TY - JOUR A1 - Abad Andrade, Carlos Enrique A1 - Florek, S. A1 - Becker-Ross, H. A1 - Huang, M.-D. A1 - de Oliveira Guilherme Buzanich, Ana A1 - Radtke, Martin A1 - Lippitz, Andreas A1 - Hodoroaba, Vasile-Dan A1 - Schmid, Thomas A1 - Heinrich, Hans-Joachim A1 - Recknagel, Sebastian A1 - Jakubowski, Norbert A1 - Panne, Ulrich T1 - Zirconium permanent modifiers for graphite furnaces used in absorption spectrometry: understanding their structure and mechanism of action N2 - The mechanism of action of zirconium permanent modifiers on graphite surfaces was investigated in order to understand its influence on the analytical signal in atomic and molecular absorption spectrometry (AAS/MAS). For this, the molecule formation of CaF was studied, which is used for the indirect analytical determination of fluorine in high-resolution continuum source graphite furnace molecular absorption spectrometry (HR-CS-GFMAS). The kinetics of this reaction was established by monitoring its molecular spectrum at different atomisation temperatures. An Arrhenius plot showed a pseudo-first order reaction with respect to fluorine (n = 1). An intermediate state was isolated, and its structure was elucidated by spectroscopic methods: scanning electron microscopy with energy dispersive X-ray spectroscopy (SEMEDX), X-ray photoelectron spectroscopy (XPS), X-ray absorption spectroscopy (XANES and EXAFS), and Raman microspectroscopy. We propose here a mechanism, where ZrO2 acts as a heterogeneous catalyst: after a pyrolytic step, an intermediate state of ZrO(OCaF) is activated, and at higher temperatures, CaF(g) is released from the zirconium-coated graphite surface. No evidence of the formation of zirconium carbide was found. Consequently, as the CaF formation is catalysed by a heterogeneous catalyst, surface modifications with ZrO2 nanoparticles and ZrO xerogels were investigated in order to increase the surface area. Their influence was evaluated in the molecule formation of CaF, CaCl, CaBr, and CaI. Graphite furnace modification with zirconium oxide nanoparticles proves to be the best choice for fluorine analysis with a signal enhancement of more than eleven times with respect a non-coated graphite furnace. However, the influence of zirconium modifications in the analytical signals of Cl, and I is lower than the F signals or even negative in case of the Br. Understanding zirconium modifiers as heterogeneous catalysts offers a new perspective to AAS and MAS, and reveals the potential of surface analytical methods for development of improved permanent modifiers and graphite furnace coatings. KW - Zirconium KW - HR-CS-MAS KW - Graphite furnace KW - Nanoparticles KW - Xerogel KW - Calcium monofluoride KW - Absorption spectrometry PY - 2018 UR - https://pubs.rsc.org/en/content/articlelanding/2018/ja/c8ja00190a DO - https://doi.org/10.1039/C8JA00190A SN - 0267-9477 VL - 33 IS - 12 SP - 2034 EP - 2042 PB - Royal Society of Chemistry AN - OPUS4-46775 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Morcillo, Dalia A1 - Winckelmann, Alexander A1 - Abad Andrade, Carlos Enrique A1 - Recknagel, Sebastian A1 - Richter, Silke A1 - Panne, Ulrich T1 - What we need to know about lithium isotopes in batteries N2 - Flash talk presentation about the relevance of lithium in our lives and its influence on the battery aging process. T2 - Make and Measure Conference SALSA CY - Berlin, Germany DA - 15.09.2022 KW - Lithium isotope KW - Battery KW - Spectroscopy PY - 2022 AN - OPUS4-56360 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Ickert, Stefanie A1 - Beck, S. A1 - Linscheid, M. A1 - Riedel, Jens T1 - VUV Photodissociation Induced by a Deuterium Lamp in an Ion Trap N2 - Tandem mass spectrometry represents an important analytical tool to unravel molecular structures and to study the gas-phase behavior of organic molecules. Besides commonly used methods like collision-induced dissociation and electron capture or transfer dissociation, new ultraviolet light–based techniques have the potential to synergistically add to the activation methods. Here, we present a new simple, yet robust, experimental design for polychromatic activation of trapped ions using the 115–160 nm output of a commercially available deuterium lamp. The resulting continuous dissociative excitation with photons of a wide energy range from 7.7 to 10.8 eV is studied for a comprehensive set of analyte classes in both positive and negative ion modes. While being simple, affordable, compact, and of low maintenance, the new setup initiates fragmentation of most precursor ions via their known dissociation pathways. Additionally, some new fragmentation patterns were discovered. Especially, electron loss and electron capture reactions with subsequent fragmentations were observed. For oligonucleotides, peptides, carbohydrates, and organic dyes, in comparison to collision-induced dissociation, a significantly wider fragment distribution was obtained, resulting in an information increase. Since the individual photons carry enough energy to post-ionize the nascent fragments, a permanent vacuum ultraviolet light exposure inside the ion trap potentially goes along with a general increase in detection capability. KW - Fragmentation activation KW - Vacuum ultraviolet (VUV) light KW - Mass spectrometry KW - Tandem MS PY - 2019 DO - https://doi.org/10.1007/s13361-019-02282-8 SN - 1044-0305 VL - 30 IS - 10 SP - 2114 EP - 2122 PB - Springer Nature CY - Heidelberg AN - OPUS4-48756 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Rosenkranz, D. A1 - Kriegel, F. L. A1 - Mavrakis, E. A1 - Pergantis, S. A. A1 - Reichardt, P. A1 - Tentschert, J. A1 - Jakubowski, N. A1 - Laux, P. A1 - Panne, Ulrich A1 - Luch, A. T1 - Versatile dual-inlet sample introduction system for multi-mode single particle inductively coupled plasma mass spectrometry N2 - Metal-containing nanoparticles (NP) can be characterized with inductively coupled plasma mass spectrometers (ICP-MS) in terms of their size and number concentration by using the single-particle mode of the instrument (spICP-MS). The accuracy of measurement depends on the setup, operational conditions of the instrument and specific parameters that are set by the user. The transport efficiency of the ICP-MS is crucial for the quantification of the NP and usually requires a reference material with homogenous size distribution and a known particle number concentration. Currently, NP reference materials are available for only a few metals and in limited sizes. If particles are characterized without a reference standard, the results of both size and particle number may be biased. Therefore, a dual-inlet Setup for characterizing nanoparticles with spICP-MS was developed to overcome this problem. This setup is based on a conventional introduction system consisting of a pneumatic nebulizer (PN) for nanoparticle solutions and a microdroplet Generator (μDG) for ionic calibration solutions. A new and flexible interface was developed to facilitate the coupling of μDG, PN and the ICP-MS system. The interface consists of available laboratory components and allows for the calibration, nanoparticle (NP) characterization and cleaning of the arrangement, while the ICP-MS instrument is still running. Three independent analysis modes are available for determining particle size and number concentration. Each mode is based on a different calibration principle. While mode I (counting) and mode III (μDG) are known from the literature, mode II (sensitivity), is used to determine the transport efficiency by inorganic ionic Standard solutions only. It is independent of NP reference materials. The μDG based inlet system described here guarantees superior analyte sensitivities and, therefore, lower detection limits (LOD). The size dependent LODs achieved are less than 15 nm for all NP (Au, Ag, CeO2) investigated. KW - Spectrometer KW - Reference KW - Calibration PY - 2020 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-536121 DO - https://doi.org/10.3791/61653 SN - 1940-087X IS - 163 SP - 1 EP - 19 PB - MyJoVE Corporation CY - Cambridge, MA, USA AN - OPUS4-53612 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Hachenberger, Y. U. A1 - Rosenkranz, D. A1 - Kriegel, Fabian L. A1 - Krause, B. A1 - Matschaß, René A1 - Reichardt, P. A1 - Tentschert, J. A1 - Laux, P. A1 - Jakubowski, Norbert A1 - Panne, Ulrich A1 - Luch, A. T1 - Tackling Complex Analytical Tasks: An ISO/TS-Based Validation Approach for Hydrodynamic Chromatography Single Particle Inductively Coupled Plasma Mass Spectrometry N2 - Nano-carrier systems such as liposomes have promising biomedical applications. Nevertheless, characterization of these complex samples is a challenging analytical task. In this study a coupled hydrodynamic chromatography-single particle-inductively coupled plasma mass spectrometry (HDC-spICP-MS) approach was validated based on the technical specification (TS) 19590:2017 of the international organization for standardization (ISO). The TS has been adapted to the hyphenated setup. The quality criteria (QC), e.g., linearity of the calibration, transport efficiency, were investigated. Furthermore, a cross calibration of the particle size was performed with values from dynamic light scattering (DLS) and transmission electron microscopy (TEM). Due to an additional Y-piece, an online-calibration routine was implemented. This approach allows the calibration of the ICP-MS during the dead time of the chromatography run, to reduce the required time and enhance the robustness of the results. The optimized method was tested with different gold nanoparticle (Au-NP) mixtures to investigate the characterization properties of HDC separations for samples with increasing complexity. Additionally, the technique was successfully applied to simultaneously determine both the hydrodynamic radius and the Au-NP content in liposomes. With the established hyphenated setup, it was possible to distinguish between different subpopulations with various NP loads and different hydrodynamic diameters inside the liposome carriers. KW - Single particle ICP-MS KW - Nanoparticle characterization KW - Nano-carrier KW - Iposomes KW - Hydrodynamic chromatography (HDC) KW - Validation PY - 2020 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-506609 DO - https://doi.org/10.3390/ma13061447 VL - 13 IS - 6 SP - 1 EP - 14 CY - Basel, Switzerland AN - OPUS4-50660 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Resch-Genger, Ute A1 - Giovannozzi, A. A1 - Rossi, A. A1 - Kovac, J. A1 - Ekar, J. A1 - Goenaga-Infante, H. A1 - Clarkson, C. A1 - Clifford, C. A1 - Cant, D. A1 - Minelli, C. A1 - Reithofer, M. A1 - Lindner, G. A1 - Venzago, C. A1 - Bohmer, N. A1 - Drexler, C.-P. A1 - Schedler, U. A1 - Thiele, T. A1 - Lechart, F. A1 - Kästner, B. A1 - Sjövall, P. A1 - Johnston, L. A1 - Tan, Gunnar A1 - Radnik, Jörg T1 - Standardised Measurements of Surface Functionalities on Nanoparticles N2 - Engineered nanoparticles (NPs) with various chemical compositions and surface functionalities are routinely fabricated for industrial applications such as medical diagnostics, drug delivery, sensing, catalysis, energy conversion and storage, opto-electronics, and information storage which improve the quality of life and European prosperity. NP function, performance, interaction with biological species, and environmental fate are largely determined by their surface functionalities. Standardized repeatable surface characterization methods are therefore vital for quality control of NPs, and to meet increasing concerns regarding their safety. Therefore, industry, regulatory agencies, and policymakers need validated traceable measurement methods and reference materials. This calls for fit-for-purpose, validated, and standardized methods, and reference data and materials on the surface chemistry of engineered NPs. Here, we present a concept for the development of such standardized measurement protocols utilizing method cross-validation and interlaboratory comparisons (ILCs) with emphasis on both advanced measurement methods such as quantitative Nuclear Magnetic Resonance (qNMR), X-ray photoelectron spectroscopy (XPS) and secondary ion mass spectrometry (SIMS) and cost-efficient, non-surface specific methods like optical assays and electrochemical titration methods. T2 - European Partnership on Metrology 2023 Review Conference CY - Amsterdam, Netherlands DA - 07.11.2023 KW - Surface chemistry KW - Quality assurance KW - Traceability PY - 2023 AN - OPUS4-59142 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Abad Andrade, Carlos Enrique A1 - Florek, S. A1 - Becker-Ross, H. A1 - Huang, M.-D. A1 - Muench, S. A1 - Okruss, M. A1 - Mao, X. A1 - Gonzalez, J. A1 - Zorba, V. A1 - Recknagel, Sebastian A1 - Tatzel, Michael A1 - Vogl, Jochen A1 - Jakubowski, Norbert A1 - Panne, Ulrich T1 - Stable isotope analysis of magnesium by optical spectrometry N2 - Magnesium is a naturally occurring element that can be found in several mineral forms in the earth crust. This element presents three stable isotopes 24Mg, 25Mg and 26Mg with a natural abundance of 79%, 10%, and 11% respectively. It is due to their relatively large mass difference (~8% between 24Mg and 26Mg) that isotope fractionation leads to slight isotope amount ratio variations n(26Mg)/n(24Mg) in biological and geological samples. Traditionally, isotope amount ratios have been measured by mass spectrometric methods. However, drawbacks of these methods include the high costs for instruments and their operation, experienced operators and elaborate chromatographic sample preparation which are time-consuming. Recently, optical spectrometric methods have been proposed as faster and low-cost alternative for the analysis of isotope ratios of selected elements by means of high-resolution continuum source graphite furnace molecular absorption spectrometry (HR-CS-GFMAS) and laser ablation molecular isotopic spectrometry (LAMIS). For the determination of Mg isotope amount ratios, the molecular spectrum of the in-situ generated MgF and MgO molecules were studied. In the case of HR-CS-GFMAS, the absorption spectrum was recorded for MgF for the electronic transitions X 2Σ → A 2 Πi and X 2Σ → B 2Σ+ around wavelengths 358 nm and 268 nm respectively. In the case of LAMIS, it was studied the MgF molecule for the electronic transitions A 2Πi → X 2Σ as well as the MgO molecule for the electronic transition A 1Π+ → X 1Σ around 500 nm. The MgF and MgO spectra are composed by the linear combination of their isotopic components or isotopologues: 24MgF, 25MgF, and 26MgF for the MgF and 24MgO, 25MgO, and 26MgO for the MgO (F is monoisotopic, and the isotope composition of O is assumed as constant). By HR-CS-GFMAS the analysis of Mg was done by deconvolution of the MgF spectrum by a partial least square regression (PLS) calibrated with enriched isotope spikes. The isotope amount ratios in rock samples with and without matrix separation were analyzed. Resulting delta values were obtained with precisions ranging between 0.2-0.5 ‰. On the other hand, LAMIS allows the direct analysis of solid samples with the extended possibility of in-situ analysis. Main advantages, limitations, and scopes of both optical techniques are going to be discussed and compared with MC-ICP-MS. T2 - ANAKON 2019 CY - Münster, Germany DA - 25.03.2019 KW - Isotope analysis KW - HR-CS-MAS KW - LIBS KW - MC-ICP-MS KW - Magnesium PY - 2019 AN - OPUS4-49876 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Bauer, M. A1 - Remmler, D. A1 - Dallmann, A. A1 - Jakubowski, Norbert A1 - Börner, H. G. A1 - Panne, Ulrich A1 - Limberg, C. T1 - Specific Decoration of a Discrete Bismuth Oxido Cluster by Selected Peptides towards the Design of Metal Tags N2 - Metal tags find application in a multitude of biomedical systems and the combination with laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) offers an opportunity for multiplexing. To lay the foundation for an increase of the signal intensities in such processes, we herein present a general approach for efficient functionalization of a well-defined metal oxido cluster [Bi6O4(OH)(4)(SO3CF3)(6)(CH3CN)(6)].2 CH3CN (1), which can be realized by selecting 7mer peptide sequences via combinatorial means from large one-bead one-compound peptide libraries. Selective cluster-binding peptide sequences (CBS) for 1 were discriminated from non-binders by treatment with H2S gas to form the reduction product Bi2S3, clearly visible to the naked eye. Interactions were further confirmed by NMR experiments. Extension of a binding peptide with a maleimide linker (Mal) introduces the possibility to covalently attach thiol-bearing moieties such as biological probes and for their analysis the presence of the cluster instead of mononuclear entities should lead to an increase of signal intensities in LA-ICP-MS measurements. To prove this, CBS-Mal was covalently bound onto thiol-presenting glass substrates, which then captured 1 effectively, so that LA-ICP-MS measurements demonstrated drastic signal amplification compared to single lanthanide tags. KW - Peptide library KW - Mass spectrometry KW - Laser ablation KW - Cluster KW - Bioconjugation PY - 2019 DO - https://doi.org/10.1002/chem.201805234 SN - 0947-6539 VL - 25 IS - 3 SP - 759 EP - 763 PB - John Wiley & Sons, Inc. AN - OPUS4-47324 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - You, Yi A1 - Bierstedt, Andreas A1 - Riedel, Jens T1 - Spatial, temporal, and spectral characterization and kinetic investigations of a high repetition-rate laser-induced micro-plasma in air N2 - Advances in laser-induced plasmas have enabled various rapid and simple analytical applications. Especially, their uses in the analyses of condensed-phase samples have drawn significant attention in the past few decades. Depending on the laser energy per pulse, various analytical goals can be achieved. Laser-induced airborne plasmas allow direct analysis of species in ambient air. Importantly, all of these applications are based on a fundamental understanding of the laser–medium interaction. Recent developments of diode-pumped solid-state lasers offer an alternative to conventional powerful, yet bulky lasers, which can specifically operate at high Repetition rates. Although these lasers deliver much lower power per pulse (mJ compared to mJ), the outstanding repetition rates offer significant improvement to meet statistical needs in some cases. In the present work, a mJ-laserinduced airborne plasma was characterized through optical emission analysis. By using a ns-timegated image detector coupled with specific bandpass filters, spatially, temporally, and spectrally resolved plasma images were recorded. Compared to conventional mJ-laser-induced plasmas, the one induced by mJ-lasers demonstrated unique features during its evolution. Specifically, measurements of the distribution of ionic and atomic species revealed distinctive energy/matter transfer processes during early ignition of the plasma. Meanwhile, dynamic investigations suggested subsequent matter transport in the later stage. KW - Laser-induced plasma KW - Plasma KW - DPSS-laser PY - 2019 UR - https://pubs.rsc.org/en/content/articlehtml/2019/ja/c9ja00163h DO - https://doi.org/10.1039/C9JA00163H SN - 0267-9477 VL - 34 IS - 8 SP - 1618 EP - 1629 PB - Royal Society of Chemistry CY - London AN - OPUS4-48622 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Neamtu, M. A1 - Nadejde, C. A1 - Hodoroaba, Vasile-Dan A1 - Schneider, Rudolf A1 - Panne, Ulrich T1 - Singlet oxygen generation potential of porphyrin-sensitized magnetite nanoparticles: Synthesis, characterization and photocatalytic application N2 - Singlet oxygen generation potential of two novel free-base-porphyrin photocatalysts was investigated. The freebase-porphyrin-sensitized Fe3O4 magnetic nanoparticles (MNPs) were tested for the degradation of the model pollutant Bisphenol A (BPA) in aqueous solution, for the first time. MNPs with either cubic or spherical shape were synthesized using the sonochemical approach, followed by sensitizing with photoactive 4,4′,4′′,4′′′- (Porphine-5,10,15,20-tetrayl)tetrakis(benzoic acid) (TCPP). The resulted photocatalysts were characterized in detail by scanning and transmission electron microscopy, Brunauer–Emmett–Teller analysis, spectral techniques and vibrating sample magnetometry. The electron spin resonance experiments have confirmed the high activity of the photocatalysts through the efficient formation of singlet oxygen in solution. The optimum operational parameters for BPA degradation were established as follows: 1.0 μmol L−1 BPA, 1.0 g L−1 of photocatalyst, 100 μmol L−1 H2O2, under UVA irradiation. In these conditions, the results for both photocatalysts revealed that after only 10 min of reaction, over 64% and ca. 90% of BPA have been removed from solution in the absence and presence of H2O2, respectively. Whereas after 60 minutes of treatment, only 24% of BPA in real wastewater effluent samples were removed under UVA irradiation in the absence of H2O2, showing the high complexity of real wastewater. Moreover, both photocatalysts were successfully used for BPA removal in three consecutive runs, without significant loss of catalytic features. KW - Bisphenol A KW - Magnetpartikel KW - Photooxidation KW - Singulettsauerstoff KW - TEM KW - SEM KW - Brunauer-Emmett-Teller KW - Katalysator KW - Abwasser KW - ESR PY - 2018 DO - https://doi.org/10.1016/j.apcatb.2018.03.079 SN - 0926-3373 VL - 232 SP - 553 EP - 561 PB - Elsevier B.V. CY - Amsterdam, NL AN - OPUS4-45267 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -