TY - CONF A1 - Faßbender, Sebastian T1 - On-line species-specific isotopic analysis of sulfur by hyphenation of capillary electrophoresis with MC-ICP-MS N2 - In many scientific fields, isotopic analysis can offer valuable information. Up to date, typically bulk analysis is aimed at measuring the isotopic composition of the entire elemental content of the sample. However, the analyte element is usually present under the form of different species. Thus, separating species of interest from one another and from matrix components prior to isotope ratio measurements can provide species-specific isotopic information, which could be used for tracing the origin of environmental pollutants and elucidation of (environmental) speciation. Using on-line hyphenations of separation techniques with multicollector-ICP-MS (MC-ICP-MS) can save time and effort and enables the analysis of different species during a single measurement. Whereas some works hyphenating GC and IC with MC-ICP-MS have already been reported, LC and CE hyphenations are still inadequately represented based on the capabilities of these separation techniques. In this work, we developed an on-line hyphenation of CE with multicollector-ICP-MS (CE/MC-ICP-MS) for isotopic analysis of sulfur species using a multiple-injection approach for instrumental mass bias correction by standard-sample bracketing. With this method, the isotopic composition of sulfur in sulfate originating from river water could be analyzed without sample preparation. The results were compared to data from off-line analysis of the same samples to ensure accuracy. The precision of the results of the on-line measurements was promising regarding the differentiation of the river systems by the isotopic signature of river water sulfate. The great potential of this method is based on the versatility of the applied separation technique, not only in the environmental field but also for, e.g., biomolecules, as sulfur is the only covalently bound constituent of proteins that can be analyzed by MC-ICP-MS. T2 - Virtual Goldschmidt 2020 CY - Online meeting DA - 21.06.2020 KW - Isotopic analysis KW - Hyphenated techniques KW - Capillary electrophoresis KW - Multicollector-ICP-MS KW - Speciation analysis PY - 2020 AN - OPUS4-50922 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Gornushkin, Igor B. A1 - Sennikov, P. A1 - Kornev, R. A1 - Ermakov, A. A1 - Shkrunin, V. T1 - Laser Induced Dielectric Breakdown for Chemical Vapor Deposition by Hydrogen Reduction of Volatile Boron Halides BCl3 and  BF3 N2 - A possibility of deposition from laser-induced plasma is investigated in search for an economic and simple method for obtaining isotopic compounds from enriched gaseous precursors although no isotopic compounds are used in this the proof-of-principle work. A breakdown in mixtures of BCl3 and BCl3 with hydrogen, argon, and methane are studied both theoretically and experimentally. Equilibrium chemistry calculations show the deposition of boron, boron carbide, and carbon is thermodynamically favorable in BCl3 systems and only carbon in BF3 systems. Dynamic calculation of expanding plasma is performed using fluid dynamics coupled with equilibrium chemistry. Condensed phases of boron, boron carbide, and graphite are predicted with maximum concentrations in peripheral zones of the plasma. In experiment, plasma is induced in mixtures BCl3, H2 + BCl3, H2 + Ar + BCl3, H2 + BCl3 + CH4, BF3, H2 + BF3, H2 + Ar + BF3, and H2 + Ar + BF3. The gases are analyzed before, during, and after laser irradiation by optical and mass spectrometry methods. The results show the composition of reaction products close to that predicted theoretically. The conversion of precursor gases BCl3 and BF3 into gaseous and condensed products is 100% for BCl3 and 80% for BF3. Solid deposits of up to 30 mg are obtained from all reaction mixtures. Due to technical reasons only FTIR characterization of the BCl3 + H2 + CH4 deposit is done. It points to presence of condensed boron and boron carbide predicted by the model. Overall, the calculations and preliminary experimental results imply the chemical vapor deposition with laser induced plasma is promising for conversion of gaseous enriched precursors into elemental isotopes and their isotopic compounds. KW - Boron halides KW - Chemical vapor deposition KW - Laser induced dielectric breakdown, Hydrogen reduction PY - 2020 DO - https://doi.org/10.1007/s11090-020-10096-w VL - 40 IS - 5 SP - 1145 EP - 1162 PB - Springer AN - OPUS4-50968 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Gornushkin, Igor B. A1 - Sennikov, P. T1 - Laser Induced Plasma for Chemical Vapor Deposition: Theory and Experiment N2 - A possibility of deposition from laser-induced plasma (LIP) is investigated in search for an economic and simple method to obtain isotopic compounds from enriched gaseous precursors. A breakdown in mixtures of BCl3 and BCl3 with hydrogen, argon, and methane are studied both theoretically and experimentally. Calculations of expanding plasma of different composition are performed with the use of the fluid dynamic code coupled to the equilibrium chemistry solver. Condensed phases of boron, boron carbide, and graphite are predicted showing maximum concentrations in peripheral zones of the plasma. In experiment LIP is induced in mixtures BCl3, Н2+BCl3, H2+Ar+BCl3, H2+BCl3+CH4, BF3, Н2+BF3, H2+Ar+BF3, and H2+Ar+BF3. The gases are analyzed before, during, and after laser irradiation by optical and mass spectroscopic methods. The composition of reaction products is found to be close to that predicted theoretically. The conversion of precursor gases BCl3 and BF3 into gaseous and condensed products is 100% for BCl3 and 80% for BF3. Solid deposits of up to 30 mg are obtained from all the reaction mixtures. FTIR analysis of BCl3+H2+CH4 deposits points to a presence of condensed boron and boron carbide that are also predicted by the model. Both calculations and preliminary experimental results suggest the chemical vapor deposition by LIP is promising for conversion of gaseous enriched precursors into elemental isotopes and their isotopic compounds. T2 - International Online Meeting on Laser Induced Breakdown Spectroscopy (IIOMLIBS) CY - Online meeting DA - 06.07.2020 KW - Chemical vapor deposition KW - Laser induced plasma PY - 2020 AN - OPUS4-50994 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Faßbender, Sebastian A1 - Rodiouchkina, K. A1 - Vanhaecke, F. A1 - Meermann, Björn T1 - Method development for on-line species-specific sulfur isotopic analysis by means of capillary electrophoresis/multicollector ICP-mass spectrometry N2 - In this work, a method for species-specific isotopic analysis of sulfur via capillary electrophoresis hyphenated on-line with multicollector ICP-MS (CE/MC-ICP-MS) was developed. Correction for the mass bias caused by instrumental mass discrimination was realized via external correction with multiple-injection sample-standard bracketing. By comparing the isotope ratio measurement results obtained using the newly developed on-line CE/MC-ICP-MS method with those obtained via traditional MC-ICP-MS measurement after analyte/matrix separation by anion exchange chromatography for isotopic reference materials and an in-house bracketing standard, the most suitable data evaluation method could be identified. The repeatability for the sulfate-δ34S value (calculated from 18 measurements of a standard conducted over seven measurement sessions) was 0.57‰ (2SD) and thereby only twice that obtained with off-line measurements (0.30‰, n = 68). As a proof of concept for analysis of samples with a real matrix, the determination of the sulfur isotopic composition of naturally present sulfate was performed for different river systems. The CE/MC-ICP-MS results thus obtained agreed with the corresponding off-line MC-ICP-MS results within the 2SD ranges, and the repeatability of consecutive δ34S measurements (n = 3) was between 0.3‰ and 1.3‰ (2SD). Finally, the isotopic analysis of two different S-species in a river water sample spiked with 2-pyridinesulfonic acid (PSA) was also accomplished. KW - River water sulfate KW - Environmental speciation KW - Sulfur isotopes KW - On-line CE/MC-ICP-MS KW - Multiple-injection sample-standard bracketing PY - 2020 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-509549 DO - https://doi.org/10.1007/s00216-020-02781-8 SN - 1618-2642 VL - 412 IS - 23 SP - 5637 EP - 5646 PB - Springer CY - Berlin, Heidelberg AN - OPUS4-50954 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Meermann, Björn T1 - Metal based pollutant assessment via diatoms - new possibilities via automated single cell-ICP-ToF-MS N2 - Diatoms are located at the bottom of the food chain. Toxicological relevant metals can possibly accumulate within the food web and cause harmful effects. Diatoms are a test system in ecotoxicology. Toxicological effects weaken the growth of algae which is by default investigated by means of fluorescence detection. On basis of the expose concentration as well as obtained fluorescence data potential threshold exceedance in e.g. surface waters is assessed. However, this approach does not allow for the determination of “real” accumulated metal concentration in diatoms. Common approaches are based on bulk analysis via e.g. ICP-MS, ICP-OES or AAS. But, biological variability is completely disregarded. To tackle this problem, alternative approaches are highly needed. Within the last years, sp-ICP-MS for nanoparticle as well as single cell analysis turned out as a powerful technique to analyze metal contents as well as size distributions on broad size range. But, common ICP-MS systems do not allow for multi-element detection within single particle/cell events. Thus, simultaneous MS detection devices are needed - just recently, ICP-ToF-MS experienced a revival. Within our previous work, we developed an automated sample introduction system based on a HPLC system on-line with single particle-ICP-MS, which allowed for ionic background separation and single algae analysis. However, for unambiguous tracing several fingerprint elements and multielement analysis in single algae (diatoms) is needed. Thus, we coupled our previous setup on-line to ICP-ToF-MS. Test diatom species were exposed to test substances (Zn) as well as nanoparticles (FeNPs). The developed setup allowed for a fast, automated and multielement analysis in single diatoms. Furthermore, we combined our approach with multivariate data assessment - multielement detection of characteristic fingerprint elements allowed for an unambiguous diatom tracing. Clustering of diatoms according to metal exposure concentration levels was enabled. Our approach is a new potential tool in ecotoxicological testing. T2 - 53. DGMS & 27th ICP-MS user meeting CY - Münster, Germany DA - 01.03.2020 KW - Single cell-ICP-ToF-MS KW - Diatoms KW - New ecotoxicological testing tools PY - 2020 AN - OPUS4-50644 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Alfeld, M. A1 - Eckhardt, H.-S. A1 - Kraft, J. A1 - Maiwald, Michael A1 - Meermann, Björn A1 - Merz, K. A1 - Prikler, S. A1 - Richert, J. A1 - Steiner, G. A1 - von Tümpling, W. T1 - Trendbericht Analytische Chemie N2 - Zusätzlich zu Methodenentwicklung, Miniaturisierung und Kopplungsverfahren zeigen sich die Hyperspektroskopie zusammen mit Imaging‐Verfahren, der Einzelmolekülnachweis und der Einsatz von 3‐D‐Druckern als neue Schwerpunkte. Hinzu kommen künstliche Intelligenz bei Sensoren, Bildgebungsverfahren und Prozesssteuerung sowie die Vernetzung von Analyse‐ und Laborgeräten. Trends und Forschungsthemen aus der analytischen Chemie, zusammengestellt von elf Autoren, koordiniert von Günter Gauglitz. KW - Multielementanalytik KW - Multimodale Analytik KW - Kristallolgraphie KW - Prozessanalytik KW - Prozessindustrie KW - Industrielle Analytik KW - Chemometrik KW - Chemometrie PY - 2020 DO - https://doi.org/10.1002/nadc.20204095786 SN - 1868-0054 VL - 68 IS - 4 SP - 52 EP - 60 PB - Wiley CY - Weinheim AN - OPUS4-50609 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Maiwald, Michael T1 - The internet of things in the lab and in process - The digital transformation challenges for the laboratory 4.0 T1 - Das Internet of Things in Labor und Prozess - Herausforderungen des digitalen Wandels für das Labor 4.0 N2 - It is a fact that much of the time spent on analytical laboratory instrumentation these days goes into system maintenance. Digital transformation could give us more time again for creativity and our actual laboratory work – if we shape it the right way. N2 - Fakt ist: Einen Großteil der Zeit, der an analytischen Laborgeräten verbracht wird, nimmt heute die Systempflege in Anspruch. Der digitale Wandel kann uns endlich wieder mehr Zeit für Kreativität und die eigentliche Laborarbeit geben – wenn wir ihn richtig gestalten. KW - Lab of the Future KW - Digitalisation KW - Automation KW - Data Analysis KW - Instrument Communication KW - Labor der Zukunft KW - Digitale Transformation KW - Automatisierung KW - Gerätekommunikation PY - 2020 IS - 4 SP - 1 EP - 3 PB - Lumitos AG CY - Darmstadt AN - OPUS4-50618 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Zhang, Zhiyang A1 - Li, Y. A1 - Frisch, J. A1 - Bär, M. A1 - Rappich, J. A1 - Kneipp, Janina T1 - In situ surface-enhanced Raman scattering shows ligand-enhanced hot electron harvesting on silver, gold, and copper nanoparticles N2 - Hot carriers (electrons and holes) generated from the decay of localized surface plasmon resonances can take a major role in catalytic reactions on metal nanoparticles. By obtaining surface enhanced Raman scattering (SERS) spectra of p-aminothiophenol as product of the reduction of p-nitrothiophenol by hot electrons, different catalytic activity is revealed here for nanoparticles of silver, gold, and copper. As a main finding, a series of different ligands, comprising halide and non-halide species, are found to enhance product formation in the reduction reaction on nanoparticles of all three metals. A comparison with the standard electrode potentials of the metals with and without the ligands and SERS data obtained at different electrode potential indicate that the higher catalytic activity can be associated with a higher Fermi level, thereby resulting in an improved efficiency of hot carrier generation. The concept of such a ligand-enhanced hot electron reduction provides a way to make light-to-chemical energy conversion more efficient due to improved electron harvesting. KW - Ligands KW - Hot electrons KW - SERS KW - p-Nitrothiophenol KW - p-Aminothiophenol PY - 2020 DO - https://doi.org/10.1016/j.jcat.2020.01.006 VL - 383 SP - 153 EP - 159 PB - Elsevier Inc. CY - Amsterdam, NL AN - OPUS4-50626 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - von der Au, Marcus T1 - SPE HR-CS GF MAS – A New Sum Parameter Method for Extractable Organically Bound Fluorine (EOF) in Surface Water N2 - Introducing fluorine into organic molecules leads to new chemical/physical properties. Up to now, the OECD identified and categorized 4730 per- and polyfluoroalkyl substances-related CAS numbers. Especially in the field of technical applications (e.g. surface coatings, fire extinguishing foams) as well as pharmaceuticals, fluorinated substances gain in importance. Thus, an increasing release of fluorinated compounds into the environment is expected. The high environmental persistence of perfluorinated compounds leads to the risk of bioaccumulation. Partially fluorinated substances (polyfluorinated compounds) undergo degradation; thus, further possible fluorine species occur, which may exhibit different toxic/chemical properties. However, current target methods (e.g., HPLC/MS-MS) are not applicable for a comprehensive screening as well as assessment of pollution. Thus, the poster presents a new sum parameter method for quantitative determination of extractable organically bound fluorine (EOF) in surface water samples. The method is based on solid-phase extraction (SPE) for fluorinated compounds as well as quantitative separation of interfering inorganic fluoride in combination with high-resolution-continuum source graphite furnace molecular absorption spectrometry (HR-CS GF MAS) for quantitative analysis. By means of this technique, the detection of high resolution molecular absorption spectra (MAS) is enabled upon the addition of a modifier and the formation of a diatomic molecule (e.g. GaF) After successful optimization of the SPE procedure (maximum concentration of extractable organic fluorine), enrichment factors of about 1000 were achieved, allowing for highly sensitive fluorine detection. Next to a species-unspecific response, limits of detection in the low nanogram per liter range were achieved and real surface water samples were analyzed. EOF values in the range of about 50-300 ng/L were detected. The developed method allows for a fast and sensitive as well as selective screening of organically bound fluorine (EOF) in surface water samples, helping to elucidate pollution hotspots as well as discharge routes. T2 - 2020 Winter Conference on Plasma Spectrochemistry CY - Tucson, AZ, USA DA - 12.01.2020 KW - SPE HR-CS GF MAS KW - Sum parameter KW - Fluorine Detection PY - 2020 AN - OPUS4-50352 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Ebel, Kenny A1 - Bald, Ilko T1 - Length and Energy Dependence of Low-Energy Electron-Induced Strand Breaks in Poly(A) DNA N2 - The DNA in living cells can be effectively damaged by high-energy radiation, which can lead to cell death. Through the ionization of water molecules, highly reactive secondary species such as low-energy electrons (LEEs) with the most probable energy around 10 eV are generated, which are able to induce DNA strand breaks via dissociative electron attachment. Absolute DNA strand break cross sections of specific DNA sequences can be efficiently determined using DNA origami nanostructures as platforms exposing the target sequences towards LEEs. In this paper, we systematically study the effect of the oligonucleotide length on the strand break cross section at various irradiation energies. The present work focuses on poly-adenine sequences (d(A4), d(A8), d(A12), d(A16), and d(A20)) irradiated with 5.0, 7.0, 8.4, and 10 eV electrons. Independent of the DNA length, the strand break cross section shows a maximum around 7.0 eV electron energy for all investigated oligonucleotides confirming that strand breakage occurs through the initial formation of negative ion resonances. When going from d(A4) to d(A16), the strand break cross section increases with oligonucleotide length, but only at 7.0 and 8.4 eV, i.e., close to the maximum of the negative ion resonance, the increase in the strand break cross section with the length is similar to the increase of an estimated geometrical cross section. For d(A20), a markedly lower DNA strand break cross section is observed for all electron energies, which is tentatively ascribed to a conformational change of the dA20 sequence. The results indicate that, although there is a general length dependence of strand break cross sections, individual nucleotides do not contribute independently of the absolute strand break cross section of the whole DNA strand. The absolute quantification of sequence specific strand breaks will help develop a more accurate molecular level understanding of radiation induced DNA damage, which can then be used for optimized risk estimates in cancer radiation therapy. KW - DNA origami KW - DNA radiation damage KW - DNA strand breaks KW - Low-energy electrons KW - Sequence dependence PY - 2020 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-503563 DO - https://doi.org/10.3390/ijms21010111 VL - 21 IS - 1 SP - 1 EP - 11 PB - MDPI CY - Basel, Switzerland AN - OPUS4-50356 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Schmidt, C. A1 - Schierack, P. A1 - Gerber, U. A1 - Schröder, C. A1 - Choi, Youngeun A1 - Bald, Ilko A1 - Lehmann, W. A1 - Rödiger, S. T1 - Streptavidin Homologues for Applications on Solid Surfaces at High Temperatures N2 - One of the most commonly used bonds between two biomolecules is the bond between biotin and streptavidin (SA) or streptavidin homologues (SAHs). A high dissociation constant and the consequent high-temperature stability even allows for its use in nucleic acid detection under polymerase chain reaction (PCR) conditions. There are a number of SAHs available, and for assay design, it is of great interest to determine as to which SAH will perform the best under assay conditions. Although there are numerous single studies on the characterization of SAHs in solution or selected solid phases, there is no systematic study comparing different SAHs for biomolecule-binding, hybridization, and PCR assays on solid phases. We compared streptavidin, core streptavidin, traptavidin, core traptavidin, neutravidin, and monomeric streptavidin on the surface of microbeads (10–15 μm in diameter) and designed multiplex microbead-based experiments and analyzed simultaneously the binding of biotinylated oligonucleotides and the hybridization of oligonucleotides to complementary capture probes. We also bound comparably large DNA origamis to capture probes on the microbead surface. We used a real-time fluorescence microscopy imaging platform, with which it is possible to subject samples to a programmable time and temperature profile and to record binding processes on the microbead surface depending on the time and temperature. With the exception of core traptavidin and monomeric streptavidin, all other SA/SAHs were suitable for our investigations. We found hybridization efficiencies close to 100% for streptavidin, core streptavidin, traptavidin, and neutravidin. These could all be considered equally suitable for hybridization, PCR applications, and melting point analysis. The SA/SAH–biotin bond was temperature-sensitive when the oligonucleotide was mono-biotinylated, with traptavidin being the most stable followed by streptavidin and neutravidin. Mono-biotinylated oligonucleotides can be used in experiments with temperatures up to 70 °C. When oligonucleotides were bis-biotinylated, all SA/SAH–biotin bonds had similar temperature stability under PCR conditions, even if they comprised a streptavidin variant with slower biotin dissociation and increased mechanostability. KW - Biopolymers Probes KW - Hybridization KW - Fluorescence KW - Genetics PY - 2020 DO - https://doi.org/10.1021/acs.langmuir.9b02339 VL - 36 IS - 2 SP - 628 EP - 636 PB - American Chemical Society Publication CY - Washington AN - OPUS4-50357 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Gornushkin, Igor B. A1 - Gaft, M. A1 - Nagli, L. A1 - Raichlin, Y. T1 - Laser-induced breakdown spectroscopy (LIBS) of BaF2-Tm3+ N2 - Our recent study was focused on the emission from Laser Induced Plasma (LIP) at the delay times of tenths of microseconds after the laser pulse. At these long delays, the spectrum is dominated by the broadband molecular emission and plasma induced luminescence (PIL) produced by a luminescent matrix; only solitary atomic emission lines can be seen. Barium fluoride BaF2 activated by thulium (Tm) is a famous scintillator that presents the promising object for LIP in terms of both the potential for BaF molecular emission and Tm3+ PIL. The detection of molecular and PIL bands presents a new opportunity for analysis of halogens and rare-earth elements, which are the difficult objects for LIBS. In this paper, we show that the UV, Green, Extreme Red, and Infrared molecular bands from BaF and blue luminescence from Tm3+ are present in the LIP emission spectra while the detection of atomic Emission from F I and Tm I was impossible with the same experimental setup. Thus, the detection of molecular emission and PIL can be more sensitive than the traditional detection of Emission from atoms and ions. KW - BaF KW - Laser-Induced Breakdown Spectroscopy (LIBS) KW - Rare-Earth elements (Tm3+) KW - Plasma-induced luminescence PY - 2020 DO - https://doi.org/10.1016/j.sab.2020.105767 VL - 164 SP - 105767 PB - Elsevier B.V. AN - OPUS4-50360 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Gornushkin, Igor B. T1 - Plasma Fundamentals and Diagnostics N2 - This course will provide an introduction to plasma diagnostic techniques. The major focus of the course will be on the discussions of the practical procedures as well as the underlying physical principles for the measurements of plasma fundamental characteristics (e.g., temperatures, thermodynamic properties, and electron number density). Particular emphasis will be placed on inductively coupled plasma–atomic emission spectrometry, but other analytical plasmas will also be used as examples when appropriate. Selected examples on how one can manipulate the operating conditions of the plasma source, based on the results of plasma diagnostic measurements, to improve its performance used for spectrochemical analysis will also be covered. Topics to be covered include thermal equilibrium, line profiles, temperatures, electron densities, excitation processes, microreactions, pump and probe diagnostics, tomography, temporal and spatial resolution. Basis of plasma computer modeling will be presented. T2 - Winter Plasma Conference CY - Tucson, AZ, USA DA - 10.01.2020 KW - Plasma modeling KW - Thermal equilibrium KW - Plasma processes KW - Electron number density KW - Temperatures KW - Emission line profiles KW - Spatial information PY - 2020 AN - OPUS4-50324 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Philipp, Rosemarie T1 - EURAMET.QM-S14 "Measurement capabilities for the quantification of ethanol in water" - Summary of results N2 - The presentation summarizes the results of the EURAMET key comparison QM-S14 “Measurement capabilities for the quantification of ethanol in water”. Possible options for the key comparison reference value are discussed. T2 - EURAMET TC-MC Meeting 2020 CY - Bern, Switzerland DA - 05.02.2020 KW - EURAMET KW - Key comparison KW - Ethanol in water PY - 2020 AN - OPUS4-50391 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Vogl, Jochen T1 - Isotope ratio working group at CCQM N2 - The presentation gives the reasons for initiation of an isotope ratio working group at CCQM level, describes the process and provides the auduince with the initial working plan. T2 - EURAMET TC-MC Workshop on Isotope Ratio Analysis CY - Bern, Switzerland DA - 05.02.2020 KW - Metrology KW - Absolute isotope ratio KW - Isotope ratio KW - Delta value PY - 2020 AN - OPUS4-50344 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Vogl, Jochen T1 - CCQM IRWG draft strategy for all elements except for noble gases and H, C, N, O N2 - The presentation describes the draft strategy for metalloids and semi-metals within the IRWG at CCQM. This includes the definition of the measurements space, a suitable set of key comparisons and pilot studies and a proposal for a harmonized CMC application. T2 - EURAMET TC-MC Workshop on Isotope Ratio Analysis CY - Bern, Switzerland DA - 05.02.2020 KW - CMC KW - Measurement space KW - Metrology KW - Isotope ratio PY - 2020 AN - OPUS4-50345 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Vogl, Jochen T1 - Absolute isotope ratios - a proposed research topic N2 - An introduction into absolute isotope ratios is given, with application fields ranging from fundamental science to geochronology and forensics. This is followed by a proposal for developing new calibration approaches for obtaining absolute isotope ratios at unrivaled uncertainty levels. This new developments will set the basis for improvements in all scientific fields. T2 - EURAMET TC-MC Workshop on Isotope Ratio Analysis CY - Bern, Switzerland DA - 05.02.2020 KW - Absolute isotope ratio KW - Isotope fractionation KW - Metrology KW - Fundamental science PY - 2020 AN - OPUS4-50346 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - GEN A1 - Hampel, U. A1 - Schütze, A. A1 - Rädle, M. A1 - Rück, T. A1 - Krawczyk-Becker, M. A1 - Musch, T. A1 - Maiwald, Michael A1 - Fröhlich, H. J. A1 - Zeck, S. T1 - Positionspapier Sensorik für die Digitalisierung chemischer Produktionsanlagen N2 - Die chemische Industrie steht derzeit, wie viele andere Industriebereiche, vor den Herausforderungen einer Digitalisierung der Produktion. Sie ist der Schlüssel für die Flexibilisierung von Prozessen und Anlagen, für die Verkürzung von Produkteinführungszeiten sowie für den Zuschnitt der Produktion auf wechselnde Nachfrage und kürzere Produktlebenszyklen. Die Messtechnik und Sensorik spielt neben der intelligenten Datenverarbeitung eine Schlüsselrolle für die Digitalisierung. Flexiblere Anlagen benötigen Sensorik zur Überwachung des Anlagenzustandes, zur Früherkennung nicht bestimmungsgemäßer Betriebszustände sowie für eine bedarfsgerechte Wartung. Da die Entwicklung neuer und verbesserter Messtechnik und Sensorik grundlegend aus verschiedenen Richtungen gedacht werden muss, haben sich Akteure aus verschiedenen Branchen zusammengetan und dieses Positionspapier erstellt. Es basiert auf einer grundlegenden Analyse des Ist-Stands sowie des Bedarfs der Industrie, die unter anderem auf einem eigens dafür durchgeführten Workshop mit Sensorentwicklern, Anlagenherstellern sowie Anlagenbetreibern am 18. Juni 2019 bei der DECHEMA in Frankfurt a. M. diskutiert wurden. Diese Aktivitäten wurden maßgeblich von der Initiative Wanted Technologies der ProcessNet sowie dem AMA Verband für Sensorik und Messtechnik e.V. initiiert. KW - Prozessindustrie KW - Smarte Sensoren KW - Prozessanalytik KW - DECHEMA KW - Positionspapier PY - 2020 UR - https://dechema.de/Sensorik SP - 1 EP - 20 PB - DECHEMA CY - Frankfurt am Main AN - OPUS4-50403 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - von der Au, Marcus A1 - Borovinskaya, O. A1 - Flamigni, L. A1 - Kuhlmeier, K. A1 - Büchel, C. A1 - Meermann, Björn T1 - Single cell-inductively coupled plasma-time of flight-mass spectrometry approach for ecotoxicological testing N2 - Diatoms play a key role in assessing the eco-toxicology of metals and are already part of several national and international guidelines and regulations. Data on metal uptake and its correlation with a natural metal composition of the diatoms are mostly lacking on a cellular basis - mainly due to the lack of a suitable method on both the preparation and detection side. Therefore, within this work a fully automated approach based on the on-line coupling of a high performance liquid chromatograph (HPLC) and an inductively coupled plasma-time of flight-mass spectrometer (ICP-ToF-MS) was applied to analyze single cells of the alga Cyclotella meneghiniana multi-elementally in order to provide a deeper insight into the metal composition and its response to environmental stress. Multi-elemental analysis in single diatoms also enables assessment of combined toxicity of a set of metals. A set of four fingerprint elements, characteristically for diatoms (Mg, P, Si, Fe), were identified and hence the investigation of environmental stress onto the cells was enabled by performing incubation experiments with environmentally relevant toxic elements. It could be shown at moderate environmental stress caused by increasing the metal concentration in the medium (zinc) that the fingerprint element concentrations remained stable and thus the suitability of the selected elements for algae tracing was demonstrated. With regard to further ecotoxicological assessments, a multivariate approach was successfully applied allowing for cell classification upon different incubation concentration levels. This multivariate approach also facilitated an effective identification of three different diatom species (Cyclotella meneghiniana, Thalassiosira weissflogii and Thalassiosira pseudonana). KW - ICP-TOF-MS KW - Ecotoxicological Testing KW - Diatoms PY - 2020 DO - https://doi.org/10.1016/j.algal.2020.101964 VL - 49 SP - 101964 PB - Elsevier B.V. AN - OPUS4-50875 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Philipp, Rosemarie T1 - EURAMET.QM-S14 Measurement capabilities for the quantification of ethanol in water - Summary of results N2 - The presentation summarizes the results of the EURAMET key comparison QM-S14 “Measurement capabilities for the quantification of ethanol in water”. Possible options for the key comparison reference value are discussed. T2 - CCQM Organic Analysis Working Group videoconference CY - Online meeting DA - 05.06.2020 KW - Certified Reference Material KW - EURAMET KW - Key comparison PY - 2020 AN - OPUS4-50890 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Marques, T. S. A1 - Schürmann, Robin A1 - Ebel, Kenny A1 - Heck, C. A1 - Smialek, M. A1 - Eden, Sam A1 - Mason, N. A1 - Bald, Ilko T1 - Kinetics of molecular decomposition under irradiation of gold nanoparticles with nanosecond laser pulses-A 5-Bromouracil case study N2 - Laser illuminated gold nanoparticles (AuNPs) efficiently absorb light and heat up the surrounding medium, leading to versatile applications ranging from plasmonic catalysis to cancer photothermal therapy. Therefore, an in-depth understanding of the thermal, optical, and electron induced reaction pathways is required. Here, the electrophilic DNA nucleobase analog 5-Bromouracil (BrU) has been used as a model compound to study its decomposition in the vicinity of AuNPs illuminated with intense ns laser pulses under various conditions. The plasmonic response of the AuNPs and the concentration of BrU and resulting photoproducts have been tracked by ultraviolet and visible (UV–Vis) spectroscopy as a function of the irradiation time. A kinetic model has been developed to determine the reaction rates of two parallel fragmentation pathways of BrU, and their dependency on laser fluence and adsorption on the AuNP have been evaluated. In addition, the size and the electric field enhancement of the decomposed AuNPs have been determined by atomic force microscopy and finite domain time difference calculations, respectively. A minor influence of the direct photoreaction and a strong effect of the heating of the AuNPs have been revealed. However, due to the size reduction of the irradiated AuNPs, a trade-off between laser fluence and plasmonic response of the AuNPs has been observed. Hence, the decomposition of the AuNPs might be limiting the achievable temperatures under irradiation with several laser pulses. These findings need to be considered for an efficient design of catalytic plasmonic systems. KW - Kinetics KW - Gold nanoparticles KW - 5-Bromouracil PY - 2020 DO - https://doi.org/10.1063/1.5137898 VL - 152 IS - 12 SP - 24712 EP - 24712 PB - AIP Publishing AN - OPUS4-50787 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kepsutlu, B. A1 - Wycisk, V. A1 - Achazi, K. A1 - Kapishnikov, S. A1 - Perez-Berna, A.J. A1 - Guttmann, P. A1 - Cossmer, Antje A1 - Pereiro, E. A1 - Ewers, H. A1 - Ballauff, M. A1 - Schneider, G. A1 - McNally, J.G. T1 - Cells Undergo Major Changes in the Quantity of Cytoplasmic Organelles after Uptake of Gold Nanoparticles with Biologically Relevant Surface Coatings N2 - Here, we use cryo soft X-ray tomography (cryo-SXT), which delivers 3D ultrastructural volumes of intact cells without chemical fixation or staining, to gain insight about nanoparticle uptake for nanomedicine. We initially used dendritic polyglycerol sulfate (dPGS) with potential diagnostic and therapeutic applications in inflammation. Although dPGS-coated gold nanoparticle (dPGS-AuNP) uptake followed a conventional endocytic/degradative pathway in human lung epithelial cell lines (A549), with cryo-SXT, we detected ∼5% of dPGS-AuNPs in the cytoplasm, a level undetectable by confocal light microscopy. We also observed ∼5% of dPGS-AuNPs in a rarely identified subcellular site, namely, lipid droplets, which are important for cellular energy metabolism. Finally, we also found substantial changes in the quantity of cytoplasmic organelles upon dPGS-AuNP uptake over the 1–6 h incubation period; the number of small vesicles and mitochondria significantly increased, and the number of multivesicular bodies and the number and volume of lipid droplets significantly decreased. Although nearly all organelle numbers at 6 h were still significantly different from controls, most appeared to be returning to normal levels. To test for generality, we also examined cells after uptake of gold nanoparticles coated with a different agent, polyethylenimine (PEI), used for nucleic acid delivery. PEI nanoparticles did not enter lipid droplets, but they induced similar, albeit less pronounced, changes in the quantity of cytoplasmic organelles. We confirmed these changes in organelle quantities for both nanoparticle coatings by confocal fluorescence microscopy. We suggest this cytoplasmic remodeling could reflect a more common cellular response to coated gold nanoparticle uptake. KW - Cellular trafficking KW - Confocal laser scanning microscopy KW - Cytoplasmic remodeling KW - Dendritic polyglycerol sulfate KW - Polyethylenimine KW - 3D ultrastructural analysis KW - Cryo-soft X-ray tomography PY - 2020 DO - https://doi.org/10.1021/acsnano.9b09264 VL - 14 IS - 2 SP - 2248 EP - 2264 AN - OPUS4-50464 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Faßbender, Sebastian T1 - On-line hyphenation of CE with multicollector-ICP-MS for species-specific isotopic analysis of sulfur N2 - In many scientific fields, isotopic analysis can offer valuable information, e.g., for tracing the origin of food products, environmental contaminants, forensic and archaeological samples (provenance determination), for age determination of minerals (geochronological dating) or for elucidating chemical processes. Up to date, typically bulk analysis is aimed at measuring the isotopic composition of the entire elemental content of the sample. However, the analyte element is usually present under the form of different species. Thus, separating species of interest from one another and from matrix components prior to isotope ratio measurements can provide species-specific isotopic information, which could be used for tracing the origin of environmental pollutants and elucidation of (environmental) speciation. Using on-line hyphenations of separation techniques with multicollector-ICP-MS (MC-ICP-MS) can save time and effort and enables the analysis of different species during a single measurement. In this work, we developed an on-line hyphenation of CE with multicollector-ICP-MS (CE/MC-ICP-MS) for isotopic analysis of sulfur species. With this method, the isotopic composition of sulfur in sulfate originating from river water could be analyzed without sample preparation. The results were compared with data from off-line analysis of the same samples to ensure accuracy. The precision of the results of the on-line measurements was high enough to distinguish the rivers from one another by the isotopic signature of the river water sulfate. Next to environmental applications, a future field could be species-specific isotopic analysis of biomolecules, as sulfur is the only covalently bound constituent of proteins which can be analyzed by MC-ICP-MS. T2 - DGMS 2020 CY - Münster, Germany DA - 01.03.2020 KW - Capillary electrophoresis KW - Hyphenated techniques KW - Isotopic analysis KW - Multicollector-ICP-MS KW - Speciation analysis PY - 2020 AN - OPUS4-50501 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - von der Au, Marcus T1 - HR-CS-GF-MAS as a new screening method for emerging pollutants - per- and polyfluorinated substances in the environment N2 - The introduction of fluorine in organic molecules leads to new chemical/physical properties. Especially in the field of pharmaceuticals, fluorinated organic molecules are becoming more and more popular and at present amount up to 25% of market share, with an upward trend. The main benefits of fluorinated pharmaceuticals are: (i) enhanced fat solubility; (ii) enhanced interaction of catalytic-center of enzymes with fluorine-drugs; (iii) a delayed metabolism within the human body. Highly fluorinated organic substances are also used in technical applications (e.g. coatings, fire-extinguishing agents). Due to the broad variety of fluorinated substances and increasing production volumes numerous and up to date unknown fluorine-species are most likely to be present in the (aquatic) environment. Analytical methods to assess the degree of contamination of surface waters with organically bound fluorine are highly needed and up to now only combustion ion chromatography based method is available, which is relatively laborious. Since a few years’ high resolution-continuum source-graphite furnace atomic absorption spectrometers (HR-CS-GFAAS) are commercially available from Analytik Jena. By means of this technique, the detection of high resolution molecular absorption spectra (MAS) is enabled. Thus, fluoride is detectable upon the addition of a modifier and the formation of a diatomic molecule (e.g. GaF). Just recently, we applied this technique for total fluorine (mainly dissolved fluoride) analysis in river water samples. In the present work a HR-CS-GFMAS method for extractable organically bound fluorine (EOF) analysis in surface water samples was developed by us. The method is based on SPE extraction of organically bound fluorine even in the presence of high fluoride concentrations followed by HR-CS-GFMAS analysis upon elution. Due to high enrichment factors, LODs in the low ng/L range were achieved. We successfully applied our SPE HR-CS-GFMAS method to Rhine water samples and EOF in the range of about 50-300 ng/L was detectable. T2 - DGMS 2020 CY - Münster, Germany DA - 01.03.2020 KW - SPE HR-CS GF MAS PY - 2020 AN - OPUS4-50503 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - von der Au, Marcus T1 - HR-CS-GF-MAS as a new screening method for emerging pollutants - per- and polyfluorinated substances in the environment N2 - The introduction of fluorine in organic molecules leads to new chemical/physical properties. Especially in the field of pharmaceuticals, fluorinated organic molecules are becoming more and more popular and at present amount up to 25% of market share, with an upward trend. The main benefits of fluorinated pharmaceuticals are: (i) enhanced fat solubility; (ii) enhanced interaction of catalytic-center of enzymes with fluorine-drugs; (iii) a delayed metabolism within the human body. Highly fluorinated organic substances are also used in technical applications (e.g. coatings, fire-extinguishing agents). Due to the broad variety of fluorinated substances and increasing production volumes numerous and up to date unknown fluorine-species are most likely to be present in the (aquatic) environment. Analytical methods to assess the degree of contamination of surface waters with organically bound fluorine are highly needed and up to now only combustion ion chromatography based method is available, which is relatively laborious. Since a few years’ high resolution-continuum source-graphite furnace atomic absorption spectrometers (HR-CS-GFAAS) are commercially available from Analytik Jena. By means of this technique, the detection of high resolution molecular absorption spectra (MAS) is enabled. Thus, fluoride is detectable upon the addition of a modifier and the formation of a diatomic molecule (e.g. GaF). Just recently, we applied this technique for total fluorine (mainly dissolved fluoride) analysis in river water samples. In the present work a HR-CS-GFMAS method for extractable organically bound fluorine (EOF) analysis in surface water samples was developed by us. The method is based on SPE extraction of organically bound fluorine even in the presence of high fluoride concentrations followed by HR-CS-GFMAS analysis upon elution. Due to high enrichment factors, LODs in the low ng/L range were achieved. We successfully applied our SPE HR-CS-GFMAS method to Rhine water samples and EOF in the range of about 50-300 ng/L was detectable. T2 - DGMS 2020 CY - Münster, Germany DA - 01.03.2020 KW - SPE HR-CS GF MAS PY - 2020 AN - OPUS4-50504 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Lemke, Nora T1 - Sulfur isotope dilution ICP MS for traceable protein quantification N2 - Inductively coupled plasma mass spectrometry (ICP-MS) is a powerful method for the matrix-independent quantitative analysis of target elements. Developed for the use in inorganic trace analysis, ICP-MS is nowadays a valuable tool for bioanalytical questions. Especially the use of ICP-MS for quantitative proteomics by measuring heteroatoms has gained recognition in the last decade, considering that established quantification methods like organic mass spectrometry depend on labelling of the target protein or the existence of matched protein and peptide standards. The need for reliable quantification of proteins is continuously growing, but only a limited number of well-characterized and quantified protein standards are available so far. Accurately quantified, traceable protein standards are necessary to ensure comparability of measurements between laboratories, not only in basic research but also in a clinical context. One example of this is the Alzheimer’s disease biomarker tau protein. However, existing tau standards lack comparability, emphasizing the need for a well-quantified protein standard. Therefore, we developed a method for the quantification of pure proteins via sulfur isotope dilution ICP-MS (IDMS). As sulfur is present in two amino acids, cysteine and methionine, it exists in nearly all proteins and can be used for the quantification of proteins of known stoichiometry. We employed simple offline strategies for the separation of non-protein bound sulfur species. Quantification of these contaminations by IDMS allows for correction of the protein content and enables reliable protein quantification. We report the protein mass fractions of a standard reference material and commercially available proteins determined by sulfur IDMS, including the expanded uncertainties. The developed method can be applied for the reliable and traceable quantification of pure proteins for use as in-house standards. Here, we successfully used this method for the quantification of the tau protein. T2 - 53rd annual conference of the DGMS including 27th ICP-MS User's Meeting CY - Münster, Germany DA - 01.03.2020 KW - ICP-MS KW - Isotope dilution KW - Protein KW - Quantification KW - Tau protein PY - 2020 AN - OPUS4-50510 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Gojani, Ardian T1 - Combined Raman and LIBS using Spatial Heterodyne Spectrometer with High Repetition Rate Laser N2 - Spatial heterodyne spectroscopy is used for Raman and laser-induced breakdown spectroscopy of six rocks with various mineral content, using high repetition rate diode-pumped solid state lasers. While LIBS data are obtained for all samples, Raman signal was determined only for half of those. This work shows that it is possible to combine LIBS and Raman spectrometry into a single instrument consisting of a DPSS laser for excitation and SHS for spectral recording. For better results and gain from complementary spectrochemical information that the system provides, it is necessary to optimize light collection. T2 - 2020 Winter Conference on Plasma Spectrochemistry CY - Tucson, Arizona, USA DA - 13.01.2020 KW - Laser-Induced Background Spectroscopy KW - Spatial heterodyne spectroscopy KW - Raman spectroscopy PY - 2020 AN - OPUS4-50265 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Galbacs, G. A1 - Keri, A. A1 - Kalomista, I. A1 - Kovacs-Szeles, E. A1 - Gornushkin, Igor B. T1 - Deuterium analysis by inductively coupled plasma mass spectrometry using polyatomic species: An experimental study supported by plasma chemistry modeling N2 - based on the use of the signal from hydrogen-containing polyatomic ions formed in the inductively coupled plasma. Prior to analytical experiments, a theoretical study was performed to assess the concentration of polyatomic species present in an equilibrium Ar-O-D-H plasma, as a function of temperature and stoichiometric composition. It was established that the highest sensitivity and linearity measurement of D concentration in a wide range can be achieved by monitoring the ions of D2 and ArD, at masses 4 and 42, respectively. Results of the calculations are in good agreement with the experiments. Signal stability, spectral interferences, as well as the effect of plasma parameters were also assessed. Under optimized conditions, the limit of detection (LOD) was found to be 3 ppm atom fraction for deuterium when measured as ArD (in calcium and potassium free water), or 78 ppm when measured as D2. The achieved LOD values and the 4 to 5 orders of magnitude dynamic range easily allow the measurement of deuterium concentrations at around or above the natural level, up to nearly 100% (or 1 Mio ppm) in a standard quadrupole ICP-MS instrument. An even better performance is expected from the method in high resolution ICP-MS instruments equipped with low dead volume sample introduction systems KW - ICP MS KW - Deuterium KW - Deuterium enriched water PY - 2020 DO - https://doi.org/10.1016/j.aca.2020.01.011 VL - 1104 SP - 28 EP - 37 PB - Elsevier B.V. AN - OPUS4-50777 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Zimmermann, T. A1 - von der Au, Marcus A1 - Reese, A. A1 - Klein, O. A1 - Hildebrandt, L. A1 - Pröfrock, D. T1 - Substituting HF by HBF4 – an optimized digestion method for multi-elemental sediment analysis via ICP-MS/MS N2 - Determination of elemental mass fractions in sediments plays a major role in evaluating the environmental status of aquatic ecosystems. Herewith, the optimization of a new total digestion protocol and the subsequent analysis of 48 elements in different sediment reference materials (NIST SRM 2702, GBW 07313, GBW 07311 and JMC-2) based on ICP-MS/MS detection is presented. The developed method applies microwave acid digestion and utilizes HBF4 as fluoride source for silicate decomposition. Similar to established protocols based on HF, HBF4 ensures the dissolution of the silicate matrix, as well as other refractory oxides. As HBF4 is not acutely toxic; no special precautions have to be made and digests can be directly measured via ICP-MS without specific sample inlet systems, evaporation steps or the addition of e.g. H3BO3, in order to mask excess HF. Different acid mixtures with and without HBF4 were evaluated in terms of digestion efficiency based on the trace metal recovery. The optimized protocol (5 mL HNO3, 2 mL HCL, 1 mL HBF4) allows a complete dissolution of the analyzed reference materials, as well as quantitative recoveries for a wide variety of certified analytes. Low recoveries for e.g. Sr, Ba and rare earth elements due to fluoride precipitation of HF-based digestions protocols, can be avoided by the usage of HBF4 instead. Based on the usage of high purity HBF4 all relevant trace, as well as matrix elements can be analyzed with sufficiently low LOQs (0.002 μg L−1 for U up to 6.7 μg L−1 for Al). In total, 34 elements were within a recovery range of 80%–120% for all three analyzed reference materials GBW 07313, GBW 07311 and JMC-2. 14 elements were outside a recovery range of 80%–120% for at least one of the analyzed reference materials. KW - Reference Materials KW - Sediment KW - HF free Digestion PY - 2020 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-510480 DO - https://doi.org/10.1039/D0AY01049A SP - 1 EP - 10 PB - Royal Society of Chemistry AN - OPUS4-51048 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Maiwald, Michael T1 - On the way to the cyber-physical lab T1 - Auf dem Weg zum cyber-physical Lab N2 - Laboratories tend to be central hubs for chemical, biotechnological, pharmaceutical or foodstuff production. They play a key role in research and development, chemical analysis, quality assurance, maintenance and process control. For process development and optimization, process analytical technology (PAT) has proven to be a powerful tool to improve our understanding of processes, increase productivity, reduce waste and costs and shorten processing times. N2 - Im Allgemeinen sind Laboratorien zentrale Drehscheiben für die chemische, biotechnologische, pharmazeutische oder Lebensmittelproduktion. Sie spielen eine Schlüsselrolle in Forschung und Entwicklung, chemischer Analytik, Qualitätssicherung, Instandhaltung und Prozesskontrolle. Für die Prozessentwicklung und -Optimierung hat sich die Prozessanalysentechnik (PAT) als leistungsfähiges Werkzeug erwiesen, um das Prozessverständnis zu verbessern, die Produktivität zu steigern, Abfall und Kosten zu reduzieren und die Prozesszeit zu verkürzen. KW - Lab of the Future KW - Digitalisation KW - Cyber-physical Lab KW - Smart Laboratoy PY - 2020 SP - 1 EP - 3 PB - Lumitos AG CY - Darmstadt AN - OPUS4-51036 LA - mul AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Climent Terol, Estela T1 - Design and synthesis of lateral flow tests containing antibody-gated materials N2 - Methods for the rapid and sensitive detection of target analytes are gaining importance in medical diagnostics and environmental monitoring, in the security, occupational health and safety as well as food sectors. Among all the methods employed for rapid tests, lateral flow assays (LFAs) are the most commonly used. However, some drawbacks are that most of these tests either indicate the analyte only indirectly, and in other cases the sensitivity is not high enough. Keeping in mind these limitations, the use of stimuli-responsive materials for small-molecule sensing relying on chemical signal amplification and utilizing specific interactions between biomolecules such as antibodies and the corresponding analytes are particularly attractive. Such materials can also be incorporated on paper strips for lateral-flow assays in a straightforward manner. These sensing materials comprise mesoporous silica nanoparticles loaded with indicator molecules and containing certain hapten derivative molecules covalently grafted at the surface, which bind to the respective antibody and inhibit the release of a dye as reporter (Scheme 1). In presence of the designated analyte, a displacement of the antibody from the material is observed, allowing the release of dye. Because a large number of indicator molecules can be released when a single analyte molecule binds to an antibody cap, a strong signal amplification is observed. Considering the modularity, high sensitivity and selectivity of these antibody-gated indicator delivery systems, the presentation discusses general aspects of system design as well as analytical performance and highlights the integration into a lateral-flow assay, showing as an example the determination of the explosives TATP, TNT and PETN with a fluorescence readout, in single-substance and multiplexing modes. T2 - International Webinar on Biosensors and Bioelectronics CY - Online meeting DA - 20.07.2020 KW - Multiplexing detection KW - Rapid testing methods KW - Gated hybrid materials KW - Lateral flow tests KW - Explosives detection PY - 2020 UR - https://europeanmeetings.net/conferences/biosensor-bioelectronics AN - OPUS4-51038 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Silva, C. P. A1 - Carvalho, T. A1 - Schneider, Rudolf A1 - Esteves, V. I. A1 - Lima, D. L. D. T1 - ELISA as an effective tool to determine spatial and seasonal occurrence of emerging contaminants in the aquatic environment N2 - During the last two decades, studies related to the occurrence and fate of emerging contaminants in the aquatic environment have received great attention from the international scientific community. The monitoring of the presence of these compounds is particularly important since they are known to induce adverse effects in aquatic environments, even at extremely low concentrations. This work aimed to apply a simple and effective methodology, such as enzyme-linked immunosorbent assay (ELISA), in the monitoring of 17a-ethinylestradiol (EE2) and 17b-estradiol (E2) (a synthetic and a natural hormone, respectively), carbamazepine (CBZ, an antiepileptic), cetirizine (CET, an antihistamine) and caffeine (CAF, a stimulant) in water matrices with differing salinity and organic matter contents. ELISA was proven to be a valid and practical tool, especially for screening purposes in contrast to traditional chromatographic techniques which are prohibitively expensive for an application on a broader base. The main originality of this work was to establish seasonal and spatial effects on the occurrence of the referred contaminants by using the effectiveness of ELISA to screen those compounds in samples with different characteristics. This work reports both the seasonal and spatial quantification of the referred contaminants in the aquatic environment of the central region of Portugal, with concentrations ranging as follows: 5–87 ng L-1, for E2, 2–17 ng L-1, for EE2, 10–1290 ng L-1, for CBZ, 10–190 ng L-1, for CET, and 62–6400 ng L-1, for CAF. KW - Estrogen KW - Estradiol KW - Ethinylestradiol KW - Carbamazepine KW - Portugal KW - Wasser PY - 2020 DO - https://doi.org/10.1039/D0AY00426J SN - 1759-9679 VL - 12 IS - 19 SP - 2517 EP - 2526 PB - Royal Society of Chemistry RSC CY - London AN - OPUS4-51340 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Raysyan, Anna A1 - Eremin, S. A. A1 - Beloglazova, N. V. A1 - De Saeger, S. A1 - Gravel, I. V. T1 - Immunochemical approaches for detection of aflatoxin B1 in herbal medicines N2 - Introduction Aflatoxin B1 (AFB1) is a toxic low‐molecular‐weight secondary metabolite of Aspergillus flavus and A. parasiticus. AFB1 was classified as a Group I carcinogen by the World Health Organisation for Research on Cancer in 1993. AFB1 is an unavoidable natural contaminant of some herbal medicine, able to cause serious health issues for humans consuming the related medicine. Objective Therefore, this study aimed to develop an efficient fluorescence polarisation immunoassay (FPIA) and a rapid, low‐cost, and easy‐to‐use membrane‐based flow‐through immunoassay (MBA) for determination of AFB1 in herbal medicine Origanum vulgare L., Rubus idaeus L., Urtica dioica L. and Sorbus aucuparia L. Results A cut‐off level of the developed MBA was 0.8 ppb. Validation of the developed test was performed with blank and spiked samples. Using three naturally contaminated or three artificially spiked samples. The FPIA showed a linear working range of 8.6 to 64 ppb, and a half maximal inhibitory concentration (IC50) of 24 ppb. Conclusion The results were in good correlation with the enzymelinked immunosorbent assay (ELISA) results (the IC50 0.1 ppb). Both the sample preparation and analysis are simple, cost‐effective and easy to perform on‐site in non‐laboratory environments. Liquid chromatography with tandem mass spectrometry (LC‐MS/MS) was used as a confirmatory technique. KW - Fluorescence Polarisation Immunoassay KW - membrane-based flow-through immunoassay KW - Mycotoxins KW - Mykotoxine KW - Schnelltest PY - 2020 DO - https://doi.org/10.1002/pca.2931 SN - 1099-1565 VL - 31 IS - 5 SP - 662 EP - 669 PB - Wiley Online Libary CY - Hoboken, NJ, USA AN - OPUS4-51341 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Raysyan, Anna A1 - Galvidis, I. A. A1 - Schneider, Rudolf A1 - Eremin, S. A. A1 - Burkin, M. A. T1 - Development of a latex particles-based lateral flow immunoassay for group determination of macrolide antibiotics in breast milk N2 - A lateral flow immunoassay (LFIA) using latex particles labeled with antibody to BSAclarithromycin (CLA) was developed for the rapid simultaneous group determination of six macrolide antibiotics. Optimization of antigen spotting on the membrane and latex probe loading allowed improving visual detectability (vLOD) 100 times, which was 1, 1, 10, 10, 50, and 1000 ng/mL for CLA, roxithromycin, erythromycin, dirithromycin, azithromycin, and oleandomycin in buffer, respectively. The calculated limits of instrumental detection (cLOD) were respectively 0.12, 0.15, 1.4, 2.1, 2.4, and 3.3 ng/mL. To avoid a strong influence of breast milk of a very diverse and variable composition, a sample pretreatment is proposed. The six macrolides mentioned can be visually detected in breast milk after 20 minutes pretreatment at concentrations of 10-1000 ng / ml or instrumentally with cLOD of 4.0, 2.5, 30, 42, 42 and 180 ng/mL. The recovery rate from the spiked samples carried out using a strip scanner device ranged from 71% to 110%, and precision expressed as relative standard deviation was between 3-14%. The described rapid on-site diagnostic assay format can be useful for monitoring the content of antibiotics in breast milk during macrolide treatment to ensure safe breastfeeding of infants. KW - Clarithromycin KW - Roxithromycin KW - Erythromycin KW - Dirithromycin KW - Azithromycin KW - Oleandomycin KW - Macrolide antibiotics KW - Makrolide KW - Antibiotika PY - 2020 DO - https://doi.org/10.1016/j.jpba.2020.113450 SN - 0731-7085 VL - 189 IS - 113450 SP - 1 EP - 9 PB - Elsevier CY - Amsterdam, NL AN - OPUS4-51343 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Ecke, Alexander T1 - Magnetpartikelbasierte Immunoassays für die Online-Trinkwasseranalyik N2 - Wir berichten hier über die Entwicklung plattenbasierter Magnetpartikel-Immunoassays für die Bestimmung des Breitbandantibiotikums Amoxicillin und des nicht-steroidalen Antirheumatikums Diclofenac im Trinkwasser. Für die beiden Analyten wurden unterschiedliche Ansätze entwickelt, mit partikelgebundenen Antikörpern für AMX und Analyt-gekoppelten Partikeln für DCF, die die simultane Detektion beider Kontaminanten im nanomolaren Konzentrationsbereich erlauben. T2 - Interdisziplinäres Doktorandenseminar des AK Prozessanalytik CY - Online meeting DA - 21.09.2020 KW - Magnetpartikel KW - Immunoassay KW - Trinkwasseranalytik KW - Diclofenac KW - Amoxicillin PY - 2020 AN - OPUS4-51345 LA - mul AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Ecke, Alexander A1 - Schneider, Rudolf T1 - Immunanalytische Bestimmung von β-Lactam-Antibiotika und deren Hydrolyseprodukten im Trinkwasser N2 - Die speziellen Herausforderungen der immunanalytischen Bestimmung von β-Lactam-Antibiotika in (Trink-)Wasserproben werden anhand eines neu entwickelten ELISA (enzyme-linked immunosorbent assay) für das Breitbandantibiotikum Amoxicillin diskutiert. Es konnte gezeigt werden, dass die Hydrolyse des Analyten einen positiven Einfluss auf die Erkennung durch den Antikörper hat. Das entsprechende Hydrolyseprodukt, zu dem der Antikörper folglich eine höhere Affinität aufweist, wurde identifiziert und ein entsprechendes Verhalten wurde auch für andere β-Lactam-Antibiotika aus der Gruppe der Penicilline beobachtet. Eine Strategie für die Analyse von Wasserproben hinsichtlich Kontamination mit den hier betrachteten β-Lactamen und deren Hydrolyseprodukten wurde ausgearbeitet. T2 - Wasser 2020 - Jahrestagung der Wasserchemischen Gesellschaft CY - Meeting was canceled DA - 18.05.2020 KW - ELISA KW - Immunoassay KW - Antibiotika KW - Hydrolyseprodukte KW - Amoxicillin PY - 2020 UR - https://www.wasserchemische-gesellschaft.de/images/pdf_veranstaltungen/2020/Wasserchemische_Gesellschaft_Tagungsband_Wasser_2020_s.pdf SP - 466 EP - 470 AN - OPUS4-51061 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Becker, Roland T1 - Non-invasive cancer detection using volatile biomarkers: Is urine superior to breath? N2 - In recent years numerous reports have highlighted the options of chemical breath analysis with regard to noninvasive cancer detection. Certain volatile organic compounds (VOC) supposedly present in higher amounts or in characteristic patterns have been suggested as potential biomarkers. However, so far no clinical application based on a specific set of compounds appears to exist. Numerous reports on the capability of sniffer dogs and sensor arrays or electronic noses to distinguish breath of cancer patients and healthy controls supports the concept of genuine cancer-related volatile profiles. However, the actual compounds responsible for the scent are completely unknown and there is no correlation with the potential biomarkers suggested on basis of chemical trace analysis. It is outlined that specific features connected with the VOC analysis in breath – namely small concentrations of volatiles, interfering background concentrations, considerable sampling effort and sample instability, impracticability regarding routine application - stand in the way of substantial progress. The underlying chemicalanalytical challenge can only be met considering the severe susceptibility of VOC determination to these adverse conditions. Therefore, the attention is drawn to the needs for appropriate quality assurance/quality control as the most important feature for the reliable quantification of volatiles present in trace concentration. Consequently, the advantages of urine as an alternative matrix for volatile biomarker search in the context of diagnosing lung and other cancers are outlined with specific focus on quality assurance and practicability in clinical chemistry. The headspace over urine samples as the VOC source allows adapting gas chromatographical procedures well-established in water analysis. Foremost, the selection of urine over breath as non-invasive matrix should provide considerably more resilience to adverse effects during sampling and analysis. The most important advantage of urine over breath is seen in the option to partition, dispense, mix, spike, store, and thus to dispatch taylor-made urine samples on demand for quality control measures. Although it is still open at this point if cancer diagnosis supported by non-invasively sampled VOC profiles will ultimately reach clinical application the advantages of urine over breath should significantly facilitate urgently required steps beyond the current proof-of-concept stage and towards standardisation. KW - VOC KW - Breath KW - Urine KW - Lung cancer KW - Volatile organic compounds PY - 2020 DO - https://doi.org/10.1016/j.mehy.2020.110060 VL - 143 SP - 110060 PB - Elsevier Ltd. AN - OPUS4-51066 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Sennikov, P. A1 - Gornushkin, Igor B. A1 - Kornev, R. A1 - Nazarov, V. A1 - Polyakov, V. A1 - Shkrunin, V. T1 - Hydrogen Reduction of MoF6 and Molybdenum Carbide Formation in RF Inductively Coupled Low‑Pressure Discharge: Experiment and Equilibrium Thermodynamics Consideration N2 - The physical plasma parameters, temperature and electron number density, are studied in the RF-IC (RF inductively coupled) discharge at a reduced pressure of 3 Torr in mixtures of MoF6 with Ar, H2 and CH4. The emission spectra of mixtures are investigated. It is shown that in the presence of argon, the concentration of free electrons in plasma and dissociation rate of MoF6 increase. A main role of molecular hydrogen is the generation of atomic hydrogen that binds atomic fuorine and leads to the formation of gaseous and solid products. Exhaust gas mixtures exiting the reactor are analyzed by mass spectrometry. It is shown that for all cases, the conversion of MoF6 into reaction products is close to 100%. A thermodynamic analysis of the equilibrium composition of MoF6 systems with Ar, H2 and CH4 was carried out and the obtained results are in good agreement with experimentally observed composition of the solid and gas phases. Analysis of solid deposits from mixture MoF6/H2/Ar revealed the presence of molybdenum powder and large amount of amorphous MoFx. The deposit obtained from mixtures with methane, MoF6/H2/Ar/CH4, contained crystalline molybdenum carbide, Mo3C2. KW - Molybdenum carbide KW - RF ICP discharge KW - Reduction of MoF6 KW - Thermodynamic KW - Molybdenum PY - 2020 DO - https://doi.org/10.1007/s11090-020-10138-3 SN - 0272-4324 VL - 41 IS - 2 SP - 673 EP - 690 PB - Springer AN - OPUS4-51569 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Weber, K. T1 - Diagenetic stability of Ca, Mg, Zn and Sr isotopes in teeth N2 - Stable isotope ratios and trace element concentrations of fossil bones and teeth are important geochemical proxies for the reconstruction of diet and past environment in archaeology and palaeontology. However, since diagenesis can significantly alter in vivo incorporated isotope signatures and elemental compositions, it is important to understand alteration processes. Here, we present the results of in vitro alteration experiments of dental tissues from a modern African elephant molar in aqueous solutions at 30 °C and 90 °C for 4 to 63 days each. Dental cubes with ≈3 mm edge length, comprising both enamel and dentin, were placed into 2 ml of an acidic (HNO3) aqueous solution (pH ≈1) enriched with different isotopes (25Mg, 44Ca, 67Zn, 86Sr). Element and isotope distribution profiles across the different dental cubes were measured with LA-(MC-)ICP-MS and EMPA, while potential changes of the bioapatite crystal structure were characterised by Raman spectroscopy. Isotope ratios measured by LA-(MC-)ICP-MS revealed an alteration of the outer ≈200-300 μm of the enamel in all experiments. Dentin was fully altered after one week (at 90 °C) and the tracer solution started to penetrate through the dentin even into the innermost enamel. However, the central part of the enamel remained unaltered. The Raman spectra suggest a strong recrystallization in the dentin and in the outer ≈40 μm of the enamel and a partial demineralisation of the outer rim of the cubes. Our results indicate that independent of time, temperature or low initial pH, enamel apatite shows a high resistance against the experimental alteration in structure and isotopic composition, in contrast to dentin apatite. T2 - Goldschmidt Conference CY - Online meeting DA - 21.06.2020 KW - Isotope ratio KW - Diagenesis KW - Alteration KW - Bio-apatite PY - 2020 AN - OPUS4-51499 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Rienitz, O. A1 - Pramann, A. A1 - Vogl, Jochen A1 - Lee, K.-S. A1 - Yim, Y.-H. A1 - Malinovskiy, D. A1 - Hill, S. A1 - Dunn, P. A1 - Goenaga-Infante, H. A1 - Ren, T. A1 - Wang, J. A1 - Vocke jr., R. D. A1 - Rabb, S: A. A1 - Narukawa, T. A1 - Yang, L. A1 - Mester, Z. A1 - Meija, J. A1 - Aref'ev, D. G. A1 - Marchin, V. A1 - Sharin, A. G. A1 - Bulanov, A. D. A1 - Potapov, A. M. A1 - Otopkova, P. A. A1 - Kessel, R. T1 - The comparability of the determination of the molar mass of silicon highly enriched in 28Si: results of the CCQM-P160 interlaboratory comparison and additional external measurements N2 - An international comparison study on the accurate determination of the molar mass M(Si) of silicon artificially enriched in 28Si (x(28Si) > 0.9999 mol mol−1) has been completed. The measurements were part of the high level CCQM-P160 pilot study assessing the ability of National Metrology Institutes (NMIs) and Designated Institutes (DIs) to make such measurements at the lowest possible levels of measurement uncertainty and to identify possible difficulties when measuring this kind of sample. This study supports the molar mass measurements critical to disseminating the silicon route to realizing the new definitions for the kilogram and the mole. Measurements were also made by one external research institute and an external company. The different institutes were free to choose their experimental (mass spectrometric) set-ups and equipment, thereby enabling also the comparison of different techniques. The investigated material was a chemically pure, polycrystalline silicon material. The subsequent modified single crystalline secondary product of this material was intended for the production of silicon which was used for two additional spheres in the context of the redetermination of the Avogadro constant NA, required for the revision of the International System of Units (SI) via fundamental constants which came into force from May 2019. The CCQM pilot study was organized by Physikalisch-Technische Bundesanstalt (PTB). Aqueous silicon solutions were shipped to all participating institutions. The data analysis as well as the uncertainty modelling and calculation of the results was predefined. The participants were provided with an uncertainty budget as a GUM Workbench® file as well as a free software license for the duration of the comparison. The agreement of the values of the molar mass (M(Si) = 27.976 942 577 g mol−1) was excellent with ten out of 11 results reported within the range of relative uncertainty of 1 × 10−8 required for the revision of the SI. KW - Absolute isotope ratio KW - Molar mass KW - Avogadro constant KW - Revision of the SI PY - 2020 DO - https://doi.org/10.1088/1681-7575/abbdbf VL - 57 IS - 6 SP - 065028 PB - IOP Science CY - Cambridge AN - OPUS4-51500 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Gehrenkemper, Lennart A1 - Simon, Fabian A1 - Roesch, Philipp A1 - Fischer, E. A1 - von der Au, Marcus A1 - Pfeifer, Jens A1 - Cossmer, Antje A1 - Wittwer, Philipp A1 - Vogel, Christian A1 - Simon, Franz-Georg A1 - Meermann, Björn T1 - Determination of organically bound fluorine sum parameters in river water samples - Comparison of combustion ion chromatography (CIC) and high resolution-continuum source-graphite furnace molecular absorption spectrometry (HR-CS-GFMAS) N2 - In this study, we compare combustion ion chromatography (CIC) and high resolution-continuum source-graphite furnace molecular absorption spectrometry (HR-CS-GFMAS) with respect to their applicability for determining organically Bound fluorine sum parameters. Extractable (EOF) and adsorbable (AOF) organically bound fluorine as well as total fluorine (TF) were measured in samples fromriver Spree in Berlin, Germany, to reveal the advantages and disadvantages of the two techniques used as well as the two established fluorine sum Parameters AOF and EOF. TF concentrations determined via HR-CS-GFMAS and CIC were comparable between 148 and 270 μg/L. On average, AOF concentrations were higher than EOF concentrations, with AOF making up 0.14–0.81% of TF (determined using CIC) and EOF 0.04–0.28% of TF (determined using HR-CSGFMAS). The results obtained by the two independent methods were in good agreement. It turned out that HR-CS-GFMAS is a more sensitive and precise method for fluorine analysis compared to CIC. EOF and AOF are comparable tools in Risk evaluation for the emerging pollutants per- and polyfluorinated alkyl substances; however, EOF is much faster to conduct. KW - High resolution-continuum source-graphite furnace molecular absorption spectrometry (HR-CS-GFMAS) KW - Combustion ion chromatography (CIC) KW - Per- and polyfluorinated alkyl substances (PFASs) KW - Adsorbable organically bound fluorine (AOF) KW - Extractable organically bound fluorine (EOF) KW - Surface waters PY - 2020 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-515351 DO - https://doi.org/10.1007/s00216-020-03010-y SN - 1618-2650 VL - 413 IS - 28 SP - 103 EP - 115 PB - Springer CY - Berlin AN - OPUS4-51535 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Gaft, M. A1 - Nagli, L. A1 - Gornushkin, Igor B. A1 - Raichlin, Y. T1 - Review on recent advances in analytical applications of molecular emission and modelling N2 - The review mainly deals with two topics that became important in applications of laser-induced breakdown spectroscopy (LIBS) in recent years: the emission of halogen- and rare-earth-containing molecules and selective excitation of molecules by molecular laser-induced fluorescence (MLIF). The first topic is related to the emission of alkaline-earth diatomic halides MX, M = Ca, Mg, Ba, Sr and X = F, Cl, Br, and I and rare-earth element (REE) oxides LaO, YO, and ScO. These molecules form in laser-induced plasma (LIP) soon after its ignition and persist for a long time, emitting broad bands in a visible part of the spectrum. They are best detected after relatively long delay times when emission from interfering plasma species (atoms and ions) has already been quenched. Such behavior of molecular spectra allows of using, for their detection, inexpensive CCD detectors equipped with simple electronic or mechanical shutters and low-resolution spectrometers. A main target for analysis by molecular spectroscopy is halogens; these elements are difficult to detect by atomic spectroscopy because their most intense atomic lines lie in the vacuum UV. Therefore, in many situations, emission from CaF and CaCl may provide a substantially more sensitive detection of F and Cl than emission from elemental F and Cl and their ions. This proved to be important in mining and concrete industries and even Mars exploration. A similar situation is observed for REEs; their detection by atomic spectroscopy sometimes fails even despite the abundance of atomic and ionic REEs' lines in the UV-VIS. For example, in minerals and rocks with low concentrations of REEs, emission from major and minor mineral elements hinders the weak emission from REEs. Many REEs do not form molecules that show strong emission bands in LIP but can still be detected with the aid of LIP. All REEs except La, Y, and Sc exhibit long-lived luminescence in solid matrices that is easily excited by LIP. The luminescence can be detected simultaneously with molecular emission of species in LIP within the same time and spectral window. The second topic is related to the combination of MLIF and LIBS, which is a technique that was proved to be efficient for analysis of isotopic molecules in LIP. For example, the characteristic spectral signals from isotopic molecules containing 10B and 11B are easier to detect with MLIF-LIBS than with laser ablation molecular isotopic spectrometry (LAMIS) because MLIF provides strong resonance excitation of only targeted isotopes. The technique is also very efficient in detection of halogen molecules although it requires an additional tunable laser that makes the experimental setup bulky and more expensive. KW - Plasma induced luminescence KW - Molecular emission KW - Laser induced plasma KW - Plasma modeling KW - Molecular analysis KW - LIBS PY - 2020 DO - https://doi.org/10.1016/j.sab.2020.105989 VL - 173 SP - 105989 PB - Elsevier B. V. AN - OPUS4-51420 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Weber, A. A1 - von Randow, M. A1 - Voigt, A.-L. A1 - von der Au, Marcus A1 - Fischer, E. A1 - Meermann, Björn A1 - Wagner, M. T1 - Ingestion and toxicity of microplastics in the freshwater gastropodLymnaea stagnalis: No microplastic-induced effects alone or incombination with copper N2 - The interaction of microplastics with freshwater biota and their interaction with other stressors is still not very well understood. Therefore, we investigated the ingestion, excretion and toxicity of microplastics in the freshwater gastropod Lymnaea stagnalis. MP ingestion was analyzed as tissues levels in L. stagnalis after 6–96 h of exposure to 5–90 μm spherical polystyrene (PS) microplastics. To understand the excretion, tissue levels were determined after 24 h of exposure followed by a 12 h–7 d depuration period. To assess the toxicity, snails were exposed for 28 d to irregular PS microplastics (<63 μm, 6.4–100,000 particles mL−1), both alone and in combination with copper as additional stressor. To compare the toxicity of natural and synthetic particles, we also included diatomite particles. Microplastics ingestion and excretion significantly depended on the particle size and the exposure/depuration duration. An exposure to irregular PS had no effect on survival, reproduction, energy reserves and oxidative stress. However, we observed slight effects on immune cell phagocytosis. Exposure to microplastics did not exacerbate the reproductive toxicity of copper. In addition, there was no pronounced difference between the effects of microplastics and diatomite. The tolerance towards microplastics may originate from an adaptation of L. stagnalis to particle-rich environments or a general stress resilience. In conclusion, despite high uptake rates, PS fragments do not appear to be a relevant stressor for stress tolerant freshwater gastropods considering current environmental levels of microplastics. KW - Lymnaea stagnalis KW - Microplastic-induced effects KW - Mixture toxicity PY - 2020 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-513551 DO - https://doi.org/10.1016/j.chemosphere.2020.128040 VL - 263 SP - 128040 PB - Elsevier Ltd. AN - OPUS4-51355 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Faßbender, Sebastian T1 - On-line Species-specific Isotopic Analysis of Sulfur by Hyphenation of Capillary Electrophoresis with Multicollector-ICP-MS N2 - In many scientific fields, isotopic analysis can offer valuable information. Up to date, typically bulk analysis is aimed at measuring the isotopic composition of the entire elemental content of the sample. However, the analyte element is usually present under the form of different species. Thus, separating species of interest from one another and from matrix components prior to isotope ratio measurements can provide species-specific isotopic information, which could be used for tracing the origin of environmental pollutants and elucidation of (environmental) speciation. Using on-line hyphenations of separation techniques with multicollector-ICP-MS (MC-ICP-MS) can save time and effort and enables the analysis of different species during a single measurement. Whereas some works hyphenating GC and IC with MC-ICP-MS have already been reported, LC and CE hyphenations are still inadequately represented based on the capabilities of these separation techniques. In this work, we developed an on-line hyphenation of CE with multicollector-ICP-MS (CE/MC-ICP-MS) for isotopic analysis of sulfur species using a multiple-injection approach for instrumental mass bias correction by standard-sample bracketing. With this method, the isotopic composition of sulfur in sulfate originating from river water could be analyzed without sample preparation. The results were compared to data from off-line analysis of the same samples for validation. The repeatability of the results of the on-line measurements was promising regarding the differentiation of the river systems by the isotopic signature of river water sulfate. The great potential of this method is based on the versatility of the applied separation technique, not only in the environmental field but also for, e.g., biomolecules because sulfur is the only covalently bound constituent of proteins that can be analyzed by MC-ICP-MS. T2 - SciX 2020 CY - Online meeting DA - 12.10.2020 KW - Capillary electrophoresis KW - Hyphenated techniques KW - Isotopic analysis KW - Speciation analysis PY - 2020 AN - OPUS4-51402 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Jenning, M. A1 - Marklein, B. A1 - Ytterberg, J. A1 - Zubarev, R. A. A1 - Joshua, V. A1 - van Schaardenburg, D. A1 - van de Stadt, L. A1 - Catrina, A. I. A1 - Nonhoff, U. A1 - Häupl, T. A1 - Konthur, Zoltán A1 - Burmester, G. R. A1 - Skriner, K. T1 - Bacterial citrullinated epitopes generated by Porphyromonas gingivalis infection—a missing link for ACPA production N2 - Objectives: Porphyromonas gingivalis (P.g.) is discussed to be involved in triggering self-reactive immune responses. The aim of this study was to investigate the autocitrullinated prokaryotic peptidylarginine deiminase (PPAD) from P.g. CH2007 (RACH2007-PPAD) from a rheumatoid arthritis (RA) patient and a synthetic citrullinated PPAD peptide (CPP) containing the main autocitrullination site as potential targets for antibody reactivity in RA and to analyse the possibility of citrullinating native human proteins by PPAD in the context of RA. Methods: Recombinant RACH2007-PPAD was cloned and expressed in Escherichia coli. Purified RACH2007-PPAD and its enzymatic activity was analysed using two-dimensional electrophoresis, mass spectrometry, immunoblot and ELISA. Autoantibody response to different modified proteins and peptides was recorded and bioinformatically evaluated. Results: RACH2007-PPAD was capable to citrullinate major RA autoantigens, such as fibrinogen, vimentin, hnRNP-A2/B1, histone H1 and multiple peptides, which identify a common RG/RGG consensus motif. 33% of RA patients (n=30) revealed increased reactivity for α-cit-RACH2007-PPAD before RA onset. 77% of RA patients (n=99) presented α-cit-specific signals to CPP amino acids 57-71 which were positively correlated to α-CCP2 antibody levels. Interestingly, 48% of the α-CPP-positives were rheumatoidfactor IgM/anti-citrullinated peptide/protein antibodies (ACPA)-negative. Anti-CPP and α-RACH2007-PPAD antibody levels increase with age. Protein macroarrays that were citrullinated by RACH2007-PPAD and screened with RA patient sera (n=6) and controls (n=4) uncovered 16 RACH2007-PPAD citrullinated RA autoantigens and 9 autoantigens associated with lung diseases. We showed that the α-CPP response could be an important determinant in parenchymal changes in the lung at the time of RA diagnosis (n=106; p=0.018). Conclusions: RACH2007-PPAD induced internal citrullination of major RA autoantigens. Anti-RACH2007-PPAD correlates with ACPA levels and interstitial lung disease autoantigen reactivity, supporting an infection-based concept for induction of ACPAs via enzymatic mimicry. KW - Zitrullin KW - Rheumatoide Arthritis KW - Proteinmodifikation KW - Autoantikörper PY - 2020 DO - https://doi.org/10.1136/annrheumdis-2019-216919 VL - 79 IS - 9 SP - 1194 EP - 1202 PB - BMJ Publishing Group Ltd AN - OPUS4-51372 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Riedel, Soraya T1 - An ELISA-inspired electrochemical detection system for the quantification of ochratoxin A N2 - Toxic secondary metabolites produced by fungi (aka mycotoxins) are often identified as contaminants in cereals or other food and pose a severe health risk, since they can be carcinogenic, neurotoxic, mutagenic or harmful in other respect. The highly nephrotoxic ochratoxin A (OTA) is one of the most important and widespread mycotoxins found in grains such as rye, wheat or oats. Thus, the fast and cost-effective detection of OTA is of great importance, to ensure that the toxin concentration is below the legal limits. Currently, the mycotoxin detection in mill operations is typically performed by means of the antibody-based ELISA method, which requires extensive laboratory equipment and specialized personnel. It was the aim of this study to develop an ELISA-inspired sensor method enabling the on-site quantification of OTA. Based on a classical competitive ELISA, an electrochemical detection system was developed. Anti-OTA-antibodies were captured on magnetic beads on which the competitive affinity reaction between OTA and an OTA- horseradish peroxidase (HRP) tracer was performed. Here the OTA concentration is inversely proportional to the amount of the bound OTA-HRP tracer, which was electrochemically quantified. For this purpose, oxidized tetramethylbenzidine (TMB), which is enzymatically produced by the reduction of H2O2 by the OTA-HRP tracer, is quantified by amperometry with screen-printed electrodes in a flow system. With this method a detection limit of 250 ng L-1 could be achieved which meets the current requirements for the detection of OTA in food and feed. T2 - Interdisziplinäres Doktorandenseminar des AK Prozessanalytik CY - Online meeting DA - 21.09.2020 KW - Ochratoxin A KW - Cyclic voltammetry KW - Amperometry KW - ELISA KW - Magnetic beads PY - 2020 N1 - Geburtsname von Riedel, Soraya: Höfs, S. - Birth name of Riedel, Soraya: Höfs, S. AN - OPUS4-51375 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Gojani, Ardian A1 - Gornushkin, Igor B. T1 - Räumlich aufgelöste Heterodyne-Spektroskopie N2 - Die räumlich aufgelöste Heterodyn-Spektroskopie (SHS) kombiniert dispersive und interferometrische Techniken zur Gewinnung spektroskopischer Informationen und kann in einem anpassbaren Instrument realisiert werden. SHS wird für die chemische Analyse von verschiedenen Materialien mit Hilfe der Laser-induzierten Plasmaspektroskopie (LIBS) und der Raman-Spektroskopie eingesetzt. KW - Raman spectroscopy KW - Spatial heterodyne spectroscopy KW - Laser-induced breakdown spectroscopy PY - 2020 UR - https://analyticalscience.wiley.com/do/10.1002/was.00080118/full VL - 5 SP - 2 EP - 4 PB - Wiley CY - Weinheim AN - OPUS4-51397 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Bröcker, S. A1 - Klaer, R.-H. A1 - Kockmann, N. A1 - Maiwald, Michael T1 - Process Industry United in the Digital World - The current landscape of research for the digitalization of the process industry N2 - The Tutzing Symposium "100 % digital: survival strategies for the process industry" (see 4.1) in April 2018 was characterized by a great momentum which has been taken up and continued until today. The aim was to implement the ideas from the Tutzing Symposium in a coordinated and targeted manner. For this purpose, development needs as well as the numerous currently planned or already started research and development activities in the context of digitalisation were first compiled and analysed. This resulted in the current research landscape for digitalization in the process industry. It now enables to identify open topics and to translate them into research funding programs as well as to define new projects in the dialogue between users, suppliers and research, which are to be meaningfully interlinked and consolidated with existing projects. Due to the strong interest in digitalisation, activities are constantly being added, so that this paper can only provide a snapshot of the situation in the period 2019-2020. KW - Process Industry KW - Digitalisation KW - Tutzing Symposion KW - research landscape KW - Process Control PY - 2020 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-512265 UR - https://processnet.org/en/TAKdigital.html SP - 1 EP - 15 AN - OPUS4-51226 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Bhuckory, S. A1 - Wegner, Karl David A1 - Qiu, X. A1 - Wu, Y.T. A1 - Jennings, T. L. A1 - Incamps, A. A1 - Hildebrandt, N. T1 - Triplexed CEA-NSE-PSA Immunoassay Using Time-Gated Terbium-to-Quantum Dot FRET N2 - Time-gated Förster resonance energy transfer (TG-FRET) between Tb complexes and luminescent semiconductor quantum dots (QDs) provides highly advantageous photophysical properties for multiplexed biosensing. Multiplexed Tb-to-QD FRET immunoassays possess a large potential for in vitro diagnostics, but their performance is often insufficient for their application under clinical conditions. Here, we developed a homogeneous TG-FRET immunoassay for the quantification of carcinoembryonic antigen (CEA), neuron-specific enolase (NSE), and prostatespecific antigen (PSA) from a single serum sample by multiplexed Tb-to-QD FRET. Tb–IgG antibody donor conjugates were combined with compact QD-F(ab’)2 antibody acceptor conjugates with three different QDs emitting at 605, 650, and 705 nm. Upon antibody–antigen–antibody Sandwich complex formation, the QD acceptors were sensitized via FRET from Tb, and the FRET ratios of QD and Tb TG luminescence intensities increased specifically with increasing antigen concentrations. Although limits of detection (LoDs: 3.6 ng/mL CEA, 3.5 ng/mL NSE, and 0.3 ng/mL PSA) for the triplexed assay were slightly higher compared to the single-antigen assays, they were still in a clinically relevant concentration range and could be quantified in 50 μL serum samples on a B·R·A·H·M·S KRYPTOR Compact PLUS clinical immunoassay plate reader. The simultaneous quantification of CEA, NSE, and PSA at different concentrations from the same serum sample demonstrated actual multiplexing Tb-to-QD FRET immunoassays and the potential of this technology for translation into clinical diagnostics. KW - Lanthanides KW - Nanoparticles KW - Biosensing KW - Multiplexing KW - FRET KW - Fluorescence KW - PSA KW - NSE KW - CEA PY - 2020 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-512290 DO - https://doi.org/10.3390/molecules25163679 VL - 25 IS - 16 SP - 3679 PB - MDPI AN - OPUS4-51229 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Képeš, E. A1 - Gornushkin, Igor B. A1 - Pořízka, P. A1 - Kaiser, J. T1 - Tomography of double-pulse laser-induced plasmas in the orthogonal geometry N2 - The temporal evolution of laser-induced plasmas is studied in the orthogonal double-pulse arrangement. Both the pre-ablation mode (an air spark is induced above the sample surface prior to the ablation pulse) and the re-heating mode (additional energy is delivered into the plasma created by the ablation pulse) is considered. The plasmas are investigated in terms of the temporal evolution of their electron density, temperature, and volume. The plasma volumes are determined using a time-resolved tomography technique based on the Radon transformation. The reconstruction is carried out for both white-light and band-pass filtered emissivities. The white-light reconstruction corresponds to the overall size of the plasmas. On the other hand, the band-pass emissivity reconstruction shows the distribution of the atomic sample species (Cu I). Moreover, through spectrally resolved tomographic reconstruction, the spatial homogeneity of the electron density and temperature of the plasmas is also investigated at various horizontal slices of the plasmas. Our results show that the pre-ablation geometry yields a more temporally stable and spatially uniform plasma, which could be beneficial for calibration-free laser-induced breakdown spectroscopy (LIBS) approaches. On the contrary, the plasma generated in the re-heating geometry exhibits significant variations in electron density and temperature along its vertical axis. Overall, our results shed further light on the mechanisms involved in the LIBS signal enhancement using double-pulse ablation. KW - Laser-induced plasma KW - Laser-induced breakdown spectroscopy KW - Double-pulse laserinduced breakdown spectroscopy KW - Plasma tomography KW - Radon reconstruction PY - 2020 DO - https://doi.org/10.1016/j.aca.2020.06.078 SN - 0003-2670 SN - 0378-4304 VL - 1135 SP - 1 EP - 11 PB - Elsevier CY - Amsterdam AN - OPUS4-51142 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Qiu, Yan A1 - Yu, H. A1 - Gornushkin, Igor B. A1 - Li, J. A1 - Wu, Q. A1 - Zhang, Z. A1 - Li, X. T1 - Measurement of trace chromium on structural steel surface from a nuclear power plant using dual-pulse fiber-optic laser-induced breakdown spectroscopy N2 - Remote and on-line measurement of chromium on structural steel surface in nuclear power plants is critical for protection against fluid accelerated corrosion. To improve the insufficient sensitivity of fiber-optic laser-induced breakdown spectroscopy toward trace element detection, a dual-pulse spectral enhancement system is set up. In an iron matrix, for the purpose of improving sensitivity of trace chromium analysis and reducing the self-absorption of iron, the effects of key parameters are investigated. The optimal values of the parameters are found to be: 450 ns inter-pulse delay, 700 ns gate delay, 30 mJ/6 mJ pulse energy ratio, and 19.8 mm lens-to-sample distance (corresponding to a 799 μm laser focused spot size). Compared to the single-pulse system, the shot number of dual-pulse ablation is limited for reducing surface damage. After the optimization of the dual-pulse system, the signal-to-noise ratio of the trace chromium emission line has been improved by 3.5 times in comparison with the single-pulse system, and the self-absorption coefficient of matrix iron has been significantly reduced with self-reversal eliminated. The number of detectable lines for trace elements has more than doubled thus increasing the input for spectral calibration without significantly increasing the ablation mass. Three calibration methods including internal standardization, partial least squares regression and random forest regression are employed to determine the chromium and manganese concentrations in standard samples of low alloy steel, and the limit of detection is respectively calculated as 36 and 515 ppm. The leave-one-out cross validation method is utilized to evaluate the accuracy of chromium quantification, and the concentration mapping of chromium is performed on the surface of a steel sample (16MND5) with a relative error of 0.02 wt.% KW - Fiber-optic laser-induced breakdown spectroscopy (FO-LIBS) KW - Dual-pulse KW - Parameter optimization KW - Spectral enhancement KW - Self-absorption coefficient KW - Concentration mapping PY - 2020 DO - https://doi.org/10.1016/j.apsusc.2020.147497 SN - 0169-4332 VL - 533 IS - 147497 SP - 1 EP - 29 PB - Elsevier CY - Amsterdam AN - OPUS4-51143 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -