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 - 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 - 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 -