stable metal isotopes receive increasing attention as medical biomarkers due to their potential to detect changes of the metal metabolism related to disease. Potential mechanisms causing isotope fractionation include biological processes that involve redox- or bond-forming reactions and interaction of metals during transmembrane import and export. In order to advance our understanding of the underlying processes responsible for isotope fractionation between normal and diseased cells, we need in situ, spatially resolved methods. Despite its frequent use, laser ablation - multi-collector - inductively coupled plasma mass spectrometry (LA-MC-ICPMS) analysis of biological material is severely limited by the scarcity of matrix-matched standards. Such matrix-matched standards are necessary to correct for instrumental sources of isotope fractionation such as particle size distribution, ablation physics and differential ionization. Copper stable isotopes have proven to be a particularly powerful tool to identify differences in isotope composition between tumors and healthy tissue suggesting application in cancer diagnosis [1, 2]. To further our knowledge of Cu isotope fractionation processes induced by diseases we have developed gelatin-based bracketing standards allowing to correct instrumentally induced isotope fractionation during LA-MC-ICPMS analysis. Since gelatin properties resemble properties of protein-rich cellular material, they mimic biological matrices and their ablation behaviour. Hence, gelatin standards are spiked with known amounts of Cu stable isotopes of a known Cu isotope composition and used as matrix-matched bracketing standard. The method achieved reproducibilities of better than 0.15‰ (2SD) for inorganic reference materials and reproducibilities of better than 0.17‰ (2SD) for biological reference materials. The developed routine was tested on a liver tumor model and in situ Cu isotope compositions between healthy (δ65/63Cu = -1.5 to 0.2 ‰) and tumorous (δ65/63Cu = 0.0 to 1.3 ‰) liver tissue could be distinguished (Figure 1) [3]. T2 - EWCPS 2025 CY - Berlin, Germany DA - 02.03.2025 KW - Laser Ablation KW - Reference Material KW - Biomarker PY - 2025 AN - OPUS4-62882 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schannor, Mathias T1 - LA-MC-ICPMS analysis of Cu isotopes in biological material N2 - Stable metal isotopes receive increasing attention as medical biomarkers due to their potential to detect changes of the metal metabolism related to disease. Potential mechanisms causing isotope fractionation include biological processes that involve redox- or bond-forming reactions and interaction of metals during transmembrane import and export. In order to advance our understanding of the underlying processes responsible for isotope fractionation between normal and diseased cells, we need in situ, spatially resolved methods. Despite its frequent use, laser ablation - multi-collector - inductively coupled plasma mass spectrometry (LA-MC-ICPMS) analysis of biological material is severely limited by the scarcity of matrix-matched standards. Such matrix-matched standards are necessary to correct for instrumental sources of isotope fractionation such as particle size distribution, ablation physics and differential ionization. Copper stable isotopes have proven to be a particularly powerful tool to identify differences in isotope composition between tumors and healthy tissue suggesting application in cancer diagnosis [1, 2]. To further our knowledge of Cu isotope fractionation processes induced by diseases we have developed gelatin-based bracketing standards allowing to correct instrumentally induced isotope fractionation during LA-MC-ICPMS analysis. Since gelatin properties resemble properties of protein-rich cellular material, they mimic biological matrices and their ablation behaviour. Hence, gelatin standards are spiked with known amounts of Cu stable isotopes of a known Cu isotope composition and used as matrix-matched bracketing standard. The method achieved reproducibilities of better than 0.15‰ (2SD) for inorganic reference materials and reproducibilities of better than 0.17‰ (2SD) for biological reference materials. The developed routine was tested on a liver tumor model and in situ Cu isotope compositions between healthy (δ65/63Cu = -1.5 to 0.2 ‰) and tumorous (δ65/63Cu = 0.0 to 1.3 ‰) liver tissue could be distinguished [3]. T2 - ANAKON 2025 CY - Leipzig, Germany DA - 10.03.2025 KW - Laser Ablation KW - Reference Material KW - Biomarker PY - 2025 AN - OPUS4-62883 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Herter, Sven-Oliver A1 - Koch, Matthias A1 - Haase, Hajo T1 - First Synthesis of Ergotamine-13CD3 and Ergotaminine-13CD3 from Unlabeled Ergotamine N2 - Ergot alkaloids (EAs) formed by Claviceps fungi are one of the most common food contaminants worldwide, affecting cereals such as rye, wheat, and barley. To accurately determine the level of contamination and to monitor EAs maximum levels set by the European Union, the six most common EAs (so-called priority EAs) and their corresponding epimers are quantified using high-performance liquid chromatography coupled with tandem mass spectrometry (HPLC-MS/MS). The quantification of EAs in complex food matrices without appropriate internal tandards is challenging but currently carried out in the standard method EN 7425:2021 due to their commercial unavailability. To address the need for isotopically labeled EAs, we focus on two semi-synthetic approaches for the synthesis of these reference standards. Therefore, we investigate the feasibility of the N6-demethylation of native ergotamine to yield norergotamine, which can subsequently be remethylated with an isotopically labeled methylating reagent, such as iodomethane (13CD3-I), to yield isotopically labeled ergotamine and its C8-epimer ergotaminine. Testing the isotopically labeled ergotamine/-inine against native ergotamine/-inine with HPLC coupled to high-resolution HR-MS/MS proved the structure of ergotamine-13CD3 and ergotaminine-13CD3. Thus, for the first time, we can describe their synthesis from unlabeled, native ergotamine. Furthermore, this approach is promising as a universal way to synthesize other isotopically labeled EAs. KW - Reference Material KW - HPLC-MS/MS KW - Mycotoxins KW - Standards KW - Organic Synthesis KW - Isotope PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-600167 DO - https://doi.org/10.3390/toxins16040199 VL - 16 IS - 4 SP - 1 EP - 12 PB - MDPI AN - OPUS4-60016 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Herter, Sven-Oliver A1 - Haase, Hajo A1 - Koch, Matthias T1 - Semisynthesis of Stable Isotope-Labeled Ergot Alkaloids for HPLC-MS/MS Analysis N2 - Ergot alkaloids (EAs) are prevalent food contaminants affecting cereals, such as rye, wheat, and barley worldwide. To ensure EU safety standards, the six most common EAs: ergometrine, ergotamine, ergosine, ergocornine, ergocristine, and ergocryptine, and their epimers, are quantified using HPLC-MS/MS, as described in the European Standard Method EN 17425:2021. However, this can be challenging and time-consuming in food matrices without appropriate internal standards and highlights the need for more robust and precise analytical tools to support their monitoring. The development of isotope-labeled EAs directly addresses this gap, offering improved accuracy and leading to more consistency across laboratories and consequently to more consumer safety. Therefore, we developed a semisynthetic approach, building upon our previous work where native ergotamine was N6-demethylated to norergotamine and subsequently remethylated using iodomethane (13CD3-I). Herein, we are now able to present the successful synthesis of all of the isotopically labeled priority EAs. These isotope-labeled standards were tested against their native counterparts using HPLC coupled with HR-MS/MS. The chromatographic and mass spectrometric properties of the unlabeled and isotopically labeled EAs match exactly, confirming their successful synthesis and structure. These standards can now be utilized to enhance the accuracy and reliability of EA quantification in food and feed. KW - Reference Material KW - HPLC-MS/MS KW - Mycotoxins KW - Ergot Alkaloids KW - Stable Isotope Dilution Analysis KW - Semisynthesis PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-639692 DO - https://doi.org/10.1021/acs.jafc.5c03345 SN - 0021-8561 VL - 73 IS - 29 SP - 18412 EP - 18419 PB - American Chemical Society (ACS) AN - OPUS4-63969 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Herter, Sven-Oliver T1 - Semi-synthesis of isotopic labeled ergot alkaloids: New reference standards N2 - We developed a two-step semi-synthesis for the preparation of isotopically labeled EAs, starting from native EAs. This universal strategy enabled the successful synthesis of all isotopically labeled priority EAs. The structure of the isotopically labeled EAs was confirmed by HPLC-HR-MS/MS using native, unlabeled EAs as a reference standard. The next step will be the implementation of the isotopically labeled standards in the European standard procedure EN 17425 to improve the quantification of EAs in foodstuffs. T2 - 45th Mycotoxin Workshop CY - Vienna, Austria DA - 02.06.2024 KW - Reference Material KW - HPLC-MS/MS KW - Mycotoxins KW - Isotop standards KW - Organic Synthesis KW - Ergot alkaloids PY - 2024 AN - OPUS4-60239 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -