TY - JOUR A1 - Preiss, J. A1 - Kage, Daniel A1 - Hoffmann, Katrin A1 - Martínez, T. J. A1 - Resch-Genger, Ute A1 - Presselt, M. T1 - Ab initio prediction of fluorescence lifetimes involving solvent environments by means of COSMO and vibrational broadening N2 - The fluorescence lifetime is a key property of fluorophores that can be utilized for microenvironment probing, analyte sensing, and multiplexing as well as barcoding applications. For the rational design of lifetime probes and barcodes, theoretical methods have been developed to enable the ab initio prediction of this parameter, which depends strongly on interactions with solvent molecules and other chemical species in the emitters' immediate environment. In this work, we investigate how a conductor-like screening model (COSMO) can account for variations in fluorescence lifetimes that are caused by such fluorophore−solvent interactions. Therefore, we calculate vibrationally broadened fluorescence spectra using the nuclear ensemble method to obtain distorted molecular geometries to sample the electronic transitions with time-dependent density functional theory (TDDFT). The influence of the solvent on fluorescence lifetimes is accounted for with COSMO. For example, for 4-hydroxythiazole fluorophore containing different heteroatoms and acidic and basic moieties in aprotic and protic solvents of varying polarity, this approach was compared to experimentally determined lifetimes in the same solvents. Our results demonstrate a good correlation between theoretically predicted and experimentally measured fluorescence lifetimes except for the polar solvents Ethanol and acetonitrile that can specifically interact with the heteroatoms and the carboxylic acid of the thiazole derivative. KW - Fluorescence lifetime KW - Ab initio calculation KW - COSMO KW - Conductor-like screening model PY - 2018 DO - https://doi.org/10.1021/acs.jpca.8b08886 SN - 1089-5639 SN - 1520-5215 VL - 122 IS - 51 SP - 9813 EP - 9820 PB - American Chemical Society CY - Washington, DC AN - OPUS4-47177 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Huang, J. A1 - Tarábek, J. A1 - Kulkarni, R. A1 - Wang, Cui A1 - Dračínský, M. A1 - Smales, Glen Jacob A1 - Pauw, Brian Richard A1 - Resch-Genger, Ute A1 - Bojdys, M. J. T1 - A π-conjugated, covalent phosphinine framework N2 - Structural modularity of polymer frameworks is a key advantage of covalent organic polymers, however, only C, N, O, Si and S have found their way into their building blocks so far. Here, we expand the toolbox available to polymer and materials chemists by one additional nonmetal, phosphorus. Starting with a building block that contains a λ⁵‐phosphinine (C₅P) moiety, we evaluate a number of polymerisation protocols, finally obtaining a π‐conjugated, covalent phosphinine‐based framework (CPF‐1) via Suzuki‐Miyaura coupling. CPF‐1 is a weakly porous polymer glass (72.4 m2 g‐1 N2 BET at 77 K) with green fluorescence (λmax 546 nm) and extremely high thermal stability. The polymer catalyzes hydrogen evolution from water under UV and visible light irradiation without the need for additional co‐catalyst at a rate of 33.3 μmol h‐¹ g‐¹. Our results demonstrate for the first time the incorporation of the phosphinine motif into a complex polymer framework. Phosphinine‐based frameworks show promising electronic and optical properties that might spark future interest in their applications in light‐emitting devices and heterogeneous catalysis. KW - Phosphinine KW - Fully aromatic frameworks KW - Suzuki-Miyaura coupling KW - Polymers KW - Fluorescence KW - Small-angle scattering PY - 2019 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-485330 DO - https://doi.org/10.1002/chem.201900281 SP - 2 EP - 10 PB - Wiley VCH-Verlag CY - Weinheim AN - OPUS4-48533 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Xiao, J. A1 - Vogl, Jochen A1 - Rosner, M. A1 - Deng, L. A1 - Jin, Z. T1 - A validated analytical procedure for boron isotope analysis in plants by MC-ICP-MS N2 - Boron (B) is an essential micronutrient for plant growth. Lack of valid methods for pretreatment and measurement of δ11B in plant restrict applications of it in the biosphere. Dry ashing, one step cation exchange and micro-sublimation were combined to separate and purify boron (B) in plant tissues. The low procedure blank, high B recovery and the accurate δ11B values of the plant reference materials demonstrate that this method is suitable and valid for B pretreatment and δ11B measurement in plant samples by MC-ICP-MS. Based on this method, the δ11B in different plants (Brassica napus, Chenopodium album L, moss, lichen, and Nostoc commune) was analyzed. For Brassica napus, δ11B increased gradually from root to leaf, and then decreased to rapeseed. For the same parts, the δ11B increased from the lower parts to the higher parts. This variation may be due to the B(OH)3 transporter of NIP6;1 and the incorporation of B into the cell. The reason for lower δ11B values in shell and rapeseed compared to those in leaves presumably is to the preferred Transport of borate in the phloem. The largest δ11B fractionation between leaf and root in Brassica napus and Chenopodium album L was +24.2‰ and +26.6‰, respectively. The large variation and fractionation of δ11B within plants indicates that δ11B is a good tracer to study the B translocation mechanisms and metabolism within plants. The δ11B in Nostoc commune, lichen, and moss showed variations of -4.1‰ to +21.5‰, −9.4‰ to +7.3‰, and −18.3‰ to +11. 9‰, respectively. In the same site, δ11B in different plants ranked Nostoc commune>moss>lichen and δ11B in mosses growing in different environment ranked soil>tree>rock. Rain and soil available B are the main B sources for these plants. The δ11B in Nostoc commune, lichen, and moss may be a useful tracer to study the atmospheric B input. In the future, plants culture experiments under certain environments and studies from molecular level are necessary to decipher the variation of δ11B and fractionation mechanisms within plants. KW - Boron isotope KW - Isotopic fractionation KW - Micro-sublimation KW - Plant tissue KW - MC-ICP-MS PY - 2019 DO - https://doi.org/10.1016/j.talanta.2018.12.087 SN - 0039-9140 SN - 1873-3573 VL - 196 SP - 389 EP - 394 PB - Elsevier B.V. CY - Amsterdam AN - OPUS4-47160 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Otto, S. A1 - Förster, C. A1 - Wang, Cui A1 - Resch-Genger, Ute A1 - Heinze, K. T1 - A Strongly Luminescent Chromium(III) ComplexAcid N2 - The synthesis, structure, reactivity,and photophysical properties of anovel acidic,luminescentchromium(III) complex [Cr(H2tpda)2]3+ (23+ +)bearing the tridentate H2tpda (2,6-bis(2-pyridylamino)pyridine) ligand are presented. Excitation of 23+ + at 442 nm results in strong, long-lived NIR luminescence at 782 nm in water and in acetonitrile. X-ray diffraction analysis and IR spectroscopy revealhydrogen-bonding interactions of the counter ions to the NH groups of 23+ + in the solidstate. Deprotonation of the NH groups of 23+ + by using anon-nucleophilic Schwesinger base in CH3CN switches off the luminescence. Re-protonation by using HClO4 restores the emission. In water,the pKa value of 23+ + amountsto8 .8, yet deprotonation is not reversible in the presence of hydroxide ions. Dioxygen quenches the emission of 23+ +,but to aweaker extent than expected. This is possibly due to the strong ion-pairing properties of 23+ + even in solution, reducing the energy transfer efficiency to O2.Deuteration of the NH groups of 23+ + approximately doubles the quantum yield and lifetime in water,demonstrating the importance of multiphoton relaxation in these NIR emitters. KW - Cr(III) complex KW - Oxygen sensor KW - pH sensor KW - Luminescence KW - Luminescence lifetime KW - Quantum yield KW - NIR emitter PY - 2018 DO - https://doi.org/10.1002/chem.201802797 SN - 0947-6539 VL - 24 IS - 48 SP - 12555 EP - 12563 PB - Wiley‐VCH Verlag GmbH & Co. KGaA CY - Weinheim AN - OPUS4-45929 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Oelze, Marcus A1 - Vogl, Jochen T1 - A second anchor Fe isotope reference material based on high purity Fe metal for the exhausted IRMM-014 N2 - Iron isotopes are used in a variety of fields from e.g., geologic question to medical applications. Measurements of iron isotopes are usually performed as delta measurements to an artificial based delta zero standard. In the case of Fe isotopes is that delta zero standard IRMM-014, a pure Fe metal. Unfortunately, that conventional delta zero reference material defining the 56/54Fe scale is out of stock and therefore unavailable. To overcome that situation and fulfill the need for laboratories that measure Fe isotope on a regular basis we will provide a set of solutions with IRMM-014 and a second anchor point for Fe isotope ratio measurements that is based on a pure Fe metal. This new second anchor point, a high purity Fe from BAM, will be calibrated against IRMM-014 and can be used as bracketing standard or as reference value for stable Fe isotope measurements. We are in the good situation that BAM ordered a large stock of IRMM-014 several years ago. That stock of IRMM-014 Fe cubes and IRMM-014 Fe wires will be dissolved in 6M HCl in a large quantity. The new anchor point, the high purity Fe metal, that is commercially available at BAM, is a pure Fe metal with only trace amounts of impurities. The high purity BAM material will also be dissolved in 6M HCl in large quantity. Several aliquots of both solutions will be measured on the Neptune Plus MC-ICP-MS to define this second anchor point with a low uncertainty. Further will we send several aliquots of both solutions to different laboratories to also measure this second anchor point of high purity Fe on the 56/54Fe scale. We will report the values of that study on BAM high purity Fe and will provide a guide for scale conversion to the IRMM-014 scale and for uncertainty calculation to use that new anchor point instead of the exhausted IRMM-014. T2 - EWCPS CY - Ljubljana, Slovenia DA - 30.01.2023 KW - Iron isotopes KW - Reference material PY - 2023 AN - OPUS4-58012 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Lehmann, Paula A1 - Carl, Peter A1 - Schneider, Rudolf T1 - A Rapid Test for Leaching Studies of Biocides from Building Materials N2 - Regardless of its ban in agricultural use, the triazine derivative terbutryn is still used as a biocide against biofouling in building materials, such as façade colors and roof tiles. From there, it is washed off and may contaminate soil and surface waters, where it shows ecotoxicological behavior. For understanding of these leaching processes, analytical methods that can detect terbutryn in traces are necessary. In contrast to separation methods (Gas (GC) or liquid chromatography (LC)) coupled to mass spectrometry (MS), enzyme immunoassays (EIAs) have proven to be adequate tools for environmental monitoring. Compared to GC-or LC-MS, they are cheap, require only limited time and experimental expertise and enable high throughput. For quantification of terbutryn, EIAs have been established, with a limit of detection (LOD) of 50 ng L-1. For leaching experiments however, a lower LOD would be advantageous. For detection of terbutryn we developed a direct competitive ELISA based on a monoclonal antibody: Terbutryn and an enzyme-terbutryn conjugate (“tracer”) compete for the binding sites of the immobilized antibody. The bound tracer converts a colourless substrate into a blue-coloured product, which can be detected via spectrophotometry. For quantification of terbutryn, a sigmoidal calibration curve is used. For establishing of the EIA, a new tracer based on a terbutryn surrogate (“hapten”) was synthesized. After optimization of the experimental conditions, the immunoassay exhibited a more than ten-fold increased sensitivity (LOD: 3 ng L-1), high stability against sample compounds (Ca2+, NaCl) and lower cross-reactivities against structurally related compounds, than reported before. Analysis of spiked samples was possible with high precision (inter-assay CV: < 10 %) and accuracy (recoveries from spiked samples: 89 % ± 10%). We therefore propose it as quick and reliable method for leaching studies of terbutryn out of building materials. T2 - Adlershofer Forschungsforum CY - Berlin, Germany DA - 11.11.2019 KW - ELISA KW - Terbutryne KW - Hapten Immunoassay KW - Triazine herbicide PY - 2019 AN - OPUS4-49595 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Ecke, Alexander A1 - Westphalen, Tanja A1 - Hornung, J. A1 - Voetz, M. A1 - Schneider, Rudolf T1 - A rapid magnetic bead-based immunoassay for sensitive determination of diclofenac N2 - Increasing contamination of environmental waters with pharmaceuticals represents an emerging threat for the drinking water quality and safety. In this regard, fast and reliable analytical methods are required to allow quick countermeasures in case of contamination. Here, we report the development of a magnetic bead-based immunoassay (MBBA) for the fast and cost-effective determination of the analgesic diclofenac (DCF) in water samples, based on diclofenac-coupled magnetic beads and a robust monoclonal anti-DCF antibody. A novel synthetic strategy for preparation of the beads resulted in an assay that enabled for the determination of diclofenac with a significantly lower limit of detection (400 ng/L) than the respective enzyme-linked immunosorbent assay (ELISA). With shorter incubation times and only one manual washing step required, the assay demands for remarkably shorter time to result (< 45 min) and less equipment than ELISA. Evaluation of assay precision and accuracy with a series of spiked water samples yielded results with low to moderate intra- and inter-assay variations and in good agreement with LC–MS/MS reference analysis. The assay principle can be transferred to other, e.g., microfluidic, formats, as well as applied to other analytes and may replace ELISA as the standard immunochemical method. KW - Immunoassay KW - Magnetic beads KW - Diclofenac KW - Water analysis KW - LC-MS/MS PY - 2021 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-542346 DO - https://doi.org/10.1007/s00216-021-03778-7 SN - 1618-2650 VL - 414 SP - 1563 EP - 1573 PB - Springer CY - Heidelberg AN - OPUS4-54234 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Lardy-Fontan, S. A1 - Piechotta, Christian A1 - Heath, E. A1 - Perkola, N. A1 - Balzamo, S. A1 - Cotman, M. A1 - Gökcen, T. A1 - Gardia-Parège, C. A1 - Budzinski, H. A1 - Lalère, B. T1 - A project to deliver reliable measurements of estrogens for better monitoring survey and risks assessments N2 - Monitoring programs should generate high-quality data on the concentrations of substances and other pollutants in the aquatic environment to enable reliable risk assessment. Furthermore, the need for comparability over space and time is critical for analysis of trends and evaluation of restoration of natural environment. Additionally, research work and exercises at the European level have highlighted that reliable measurements of estrogenic substances at the PNEC level are still challenging to achieve. The project EDC-WFD “Metrology for monitoring endocrine disrupting compounds under the EU Water Framework Directive” aims to develop traceable analytical methods for determining endocrine disrupting compounds and their effects, with a specific focus on three estrogens of the first watch list (17-beta-estradiol (17βE2), 17-alpha-ethinylestradiol (EE2), and estrone (E1)). Estrogens 17-alpha-estradiol (17aE2) and estriol (E3) will be included to demonstrate the reliability of the developed methods - Mass Spectrometry based method and effect-based methods (EBM) - and to support the requirements of Directive 2013/39/EC, Directive 2009/90/EC and Commission Implementation Decision (EU) 2018/840, hence improving the comparability and compatibility of measurement results within Europe. During the EDC-WFD project four EBM will be deeply investigated in order to improve their rationale use and their support in water quality assessment. T2 - Eurachem Workshop - Uncertainty from sampling and analysis for accredited laboratories CY - Berlin, Germany DA - 19.11.2019 KW - MS based method KW - Estrogens KW - Reliable measurements KW - Comparability KW - Effect based Method PY - 2019 AN - OPUS4-49738 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Lardy-Fontan, S. A1 - Piechotta, Christian A1 - Heath, E. A1 - Perkola, N. A1 - Balzamo, S. A1 - Cotman, M. A1 - Gökcen, T. A1 - Gardia-Parège, C. A1 - Budzinski, H. A1 - Lalère, B. T1 - A project to deliver reliable measurements of estrogens for better monitoring survey and risks assessments N2 - Monitoring programs should generate high-quality data on the concentrations of substances and other pollutants in the aquatic environment to enable reliable risk assessment. Furthermore, the need for comparability over space and time is critical for analysis of trends and evaluation of restoration of natural environment. Additionally, research work and exercises at the European level have highlighted that reliable measurements of estrogenic substances at the PNEC level are still challenging to achieve. The project EDC-WFD “Metrology for monitoring endocrine disrupting compounds under the EU Water Framework Directive” aims to develop traceable analytical methods for determining endocrine disrupting compounds and their effects, with a specific focus on three estrogens of the first watch list (17-beta-estradiol (17βE2), 17-alpha-ethinylestradiol (EE2), and estrone (E1)). Estrogens 17-alpha-estradiol (17aE2) and estriol (E3) will be included to demonstrate the reliability of the developed methods - Mass Spectrometry based method and effect-based methods (EBM) - and to support the requirements of Directive 2013/39/EC, Directive 2009/90/EC and Commission Implementation Decision (EU) 2018/840, hence improving the comparability and compatibility of measurement results within Europe. During the EDC-WFD project four EBM will be deeply investigated in order to improve their rationale use and their support in water quality assessment. T2 - ICRAPHE - Second International Conference on Risk Assessment of Pharmaceuticals in the Environment CY - Barcelona, Spanien DA - 28.11.2019 KW - Estrogens KW - Effect based Method KW - Comparability KW - Reliable measurements KW - MS based method PY - 2019 AN - OPUS4-49739 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Eisenreich, F. A1 - Kathan, M. A1 - Dallmann, A. A1 - Ihrig, S. P. A1 - Schwaar, Timm A1 - Schmidt, B. M. A1 - Hecht, S. T1 - A photoswitchable catalyst system for remote-controlled (co)polymerization in situ N2 - The fundamental properties of a polymeric material are ultimately governed by its structure, which mainly relies on monomercomposition and connection, topology, chain length, and polydispersity. Thus far, these structural characteristics are typicallyset ex situ by the specific polymerization procedure, eventually limiting the future design space for the creation of moresophisticated polymers. Herein, we report on a single photoswitchable catalyst system, which enables in situ remote controlover the ring-opening polymerization of l-lactide and further allows regulation of the incorporation of trimethylene carbonateand δ -valerolactone monomers in copolymerizations. By implementing a phenol moiety into a diarylethene-type structure,we exploit light-induced keto–enol tautomerism to switch the hydrogen-bonding-mediated monomer activation reversiblyON and OFF. This general and versatile principle allows for exquisite external modulation of ground-state catalysis of a livingpolymerization process in a closed system by ultraviolet and visible light and should thereby facilitate the generation of newpolymer structures. KW - Polymers PY - 2018 DO - https://doi.org/10.1038/s41929-018-0091-8 SN - 2520-1158 VL - 1 IS - 7 SP - 516 EP - 522 PB - Nature CY - London AN - OPUS4-45407 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Bayerlein, Bernd A1 - Hanke, T. A1 - Muth, Thilo A1 - Riedel, Jens A1 - Schilling, Markus A1 - Schweizer, C. A1 - Skrotzki, Birgit A1 - Todor, A. A1 - Moreno Torres, Benjami A1 - Unger, Jörg F. A1 - Völker, Christoph A1 - Olbricht, Jürgen T1 - A Perspective on Digital Knowledge Representation in Materials Science and Engineering N2 - The amount of data generated worldwide is constantly increasing. These data come from a wide variety of sources and systems, are processed differently, have a multitude of formats, and are stored in an untraceable and unstructured manner, predominantly in natural language in data silos. This problem can be equally applied to the heterogeneous research data from materials science and engineering. In this domain, ways and solutions are increasingly being generated to smartly link material data together with their contextual information in a uniform and well-structured manner on platforms, thus making them discoverable, retrievable, and reusable for research and industry. Ontologies play a key role in this context. They enable the sustainable representation of expert knowledge and the semantically structured filling of databases with computer-processable data triples. In this perspective article, we present the project initiative Materials-open-Laboratory (Mat-o-Lab) that aims to provide a collaborative environment for domain experts to digitize their research results and processes and make them fit for data-driven materials research and development. The overarching challenge is to generate connection points to further link data from other domains to harness the promised potential of big materials data and harvest new knowledge. KW - Data infrastructures KW - Digital representations KW - Digital workflows KW - Knowledge graphs KW - Materials informatics KW - Ontologies KW - Vocabulary providers PY - 2022 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-546729 DO - https://doi.org/10.1002/adem.202101176 SN - 1438-1656 SP - 1 EP - 14 PB - Wiley-VCH GmbH CY - Weinheim AN - OPUS4-54672 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Ruhe, L. A1 - Ickert, Stefanie A1 - Beck, S. A1 - Linscheid, M. W. T1 - A new strategy for metal labeling of glycan structures in antibodies N2 - Quantitative analysis of complex proteins is a challenging task in modern bioanalytical chemistry. Commonly available isotope labels are still suffering from limitations and drawbacks, whereas new metal labels open numerous possibilities in mass spectrometric analyses. In this work, we have developed a newmetal labeling strategy to tag glycan structures of proteins, more particularly antibodies. The oligosaccharide glycans were selectively trimmed to the last N-acetylglucosamine to which an artificial azide containing galactose residue was bound. This azide can be used for subsequent cycloaddition of an alkyne. Therefore, we developed a lanthanide-containing macrocyclic reagent to selectively connect to this azido galactose. In summary, the glycan structures of an antibody can be labeled with a metal functionality using this approach. Furthermore, the functionality of the antibodies can be fully maintained by labeling the Fc glycans instead of using labeling reagents that target amino or thiol groups. This approach enables the possibility of using elemental, besides molecular mass spectrometry, for quantitative analyses or imaging experiments of antibodies in complex biological samples. KW - Antibody KW - Metal labeling KW - Glycans KW - DOTA KW - Lanthanide PY - 2018 DO - https://doi.org/10.1007/s00216-017-0683-1 SN - 1618-2650 SN - 1618-2642 VL - 410 IS - 1 SP - 21 EP - 25 PB - Springer AN - OPUS4-44000 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Recknagel, Sebastian A1 - Hoffmann, V. A1 - Weiher, N. A1 - Brixius, Th. A1 - Schlothmann, B.-J. T1 - A new set of zinc based calibration samples for GD-OES N2 - The analysis of Zinc layers on Iron sheets is one of the most essential application of Glow Discharge - Optical Emission Spectrometry (GD-OES). Since the year 2000 for this application calibration of GD-OES instruments mostly included the set of the six calibration samples CZ 2009-CZ 2014 from CKD. These CRMs are no longer available. Furthermore, in this application the analysis of Al and Mg became essential. To overcome this lack of calibration materials, the working group VDEh FA II.47 decided to organize the production and characterization of a new set of certified reference materials. T2 - BERM CY - Berlin, Germany DA - 23.09.2018 KW - GD-OES KW - CRM KW - Zinc PY - 2018 AN - OPUS4-46718 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Recknagel, Sebastian A1 - Hoffmann, V. A1 - Weiher, N. A1 - Brixius, Th. A1 - Schlothmann, B.-J. T1 - A new set of zinc based calibration samples for GD-OES N2 - The analysis of Zinc layers on Iron sheets is one of the most essential application of Glow Discharge - Optical Emission Spectrometry (GD-OES). Since the year 2000 for this application calibration of GD-OES instruments mostly included the set of the six calibration samples CZ 2009-CZ 2014 from CKD. These CRMs are no longer available. Furthermore, in this application the analysis of Al and Mg became essential. To overcome this lack of calibration materials, the working group VDEh FA II.47 decided to organize the production and characterization of a new set of certified reference materials. T2 - 4th International Glow Discharge Spectroscopy Symposium CY - Berlin, Germany DA - 15.04.2018 KW - GD-OES KW - CRM KW - Zinc PY - 2018 AN - OPUS4-46719 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Choi, Youngeun A1 - Schmidt, Carsten A1 - Tinnefeld, Philip A1 - Bald, Ilko A1 - Roedinger, Stefan T1 - A new reporter design based on DNA origami nanostructures for quantification of short oligonucleotides using microbeads N2 - The DNA origami technique has great potential for the development of brighter and more sensitive reporters for fluorescence based detection schemes such as a microbead-based assay in diagnostic applications. The nanostructures can be programmed to include multiple dye molecules to enhance the measured signal as well as multiple probe strands to increase the binding strength of the target oligonucleotide to these nanostructures. Here we present a proof-of-concept study to quantify short oligonucleotides by developing a novel DNA origami based reporter system, combined with planar microbead assays. Analysis of the assays using the VideoScan digital imaging platform showed DNA origami to be a more suitable reporter candidate for quantification of the target oligonucleotides at lower concentrations than a conventional reporter that consists of one dye molecule attached to a single stranded DNA. Efforts have been made to conduct multiplexed analysis of different targets as well as to enhance fluorescence signals obtained from the reporters. We therefore believe that the quantification of short oligonucleotides that exist in low copy numbers is achieved in a better way with the DNA origami nanostructures as reporters. KW - Origami KW - Nanostructures KW - Microbeads KW - DNA origami KW - Oligonucleotides PY - 2019 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-476443 DO - https://doi.org/10.1038/s41598-019-41136-x SN - 2045-2322 VL - 9 SP - 4769, 1 EP - 8 PB - Nature AN - OPUS4-47644 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Phukphatthanachai, Pranee A1 - Vogl, Jochen A1 - Traub, Heike A1 - Jakubowski, Norbert A1 - Panne, Ulrich T1 - A new approach of using polyethylene frits for the quantification of sulphur in copper metals by isotope dilution LA-ICP-MS and comparison with conventional IDMS techniques N2 - Polyethylene (PE) frits were used to quantify sulphur in copper and its alloys by isotope dilution combined with LA-ICP-MS as an alternative approach to conventional sample preparation: the copper samples were spiked, the spiked samples were dissolved, the resulting solutions were absorbed in the PE frits and finally the PE frits were analysed by LA-ICP-MS. A prerequisite for such a support material is a low sulphur blank and thus PE was selected for this purpose. The absorption efficiency of the PE frits was studied for varying sulphur amounts ranging from 2 mg S to 80 mg S showing that more than 99.5% of the loaded sulphur was absorbed by the frit. The so prepared PE frits were measured by LA-ICP-MS and yielded a good linearity (R2 ¼ 0.999) for the sulphur ion intensities corresponding to sulphur amounts up to 40 mg S; the associated sensitivity is approximately 3.4 x 10⁴ cps μg⁻¹ for ³²S. For the validation of the developed procedure the reference materials BAM-M376a, BAM-228 and BAM-227 were applied such that 2 μg S, 5 μg S and 11 μg S were absorbed in the PE frits, respectively. These samples were pre-quantified for the adsorbed sulphur amount by external calibration LA-ICP-MS yielding sulphur amounts of 0.9 μg, 5.1 μg and 8.5 μg (quantified for ³²S only), respectively. Relative Standard deviations of the isotope ratios were below 5% in average (n ¼ 3 lines) in all cases (except for the pure spike solution). These samples were then analysed by LA-ICP-IDMS and the measurement results were validated by comparing them with the results obtained by conventional ICP-IDMS. The obtained relative expanded measurement uncertainties ranged between 10% and 26%. Pearson's coefficient was used to express the correlation between both techniques; the obtained value was 0.999 demonstrating a strong correlation. Contrary to most published LA-ICP-IDMS procedures, the developed procedure enables SI-traceability for the measurement results. The metrological traceability to the SI for the sulphur mass fractions in copper was established by an unbroken chain of comparisons, each accompanied by an uncertainty budget. Thus, the measurement results are considered reliable, acceptable and comparable within the stated measurement uncertainty. The metrological traceability chain from the kg down to mass fraction in the samples obtained by LA-ICP-IDMS is presented as well. KW - Laser ablation KW - IDMS KW - Traceability KW - Uncertainty KW - Purity PY - 2018 DO - https://doi.org/10.1039/c8ja00116b SN - 0267-9477 SN - 1364-5544 VL - 33 IS - 9 SP - 1506 EP - 1517 PB - Royal Society of Chemistry CY - Cambridge AN - OPUS4-45899 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Phukphatthanachai, Pranee A1 - Vogl, Jochen A1 - Traub, Heike A1 - Jakubowski, Norbert A1 - Panne, Ulrich T1 - A new approach of using polyethylene frits for the quantification of sulphur in copper metals by isotope dilution LA-ICP-MS N2 - For the first time polyethylene (PE) frits were used to quantify sulphur in copper metal and its alloys by isotope dilution combined with LA-ICP-MS: an alternative approach for sample preparation. The properties of the PE frit meet the requirements for isotope dilution LA-ICPMS which are porous material, thermal and chemical resistance and high absorption efficiency. The breakthrough, however, as a support material, is the low sulphur blank, which is only two times of the gas flow blank (2.3-4.0 x 10⁴ cps). Additionally, the porosity of the frit was considered, as it directly affects the absorption efficiency for the sample solution, which is present in the cavities of the frit. The absorption efficiency was studied by loading sulphur standards with varying sulphur amounts (0 - 80 µg S) onto the frits. The remaining sulphur which was not absorbed by the frit was rinsed off and was measured by ICP-MS. This indirect method shows that more than 99.5 % of the loaded sulphur was absorbed by the frit. The so prepared frits with increasing sulphur amount were measured by LA-ICP-MS showing a good linearity between 0 µg S and 40 µg S with a coefficient of determination, r2 of 0.9987 and a sensitivity of 3.4x10⁴ cps µgˉ¹ for 32S. Three copper reference materials produced by BAM (BAM-M376a, BAM-228 and BAM-227) were selected to develop and validate the LA-ICP-IDMS procedure. The IDMS technique was applied to these samples as follows: the samples were spiked, dissolved, digested and then the digested solution was absorbed on the frits. The dried frit samples were then analyzed by LA-ICP-IDMS and it could be demonstrated that the sample solution dispersed on the frits did not influence the 32S/34S ratio significantly even though the sulphur intensities were fluctuating along the scan lines. Relative standard deviations of the isotope ratios were below 5 % in average between 3 lines (except for the pure spike solution and procedure blank). The measurement results were validated by comparing them with the results obtained by conventional ICP-IDMS. Plotting the mass fraction of sulphur in copper obtained by LA-ICP-IDMS versus those obtained by ICP-IDMS yields a linear curve with a correlation coefficient of 0.9999 showing a strong agreement between both techniques. The metrological traceability to the SI for the mass fraction of sulphur in copper is established by an unbroken chain of comparisons, each accompanied by an uncertainty budget. Thus, the measurement results are considered reliable, acceptable and comparable within the stated measurement uncertainty. The metrological traceability chain from the kg down to the final mass fraction in the samples obtained by LA-ICP-IDMS is illustrated in this presentation. T2 - ESAS & CANAS 2018 CY - Berlin, Germany DA - 20.03.2018 KW - Laser ablation KW - Isotope dilution mass spectrometry KW - SI traceability KW - Measurement uncertainty PY - 2018 AN - OPUS4-44641 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Tavernaro, Isabella A1 - Nirmalananthan-Budau, Nithiya A1 - Di Giacomo, Bruno A1 - Srivastava, Priyanka A1 - Scholtz, Lena A1 - Resch-Genger, Ute T1 - A Multimodal Approach to Quantify Surface Functional Groups and Ligands on Amorphous Silica Nanoparticles N2 - Nowadays amorphous silica nanoparticles (SiO2-NP) are one of the most abundant engineered nanomaterials, that are highly stable and can be easily produced on a large scale at low cost. Surface functionalized SiO2-NP are of great interest in the life and material sciences, as they can be used e.g. as drug carriers, fluorescent sensors, and multimodal labels in bioanalytical assays and imaging applications. Their performance in such applications depends not only on particle size, size distribution, and morphology, but also on surface chemistry, i.e. the total number of surface functional groups (FG) and the number of FG accessible for subsequent functionalization with ligands or biomolecules, which in turn determines surface charge, colloidal stability, biocompatibility, and toxicity. Aiming at the development of simple, versatile, and multimodal tools for the quantification of many bioanalytically relevant FG and ligands, we investigated and compared various analytical methods commonly used for FG quantification. This includes electrochemical titration methods, dye-based optical assays, and other instrumental analytical techniques such as nuclear magnetic resonance and thermal analysis methods. The potential of our multimodal approach for FG quantification was demonstrated for commercial and custom-made silica particles of varying FG, showing not only an influence of the synthesis methods on the number of FG but also on the performance. In the future, our strategy can contribute to establish multi-method characterization strategies to provide a more detailed picture of the structure-properties relationship. T2 - Advanced Materials Safety 2023 CY - Saarbrücken, Germany DA - 08.11.2023 KW - Amorphous silica particles KW - Surface group analysis KW - Ligands KW - Reference material KW - Optical spectroscopy KW - Quantitative NMR KW - Optical assays KW - Titration KW - Engineered nanomaterials KW - Advanced Materials PY - 2023 AN - OPUS4-59124 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Tavernaro, Isabella A1 - Nirmalananthan-Budau, Nithiya A1 - Scholtz, Lena A1 - Resch-Genger, Ute T1 - A Multimodal Approach to Quantify Surface Functional Groups on Nanomaterials for Safe and Sustainable by Design N2 - Engineered nanomaterials (NM) with their large surface-to-volume ratios and their for some materials observed size-dependent functional properties are of increasing relevance for current and future developments in various fields such as medical and pharmaceutical industry, computing and electronics or food and consumer products. The performance and safety of NM are determined by the sum of their intrinsic physicochemical properties. Especially, the particle surface chemistry, which is largely controlled by the chemical nature and density of functional groups (FG) and ligands, is an important key driver for NM performance, stability, and processibility as well as the interaction of NM with the environment. Thus, methods for FG quantification can foster the sustainable development of functional and safe(r) NM. Aiming at the development of simple, versatile, and multimodal tools for the quantification of many bioanalytically relevant FG and ligands, we investigated and compared various analytical methods commonly used for FG quantification. This includes electrochemical titration methods, dye-based optical assays, and other instrumental analytical techniques such as nuclear magnetic resonance and thermal analysis methods. The potential of our multimodal approach for FG quantification was demonstrated for commercial and custom-made polymeric and silica particles of varying FG, used as optical pH sensors. In the future, our strategy can contribute to establish multi-method characterization strategies to provide a more detailed picture of the structure-properties relationship. T2 - NanoSAFE & NanoSafety Cluster 2023 CY - Grenoble, France DA - 05.06.2023 KW - Engineered Nanomaterials KW - Safe-by-Design KW - Sustainable-by-Design KW - Surface Group Analysis KW - Silica and Polystyrene Particles KW - Surface Modification KW - Dye KW - Optical Spectroscopy KW - Quantitative NMR KW - Electrochemical Titration KW - Functionalized Nanomaterials KW - Nanosafety PY - 2023 AN - OPUS4-59126 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Hildebrandt, L. A1 - von der Au, Marcus A1 - Zimmermann, T. A1 - Reese, A. A1 - Ludwig, J. A1 - Pröfrock, D. T1 - A metrologically traceable protocol for the quantification of trace metals in different types of microplastic N2 - The presence of microplastic (MP) particles in aquatic environments raised concern About possible enrichment of organic and inorganic pollutants due to their specific surface and chemical properties. In particular the role of metals within this context is still poorly understood. Therefore, the aim of this work was to develop a fully validated acid digestion protocol for metal analysis in different polymers, which is a prerequisite to study such interactions. The proposed digestion protocol was validated using six different certified reference materials in the microplastic size range consisting of polyethylene, polypropylene, acrylonitrile butadiene styrene and polyvinyl chloride. As ICP-MS/MS enabled time-efficient, sensitive and robust analysis of 56 metals in one measurement, the method was suitable to provide mass fractions for a multitude of other elements beside the certified ones (As, Cd, Cr, Hg, Pb, Sb, Sn and Zn). Three different microwaves, different acid mixtures as well as different temperatures in combination with different hold times were tested for optimization purposes. With the exception of Cr in acrylonitrile butadiene styrene, recovery rates obtained using the optimized protocol for all six certified reference materials fell within a range from 95.9% ± 2.7% to 112% ± 7%. Subsequent optimization further enhanced both precision and recoveries ranging from 103% ± 5% to 107 ± 4% (U; k = 2 (n = 3)) for all certified metals (incl. Cr) in acrylonitrile butadiene styrene. The results clearly show the analytical challenges that come along with metal analysis in chemically resistant plastics. Addressing specific analysis Tools for different sorption scenarios and processes as well as the underlying kinetics was beyond this study’s scope. However, the future application of the two recommended thoroughly validated total acid digestion protocols as a first step in the direction of harmonization of metal analysis in/on MP will enhance the significance and comparability of the generated data. It will contribute to a better understanding of the role of MP as vector for trace metals in the environment. KW - Microplatic KW - Digestion KW - Analytical Chemistry PY - 2020 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-510727 DO - https://doi.org/10.1371/journal.pone.0236120 VL - 15 IS - 7 SP - e0236120 AN - OPUS4-51072 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -