TY - JOUR A1 - Kazlagic, Anera A1 - Russo, Francesco A1 - Vogl, Jochen A1 - Sturm, Patrick A1 - Stephan, D. A1 - Gluth, Gregor ED - Resch-Genger, Ute ED - Koch, Matthias ED - Meermann, Björn ED - Weller, Michael G. T1 - Development of a sample preparation procedure for Sr isotope analysis of Portland cements N2 - The 87Sr/86Sr isotope ratio can, in principle, be used for provenancing of cement. However, while commercial cements consist of multiple components, no detailed investigation into their individual 87Sr/86Sr isotope ratios or their influence on the integral 87Sr/86Sr isotope ratio of the resulting cement was conducted previously. Therefore, the present study aimed at determining and comparing the conventional 87Sr/86Sr isotope ratios of a diverse set of Portland cements and their corresponding Portland clinkers, the major component of these cements. Two approaches to remove the additives from the cements, i.e. to measure the conventional 87Sr/86Sr isotopic fingerprint of the clinker only, were tested, namely, treatment with a potassium hydroxide/sucrose solution and sieving on a 11-µm sieve. Dissolution in concentrated hydrochloric acid/nitric acid and in diluted nitric acid was employed to determine the 87Sr/86Sr isotope ratios of the cements and the individual clinkers. The aim was to find the most appropriate sample preparation procedure for cement provenancing, and the selection was realised by comparing the 87Sr/86Sr isotope ratios of differently treated cements with those of the corresponding clinkers. None of the methods to separate the clinkers from the cements proved to be satisfactory. However, it was found that the 87Sr/86Sr isotope ratios of clinker and cement generally corresponded, meaning that the latter can be used as a proxy for the clinker 87Sr/86Sr isotope ratio. Finally, the concentrated hydrochloric acid/nitric acid dissolution method was found to be the most suitable sample preparation method for the cements; it is thus recommended for 87Sr/86Sr isotope analyses for cement provenancing. KW - Cement KW - Provenancing KW - Sr isotopes KW - Portland clinker KW - Dissolution PY - 2022 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-542239 DO - https://doi.org/10.1007/s00216-021-03821-7 SN - 1618-2642 SN - 1618-2650 VL - 414 IS - 15 (Topical collection: Analytical methods and applications in the materials and life sciences) SP - 4379 EP - 4389 PB - Springer CY - Berlin AN - OPUS4-54223 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - von der Au, Marcus A1 - Schwinn, M. A1 - Kuhlmeier, K. A1 - Büchel, C. A1 - Meermann, Björn T1 - Development of an automated on-line purification HPLC single cell-ICP-MS approach for fast diatom analysis N2 - The most challenging part in performing a single cell ICP-MS (sc-ICP-MS) approach is the sample preparation, in particular the reduction of the ionic background. This step is, in many cases, time-consuming and required for each sample separately. Furthermore, sc-ICP-MS measurements are mostly carried out "manually", given the fact that present systems are not allowing for an automated change of samples. Thus, within this work, we developed an approach based on a HPLC system coupled on-line with sc-ICP-MS via a set of switching valves as well as an in-line filter for automated cell washing. This set-up enables the ionic background removal as well as analysis of single cells completely automated without any manual sample pretreatment. Our approach was applied for the analysis of the single celled diatom species Cyclotella meneghiniana, a marine diatom species, on the basis of Mg24 and facilitates testing in 11 min per sample, requiring only around 10,000 cells in a volume of 10 µL and approx. 10 mL of a 5% MeOH/95% deionized water (v/v) mixture. Even at extremely saline culturing media concentrations (up to 1000 mg L-1 magnesium) our on-line approach worked sufficiently allowing for distinction of ionic and particulate fractions. Furthermore, a set of diatom samples was analyzed completely automated without the need for changing samples manually. So, utilizing this approach enables analyzing a high quantity of samples in a short time and therefore in future the investigation of ecotoxicological effects is simplified for example in terms of metal accumulation by taking biovariability into account. KW - Single cell-ICP-MS KW - Diatoms KW - Ecotoxicology testing KW - Automated system PY - 2019 DO - https://doi.org/10.1016/j.aca.2019.05.045 SN - 1873-4324 VL - 1077 SP - 87 EP - 94 PB - Elsevier AN - OPUS4-48567 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Tukhmetova, Dariya A1 - Lisec, Jan A1 - Vogl, Jochen A1 - Meermann, Björn T1 - Development of an Online Isotope Dilution CE/ICP–MS Method for the Quantification of Sulfur in Biological Compounds N2 - We report an analytical methodology for the quantification of sulfur in biological molecules via a speciesunspecific postcolumn isotope dilution (online ID) approach using capillary electrophoresis (CE) coupled online with inductively coupled plasma−mass spectrometry (online ID CE/ICP−MS). The method was optimized using a mixture of standard compounds including sulfate, methionine, cysteine, cystine, and albumin, yielding compound recoveries between 98 and 105%. The quantity of sulfur is further converted to the quantity of the compounds owing to the prior knowledge of the sulfur content in the molecules. The limit of detection and limit of quantification of sulfur in the compounds were 1.3−2.6 and 4.1−8.4 mg L−1, respectively, with a correlation coefficient of 0.99 within the concentration range of sulfur of 5−100 mg L−1. The capability of the method was extended to quantify albumin in its native matrix (i.e., in serum) using experimentally prepared serum spiked with a pure albumin standard for validation. The relative expanded uncertainty of the method for the quantification of albumin was 6.7% (k = 2). Finally, we tested the applicability of the method on real samples by the analysis of albumin in bovine and human sera. For automated data assessment, a software application (IsoCor) which was developed by us in a previous work was developed further for handling of online ID data. The method has several improvements compared to previously published setups: (i) reduced adsorption of proteins onto the capillary wall owing to a special capillary-coating procedure, (ii) baseline separation of the compounds in less than 30 min via CE, (iii) quantification of several sulfur species within one run by means of the online setup, (iv) SI traceability of the quantification results through online ID, and (v) facilitated data processing of the transient signals using the IsoCor application. Our method can be used as an accurate approach for quantification of proteins and other biological molecules via sulfur analysis in complex matrices for various fields, such as environmental, biological, and pharmaceutical studies as well as clinical diagnosis. Sulfur is an essential element in living organisms, where it plays important roles in various biological processes, such as protein synthesis, enzyme activity, and antioxidant defense. However, the biological effects of different sulfur species can vary widely, and imbalances in sulfur speciation have been observed in a range of diseases, including cancer, Alzheimer’s disease, and diabetes.1−3 The accurate quantification of sulfur and its species in biological samples requires sensitive and selective analytical techniques. In recent years, separation techniques coupled online with inductively coupled plasma−mass spectrometry (ICP−MS) have emerged as powerful online analytical tools complementary to molecular spectrometric methods for speciation analysis of biological compounds. External calibration4−9 and isotope dilution (ID)10−15 are common calibration approaches applied for online quantification of sulfur species in complex samples. The ID analysis is advantageous over. KW - Analytical Chemistry KW - CE/MC-ICP-MS KW - species-specific isotope information PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-594736 DO - https://doi.org/10.1021/acs.analchem.3c03553 SN - 0003-2700 SP - 1 EP - 8 PB - American Chemical Society (ACS) AN - OPUS4-59473 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Faßbender, Sebastian A1 - Döring, A.-K. A1 - Meermann, Björn T1 - Development of complementary CE-MS methods for speciation analysis of pyrithione-based antifouling agents N2 - In the recent decade, metal pyrithione complexes have become important biocides for antifouling purposes in shipping. The analysis of metal pyrithione complexes and their degradation products/species in environmental samples is challenging because they exhibit fast UV degradation, transmetalation, and ligand substitution and are known to be prone to spontaneous species transformation within a chromatographic system. The environmental properties of the pyrithione species, e.g., toxicity to target and non-target organisms, are differing strongly, and it is therefore inevitable to identify as well as quantify all species separately. To cope with the separation of metal pyrithione species with minimum species transformation during analysis, a capillary electrophoresis (CE)–based method was developed. The hyphenation of CE with selective electrospray ionization- and inductively coupled plasma–mass spectrometry (ESI-, ICP-MS) provided complementary molecular and elemental information for the identification and quantification of pyrithione species. To study speciation of pyrithiones, a leaching experiment of several commercial antifouling paints containing zinc pyrithione in ultrapure and river water was conducted. Only the two species pyrithione (HPT) and dipyrithione ((PT)2) were found in the leaching media, in concentrations between 0.086 and 2.4 μM (HPT) and between 0.062 and 0.59 μM ((PT)2), depending on the paint and leaching medium. The limits of detection were 20 nM (HPT) and 10 nM ((PT)2). The results show that complementary CE-MS is a suitable tool for mechanistical studies concerning species transformation (e.g., degradation) and the identification of target species of metal pyrithione complexes in real surface water matrices, laying the ground for future environmental studies. KW - Complementary MS KW - Environmental speciation KW - Capillary electrophoresis-mass spectrometry KW - Antifouling biocides PY - 2019 DO - https://doi.org/10.1007/s00216-019-02094-5 SN - 1618-2642 VL - 411 IS - 27 SP - 7261 EP - 7272 PB - Springer CY - Berlin, Heidelberg AN - OPUS4-48962 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Weber, K. A1 - Weber, M. A1 - Menneken, M. A1 - Kral, A. G. A1 - Mertz-Kraus, R. A1 - Geisler, T. A1 - Vogl, Jochen A1 - Tütken, T. T1 - Diagenetic stability of non-traditional stable isotope systems (Ca, Sr, Mg, Zn) in teeth – An in-vitro alteration experiment of biogenic apatite in isotopically enriched tracer solution 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 primary diet-related isotope signatures and elemental compositions, it is important to understand and quantify alteration processes. Here, we present the results of in-vitro Alteration experiments of dental tissues from a modern African elephant molar reacted in aqueous solutions at 30 °C and 90 °C for 4 to 63 days. Dental cubes with ≈ 3 mm edge length, comprising both enamel and dentin, were placed into 2 mL of acidic aqueous solution enriched in different isotopes (25Mg, 44Ca, 67Zn, 86Sr, initial pH 1). Element and isotope distribution profiles across the reacted cubes were measured with LA-(MC-)ICP-MS and EMPA, while potential effects on the bioapatite crystal structure were characterised by Raman spectroscopy. In all experiments isotope ratios measured by LA-(MC-)ICP-MS revealed an alteration of the enamel in the outer ≈ 200–300 μm. In contrast, dentin was fully altered (≈ 1.4 mm) after one week at 90 °C while the alteration did not exceed a depth of 150–200 μm during the 30 °C experiments. Then, the tracer solution started also to penetrate through the enamel-dentin junction into the innermost enamel, however, leaving the central part of the enamel unaltered, even after three months. The Raman spectra suggest an initial demineralisation in the acidic environment while organic matter (i.e. collagen) is still preserved. In the 90 °C experiment, Raman spectra of the v1 PO4) band of the dentin shift over time towards synthetic hydroxylapatite patterns and the Ca (and Sr) concentrations in the respective solutions decrease. This indicates precipitation of newly formed apatite. Isotope and element concentration profiles across the dental tissues reveal different exchange mechanisms for different isotope systems. Magnesium is leached from enamel and dentin, while Zn is incorporated into the apatite crystal structure. However, the distribution of both elements is not affected in the innermost enamel where their concentrations do not change over the whole duration of the experiments. We found no correlation of reaction depth in the cubes and experimental duration, which might be caused by natural variability of the dental material already at the beginning of the experiment. Our alteration experiments in a closed system at high temperatures ≤90 °C and low initial pH demonstrate that at least the central part of mm-thick mammalian enamel apatite seems to be resistant against alteration preserving its pristine bioapatite mineral structure as well as its in-vivo elemental and isotopic composition. The experiments assess diagenetic alteration in a novel multi-proxy approach using in-situ analyses in high spatial resolution. It is demonstrated that the isotopes of Ca, Sr, Zn and Mg in the dentin are prone for diagenetic alteration, while enamel is more resistant against alteration and could be used for dietary and physiological reconstructions in fossil teeth. KW - Bioapatite KW - Isotopes KW - Raman spectroscopy KW - Diagenesis KW - LA-(MC-)ICP-MS KW - EPMA PY - 2021 DO - https://doi.org/10.1016/j.chemgeo.2021.120196 VL - 572 SP - 120196 PB - Elsevier B.V. CY - Amsterdam AN - OPUS4-52447 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Anderhalten, L. A1 - Silva, R. V. A1 - Morr, A. A1 - Wang, S. A1 - Smorodchenko, A. A1 - Saatz, Jessica A1 - Traub, Heike A1 - Mueller, S. A1 - Boehm-Sturm, P. A1 - Rodriguez-Sillke, Y. A1 - Kunkel, D. A1 - Hahndorf, J. A1 - Paul, F. A1 - Taupitz, M. A1 - Sack, I. A1 - Infante-Duarte, C. T1 - Different Impact of Gadopentetate and Gadobutrol on Inflammation-Promoted Retention and Toxicity of Gadolinium Within the Mouse Brain N2 - Objectives: Using a murine model of multiple sclerosis, we previously showed that repeated administration of gadopentetate dimeglumine led to retention of gadolinium (Gd) within cerebellar structures and that this process was enhanced with inflammation. This study aimed to compare the kinetics and retention profiles of Gd in inflamed and healthy brains after application of the macrocyclic Gd-based contrast agent (GBCA) gadobutrol or the linear GBCA gadopentetate. Moreover, potential Gd-induced neurotoxicity was investigated in living hippocampal slices ex vivo. Materials and Methods: Mice at peak of experimental autoimmune encephalomyelitis (EAE; n = 29) and healthy control mice (HC; n = 24) were exposed to a cumulative dose of 20 mmol/kg bodyweight of either gadopentetate dimeglumine or gadobutrol (8 injections of 2.5 mmol/kg over 10 days). Magnetic resonance imaging (7 T) was performed at baseline as well as at day 1, 10, and 40 post final injection (pfi) of GBCAs. Mice were sacrificed after magnetic resonance imaging and brain and blood Gd content was assessed by laser ablation-inductively coupled plasma (ICP)-mass spectrometry (MS) and ICP-MS, respectively. In addition, using chronic organotypic hippocampal slice cultures, Gd-induced neurotoxicity was addressed in living brain tissue ex vivo, both under control or inflammatory (tumor necrosis factor α [TNF-α] at 50 ng/μL) conditions. Results: Neuroinflammation promoted a significant decrease in T1 relaxation times after multiple injections of both GBCAs as shown by quantitative T1 mapping of EAE brains compared with HC. This corresponded to higher Gd retention within the EAE brains at 1, 10, and 40 days pfi as determined by laser ablation-ICP-MS. In inflamed cerebellum, in particular in the deep cerebellar nuclei (CN), elevated Gd retention was observed until day 40 after last gadopentetate application (CN: EAE vs HC, 55.06 ± 0.16 μM vs 30.44 ± 4.43 μM). In contrast, gadobutrol application led to a rather diffuse Gd content in the inflamed brains, which strongly diminished until day 40 (CN: EAE vs HC, 0.38 ± 0.08 μM vs 0.17 ± 0.03 μM). The analysis of cytotoxic effects of both GBCAs using living brain tissue revealed an elevated cell death rate after incubation with gadopentetate but not gadobutrol at 50 mM. The cytotoxic effect due to gadopentetate increased in the presence of the inflammatory mediator TNF-α (with vs without TNF-α, 3.15% ± 1.18% vs 2.17% ± 1.14%; P = 0.0345). Conclusions: In the EAE model, neuroinflammation promoted increased Gd retention in the brain for both GBCAs. Whereas in the inflamed brains, efficient clearance of macrocyclic gadobutrol during the investigated time period was observed, the Gd retention after application of linear gadopentetate persisted over the entire observational period. Gadopentetate but not gadubutrol appeared to be neurotoxic in an ex vivo paradigm of neuronal inflammation. KW - Imaging KW - ICP-MS KW - Gadolinium KW - Contrast agent KW - Laser ablation KW - Brain KW - Multiple sclerosis PY - 2022 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-546910 DO - https://doi.org/10.1097/RLI.0000000000000884 SN - 0020-9996/22/0000–0000 VL - 57 IS - 10 SP - 677 EP - 688 PB - Wolters Kluwer N.V. CY - Alphen aan den Rijn, The Netherlands AN - OPUS4-54691 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Resch-Genger, Ute A1 - Meermann, Björn A1 - Koch, Matthias A1 - Weller, Michael G. T1 - Editorial: Analytical methods and applications in materials and life sciences N2 - Current trends in materials and life sciences are flanked by the need to push detection limits to single molecules or single cells, enable the characterization of increasingly complex matrices or sophisticated nanostructures, speed up the time of analysis, reduce instrument complexity and costs, and improve the reliability of data. This requires suitable analytical tools such as spectroscopic, separation and imaging techniques, mass spectrometry, and hyphenated techniques as well as sensors and their adaptation to application-specific challenges in the environmental, food, consumer product, health sector, nanotechnology, and bioanalysis. Increasing concerns about health threatening known or emerging pollutants in drinking water, consumer products, and food and about the safety of nanomaterials led to a new awareness of the importance of analytical sciences. Another important driver in this direction is the increasing demand by legislation, particularly in view of the 17 sustainable development goals by the United Nations addressing clean energy, industry, and innovation, sustainable cities, clean water, and responsible consumption and production. In this respect, also the development of analytical methods that enable the characterization of material flows in production processes and support recycling concepts of precious raw materials becomes more and more relevant. In the future, this will provide the basis for greener production in the chemical industry utilizing recycled or sustainable starting materials. This makes analytical chemistry an essential player in terms of the circular economy helping to increase the sustainability of production processes. In the life sciences sector, products based on proteins, such as therapeutic and diagnostic antibodies, increase in importance. These increasingly biotechnologically produced functional biomolecules pose a high level of complexity of matrix and structural features that can be met only by highly advanced methods for separation, characterization, and detection. In addition, metrological traceability and target definition are still significant challenges for the future, particularly in the life sciences. However, innovative reference materials as required for the health and food sector and the characterization of advanced materials can only be developed when suitable analytical protocols are available. The so-called reproducibility crisis in sciences underlines the importance of improved measures of quality control for all kinds of measurements and material characterization. This calls for thorough method validation concepts, suitable reference materials, and regular interlaboratory comparisons of measurements as well as better training of scientists in analytical sciences. The important contribution of analytical sciences to these developments is highlighted by a broad collection of research papers, trend articles, and critical reviews from these different application fields. Special emphasis is dedicated to often-overlooked quality assurance and reference materials. T2 - 150 years BAM: Science with impact CY - Berlin, Germany DA - 01.01.2021 KW - Analysis KW - Life sciences KW - Analytical sciences KW - Quality assurance KW - Reference material KW - Fluorescence KW - Nanoparticle KW - Sensor KW - Material sciences KW - Pollutant KW - Environment KW - Method KW - Limit of detection KW - 150th anniversary KW - ABC KW - BAM KW - Collection KW - Editorial KW - Special issue KW - Bundesanstalt für Materialforschung und -prüfung KW - Jahrestag PY - 2022 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-550720 DO - https://doi.org/10.1007/s00216-022-04082-8 SN - 1618-2642 SN - 1618-2650 VL - 414 IS - Topical collection: Analytical methods and applications in the materials and life sciences SP - 4267 EP - 4268 PB - Springer CY - Berlin AN - OPUS4-55072 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Völzke, Jule L. A1 - Smatty, Sarah A1 - Döring, Sarah A1 - Ewald, Shireen A1 - Oelze, Marcus A1 - Fratzke, Franziska A1 - Flemig, Sabine A1 - Konthur, Zoltán A1 - Weller, Michael G. T1 - Efficient Purification of Polyhistidine-Tagged Recombinant Proteins Using Functionalized Corundum Particles N2 - Immobilized metal affinity chromatography (IMAC) is a widely used technique for purifying polyhistidine-tagged recombinant proteins. However, it often has practical limitations that require complex optimizations and additional steps for purification. In this study, we introduce functionalized corundum particles as a novel, efficient, and economical method for purifying recombinant proteins in a column-free format. The corundum surface is modified with amino silane APTES, followed by EDTA dianhydride, and then loaded with nickel ions. We used the Kaiser test to monitor the modification process and ICP-MS to quantify the metal-binding capacity. To evaluate the system, we used His-tagged protein A/G (PAG) mixed with bovine serum albumin (BSA). The corundum particles exhibited a binding capacity of approximately 3 mg of protein per gram of corundum or 2.4 mg per 1 mL of corundum suspension. We also examined cytoplasm obtained from different E. coli strains as an example of a complex matrix. Varying the imidazole concentration in the loading and washing buffers showed that higher concentrations during loading improved purity. Even with sample volumes as large as one liter, we successfully isolated recombinant proteins down to a concentration of 1 µg/mL. We found higher purity levels with corundum when comparing the corundum material to standard Ni–NTA agarose beads. We successfully purified His6-MBP-mSA2, a fusion protein comprising monomeric streptavidin and maltose-binding protein, from E. coli cytoplasm, demonstrating the method's applicability. We also purified SARS-CoV-2-S-RBD-His8 expressed in human Expi293F cells, confirming its suitability for mammalian cell culture supernatants. The material cost of the nickel-loaded corundum material (without regeneration) is estimated to be less than 30 cents per gram of functionalized support or 10 cents per milligram of isolated protein. Another advantage of this system is the exceptional physical and chemical stability of corundum particles. Overall, we have demonstrated that this novel material offers an efficient, robust, and cost-effective purification platform for His-tagged proteins, even in challenging, complex matrices and large sample volumes with low product concentrations. This method has potential applications in both small laboratories and large-scale industrial settings. N2 - Die immobilisierte Metallaffinitätschromatographie (IMAC) ist eine weit verbreitete Technik zur Reinigung von rekombinanten Proteinen mit Polyhistidin-Markierung. Sie hat jedoch oft praktische Einschränkungen, die komplexe Optimierungen und zusätzliche Schritte für die Aufreinigung erfordern. In dieser Studie stellen wir funktionalisierte Korundpartikel als neuartige, effiziente und wirtschaftliche Methode zur Reinigung rekombinanter Proteine in einem säulenfreien Format vor. Die Korundoberfläche wird mit dem Aminosilan APTES und anschließend mit EDTA-Dianhydrid modifiziert und dann mit Nickelionen beladen. Wir haben den Kaiser-Test zur Überwachung des Modifizierungsprozesses und ICP-MS zur Quantifizierung der Metallbindungskapazität verwendet. Zur Charakterisierung des Systems verwendeten wir His-markiertes Protein A/G (PAG) in Kombination mit Rinderserumalbumin (BSA). Die Korundpartikel wiesen eine Bindungskapazität von etwa 3 mg Protein pro Gramm Korund oder 2,4 mg pro 1 ml Korundsuspension auf. Als Beispiel für eine komplexe Matrix untersuchten wir auch Zytoplasma, das aus verschiedenen E. coli-Stämmen gewonnen wurde. Die Variation der Imidazolkonzentration in den Lade- und Waschpuffern zeigte, dass höhere Konzentrationen beim Laden die Reinheit verbesserten. Selbst bei einem Probenvolumen von bis zu einem Liter konnten wir rekombinante Proteine von 1 µg/mL isolieren. Beim Vergleich des Korundmaterials mit Standard-Ni-NTA-Agarose-Beads stellten wir einen höheren Reinheitsgrad mit Korund fest. Wir reinigten erfolgreich His6-MBP-mSA2 aus E. coli-Zytoplasma, ein Fusionsprotein, das aus monomerem Streptavidin und Maltose-bindendem Protein besteht. Wir reinigten auch SARS-CoV-2-S-RBD-His8, das in humanen Expi293F-Zellen exprimiert wurde, und bestätigten damit die Eignung des Materials für Zellkulturüberstände von Säugetieren. Die Materialkosten für nickelbeladenen Korund (ohne Regenerierung) werden auf weniger als 30 Cent pro Gramm funktionalisierten Trägers oder 10 Cent pro Milligramm isolierten Proteins geschätzt. Ein weiterer Vorteil dieses Systems ist die außergewöhnliche physikalische und chemische Stabilität der Korundpartikel. Insgesamt haben wir gezeigt, dass dieses neuartige Material eine effiziente, robuste und kostengünstige Reinigungsplattform für His-markierte Proteine bietet, selbst bei schwierigen, komplexen Matrices und großen Probenmengen mit niedrigen Produktkonzentrationen. Diese Methode könnte sowohl in kleinen Labors als auch in der Großindustrie eingesetzt werden. KW - Aluminum oxide KW - Sapphire KW - Ethylenediaminetetraacetic acid KW - Nickel chelate KW - EDTAD KW - HexaHis-Tag KW - His6 KW - 6xHis KW - His8 KW - Bioseparation KW - IMAC purification KW - Immunocapture KW - Affinity chromatography KW - Carrier KW - Nickel KW - Recombinant protein KW - Escherichia coli KW - Bacterial lysates KW - Cytoplasm KW - Polishing KW - Downstream processing PY - 2023 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-575672 DO - https://doi.org/10.3390/biotech12020031 VL - 12 IS - 2 SP - 1 EP - 18 PB - MDPI CY - Basel, Schweiz AN - OPUS4-57567 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Nxumalo, T. A1 - Akhdhar, A. A1 - Mueller, V. A1 - Simon, Fabian A1 - von der Au, Marcus A1 - Cossmer, Antje A1 - Pfeifer, Jens A1 - Krupp, E. A1 - Meermann, Björn A1 - Kindness, A. A1 - Feldmann, J. T1 - EOF and target PFAS analysis in surface waters affected by sewage treatment effluents in Berlin, Germany N2 - Per- and polyfuoroalkyl substances (PFAS) are emerging organic pollutants and can occur in surface and groundwater. To identify the degree of pollution in surface water with PFAS, often targeted HPLC–ESI–MS/MS has been employed in which commonly 30–40 compounds are analyzed. However, other PFAS and organofuorines remain undetected. We sampled surface water of the river Spree and the Teltow Canal in Berlin, Germany, which are afected by the efuent discharge of wastewater treatment plants. Here, we employed high-resolution continuum source graphite furnace molecular absorption spectrometry (HR-CS-GFMAS) for measuring extractable organofuorines (EOF) and compared in a mass balance approach the total fuorine to the identifed and quantifed PFAS from the targeted analysis. The analysis highlights that the EOF are in the range expected for an urban river system (Winchell et al. in Sci Total Environ 774, 2021). However, downstream of an efuent discharge, the EOF increased by one order of magnitude, e.g., 40.3 to 574 ng F L−1, along the Teltow Canal. From our target analytes, mostly short-chained perfuorinated carboxylic acids and sulfonates occur in the water, which however makes up less than 10% of the EOF. The increase in EOF in the Teltow Canal correlates well with the increase of perfuorohexanoic acid (PFHxA), indicating that PFHxA is characteristic for the discharged EOF but not responsible for the increase. Hence, it points to PFHxA precursor discharge. The study highlights that EOF screening using HR-CS-GFMAS is necessary to identify the full scale of pollution with regard to PFAS and other organofuorines such as pharmaceutical compounds from the efuent of WWTPs. KW - PFAS KW - WWTP KW - GF-MAS PY - 2023 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-580341 DO - https://doi.org/10.1007/s00216-022-04500-x VL - 415 SP - 1195 EP - 1204 PB - Springer AN - OPUS4-58034 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Vogl, Jochen A1 - Kipphardt, Heinrich A1 - Richter, Silke A1 - Bremser, Wolfram A1 - Arvizu Torres, M. A1 - Lara Manzano, J. A1 - Buzoianu, M. A1 - Hill, S. A1 - Petrov, P. A1 - Goenaga-Infante, H. A1 - Sargent, M. A1 - Fisicaro, P. A1 - Labarraque, G. A1 - Zhou, T. A1 - Turk, G. C. A1 - Winchester, M. A1 - Miura, T. A1 - Methven, B. A1 - Sturgeon, R. A1 - Jährling, R. A1 - Rienitz, O. A1 - Mariassy, M. A1 - Hankova, Z. A1 - Sobina, E. A1 - Krylov, A. I. A1 - Kustikov, Y. A. A1 - Smirnov, V. V. T1 - Establishing comparability and compatibility in the purity assessment of high purity zinc as demonstrated by the CCQM-P149 intercomparison N2 - For the first time, an international comparison was conducted on the determination of the purity of a high purity element. Participants were free to choose any analytical approach appropriate for their institute’s applications and services. The material tested was a high purity zinc, which had earlier been assessed for homogeneity and previously used in CCQM-K72 for the determination of six defined metallic impurities. Either a direct metal assay of the Zn mass fraction was undertaken by EDTA titrimetry, or an indirect approach was used wherein all impurities, or at least the major ones, were determined and their sum subtracted from ideal purity of 100 %, or 1 kg/kg. Impurity assessment techniques included glow discharge mass spectrometry, inductively coupled plasma mass spectrometry and carrier gas hot extraction/combustion analysis. Up to 91 elemental impurities covering metals, non-metals and semi-metals/metalloids were quantified. Due to the lack of internal experience or experimental capabilities, some participants contracted external laboratories for specific analytical tasks, mainly for the analysis of non-metals. The reported purity, expressed as zinc mass fraction in the high purity zinc material, showed excellent agreement for all participants, with a relative standard deviation of 0.011 %. The calculated reference value, w(Zn) = 0.999 873 kg/kg, was assigned an asymmetric combined uncertainty of + 0.000025 kg/kg and – 0.000028 kg/kg. Comparability amongst participating metrology institutes is thus demonstrated for the purity determination of high purity metals which have no particular difficulties with their decomposition / dissolution process when solution-based analytical methods are used, or which do not have specific difficulties when direct analysis approaches are used. Nevertheless, further development is required in terms of uncertainty assessment, quantification of non-metals and the determination of purity of less pure elements and/or for those elements suffering difficulties with the decomposition process. KW - Purity assessment KW - Direct metal assay KW - Impurity assessment KW - Non-metal analysis KW - High-purity elements KW - SI-traceability PY - 2018 DO - https://doi.org/10.1088/1681-7575/aaa677 SN - 1681-7575 SN - 0026-1394 VL - 55 IS - 2 SP - 211 EP - 221 PB - Institute of Physics Publishing CY - Bristol AN - OPUS4-44257 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Ecke, Alexander A1 - Westphalen, Tanja A1 - Retzmann, Anika A1 - Schneider, Rudolf T1 - Factors affecting the hydrolysis of the antibiotic amoxicillin in the aquatic environment N2 - The environmental fate of the frequently used broad-spectrum β-lactam antibiotic amoxicillin (AMX) is of high concern regarding the potential evolution of antimicrobial resistance (AMR). Moreover, it is known that AMX is prone to hydrolysis, yielding a variety of hydrolysis products (HPs) with yet unknown effects. Studies to identify those HPs and investigate their formation mechanisms have been reported but a long-term study on their stability in real water samples was missing. In this regard, we investigated the hydrolysis of AMX at two concentration levels in four distinct water types under three different storage conditions over two months. Concentrations of AMX and four relevant HPs were monitored by an LC-MS/MS method revealing pronounced differences in the hydrolysis rate of AMX in tap water and mineral water on the one hand (fast) and surface water on the other(slow). In this context, the occurrence, relative intensities, and stability of certain HPs are more dependent on the water type than on the storage condition. As clarified by ICP-MS, the main difference between the water types was the content of the metals copper and zinc which are supposed to catalyze AMX hydrolysis demonstrating an effective method to degrade AMX at ambient conditions. KW - β-lactam KW - Stability KW - Degradation KW - Hydrolysis products KW - LC-MS/MS KW - ICP-MS PY - 2023 DO - https://doi.org/10.1016/j.chemosphere.2022.136921 SN - 0045-6535 VL - 311 SP - 136921 PB - Elsevier Ltd. AN - OPUS4-56124 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kazlagić, Anera A1 - Stephan, D. A1 - Ostermann, Markus A1 - Possolo, A. A1 - Vogl, Jochen T1 - Fingerprinting Portland cements by means of 87Sr/86Sr and 143Nd/144Nd isotope ratios and geochemical profiles N2 - This study uses conventional 87Sr/86Sr and 143Nd/144Nd isotope and interelement ratios of Ca, Sr, K, Mn, Mg and Ti as fingerprints for provenancing ordinary Portland cements (OPC). Herein, the first database of Sr and Nd isotope ratios investigated in OPCs, stemming from 29 cement plants located worldwide, was created. The results show that the Sr isotope ratios of OPCs are higher than those of seawater from the observed geological period. The spread of 143Nd/144Nd in OPCs is not as large as the spread for 87Sr/86Sr isotope ratios. However, the combination of both Sr and Nd isotope ratios provides the potential for distinguishing between cements of different production sites. Most of the OPCs investigated have measurable differences in their 87Sr/86Sr and 143Nd/144Nd isotope ratios, which can be employed as a valuable analytical fingerprinting tool. In the case of equivocal results, divisive hierarchical clustering was employed to help overcome this issue. The construction of geochemical profiles allowed the computing of suitably defined distances between cements and clustering them according to their chemical similarity. By applying this methodology, successful fingerprinting was achieved in 27 out of the 29 ordinary Portland cements that were analysed. KW - Elemental fingerprints KW - Geochemistry KW - Portland cement KW - Sr and Nd isotope analysis KW - Statistical analysis PY - 2023 DO - https://doi.org/10.1680/jadcr.23.00018 SN - 0951-7197 VL - 36 IS - 6 SP - 260 EP - 271 PB - Emerald Publishing Limited AN - OPUS4-57979 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - El-Khatib, A. H. A1 - Radbruch, H. A1 - Trog, S. A1 - Neumann, B. A1 - Paul, F. A1 - Koch, A. A1 - Linscheid, M. W. A1 - Jakubowski, Norbert A1 - Schellenberger, E. T1 - Gadolinium in human brain sections and colocalization with other elements N2 - Recent recommendations by the Food and Drug Administration1 and the European Medicines Agency2 are to limit the clinical use of linear gadolinium-based contrast agents (GBCAs) due to convincing evidence of deposition in tissues. Macrocyclic GBCA continued to be considered safe, provided that patients have normal renal function. To date, given the low sensitivity of conventional MRI, there has been a debate about the signal increase following the injections of a macrocyclic GBCA. KW - Gadolinium PY - 2019 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-471309 DO - https://doi.org/10.1212/NXI.0000000000000515 SN - 2332-7812 VL - 6 IS - 1 SP - e515, 1 EP - 3 PB - American Academy of Neurology AN - OPUS4-47130 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Tvrdonova, M. A1 - Vlcnovska, M. A1 - Pompeiano Vanickova, L. A1 - Kanicky, V. A1 - Adam, V. A1 - Ascher, Lena A1 - Jakubowski, Norbert A1 - Vaculovicova, M. A1 - Vaculovic, T. T1 - Gold nanoparticles as labels for immunochemical analysis using laser ablation inductively coupled plasma mass spectrometry N2 - In this paper, we describe the labelling of antibodies by gold nanoparticles (AuNPs) with diameters of 10 and 60 nm with detection by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). Additionally, the AuNPs labelling strategy is compared with commercially available labelling reagents based on MeCAT (metal coded affinity tagging). Proof of principle experiments based on dot blot experiments were performed. The two labelling methods investigated were compared by sensitivity and limit of detection (LOD). The absolute LODs achieved were in the range of tens of picograms for AuNP labelling compared to a few hundred picograms by the MeCAT labelling. KW - Nanoparticle KW - LA-ICP-MS KW - Labeling PY - 2019 DO - https://doi.org/10.1007/s00216-018-1300-7 SN - 1618-2642 SN - 1618-2650 VL - 411 IS - 3 SP - 559 EP - 564 PB - Springer-Verlag GmbH CY - Berlin, Heidelberg AN - OPUS4-47093 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Winckelmann, Alexander A1 - Nowak, S. A1 - Richter, Silke A1 - Recknagel, Sebastian A1 - Riedel, Jens A1 - Vogl, Jochen A1 - Panne, Ulrich A1 - Abad Andrade, Carlos Enrique T1 - High-Resolution Atomic Absorption Spectrometry Combined With Machine Learning Data Processing for Isotope Amount Ratio Analysis of Lithium N2 - An alternative method for lithium isotope amount ratio analysis based on a combination of high-resolution atomic absorption spectrometry and spectral data analysis by machine learning (ML) is proposed herein. It is based on the well-known isotope shift of approximately 15 pm for the electronic transition 22P←22S at around the wavelength of 670.8 nm, which can be measured by the state-of-the-art high-resolution continuum source graphite furnace atomic absorption spectrometry. For isotope amount ratio analysis, a scalable tree boosting ML algorithm (XGBoost) was employed and calibrated using a set of samples with 6Li isotope amount fractions, ranging from 0.06 to 0.99 mol mol–1, previously determined by a multicollector inductively coupled plasma mass spectrometer (MC-ICP-MS). The calibration ML model was validated with two certified reference materials (LSVEC and IRMM-016). The procedure was applied toward the isotope amount ratio determination of a set of stock chemicals (Li2CO3, LiNO3, LiCl, and LiOH) and a BAM candidate reference material NMC111 (LiNi1/3Mn1/3Co1/3O2), a Li-battery cathode material. The results of these determinations were compared with those obtained by MC-ICP-MS and found to be metrologically comparable and compatible. The residual bias was −1.8‰, and the precision obtained ranged from 1.9 to 6.2‰. This precision was sufficient to resolve naturally occurring variations, as demonstrated for samples ranging from approximately −3 to +15‰. To assess its suitability to technical applications, the NMC111 cathode candidate reference material was analyzed using high-resolution continuum source atomic absorption spectrometry with and without matrix purification. The results obtained were metrologically compatible with each other. KW - Lithium KW - Isotope KW - Machine learning KW - Algorithms KW - Reference material KW - AAS KW - Atomic Absorption Spectrometry PY - 2021 DO - https://doi.org/10.1021/acs.analchem.1c00206 SN - 1520-6882 VL - 93 IS - 29 SP - 10022 EP - 10030 PB - American Chemical Society CY - Washington, DC, USA AN - OPUS4-53028 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Arakawa, Akihiro A1 - Jakubowski, Norbert A1 - Flemig, Sabine A1 - Koellensperger, G. A1 - Rusz, M. A1 - Iwahata, D. A1 - Traub, Heike A1 - Hirata, T. T1 - High-resolution laser ablation inductively coupled plasma mass spectrometry used to study transport of metallic nanoparticles through collagen-rich microstructures in fibroblast multicellular spheroids N2 - We have efficiently produced collagen-rich microstructures in fibroblast multicellular spheroids (MCSs) as a three-dimensional in vitro tissue analog to investigate silver (Ag) nanoparticle (NP) penetration. The MCS production was examined by changing the seeding cell number (500 to 40,000 cells) and the growth period (1 to 10 days). MCSs were incubated with Ag NP suspensions with a concentration of 5 μg/mL for 24 h. For this study, laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) was used to visualize Ag NP localization quantitatively. Thin sections of MCSs were analyzed by LA-ICP-MS with a laser spot size of 8 μm to image distributions of 109Ag, 31P, 63Cu, 66Zn, and 79Br. A calibration using a NP suspension was applied to convert the measured Ag intensity into the number of NPs present. The determined numbers of NPs ranged from 30 to 7200 particles in an outer rim of MCS. The particle distribution was clearly correlated with the presence of 31P and 66Zn and was localized in the outer rim of proliferating cells with a width that was equal to about twice the diameter of single cells. Moreover, abundant collagens were found in the outer rim of MCSs. For only the highest seeding cell number, NPs were completely captured at the outer rim, in a natural barrier reducing particle transport, whereas Eosin (79Br) used as a probe of small molecules penetrated into the core of MCSs already after 1 min of exposure. KW - Laser ablation KW - ICP-MS KW - Nanoparticle KW - Cell KW - Speroid PY - 2019 DO - https://doi.org/10.1007/s00216-019-01827-w SN - 1618-2642 SN - 1618-2650 VL - 411 IS - 16 SP - 3497 EP - 3506 PB - Springer CY - Berlin, Heidelberg AN - OPUS4-47900 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Boyraz, B. A1 - Saatz, Jessica A1 - Pompös, I.-M. A1 - Gad, Michel A1 - Dernedde, J. A1 - Maier, A.-M. B. A1 - Moscovitz, O. A1 - Seeberger, P. H. A1 - Traub, Heike A1 - Tauber, R. T1 - Imaging Keratan Sulfate in Ocular Tissue Sections by Immunofluorescence Microscopy and LA-ICP-MS N2 - Carbohydrate-specific antibodies can serve as valuable tools to monitor alterations in the extracellular matrix resulting from pathologies. Here, the keratan sulfate-specific monoclonal antibody MZ15 was characterized in more detail by immunofluorescence microscopy as well as laser ablation ICP-MS using tissue cryosections and paraffin-embedded samples. Pretreatment with keratanase II prevented staining of samples and therefore demonstrated efficient enzymatic keratan sulfate degradation. Random fluorescent labeling and site-directed introduction of a metal cage into MZ15 were successful and allowed for a highly sensitive detection of the keratan sulfate landscape in the corneal stroma from rats and human tissue. KW - Laser ablation KW - Imaging KW - Glycosaminoglycan KW - ICP-MS KW - Immunohistochemistry KW - Immunofluorescence KW - Tissue PY - 2022 DO - https://doi.org/10.1021/acsabm.1c01240 VL - 5 IS - 2 SP - 853 EP - 861 PB - American Chemical Society CY - Washington AN - OPUS4-54341 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Arakawa, Akihiro A1 - Jakubowski, Norbert A1 - Koellensperger, G. A1 - Theiner, S. A1 - Schweikert, A. A1 - Flemig, Sabine A1 - Iwahata, D. A1 - Traub, Heike A1 - Hirata, T. T1 - Imaging of Ag NP transport through collagen-rich microstructures in fibroblast multicellular spheroids by high-resolution laser ablation inductively coupled plasma time-of-flight mass spectrometry N2 - We investigated the penetration of silver nanoparticles (Ag NPs) into a three-dimensional in vitro tissue analog using NPs with various sizes and surface coatings, and with different incubation times. A high-Resolution laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) time-of-flight (TOF) instrument was applied for imaging the distributions of elements in thin sample sections (20 μm thick). A fibroblast multicellular spheroid (MCS) was selected as the model system and cultured for more than 8 days to produce a natural barrier formed by the extracellular matrix containing collagen. The MCS was then exposed for up to 48 h to one of four types of Ag NPs (∅ 5 nm citrate coated, ∅ 20 nm citrate coated, ∅ 20 nm polyvinylpyrrolidone coated, and ∅ 50 nm citrate coated). Imaging showed that the penetration pathway was strongly related to steric networks formed by collagen fibrils, and Ag NPs with a hydrodynamic diameter of more than 41 nm were completely trapped in an outer rim of the MCSs even after incubation for 48 h. In addition, we examined the impact of these NPs on essential elements (P, Fe, Cu, and Zn) in areas of Ag NP accumulation. We observed a linear increase at the sub-femtogram level in the total concentration of Cu (fg per pixel) in samples treated with small or large Ag NPs (∅ 5 nm or ∅ 50 nm) for 48 h. KW - Nanoparticle KW - Laser ablation KW - ICP-MS KW - Imaging KW - Cell PY - 2019 DO - https://doi.org/10.1039/c9an00856j SN - 0003-2654 VL - 144 IS - 16 SP - 4935 EP - 4942 PB - Royal Society of Chemistry RSC CY - Cambridge AN - OPUS4-48531 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Rosenkranz, Daniel A1 - Kriegel, F. L. A1 - Mavrakis, E. A1 - Pergantis, S. A. A1 - Reichardt, Ph. A1 - Tentschert, J. A1 - Jakubowski, Norbert A1 - Laux, P. A1 - Panne, Ulrich T1 - Improved validation for single particle ICP-MS analysis using a pneumatic nebulizer / microdroplet generator sample introduction system for multi-mode nanoparticle determination N2 - This study reports on the development of a single-particle (sp) inductively coupled plasma mass spectrometry (ICP-MS) technique suitable for the multi-mode determination of nanoparticle (NP) metal mass fraction and number concentration. The described technique, which is based on a dual inlet System consisting of a pneumatic nebulizer (PN) and a microdroplet generator (MDG), allows for the sequential introduction of ionic metal calibrant solutions and nanoparticle suspensions via all combinations of the two inlets; thus allowing for a combination of three independent modes of analysis. A novel interface, assembled using standard analytical components (a demountable quartz ICP-MS torch, flexible nonconducting silicon tubing and various connectors), was used to interface the dual inlet system to an ICP-MS. The interface provided improved functionality, compared to a previous design. It is now possible to conveniently exchange and introduce standard solutions and samples via all inlet combinations, analyze them, and also wash the sample inlet systems while the whole setup is still connected to an operating ICP-MS. This setup provided seamless and robust operation in a total of three analysis modes, i.e. three ways to independently determine the metal mass fraction and NP number concentration. All three analyses modes could be carried out within a single analytical run lasting approximately 20 min. The unique feature of the described approach is that each analysis mode is based on a different. KW - Nanomaterials KW - Nanoparticles KW - Single particle ICP-MS KW - Microdroplet generator PY - 2020 DO - https://doi.org/10.1016/j.aca.2019.11.043 VL - 1099 SP - 16 EP - 25 PB - Elsevier B.V. AN - OPUS4-50361 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Garcia-Fernandez, J. A1 - Turiel, D. A1 - Bettmer, J. A1 - Jakubowski, Norbert A1 - Panne, Ulrich A1 - Rivas Garcia, L. A1 - Llopis, J. A1 - Sanchez-Gonzalez, C. A1 - Montes-Bayon, M. T1 - In vitro and in situ experiments to evaluate the biodistribution and cellular toxicity of ultrasmall iron oxide nanoparticles potentially used as oral iron supplements N2 - Well-absorbed iron-based nanoparticulated materials are a promise for the oral management of iron deficient anemia. In this work, a battery of in vitro and in situ experiments are combined for the evaluation of the uptake, distribution and toxicity of new synthesized ultrasmall (4 nm core) Fe2O3 nanoparticles coated with tartaric/adipic acid with potential to be used as oral Fe supplements. First, the in vitro simulated gastric acid solubility studies by TEM and HPLC-ICP-MS reveal a partial reduction of the core size of about 40% after 90 min at pH3. Such scenario confirms the arrival of the nanoparticulate material in the small intestine. In the next step, the in vivo absorption through the small intestine by intestinal perfusion experiments is conducted using the sought nanoparticles in Wistar rats. The quantification of Fe in the NPs Suspension before and after perfusion shows Fe absorption levels above 79%, never reported for other Fe treatments. Such high absorption levels do not seem to compromise cell viability, evaluated in enterocytes-like models (Caco-2 and HT-29) using cytotoxicity, ROS production, genotoxicity and lipid peroxidation tests. Moreover, regional differences in terms of Fe concentration are obtained among different parts of the small intestine as duodenum>jejunum>ileum. Complementary transmission electron microscopy (TEM) images show the presence of the intact particles around the intestinal microvilli without significant tissue damage. These studies show the high potential of these NP preparations for their use as oral management of anemia. KW - Iron nanoparticles KW - Anemia KW - ICP-MS KW - In vitro KW - In situ PY - 2020 DO - https://doi.org/10.1080/17435390.2019.1710613 VL - 14 IS - 3 SP - 388 EP - 403 PB - Taylor & Francis Online CY - London AN - OPUS4-50314 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Drescher, D. A1 - Büchner, T. A1 - Schrade, P. A1 - Traub, Heike A1 - Werner, S. A1 - Guttmann, P. A1 - Bachmann, S. A1 - Kneipp, J. T1 - Influence of Nuclear Localization Sequences on the Intracellular Fate of Gold Nanoparticles N2 - Directing nanoparticles to the nucleus by attachment of nuclear localization sequences (NLS) is an aim in many applications. Gold nanoparticles modified with two different NLS were studied while crossing barriers of intact cells, including uptake, endosomal escape, and nuclear translocation. By imaging of the nanoparticles and by characterization of their molecular interactions with surface-enhanced Raman scattering (SERS), it is shown that nuclear translocation strongly depends on the particular incubation conditions. After an 1 h of incubation followed by a 24 h chase time, 14 nm gold particles carrying an adenoviral NLS are localized in endosomes, in the cytoplasm, and in the nucleus of fibroblast cells. In contrast, the cells display no nanoparticles in the cytoplasm or nucleus when continuously incubated with the nanoparticles for 24 h. The ultrastructural and spectroscopic data indicate different processing of NLS-functionalized particles in endosomes compared to unmodified particles. NLS functionalized nanoparticles form larger intraendosomal aggregates than unmodified gold nanoparticles. SERS spectra of cells with NLS-functionalized gold nanoparticles contain bands assigned to DNA and were clearly different from those with unmodified gold nanoparticles. The different processing in the presence of an NLS is influenced by a continuous exposure of the cells to nanoparticles and an ongoing nanoparticle uptake. This is supported by mass-spectrometry-based quantification that indicates enhanced uptake of NLS-functionalized nanoparticles compared to unmodified particles under the same conditions. The results contribute to the optimization of nanoparticle analysis in cells in a variety of applications, e.g., in theranostics, biotechnology, and bioanalytics. KW - Nanoparticle KW - Laser ablation KW - SERS KW - ICP-MS PY - 2021 DO - https://doi.org/10.1021/acsnano.1c04925 SN - 1936-086X VL - 15 IS - 9 SP - 14838 EP - 14849 PB - American Chemical Society AN - OPUS4-54047 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 - JOUR A1 - Vogl, Jochen A1 - Rosner, M. A1 - Kasemann, S. A. A1 - Kraft, R. A1 - Meixner, A. A1 - Noordmann, J. A1 - Rabb, S. A1 - Rienitz, O. A1 - Schuessler, J. A. A1 - Tatzel, Michael A1 - Vocke, R. D. T1 - Intercalibration of Mg isotope delta scales and realisation of SI traceability for Mg isotope amount ratios and isotope delta values N2 - The continuous improvement of analytical procedures using multi-collector technologies in ICP-mass spectrometry has led to an increased demand for isotope standards with improved homogeneity and reduced measurement uncertainty. For magnesium, this has led to a variety of available standards with different quality levels ranging from artefact standards to isotope reference materials certified for absolute isotope ratios. This required an intercalibration of all standards and reference materials, which we present in this interlaboratory comparison study. The materials Cambridge1, DSM3, ERMAE143, ERM-AE144, ERM-AE145, IRMM-009 and NIST SRM 980 were cross-calibrated with expanded measurement uncertainties (95% confidence level) of less than 0.030‰ for the δ25/24Mg values and less than 0.037‰ for the δ26/24Mg values. Thus, comparability of all magnesium isotope delta (δ) measurements based on these standards and reference materials is established. Further, ERM-AE143 anchors all magnesium δ-scales to absolute isotope ratios and therefore establishes SI traceability, here traceability to the SI base unit mole. This applies especially to the DSM3 scale, which is proposed to be maintained. With ERM-AE144 and ERM-AE145, which are product and educt of a sublimation-condensation process, for the first time a set of isotope reference materials is available with a published value for the apparent triple isotope fractionation exponent θapp, the fractionation relationship ln α(25/24Mg)/ln α(26/24Mg). KW - Delta scale KW - Traceability KW - Scale anchor KW - Absolute isotope ratio KW - Comparability KW - Triple isotope fractionation PY - 2020 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-511557 DO - https://doi.org/10.1111/ggr.12327 SN - 1751-908X VL - 44 IS - 3 SP - 439 EP - 457 PB - Wiley-Blackwell CY - Oxford AN - OPUS4-51155 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Gehrenkemper, Lennart A1 - Rühl, Isabel A1 - Westphalen, Tanja A1 - Simon, Fabian A1 - von der Au, Marcus A1 - Cossmer, Antje A1 - Meermann, Björn T1 - Investigating the uptake and fate of per- and polyfluoroalkylated substances (PFAS) in bean plants (Phaseolus vulgaris): comparison between target MS and sum parameter analysis via HR-CS-GFMAS N2 - AbstractIn this study, we present a screening method based on molecular absorption spectrometry to study PFAS uptake and fate in plants. To evaluate the suitability of this method we analyzed plant extracts with molecular absorption spectrometry (MAS) as well as liquid chromatography–tandem mass spectrometry (LC–MS/MS) for mass balance studies (w(F)). French bean plants (Phaseolus vulgaris) were grown on soil spiked using eight PFAS substances that vary in chain length and functional group composition. Specifically, these include three short-chained (C4–C5), five long-chained (C7–C10) carboxylic acids, one sulfonic acid and one sulfonic amide moieties. To investigate substance-specific PFAS uptake systematically, PFAS were spiked as single substance spike. Additionally, we studied one mixture of the investigated substances in equal proportions regarding w(F) and four PFAS mixtures of unknown composition. After 6 weeks, the plants were separated into four compartments. We analyzed the four compartments as well as the soil for extractable organically bound fluorine (EOF) by high resolution-continuum source-graphite furnace-molecular absorption spectrometry (HR-CS-GFMAS) as well as for sum of ten target-PFAS by LC–MS/MS. All three short-chained PFAS perfluorobutanoic acid (PFBA), perfluorobutanoic sulfonic acid (PFBS) and perfluoropentanoic acid (PFPeA) were determined in high concentrations mainly in the fruits of the investigated plants while long-chained PFAS perfluorononanoic acid (PFNA) and perfluorodecanoic acid (PFDA) were mainly determined in roots. PFBS was determined in remarkably high concentrations in leaves compartment by both quantification methods. Overall, comprehensive results of single substance spikes were in good agreement for both methods except for a few cases. Hence, two phenomena were identified: for mixed PFAS spikes of unknown composition huge differences between EOF and sum of target PFAS were observed with systematically higher EOF values. Overall, both methods indicate comparable results with MS being more reliable for known PFAS contamination and MAS being more valuable to identify PFAS exposure of unknown composition. Graphical Abstract KW - Pollution PY - 2023 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-589394 DO - https://doi.org/10.1186/s12302-023-00811-7 VL - 35 IS - 104 SP - 1 EP - 13 PB - Springer Science and Business Media LLC AN - OPUS4-58939 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Abbas, Ioana M. A1 - Vranic, M. A1 - Hoffmann, Holger A1 - El-Khatib, Ahmed H. A1 - Montes-Bayón, M. A1 - Möller, H. M. A1 - Weller, Michael G. T1 - Investigations of the copper peptide hepcidin-25 by LC-MS/MS and NMR (+) N2 - Hepcidin-25 was identified as the main iron regulator in the human body, and it by binds to the sole iron-exporter ferroportin. Studies showed that the N-terminus of hepcidin is responsible for this interaction, the same N-terminus that encompasses a small copper(II)-binding site known as the ATCUN (amino-terminal Cu(II)- and Ni(II)-binding) motif. Interestingly, this copper-binding property is largely ignored in most papers dealing with hepcidin-25. In this context, detailed investigations of the complex formed between hepcidin-25 and copper could reveal insight into its biological role. The present work focuses on metal-bound hepcidin-25 that can be considered the biologically active form. The first part is devoted to the reversed-phase chromatographic separation of copper-bound and copper-free hepcidin-25 achieved by applying basic mobile phases containing 0.1% ammonia. Further, mass spectrometry (tandem mass spectrometry (MS/MS), high-resolution mass spectrometry HRMS)) and nuclear magnetic resonance (NMR) spectroscopy were employed to characterize the copper-peptide. Lastly, a three-dimensional (3D)model of hepcidin-25with bound copper(II) is presented. The identification of metal complexes and potential isoforms and isomers, from which the latter usually are left undetected by mass spectrometry, led to the conclusion that complementary analytical methods are needed to characterize a peptide calibrant or reference material comprehensively. Quantitative nuclear magnetic resonance (qNMR), inductively-coupled plasma mass spectrometry (ICP-MS), ion-mobility spectrometry (IMS) and chiral amino acid analysis (AAA) should be considered among others. KW - Metalloprotein KW - Peptide KW - Chromatography KW - High pH KW - Mobile phase KW - Metrology KW - Purity KW - Reference material KW - ATCUN KW - Copper KW - Nickel PY - 2018 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-457796 UR - http://www.mdpi.com/1422-0067/19/8/2271 DO - https://doi.org/10.3390/ijms19082271 SN - 1422-0067 VL - 19 IS - 8 SP - 2271, 1 EP - 16 PB - MDPI CY - Basel AN - OPUS4-45779 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kader, A. A1 - Kaufmann, Jan Ole A1 - Mangarova, D. B. A1 - Moeckel, J. A1 - Brangsch, J. A1 - Adams, L. C. A1 - Zhao, J. A1 - Reimann, C. A1 - Saatz, Jessica A1 - Traub, Heike A1 - Buchholz, R. A1 - Karst, U. A1 - Hamm, B. A1 - Makowski, M. R. T1 - Iron Oxide Nanoparticles for Visualization of Prostate Cancer in MRI N2 - Prostate cancer (PCa) is one of the most common cancers in men. For detection and diagnosis of PCa, non-invasive methods, including magnetic resonance imaging (MRI), can reduce the risk potential of surgical intervention. To explore the molecular characteristics of the tumor, we investigated the applicability of ferumoxytol in PCa in a xenograft mouse model in two different tumor volumes, 500 mm3 and 1000 mm3. Macrophages play a key role in tumor progression, and they are able to internalize iron-oxide particles, such as ferumoxytol. When evaluating T2*-weighted sequences on MRI, a significant decrease of signal intensity between pre- and post-contrast images for each tumor volume (n = 14; p < 0.001) was measured. We, furthermore, observed a higher signal loss for a tumor volume of 500 mm3 than for 1000 mm3. These findings were confirmed by histological examinations and laser ablation inductively coupled plasma-mass spectrometry. The 500 mm3 tumors had 1.5% iron content (n = 14; sigma = 1.1), while the 1000 mm3 tumors contained only 0.4% iron (n = 14; sigma = 0.2). In vivo MRI data demonstrated a correlation with the ex vivo data (R2 = 0.75). The results of elemental analysis by inductively coupled plasma-mass spectrometry correlated strongly with the MRI data (R2 = 0.83) (n = 4). Due to its long retention time in the blood, biodegradability, and low toxicity to patients, ferumoxytol has great potential as a contrast agent for visualization PCa. KW - Imaging KW - Nanoparticle KW - Cancer KW - Iron oxide KW - ICP-MS KW - Magnetic resonance imaging PY - 2022 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-550075 DO - https://doi.org/10.3390/cancers14122909 VL - 14 IS - 12 SP - 1 EP - 13 PB - MDPI CY - Basel, Switzerland AN - OPUS4-55007 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Vogl, Jochen A1 - Rosner, M. A1 - Curbera, J. A1 - Peltz, U. A1 - Peplinski, Burkhard T1 - Lead isotope analysis in magic artefacts from the Berlin museums N2 - A set of 59 ancient magical artefacts, mainly made of lead, was selected from the collections of the Staatliche Museen zu Berlin in order to unravel their origins. All the selected artefacts have been studied for their Pb isotope compositions, which covered the whole range of the Mediterranean ore deposits. However, the majority (≈86%) were made of lead matching the small compositional range of the Laurion ore deposits. Only eight out of the 59 artefacts were made of recycled lead or lead from other ore deposits. Additionally, all but two were approximately dated based on their inscriptions. The lead isotopic composition together with information obtained from the inscriptions, the resulting dating, the context of the find and the known history of each item allowed us to gain more detailed information about the origins of these magical artefacts. The Attic provenance of 36 curse tablets was confirmed, whereas for 11 curse tablets previously classified as non-Attic, the provenance was either confirmed and specified (six artefacts) or changed to Attic (five artefacts). Surprisingly, the majority (six out of eight) of the analysed curse tablets from the Egyptian collection showed a lead isotopic composition closely matching that of Laurion. A Laurion-like lead isotopic composition was also observed for three of the four analysed oracular tablets from Dodona. Together with the dating information, this points to Laurion as the major and dominant lead source in the Aegean, at least during the fourth–third century B.C. The few curse tablets from earlier than the fourth–third century B.C. point to the use of multiple and thus isotopically more variable lead sources compared with the Roman times. KW - Lead isotopes KW - Pb isotopes KW - Greek curse tablets KW - Antikensammlung Berlin KW - Ägyptisches Museum Berlin PY - 2018 DO - https://doi.org/10.1007/s12520-016-0445-6 SN - 1866-9557 SN - 1866-9565 VL - 10 IS - 5 SP - 1111 EP - 1127 PB - Springer Verlag CY - Berlin AN - OPUS4-45628 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Vogel, Christian A1 - Roesch, Philipp A1 - Wittwer, Philipp A1 - Piechotta, Christian A1 - Lisec, Jan A1 - Sommerfeld, Thomas A1 - Kluge, Stephanie A1 - Herzel, Hannes A1 - Huthwelker, T. A1 - Borca, C. A1 - Simon, Franz-Georg T1 - Levels of per- and polyfluoroalkyl substances (PFAS) in various wastewater-derived fertilizers - Analytical investigations from different perspectives N2 - Solid wastewater-based fertilizers were screened for per- and polyfluoroalkyl substances (PFAS) by the extractable organic fluorine (EOF) sum parameter method. The EOF values for ten sewage sludges from Germany and Switzerland range from 154 to 7209 mg kg−1. For thermal treated sewage sludge and struvite the EOF were lower with values up to 121 mg kg−1. Moreover, the application of PFAS targeted and suspect screening analysis of selected sewage sludge samples showed that only a small part of the EOF sum parameter values can be explained by the usually screened legacy PFAS. The hitherto unknown part of EOF sum parameter contains also fluorinated pesticides, pharmaceutical and aromatic compounds. Because these partly fluorinated compounds can degrade to (ultra-)short PFAS in wastewater treatment plants they should be considered as significant sources of organic fluorine in the environment. The combined results of sum parameter analysis and suspect screening reveal the need to update current regulations, such as the German fertilizer ordinance, to focus not solely on a few selected PFAS such as perfluorooctane sulfonic acid (PFOS) and perfluorooctanoic acid (PFOA) but consider an additional sum parameter approach as a more holistic alternative. Moreover, diffusion gradient in thin-films (DGT) passive samplers were utilized as an alternative simplified extraction method for PFAS in solid wastewater-based fertilizers and subsequently quantified via combustion ion chromatography. However, the DGT method was less sensitive and only comparable to the EOF values of the fertilizers in samples with >150 mg kg−1, because of different diffusion properties for various PFAS, but also kinetic exchange limitations. KW - Combustion ion chromatography KW - Per- and polyfluoroalkyl substances (PFAS) KW - Sewage sludge KW - Fertilizer PY - 2023 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-583429 DO - https://doi.org/10.1039/d3va00178d SN - 2754-7000 VL - 2 IS - 10 SP - 1436 EP - 1445 PB - Royal Society of Chemistry (RSC) CY - London AN - OPUS4-58342 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Spallanzani, Roberta A1 - Koga, K. A1 - Cichy, S. A1 - Wiedenbeck, M. A1 - Schmidt, B. A1 - Oelze, Marcus A1 - Wilke, M. T1 - Lithium and boron difusivity and isotopic fractionation in hydrated rhyolitic melts N2 - Lithium and boron are trace components of magmas, released during exsolution of a gas phase during volcanic activity. In this study, we determine the difusivity and isotopic fractionation of Li and B in hydrous silicate melts. Two glasses were synthesized with the same rhyolitic composition (4.2 wt% water), having diferent Li and B contents; these were studied in difusion-couple experiments that were performed using an internally heated pressure vessel, operated at 300 MPa in the temperature range 700–1250 °C for durations from 0 s to 24 h. From this we determined activation energies for Li and B difusion of 57±4 kJ/mol and 152±15 kJ/mol with pre-exponential factors of 1.53 × 10–7 m2/s and 3.80× 10–8 m2 /s, respectively. Lithium isotopic fractionation during difusion gave β values between 0.15 and 0.20, whereas B showed no clear isotopic fractionation. Our Li difusivities and isotopic fractionation results difer somewhat from earlier published values, but overall confrm that Li difusivity increases with water content. Our results on B difusion show that similarly to Li, B mobility increases in the presence of water. By applying the Eyring relation, we confrm that B difusivity is limited by viscous fow in silicate melts. Our results on Li and B difusion present a new tool for understanding degassing-related processes, ofering a potential geospeedometer to measure volcanic ascent rates. KW - Hydrated silicate melts KW - Stable isotopes KW - Diffusion KW - Isotopic fractionation PY - 2022 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-554496 DO - https://doi.org/10.1007/s00410-022-01937-2 VL - 177 IS - 8 SP - 1 EP - 17 PB - Springer AN - OPUS4-55449 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Haeckel, A. A1 - Ascher, Lena A1 - Beindorff, N. A1 - Prasad, S. A1 - Garczynska, K. A1 - Guo, J. A1 - Schellenberger, E. T1 - Long‑circulating XTEN864‑annexin A5 fusion protein for phosphatidylserine‑related therapeutic applications N2 - Annexin A5 (anxA5) is a marker for apoptosis, but has also therapeutic potential in cardiovascular diseases, cancer, and, due to apoptotic mimicry, against dangerous viruses, which is limited by the short blood circulation. An 864-amino-acid XTEN polypeptide was fused to anxA5. XTEN864-anxA5 was expressed in Escherichia coli and purified using XTEN as tag. XTEN864-anxA5 was coupled with DTPA and indium-111. After intravenous or subcutaneous injection of 111In-XTEN864-anxA5, mouse blood samples were collected for blood half-life determination and organ samples for biodistribution using a gamma counter. XTEN864-anxA5 was labeled with 6S-IDCC to confirm binding to apoptotic cells using flow cytometry. To demonstrate targeting of atherosclerotic plaques, XTEN864-anxA5 was labeled with MeCAT(Ho) and administered intravenously to atherosclerotic ApoE−/−mice. MeCAT(Ho)-XTEN864-anxA5 was detected together with MeCAT(Tm)-MAC-2 macrophage antibodies by imaging mass cytometry (CyTOF) of aortic root sections. The ability of anxA5 to bind apoptotic cells was not affected by XTEN864. The blood half-life of XTEN864-anxA5 was 13 h in mice after IV injection, markedly longer than the 7-min half-life of anxA5. 96 h after injection, highest amounts of XTEN864-anxA5 were found in liver, spleen, and kidney. XTEN864-anxA5 was found to target the adventitia adjacent to atherosclerotic plaques. XTEN864-anxA5 is a long-circulating fusion protein that can be efficiently produced in E. coli and potentially circulates in humans for several days, making it a promising therapeutic drug. KW - Programmed cell death KW - LA/ICP-MS Imaging KW - Medicinal application PY - 2021 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-533811 DO - https://doi.org/10.1007/s10495-021-01686-w VL - 26 IS - 9-10 SP - 534 EP - 547 PB - Springer AN - OPUS4-53381 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Lopez-Serrano Oliver, Ana A1 - Haase, A. A1 - Peddinghaus, A. A1 - Wittke, D. A1 - Jakubowski, Norbert A1 - Luch, A. A1 - Grützkau, A. A1 - Baumgart, S. T1 - Mass cytometry enabling absolute and fast quantification of silver nanoparticle uptake at the single cell level N2 - In the last decades, significant efforts have been made to investigate possible cytotoxic effects of metallic nanoparticles (NPs). Methodologies enabling precise information regarding uptake and intracellular distribution of NPs at the single cell level remain to be established. Mass cytometry (MC) has been developed for high-dimensional single cell analyses and is a promising tool to quantify NP−cell interactions. Here, we aim to establish a new MC-based quantification procedure to receive absolute numbers of NPs per single cell by using a calibration that considers the specific transmission efficiency (TE) of suspended NPs. The current MC-quantification strategy accept TE values of complementary metal solutions. In this study, we demonstrate the different transmission behavior of 50 nm silver NPs (AgNP) and silver nitrate solution. We have used identical AgNPs for calibration as for in vitro-differentiated macrophages (THP-1 cell line) in a time- and dose-dependent manner. Our quantification relies on silver intensities measuring AgNPs in the same detection mode as the cells. Results were comparable with the TE quantification strategy using AgNPs but differed when using ionic silver. Furthermore, intact and digested cell aliquots were measured to investigate the impact of MC sample processing on the amount of AgNPs/cell. Taken together, we have provided a MC-specific calibration procedure to precisely calculate absolute numbers of NPs per single cell. Combined with its unique feature of multiplexing up to 50 parameters, MC provides much more information on the single cell level than single cell-inductively coupled plasma mass spectrometry (SC-ICP-MS) and, therefore, offers new opportunities in nanotoxicology. KW - ICP-MS KW - Nanoparticle KW - Cell KW - SC-ICP-MS KW - Mass cytometry PY - 2019 DO - https://doi.org/10.1021/acs.analchem.9b01870 SN - 0003-2700 SN - 1520-6882 VL - 91 IS - 18 SP - 11514 EP - 11519 PB - American Chemical Society (ACS Publications) CY - Washington AN - OPUS4-48986 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Meermann, Björn A1 - Lisec, Jan A1 - Jaeger, Carsten A1 - Saatz, Jessica A1 - Traub, Heike A1 - von der Au, Marcus T1 - Mehr Analyten, kleinere Proben N2 - Molekülmassenspektrometrie entwickelt sich weg von klassischer Target- hin zu Nontarget-Analytik. Elementmassenspektrometrie liefert hohe Ortsauflösung beim Element-Imaging und analysiert einzelne Zellen. Aufgrund der Fortschritte bei den Geräten für Timeof-Flight-Massenspektrometrie mit induktiv gekoppeltem Plasma (ICPToF-MS) lässt sich das gesamte Periodensystem der Elemente in kurzen transienten Signalen quasi-simultan massenspektrometrisch erfassen. KW - Massenspektrometrie KW - Non-target KW - ICP-ToF-MS KW - Laser Ablation/Imaging PY - 2021 VL - 69 IS - Juni SP - 64 EP - 67 PB - Wiley-VCH AN - OPUS4-52800 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Sieber, M. J. A1 - Wilke, M. A1 - Appelt, O. A1 - Oelze, Marcus A1 - Koch-Müller, M. T1 - Melting relations of Ca–Mg carbonates and trace element signature of carbonate melts up to 9 GPa – A proxy for melting of carbonated mantle lithologies N2 - The most profound consequences of the presence of Ca–Mg carbonates (CaCO3–MgCO3) in the Earth’s upper mantle may be to lower the melting temperatures of the mantle and control the melt composition. Low-degree partial melting of a carbonate-bearing mantle produces CO2-rich, silica-poor melts compositionally imposed by the melting relations of carbonates. Thus, understanding the melting relations in the CaCO3–MgCO3 system facilitates the interpretation of natural carbonate-bearing silicate systems. We report the melting relations of the CaCO3–MgCO3 system and the partition coefficient of trace elements between carbonates and carbonate melt from experiments at high pressure (6 and 9 GPa) and temperature (1300–1800 ◦C) using a rocking multi-anvil press. In the absence of water, Ca–Mg carbonates are stable along geothermal gradients typical of subducting slabs. Ca–Mg carbonates (∼ Mg0.1–0.9Ca0.9–0.1CO3) partially melt beneath mid-ocean ridges and in plume settings. Ca–Mg carbonates melt incongruently, forming periclase crystals and carbonate melt between 4 and 9 GPa. Furthermore, we show that the rare earth element (REE) signature of Group-I kimberlites, namely strong REE fractionation and depletion of heavy REE relative to the primitive mantle, is resembled by carbonate melt in equilibrium with Ca-bearing magnesite and periclase at 6 and 9 GPa. This suggests that the dolomite–magnesite join of the CaCO3–MgCO3 system might be useful to approximate the REE signature of carbonate-rich melts parental to kimberlites. KW - High pressure experiments KW - Laser Ablation PY - 2022 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-561197 DO - https://doi.org/10.5194/ejm-34-411-2022 SN - 0935-1221 VL - 34 IS - 5 SP - 411 EP - 424 PB - Copernicus Publications CY - Göttingen AN - OPUS4-56119 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 - JOUR A1 - Climent Terol, Estela A1 - Hecht, Mandy A1 - Witthuhn, Heike A1 - Gawlitza, Kornelia A1 - Rurack, Knut T1 - Mix‐&‐read determination of Mercury(II) at trace levels with hybrid mesoporous silica materials incorporating fluorescent probes by a simple mix‐&‐load technique N2 - The synthesis, characterization, and application of mesoporous materials containing boron–dipyrromethene (BODIPY) moieties that allow the sensitive and selective detection of HgII in aqueous environments by fluorescence enhancement is reported. For this purpose, BODIPY dye I containing a thia‐aza crown ether receptor as the fluorescent probe for the detection of HgII in aqueous environments is encapsulated into mesoporous materials to avoid self‐quenching or aggregation in water. Determination of HgII is accomplished within a few seconds with high selectivity and sensitivity, reaching a limit of detection of 12 ppt. The determination of trace amounts of HgII in natural waters and in fish extracts is demonstrated by using our sensing material. The incorporation of the material into several μ‐PAD strips yields a portable, cheap, quick, and easy‐to‐handle tool for trace HgII analysis in water. KW - Dyes/pigments KW - Test strips KW - Mesoporous materials KW - Mercury KW - Fluorescence PY - 2018 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-460138 DO - https://doi.org/10.1002/open.201800277 SN - 2191-1363 VL - 7 IS - 12 SP - 957 EP - 968 PB - Wiley-VCH CY - Weinheim AN - OPUS4-46013 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Grunert, B. A1 - Saatz, Jessica A1 - Hoffmann, Katrin A1 - Appler, F. A1 - Lubjuhn, Dominik A1 - Jakubowski, Norbert A1 - Resch-Genger, Ute A1 - Emmerling, Franziska A1 - Briel, A. T1 - Multifunctional rare-earth element nanocrystals for cell labeling and multimodal imaging N2 - In this work, we describe a simple solvothermal route for the synthesis of Eu3+-doped gadolinium orthovanadate nanocrystals (Eu:GdVO4−PAA) functionalized with poly(acrylic)acid (PAA), that are applicable as cell labeling probes for multimodal cellular imaging. The Eu3+ doping of the vanadate matrix provides optical functionality, due to red photoluminescence after illumination with UV light. The Gd3+ ions of the nanocrystals reduce the T1 relaxation time of surrounding water protons, allowing these nanocrystals to act as a positive MRI contrast agent with a r1 relaxivity of 1.97 mM−1 s−1. Low background levels of Eu3+, Gd3+, and V5+ in biological systems make them an excellent label for elemental microscopy by Laser Ablation (LA)-ICP-MS. Synthesis resulted in polycrystalline nanocrystals with a hydrodynamic diameter of 55 nm and a crystal size of 36.7 nm, which were further characterized by X-ray diffraction (XRD), photoluminescence spectroscopy (PL) and transmission electron microscopy (TEM). The multifunctional nanocrystals were subsequently used for intracellular labeling of both human adipose-derived stem cells (MSCs) and A549 (adenocarcinomic human alveolar basal epithelial) cells. KW - Bioimaging KW - Nanoparticle KW - Multimodal KW - Lanthanide PY - 2018 DO - https://doi.org/10.1021/acsbiomaterials.8b00495 SN - 2373-9878 VL - 4 IS - 10 SP - 3578 EP - 3587 PB - ACS Publications CY - Washington, USA AN - OPUS4-46244 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Laux, P. A1 - Tentschert, J. A1 - Riebeling, Ch. A1 - Braeuning, A. A1 - Creutzenberg, O. A1 - Epp, A. A1 - Fessard, V. A1 - Haas, K.-H. A1 - Haase, A. A1 - Hund-Rinke, K. A1 - Jakubowski, Norbert A1 - Kearns, P. A1 - Lampen, A. A1 - Rauscher, H. A1 - Schoonjans, R. A1 - Störmer, A. A1 - Thielmann, A. A1 - Mühle, U. A1 - Luch, A. T1 - Nanomaterials: certain aspects of application, risk assessment and risk communication N2 - Development and market introduction of new nanomaterials trigger the need for an adequate risk assessment of such products alongside suitable risk communication measures. Current application of classical and new nanomaterials is analyzed in context of regulatory requirements and standardization for chemicals, food and consumer products. The challenges of nanomaterial characterization as the main bottleneck of risk assessment and regulation are presented. In some areas, e.g., quantification of nanomaterials within complex matrices, the establishment and adaptation of analytical techniques such as laser ablation inductively coupled plasma mass spectrometry and others are potentially suited to meet the requirements. As an example, we here provide an approach for the reliable characterization of human exposure to nanomaterials resulting from food packaging. Furthermore, results of nanomaterial toxicity and ecotoxicity testing are discussed, with concluding key criteria such as solubility and fiber rigidity as important parameters to be considered in material development and regulation. Although an analysis of the public opinion has revealed a distinguished rating depending on the particular field of application, a rather positive perception of nanotechnology could be ascertained for the German public in general. An improvement of material characterization in both toxicological testing as well as end-product control was concluded as being the main obstacle to ensure not only safe use of materials, but also wide acceptance of this and any novel technology in the general public. KW - Nanomaterials KW - Toxicity KW - Ecotoxicity KW - Standardization KW - Exposure PY - 2018 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-441096 DO - https://doi.org/10.1007/s00204-017-2144-1 VL - 92 IS - 1 SP - 121 EP - 141 PB - Springer AN - OPUS4-44109 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Zweigle, J. A1 - Capitain, C. A1 - Simon, Fabian Michael A1 - Roesch, Philipp A1 - Bugsel, B. A1 - Zwiener, C. T1 - Non-extractable PFAS in functional textiles − Characterization by complementary methods: oxidation, hydrolysis, and fluorine sum parameters N2 - Per- and polyfluoroalkyl substances (PFAS) are widely used for durable water-repellent finishing of different fabrics and textiles like outdoor clothing, carpets, medical textiles and more. Existing PFAS extraction techniques followed by target analysis are often insufficient in detecting widely used side-chain fluorinated polymers (SFPs) that are barely or non-extractable. SFPs are typically copolymers consisting of a non-fluorinated backbone with perfluoroalkyl side-chains to obtain desired properties. We compared the accessible analytical information and performance of complementary techniques based on oxidation (dTOP assay, PhotoTOP), hydrolysis (THP assay), standard extraction, extractable organic fluorine (EOF), and total fluorine (TF) with five functional textiles and characterized 7 further textiles only by PhotoTOP oxidation. The results show that when applied directly to textile samples, oxidation by dTOP and PhotoTOP and also hydrolysis by the THP are able to capture large fractions of the TF in form of perfluoroalkyl side-chains present in the textiles while methods relying on extracts (EOF, target and non-target analysis) were much lower (e.g., factor ~25-50 lower). The conversion of large fractions of the measured TF into PFCAs or FTOHs from fluorinated side chains is in contrast to previous studies. Concentrations ranged from 84% at all sampling sites. Mass balance approach (ii) showed that the unidentified EOF (uEOF) fraction increased over time from82% (2005) to 99% (2019). Furthermore, along the river courses the uEOF increased. In the combined mass balance approach (iii) using 4 different analytical approaches EOF fractions were further unraveled. The EOF pattern was fully explainable at the sampling sites at Saar and Elbe rivers. For the time resolved analysis, an increased proportion of the EOF was now explainable. However, still 27% of the EOF for the time resolved analysis and 25% of the EOF for the spatial resolved analysis remained unknown. Therefore, in a complementary approach, both the EOF and dTOPA reveal unknown gaps in the PFAS mass balance and are valuable contributions to PFAS risk assessment. Further research is needed to identify organofluorines summarized in the EOF parameter. KW - PFAS KW - HR-CS-GFMAS KW - Fluorine KW - SPM KW - LC-MS/MS PY - 2023 DO - https://doi.org/10.1016/j.scitotenv.2023.163753 SN - 1879-1026 SN - 0048-9697 VL - 885 SP - 1 EP - 12 PB - Elsevier Science CY - Amsterdam AN - OPUS4-57429 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Loehr, Konrad A1 - Jakubowski, Norbert A1 - Wanka, Antje Jutta A1 - Traub, Heike A1 - Panne, Ulrich T1 - Quantification of metals in single cells by LA-ICP-MS comparison of single spot analysis and imaging N2 - LA-ICP-MS is increasingly used for single cell analysis in two different detection modes using either the imaging mode with subcellular resolution or alternatively single spot analysis of cells with a larger laser spot size. This study compares the analytical figures of merit of both detection modes (signal to noise, precision, accuracy, throughput), as well as ease of operation and data evaluation. Adherent 3T3 fibroblast cells were stained with two metal dyes (mDOTA-Ho, Ir-DNA-intercalator) and several dozen cells were measured using both modes. We found a ten times higher throughput for single spot analysis, which has as well a straightforward data analysis, shortening the total analysis time further. The signal to noise ratio for single spot analysis was found to be slightly better compared to the signal to noise of pixels in imaging. The mean metal intensity per single cell differed by only 10% between both modes and obtained distributions were found to show no statistically significant differences. Using matrix matched calibration based on standards spotted onto nitrocellulose membrane, we achieved detection limits (10 σ) of 12 fg for Ir and 30 fg for Ho and quantified 57 ± 35 fg Ir and 1,192 ± 707 fg Ho per single cell. Compared to a conventional ICP-MS measurement of a digest of ~60,000 cells, 54 % of Ir content and 358 % Ho content was found using quantitative LA-ICP-MS. The difference might be a consequence of the two metal dyes binding to different structures of the cell and therefore might behave differently in sample preparation for conventional and LA-ICP-MS. KW - Single cell analysis KW - LA-ICP-MS PY - 2018 DO - https://doi.org/10.1039/c8ja00191j SN - 0267-9477 SN - 1364-5544 VL - 33 IS - 9 SP - 1579 EP - 1587 PB - Royal Society of Chemistry AN - OPUS4-45903 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Löhr, Konrad A1 - Traub, Heike A1 - Wanka, Antje Jutta A1 - Panne, Ulrich A1 - Jakubowski, Norbert T1 - Quantification of metals in single cells by LA-ICP-MS: Comparison of single spot analysis and imaging N2 - LA-ICP-MS is increasingly used for single cell analysis in two different detection modes using either the imaging mode with subcellular resolution or alternatively single spot analysis of cells with a larger laser spot size. This study compares the analytical figures of merit of both detection modes (signal to noise, precision, accuracy, throughput), as well as ease of operation and data evaluation. Adherent 3T3 fibroblast cells were stained with two metal dyes (mDOTA-Ho, Ir-DNA-intercalator) and several dozen cells were measured using both modes. We found a ten times higher throughput for single spot analysis, which has as well a straightforward data analysis, shortening the total analysis time further. The signal to noise ratio for single spot analysis was found to be slightly better compared to the signal to noise of pixels in imaging. The mean metal intensity per single cell differed by only 10% between both modes and obtained distributions were found to show no statistically significant differences. Using matrix matched calibration based on standards spotted onto nitrocellulose membrane, we achieved detection limits (10s) of 12 fg for Ir and 30 fg for Ho and quantified 57 +/-35 fg Ir and 1192 +/- 707 fg Ho per single cell. Compared to a conventional ICP-MS measurement of a digest of about 60000 cells, 54% of Ir content and 358% Ho content was found using quantitative LA-ICP-MS. The difference might be a consequence of the two metal dyes binding to different structures of the cell and therefore might behave differently in sample preparation for conventional and LA-ICP-MS. KW - Cells KW - Laser ablation KW - ICP-MS KW - Metals KW - Quantification PY - 2018 DO - https://doi.org/10.1039/c8ja00191j SN - 0267-9477 VL - 33 IS - 9 SP - 1579 EP - 1587 PB - RSC Royal Society of Chemistry CY - London AN - OPUS4-46441 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - López-Serrano Oliver, Ana A1 - Baumgart, S. A1 - Bremser, Wolfram A1 - Flemig, Sabine A1 - Wittke, D. A1 - Grützkau, A. A1 - Luch, A. A1 - Haase, A. A1 - Jakubowski, Norbert T1 - Quantification of silver nanoparticles taken up by single cells using inductively coupled plasma mass spectrometry in the single cell measurement mode N2 - The impact of nanoparticles, NPs, at the single cell level has become a major field of toxicological research and different analytical methodologies are being investigated to obtain biological and toxicological information to better understand the mechanisms of cell–NP interactions. Here, inductively coupled plasma mass spectrometry in the single cell measurement mode (SC-ICP-MS) is proposed to study the uptake of silver NPs, AgNPs, with a diameter of 50 nm by human THP-1 monocytes in a proof-ofprinciple experiment. The main operating parameters of SC-ICP-MS have been optimized and applied for subsequent quantitative analysis of AgNPs to determine the number of particles in individual cells using AgNP suspensions for calibration. THP-1 cells were incubated with AgNP suspensions with concentrations of 0.1 and 1 µg/mL for 4 and 24 hours. The results reveal that the AgNP uptake by THP-1 monocytes is minimal at the lower dose of 0.1 µg/mL (roughly 1 AgNP per cell was determined), whereas a large cell-to-cell variance dependent on the exposure time is observed for a 10 times higher concentration (roughly 7 AgNPs per cell). The method was further applied to monitor the AgNP uptake by THP-1 cells differentiated macrophages incubated at the same AgNP concentration levels and exposure times demonstrating a much higher AgNP uptake (roughly from 9 to 45 AgNPs per cell) that was dependent on exposure concentration and remained constant over time. The results have been compared and validated by sample digestion followed by ICP-MS analysis as well as with other alternative promising techniques providing single cell analysis. KW - Silbernanopartikel KW - ICP-MS KW - Einzelzellanalyse PY - 2018 DO - https://doi.org/10.1039/C7JA00395A SN - 0267-9477 VL - 33 IS - 7 SP - 1256 EP - 1263 PB - Royal Society of Chemistry CY - London AN - OPUS4-45473 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Phukphatthanachai, P. A1 - Panne, Ulrich A1 - Traub, Heike A1 - Pfeifer, Jens A1 - Vogl, Jochen T1 - Quantification of sulphur in copper and copper alloys by GDMS and LA-ICP-MS, demonstrating metrological traceability to the international system of units N2 - The quantification of the sulphur mass fraction in pure copper and copper alloys by GDMS and LA-ICP-MS revealed a lack of traceability mainly due to a lack of suitable certified reference materials for calibrating the instruments. Within this study GDMS and LA-ICP-MS were applied as routine analytical tools to quantify sulphur in copper samples by applying reference materials as calibrators, which were characterized for their sulphur mass fraction by IDMS beforehand. Different external calibration strategies were applied including a matrix cross type calibration. Both techniques with all calibration strategies were validated by using certified reference materials (others than those used for calibration) and good agreement with the reference values was achieved except for the matrix cross type calibration, for which the agreement was slightly worse. All measurement results were accompanied by an uncertainty statement. For GDMS, the relative expanded (k = 2) measurement uncertainty ranged from 3% to 7%, while for LA-ICP-MS it ranged from 11% to 33% when applying matrix-matched calibration in the sulphur mass fraction range between 25 mg kg-1 and 1300 mg kg-1. For cross-type calibration the relative expanded (k = 2) measurement uncertainty need to be increased to at least 12% for GDMS and to at least 54% for LA-ICP-MS to yield metrological compatibility with the reference values. The so obtained measurement results are traceable to the international system of units (SI) via IDMS reference values, which is clearly illustrated by the unbroken chain of calibrations in the metrological traceability scheme. KW - Sulfur KW - Copper KW - GDMS KW - LA-ICP-MS KW - Uncertainty KW - Traceability KW - SI PY - 2021 DO - https://doi.org/10.1039/d1ja00137j SN - 0267-9477 VL - 36 IS - 11 SP - 2404 EP - 2414 PB - Royal Society of Chemistry AN - OPUS4-53412 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - García Fernández, J. A1 - Sánchez-González, C. A1 - Bettmer, J. A1 - Llopi, J. A1 - Jakubowski, Norbert A1 - Panne, Ulrich A1 - Montes-Bayón, M. T1 - Quantitative assessment of the metabolic products of iron oxide nanoparticles to be used as iron supplements in cell cultures N2 - Iron nanoparticles (NPs) metabolism is directly associated to human health due to their use as anemia treatment and should be studied in detail in cells. Here we present a speciation strategy for the determination of the metabolic products of iron oxide nanoparticles coated by tartaric and adipic acids in enterocytes-like cell models (Caco-2 and HT-29). Such methodology is based on the use of SDS-modified reversed phase high performance liquid chromatography (HPLC) separation using inductively coupled plasma-mass spectrometry (ICP-MS) as Fe selective detector. Post-column isotope dilution analysis is used as quantification tool by adding Fe-57 as isotopically enriched standard. To assess the separation capability of the method, two different iron nanostructures: iron sucrose nanoparticles -Venofer®- used as model suspension and iron tartrate/adipate-modified nanoparticles, both of about 4 nm (core size) were evaluated. The two nanostructures were injected into the system showing good peak profiles and quantitative elution recoveries (>80%) in both cases. In addition, both nanoparticulate fractions could be based-line separated from ionic iron species, which needed to be complexed with 1mM citrate to elute from the column. Exposed cells up to 0.5mM of iron tartrate/adipate-modified nanoparticles were specifically treated to extract the internalized NPs and the extracts examined using the proposed strategy. The obtained results revealed the presence of three different fractions corresponding to nanoparticle aggregates, dispersed nanoparticles and soluble iron respectively in a single chromatographic run. Quantitative experiments (column recoveries ranging from 60 to 80%) revealed the presence of the majority of the Fe in the nanoparticulated form (>75%) by summing up the dispersed and aggregate particles. Such experiments point out the high uptake and low solubilization rate of the tartrate/adipate NPs making these structures highly suitable as Fe supplements in oral anemia treatments. KW - Fe nanoparticles metabolism KW - Cells KW - HPLC-ICP-MS KW - Species-unspecific on-line isotope dilution PY - 2018 DO - https://doi.org/10.1016/j.aca.2018.08.003 SN - 0003-2670 VL - 1039 SP - 24 EP - 30 PB - Elsevier CY - Amsterdam AN - OPUS4-46817 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Arakawa, Akihiro A1 - Jakubowski, Norbert A1 - Koellensperger, G. A1 - Theiner, S. A1 - Schweikert, A. A1 - Flemig, Sabine A1 - Iwahata, D. A1 - Traub, Heike A1 - Hirata, T. T1 - Quantitative Imaging of Silver Nanoparticles and Essential Elements in Thin Sections of Fibroblast Multicellular Spheroids by High Resolution Laser Ablation Inductively Coupled Plasma Time-of-Flight Mass Spectrometry N2 - We applied high resolution laser ablation inductively coupled plasma time-of-flight mass spectrometry (LA-ICP-TOF-MS) with cellular spatial resolution for bioimaging of nanoparticles uptaken by fibroblast multicellular spheroids (MCS). This was used to quantitatively investigate interactions of silver nanoparticles (Ag NPs) and the distributions of intrinsic minerals and biologically relevant elements within thin sections of a fibroblast MCS as a three-dimensional in vitro tissue model. We designed matrix-matched calibration standards for this purpose and printed them using a noncontact piezo-driven array spotter with a Ag NP suspension and multielement standards. The limits of detection for Ag, Mg, P, K, Mn, Fe, Co, Cu, and Zn were at the femtogram (fg) level, which is sufficient to investigate intrinsic minerals in thin MCS sections (20 μm thick). After incubation for 48 h, Ag NPs were enriched in the outer rim of the MCS but not detected in the core. The localization of Ag NPs was inhomogeneous in the outer rim, and they were colocalized with a single-cell-like structure visualized by Fe distribution (pixel size of elemental images: 5 × 0.5 μm). The quantitative value for the total mass of Ag NPs in a thin section by the present method agreed with that obtained by ICP-sector field (SF)-MS with a liquid mode after acid digestion. KW - Laser ablation KW - ICP-MS KW - Imaging KW - Nanoparticle KW - Cell KW - Spheroid PY - 2019 UR - https://pubs.acs.org/doi/10.1021/acs.analchem.9b02239 DO - https://doi.org/10.1021/acs.analchem.9b02239 SN - 0003-2700 VL - 91 IS - 15 SP - 10197 EP - 10203 PB - American Chemical Society, ACS Publications CY - Washington D.C. AN - OPUS4-48719 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Reynolds, Merilie A. A1 - Kamber, Balz S. A1 - McKenna, Cora A. A1 - Oelze, Marcus A1 - Gleeson, Sarah A. T1 - Repeat, fast, and high-resolution mapping of fine-scale trace element distribution in pyrite and marcasite by LA-Q-ICP-MS with the Aerosol Rapid Introduction System (ARIS) N2 - AbstractThe minor and trace element composition of minerals provides critical insights into a variety of geological processes. Multi-element mapping by laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) is an important technique applied for this purpose and although the method is rapidly advancing, there remains a fundamental compromise between spatial resolution, detection limit, and experiment duration when using sequential mass analyzers. To address the limitation of limited analyte selection for high spatial resolution maps imposed by the sequential nature of typical quadrupole (Q)-ICP-MS, we tested the Aerosol Rapid Introduction System (ARIS) for repeat mapping of the same area. The ARIS is a high-speed transfer tubing system that reduces aerosol washout times, permitting resolution of individual pulses at 40–60 Hz. Here, the ARIS was tested not for pulse resolution but with novel operating conditions optimized to perform fast, high spatial resolution mapping of minor and trace element distribution in pyrite and marcasite. For this purpose, ablation was conducted with a 5 µm beam aperture, a repetition rate of 50 Hz, and a continuous stage scan speed of 40 µm s−1. For each LA-Q-ICP-MS map, data were acquired for six elements with an acquisition time of 20 ms per element. This deliberately reduced the individual pulse resolution of the ARIS but instead exploited the spatial resolution and sensitivity gains afforded by the high-laser repetition rate combined with efficient aerosol transfer. The new method successfully mapped trace elements at single to double-digit parts per million levels, and the maps reveal fine-scale zoning of trace elements with an effective x and y resolution of 5 µm, while white light interferometry showed that for each experiment, only ca. 1 µm of the sample was removed. Repeated mapping of the same area showed excellent correspondence not only between element concentrations in successive experiments but also in the shape, dimension, and location of regions of interest defined by concentration criteria. The very good repeatability of the elemental maps indicates that for studies requiring more analytes, successive mapping of additional elements is possible. By contrast with conventional very small spot (i.e., 5 µm) analysis, fast repetition rate and stage scan speed mapping avoids down-hole fractionation effects and minimizes accidental analysis of buried invisible inclusions. Compared to conventional LA-ICP-MS mapping, the method reduces the experiment time by 4–8 times. KW - Geochemistry and Petrology KW - Geophysics PY - 2023 DO - https://doi.org/10.2138/am-2022-8168 SN - 0003-004X VL - 108 IS - 1 SP - 18 EP - 30 PB - Mineralogical Society of America AN - OPUS4-59038 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Hendriks, L. A1 - Brunjes, R. A1 - Taskula, S. A1 - Kocic, J. A1 - Hattendorf, B. A1 - Bland, G. A1 - Lowry, G. A1 - Bolea-Fernandez, E. A1 - Vanhaecke, F. A1 - Wang, J. A1 - Baalousha, M. A1 - von der Au, Marcus A1 - Meermann, Björn A1 - Holbrook, T. A1 - Wagner, S. A1 - Harycki, S. A1 - Gundlach-Graham, A. A1 - von der Kammer, F. T1 - Results of an interlaboratory comparison for characterization of Pt nanoparticles using single-particle ICP-TOFMS N2 - This study describes an interlaboratory comparison (ILC) among nine (9) laboratories to evaluate and validate the standard operation procedure (SOP) for single-particle (sp) ICP-TOFMS developed within the context of the Horizon 2020 project ACEnano. The ILC was based on the characterization of two different Pt nanoparticle (NP) suspensions in terms of particle mass, particle number concentration, and isotopic composition. The two Pt NP suspensions were measured using icpTOF instruments (TOFWERK AG, Switzerland). Two Pt NP samples were characterized and mass equivalent spherical sizes (MESSs) of 40.4 ± 7 nm and 58.8 ± 8 nm were obtained, respectively. MESSs showed <16% relative standard deviation (RSD) among all participating labs and <4% RSD after exclusion of the two outliers. A good agreement was achieved between the different participating laboratories regarding particle mass, but the particle number concentration results were more scattered, with <53% RSD among all laboratories, which is consistent with results from previous ILC studies conducted using ICP-MS instrumentation equipped with a sequential mass spectrometer. Additionally, the capabilities of sp-ICP-TOFMS to determine masses on a particle basis are discussed with respect to the potential for particle density determination. Finally, because quasi-simultaneous multi-isotope and multielement determinations are a strength of ICP-TOFMS instrumentation, the precision and trueness of isotope ratio determinations were assessed. The average of 1000 measured particles yielded a precision of below ±1% for intensity ratios of the most abundant Pt isotopes, i.e. 194Pt and 195Pt, while the accuracy of isotope ratios with the lower abundant isotopes was limited by counting statistics. KW - ILC KW - spICP-MS KW - PtNP KW - Nanopartikel PY - 2023 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-580353 DO - https://doi.org/10.1039/d3nr00435j SN - 2040-3364 VL - 15 IS - 26 SP - 11268 EP - 11279 PB - Royal Society of Chemistry (RSC) AN - OPUS4-58035 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Vogl, Jochen A1 - Rienitz, O. A1 - Pramann, A. A1 - Flierl, L. T1 - Scale Conversion and Uncertainty Calculations in Isotope Delta Measurements N2 - Isotope ratio applications are on the increase and a major part of which are delta measurements, because they are easier to perform than the determination of absolute isotope ratios while offering lower measurement uncertainties. Delta measurements use artefact-based scales and therefore scale conversions are required due to the lack of the scale defining standards. Such scale conversions often form the basis for comparing data being generated in numerous projects andtherefore need to be as accurate as possible. In practice, users are tempted to apply linear approximations, which are not sufficiently exact, because delta values are defined by nonlinear relationships. The bias of such approximations often is beyond typical measurement uncertainties and its extent can hardly be predicted. Therefore, exact calculations are advised. Here, the exact equations and the bias of the approximations are presented, and calculations are illustrated by real-world examples. Measurement uncertainty is indispensable in this context and therefore, its calculation is described as well for determining delta values but also for scale conversions. Approaches for obtaining a single delta measurement and for repeated measurements are presented. For the latter case, a new approach for calculating the measurement uncertainty is presented, which considers covariances between the isotope ratios. KW - Delta isotope standard KW - Delta scale KW - In-house calibration solution KW - Isotope ratios KW - Isotope reference material KW - Measurement uncertainty KW - Scale conversion PY - 2022 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-557254 DO - https://doi.org/10.1111/ggr.12450 SN - 1639-4488 VL - 46 IS - 4 SP - 773 EP - 787 PB - Wiley AN - OPUS4-55725 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Gehrenkemper, Lennart A1 - Simon, Fabian A1 - Meermann, Björn T1 - Schnelle und einfache Extraktion von PFAS aus Bodenproben: Optimierte EOF-Bestimmung mittels HR-CS-GFMAS N2 - Per- und polyfluorierte Alkylsubstanzen (PFAS) bilden eine sehr komplexe Schadstoffgruppe mit über 6300 Einzelsubstanzen, die in vielfältiger Form in die Umwelt eingetragen werden. Für ein effektives Monitoring dieser Schadstoffklasse benötigt es ein Zusammenspiel aus Summenparameter-Analytik zur hot-spot-Identifizierung und Klassifizierung von Belastungssituationen sowie einer nachgeschalteten target-Analytik zur Identifizierung von Eintragswegen, die zugleich ein tieferes Verständnis von Transformationsprozessen ermöglicht. In diesem Beitrag präsentieren wir eine optimierte Extraktions-Methode für die PFAS-Summenparameteranalytik. Mit Hilfe dieser können bisher verwendete zeit- und kostenintensive Festphasenextraktionen (SPE) umgangen und PFAS-Extraktionseffizienzen gesteigert werden. Die methodische Bestimmungsgrenze (LOQ) war mit 10,30 μg/kg (Fluor pro Bodenprobe) ausreichend für alle 9 untersuchten Realbodenproben. KW - High resolution-continuum source-graphite furnace molecular absorption spectrometry (HR-CS-GFMAS) KW - PFAS KW - Per- and polyfluorinated alkyl substances (PFASs) KW - Extractable organically bound fluorine (EOF) KW - Solid-liquid extraction KW - Böden PY - 2022 UR - https://www.gdch.de/fileadmin/downloads/Netzwerk_und_Strukturen/Fachgruppen/Umweltchemie_Oekotoxikologie/mblatt/2022/Heft122.pdf SN - 1618-3258 VL - 28 IS - 1 SP - 12 EP - 15 PB - Gesellschaft Deutscher Chemiker AN - OPUS4-54417 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Von der Au, M. A1 - Meermann, Björn T1 - Screening von Organofluorverbindungen im Oberflächenwasser N2 - Organofluorverbindungen kommen in vielen Bereichen zum Einsatz und gelangen in die aquatische Umwelt. Die Belastungssituation der Gewässer ist bisher wenig untersucht – hier kommt die HR-CS GF MAS als leistungsstarkes Screeningtool zum Einsatz. KW - HR-CS-GFMAS KW - Extrahierbar organisch gebundenes Fluor (EOF) KW - Oberflächengewässer PY - 2019 UR - https://analytik.news/Fachartikel/Volltext/bam5.pdf SP - 1 EP - 3 PB - Dr. Beyer Internet-Beratung AN - OPUS4-49750 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Phukphatthanachai, Pranee A1 - Panne, Ulrich A1 - Jakubowski, Norbert A1 - Vogl, Jochen T1 - SI-traceable quantification of sulphur in copper metal and its alloys by ICP-IDMS N2 - Previously applied methods for the quantification of sulphur in copper and other pure metals revealed a lack of SI-traceability and additionally showed inconsistent results, when different methods were compared. Therefore, a reference procedure is required which allows SI-traceable values accompanied by a Sound uncertainty budget. In this study a procedure was developed for the quantification of total sulphur in copper at low concentration levels using inductively coupled plasma-isotope dilution mass spectrometry (ICP-IDMS). The major part of the copper matrix was separated by adding ammonia which forms a complex with the copper while releasing the sulphur followed by chromatographic separation using a weak cation resin. After that the sulphur fraction was further purified by chromatographic means using first an anion exchange method and second a chelating resin. The developed procedure shows high performance, especially concerning high efficiency in matrix removal (>99.999%) while keeping the recovery of sulphur above 80%. Procedure blanks are in the order of 3–53 ng resulting in LOD and LOQ values of 0.2 mg g1 and 0.54 mg g1, respectively. The procedure is sufficient to facilitate value assignment of the total sulphur mass fraction in reference materials. Additionally, relative measurement uncertainties were calculated to be below 1% and the measurement results were traceable to the SI. The procedure reported in this study is a new reference procedure for sulphur measurement in copper, being fit for two major purposes, certification of reference materials and assignment of reference values for inter-laboratory comparison. KW - Traceability KW - Measuremment uncertainty KW - Isotope dilution mass spectrometry KW - Reference measurements PY - 2018 DO - https://doi.org/10.1039/c7ja00338b SN - 0267-9477 SN - 1364-5544 VL - 33 IS - 1 SP - 90 EP - 101 PB - Royal Society of Chemistry CY - Cambridge, UK AN - OPUS4-43614 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Tatzel, Michael A1 - Oelze, Marcus A1 - Frick, Daniel A. A1 - Di Rocco, Tommaso A1 - Liesegang, Moritz A1 - Stuff, Maria A1 - Wiedenbeck, Michael T1 - Silicon and oxygen isotope fractionation in a silicified carbonate rock N2 - Silicon isotope fractionation during silicification is poorly understood and impedes our ability to decipher paleoenvironmental conditions from Si isotopes in ancient cherts. To investigate isotope fractionation during silica-for-carbonate replacement we analyzed the microscale Si and O isotope composition in different silica phases in a silicified zebra dolostone as well as their bulk δ18O and Δ’17O compositions. The subsequent replacement of carbonate layers is mimicked by decreasing δ18O and δ30Si. The textural relationship and magnitude of Si and O isotope fractionation is best explained by near-quantitative silica precipitation in an open system with finite Si. A Rayleigh model for silicification suggests positive Ɛ30/28Si during silicification, conforming with predictions for isotope distribution at chemical equilibrium from ab-initio models. Application of the modelled Ɛ30Si-T relationship yields silicification temperatures of approx. 50°C. To reconcile the δ18Ochert composition with these temperatures, the δ18O of the fluid must have been between -2.5 and -4 ‰, compositions for which the quartz phases fall close to the oxygen equilibrium fractionation line in three-isotope space. Diagenetic silica replacement appears to occur in O and Si isotopic equilibrium allowing reconstructions of temperatures of silicification from Si isotopes and derive the δ18O composition of the fluid – a highly desired value needed for accurate reconstructions of the temperature- and δ18O histories of the oceans. KW - Silicon isotopes PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-603430 DO - https://doi.org/10.1016/j.chemgeo.2024.122120 SN - 0009-2541 VL - 658 SP - 1 EP - 13 PB - Elsevier B.V. AN - OPUS4-60343 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Michail Ioannis, Chronakis A1 - Marcus, von der Au A1 - Meermann, Björn T1 - Single cell-asymmetrical flow field-flow fractionation/ICP-time of flight-mass spectrometry (sc-AF4/ICP-ToF-MS): an efficient alternative for the cleaning and multielemental analysis of individual cells N2 - Asymmetrical Flow Field-Flow Fractionation (AF4), as a cleaning technique, was combined on-line with the multielemental analytical capabilities of an Inductively Coupled Plasma-Time of Flight-Mass Spectrometer (ICP-ToF-MS). In that manner, the heavy ionic matrix effect of untreated cells' samples can be significantly reduced. As a proof of concept, commercial baker's yeast cells were analysed. KW - AF4 KW - Single Cell KW - Cleaning PY - 2022 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-576419 DO - https://doi.org/10.1039/d2ja00264g SN - 0267-9477 VL - 37 IS - 12 SP - 2691 EP - 2700 PB - Royal Society of Chemistry AN - OPUS4-57641 LA - eng 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 - JOUR A1 - Menero-Valdés, P. A1 - Chronakis, Michail Ioannis A1 - Fernández, B. A1 - Quarles Jr., C. D. A1 - González-Iglesias, H. A1 - Meermann, Björn A1 - Pereiro, R. T1 - Single Cell–ICP–ToF-MS for the Multiplexed Determination of Proteins: Evaluation of the Cellular Stress Response N2 - An automated and straightforward detection and data treatment strategy for the determination of the protein relative concentration in individual human cells by single cell–inductively coupled plasma–time-of-flight mass spectrometry (sc-ICP-ToF-MS) is proposed. Metal nanocluster (NC)-labeled specific antibodies for the target proteins were employed, and ruthenium red (RR) staining, which binds to the cells surface, was used to determine the number of cell events as well as to evaluate the relative volume of the cells. As a proof of concept, the expression of hepcidin, metallothionein-2, and ferroportin employing specific antibodies labeled with IrNCs, PtNCs, and AuNCs, respectively, was investigated by sc-ICP-ToF-MS in human ARPE-19 cells. Taking into account that ARPE-19 cells are spherical in suspension and RR binds to the surface of the cells, the Ru intensity was related to the cell volume (i.e., the cell volume is directly proportional to (Ru intensity)3/2), making it possible to determine not only the mass of the target proteins in each individual cell but also the relative concentration. The proposed approach is of particular interest in comparing cell cultures subjected to different supplementations. ARPE-19 cell cultures under two stress conditions were compared: a hyperglycemic model and an oxidative stress model. The comparison of the control with treated cells shows not only the mass of analyzed species but also the relative changes in the cell volume and concentration of target proteins, clearly allowing the identification of subpopulations under the respective treatment. KW - Peptides and Proteins KW - Immunology KW - Metals PY - 2023 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-581630 DO - https://doi.org/10.1021/acs.analchem.3c02558 VL - 95 IS - 35 SP - 13322 EP - 13329 PB - ACS Publications AN - OPUS4-58163 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Meyer, S. A1 - López-Serrano, Ana A1 - Mitze, H. A1 - Jakubowski, Norbert A1 - Schwerdtle, T. T1 - Single-cell analysis by ICP-MS/MS as a fast tool for cellular bioavailability studies of arsenite N2 - Single-cell inductively coupled plasma mass spectrometry (SC-ICP-MS) has become a powerful and fast tool to evaluate the elemental composition at a single-cell level. In this study, the cellular bioavailability of arsenite (incubation of 25 and 50 μM for 0-48 h) has been successfully assessed by SC-ICP-MS/MS for the first time directly after re-suspending the cells in water. This procedure avoids the normally arising cell membrane permeabilization caused by cell fixation methods (e.g. methanol fixation). The reliability and feasibility of this SC-ICP-MS/MS approach with a limit of detection of 0.35 fg per cell was validated by conventional bulk ICP-MS/MS analysis after cell digestion and parallel measurement of sulfur and phosphorus. KW - Single-cell analysis KW - ICP-MS/MS KW - Arsenite PY - 2018 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-441105 DO - https://doi.org/10.1039/c7mt00285h SN - 1756-5901 VL - 10 IS - 1 SP - 73 EP - 76 PB - RSC Publ. CY - Cambridge AN - OPUS4-44110 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Hendriks, L. A1 - Ramkorun-Schmidt, Benita A1 - Grundlach-Graham, A. A1 - Koch, J. A1 - Grass, R. N. A1 - Jakubowski, Norbert A1 - Günther, D. T1 - Single-particle ICP-MS with online microdroplet calibration: toward matrix independent nanoparticle sizing N2 - Single-particle inductively coupled plasma mass spectrometry (sp-ICP-MS) has become an effective tool for the detection and quantification of inorganic nanoparticles (NPs). While sizing of NPs suspended in water is relatively straightforward by sp-ICP-MS, accurate mass quantification of NPs in complex media, such as consumer products and natural systems still remains a challenge. When NPs are suspended in a complex medium, the matrix may affect the analyte sensitivity and lead to inaccurate NP sizing. Here, we investigate the use of an online microdroplet calibration system to size NPs in a single step. In this setup, microdroplets—which are used as the calibrant to determine elemental sensitivities—and nebulized NP-containing solutions are introduced concurrently into the ICP via a dual-inlet sample introduction system. Because calibrant microdroplets and analyte NPs experience the same plasma conditions, both the microdroplets and the NPs are subjected to the same matrix-related signal enhancement or suppression. In this way, the microdroplet calibration standards are automatically matrix matched with the NP-containing solution. The online microdroplet calibration system is combined with an ICP-TOFMS instrument for simultaneous measurement of multiple elements in microdroplets and NPs. We investigate the ability of online microdroplet calibration to compensate for matrix effects through a series of experiments, in which Ag and Au NPs are measured with variable plasma-sampling positions, varying concentrations of HCl and HNO3, varying concentrations of single element solutions, and high concentrations of a salt matrix, i.e. phosphate buffered saline (PBS). Through these experiments, we demonstrate that the online microdroplet calibration strategy provides a matrix-independent mass quantification of analyte NPs in the presence of several established types of matrix effects, including acid effects, space-charge effects, and ionisation suppression. In results presented here, we focus on the size determination of the NPs. KW - Nanoparticle KW - ICP-MS KW - Calibration PY - 2019 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-477589 DO - https://doi.org/10.1039/c8ja00397a SN - 0267-9477 VL - 34 IS - 4 SP - 716 EP - 728 PB - Royal Society of Chemistry CY - London AN - OPUS4-47758 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - von der Au, Marcus A1 - Faßbender, Sebastian A1 - Chronakis, Michail A1 - Vogl, Jochen A1 - Meermann, Björn T1 - Size determination of nanoparticles by ICP-ToF-MS using isotope dilution in microdroplets N2 - Within this work, the combination of a microdroplet generator and an ICP-ToF-MS for nanoparticle analysis is presented. For the size determination of platinum nanoparticles an on-line isotope dilution analysis approach was developed. The 194Pt/195Pt isotopic ratio was used for the characterization of the particles, while the 182W/183W isotopic ratio was monitored simultaneously for mass bias correction. The on-line ID-MDG-sp-ICP-ToF-MS approach was deployed for the size determination of three platinum nanoparticle samples (50 nm, 63 nm, 70 nm); for validation, complementary size characterization techniques (sp-ICP-ToF-MS and TEM) were used. The robustness of this technique was evidenced, by using sodium chloride concentrations up to 100 mg L−1 as a matrix component. Our new on-line ID MDG-sp-ICP-ToF-MS approach is a promising tool for the fast and reliable determination of nanoparticles' size in severe matrix concentrations, e.g., environmental samples. KW - ICP-ToF-MS KW - Nanoparticles KW - Isotope Dilution PY - 2022 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-552727 DO - https://doi.org/10.1039/D2JA00072E SN - 0267-9477 VL - 37 IS - 6 SP - 1203 EP - 1207 PB - Royal Society of Chemistry AN - OPUS4-55272 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Faßbender, Sebastian A1 - von der Au, Marcus A1 - Koenig, Maren A1 - Pelzer, J. A1 - Piechotta, Christian A1 - Vogl, Jochen A1 - Meermann, Björn T1 - Species-specific isotope dilution analysis of monomethylmercury in sediment using GC/ICP-ToF-MS and comparison with ICP-Q-MS and ICP-SF-MS N2 - A recently introduced inductively coupled plasma-time-of-flight-mass spectrometer (ICP-ToF-MS) shows enhanced sensitivity compared to previous developments and superior isotope ratio precision compared to other ToF and commonly used single-collector ICP-MS instruments. Following this fact, an improvement for isotope dilution ICP-MS using the new instrumentation has been reported. This study aimed at investigating whether this improvement also meets the requirements of species-specific isotope dilution using GC/ICP-MS, where short transient signals are recorded. The results of the analysis of monomethylmercury (MMHg) of a sediment reference material show that isotope ratio precision of ICP-MS instruments equipped with quadrupole, sector-field, and time-of-flight mass analyzers is similar within a broad range of peak signal-to-noise ratio when analyzing one isotopic system. The procedural limit of quantification (LOQ) for MMHg, expressed as mass fraction of Hg being present as MMHg, w(Hg)MMHg, was similar as well for all investigated instruments and ranged between 0.003 and 0.016 μg/kg. Due to the simultaneous detection capability, the ICP-ToF-MS might, however, be more favorable when several isotopic systems are analyzed within one measurement. In a case study, the GC/ICP-ToF-MS coupling was applied for analysis of MMHg in sediments of Finow Canal, a historic German canal heavily polluted with mercury. Mass fractions between 0.180 and 41 μg/kg (w(Hg)MMHg) for MMHg, and 0.056 and 126 mg/kg (w(Hg)total) for total mercury were found in sediment samples taken from the canal upstream and downstream of a former chemical plant. KW - Methylmercury KW - Legacy pollution KW - Finow Canal KW - Isotope dilution KW - Mercury speciation PY - 2021 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-529967 DO - https://doi.org/10.1007/s00216-021-03497-z SN - 1618-2642 VL - 413 IS - 21 SP - 5279 EP - 5289 PB - Springer CY - Berlin AN - OPUS4-52996 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 - Prohaska, T. A1 - Irrgeher, J. A1 - Benefield, J. A1 - Böhlke, J. K. A1 - Chesson, L. A. A1 - Coplen, T. B. A1 - Ding, T. A1 - Dunn, P. J. H. A1 - Gröning, M. A1 - Holden, N. E. A1 - Meijer, H. A. J. A1 - Moossen, H. A1 - Possolo, A. A1 - Takahashi, Y. A1 - Vogl, Jochen A1 - Walczyk, T. A1 - Wang, J. A1 - Wieser, M. E. A1 - Yoneda, S. A1 - Zhu, X.-K. A1 - Meija, J. T1 - Standard atomic weights of the elements 2021 (IUPAC Technical Report) N2 - Following the reviews of atomic-weight determinations and other cognate data in 2015, 2017, 2019 and 2021, the IUPAC (International Union of Pure and Applied Chemistry) Commission on Isotopic Abundances and Atomic Weights (CIAAW) reports changes of standard atomic weights. The symbol Ar(E) was selected for standard atomic weight of an element to distinguish it from the atomic weight of an element E in a specific substance P, designated Ar(E, P). The CIAAW has changed the values of the standard atomic weights of five elements based on recent determinations of terrestrial isotopic abundances: Ar (argon): from 39.948 ± 0.001 to [39.792, 39.963] Hf (hafnium): from 178.49 ± 0.02 to 178.486 ± 0.006 Ir (iridium): from 192.217 ± 0.003 to 192.217 ± 0.002 Pb (lead): from 207.2 ± 0.1 to [206.14, 207.94] Yb (ytterbium): from 173.054 ± 0.005 to 173.045 ± 0.010 The standard atomic weight of argon and lead have changed to an interval to reflect that the natural variation in isotopic composition exceeds the measurement uncertainty of Ar(Ar) and Ar(Pb) in a specific substance. The standard atomic weights and/or the uncertainties of fourteen elements have been changed based on the Atomic Mass Evaluations 2016 and 2020 accomplished under the auspices of the International Union of Pure and Applied Physics (IUPAP). Ar of Ho, Tb, Tm and Y were changed in 2017 and again updated in 2021: Al (aluminium), 2017: from 26.981 5385 ± 0.000 0007 to 26.981 5384 ± 0.000 0003 Au (gold), 2017: from 196.966 569 ± 0.000 005 to 196.966 570 ± 0.000 004 Co (cobalt), 2017: from 58.933 194 ± 0.000 004 to 58.933 194 ± 0.000 003 F (fluorine), 2021: from 18.998 403 163 ± 0.000 000 006 to 18.998 403 162 ± 0.000 000 005 (Ho (holmium), 2017: from 164.930 33 ± 0.000 02 to 164.930 328 ± 0.000 007) Ho (holmium), 2021: from 164.930 328 ± 0.000 007 to 164.930 329 ± 0.000 005 Mn (manganese), 2017: from 54.938 044 ± 0.000 003 to 54.938 043 ± 0.000 002 Nb (niobium), 2017: from 92.906 37 ± 0.000 02 to 92.906 37 ± 0.000 01 Pa (protactinium), 2017: from 231.035 88 ± 0.000 02 to 231.035 88 ± 0.000 01 Pr (praseodymium), 2017: from 140.907 66 ± 0.000 02 to 140.907 66 ± 0.000 01 Rh (rhodium), 2017: from 102.905 50 ± 0.000 02 to 102.905 49 ± 0.000 02 Sc (scandium), 2021: from 44.955 908 ± 0.000 005 to 44.955 907 ± 0.000 004 (Tb (terbium), 2017: from 158.925 35 ± 0.000 02 to 158.925 354 ± 0.000 008) Tb (terbium), 2021: from 158.925 354 ± 0.000 008 to 158.925 354 ± 0.000 007 (Tm (thulium), 2017: from 168.934 22 ± 0.000 02 to 168.934 218 ± 0.000 006) Tm (thulium), 2021: from 168.934 218 ± 0.000 006 to 168.934 219 ± 0.000 005 (Y (yttrium), 2017: from 88.905 84 ± 0.000 02 to 88.905 84 ± 0.000 01) Y (yttrium), 2021: from 88.905 84 ± 0.000 01 to 88.905 838 ± 0.000 002 KW - Argon KW - Ciaaw.org KW - Hafnium KW - Iridium KW - Lead KW - LSVEC KW - Ytterbium PY - 2022 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-548443 DO - https://doi.org/10.1515/pac-2019-0603 SN - 0033-4545 VL - 94 IS - 5 SP - 573 EP - 600 PB - De Gruyter Verlag CY - Berlin AN - OPUS4-54844 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 - Kirilina, E. A1 - Helbling, S. A1 - Morawski, M. A1 - Pine, K. A1 - Reimann, K. A1 - Jankuhn, S. A1 - Dinse, J. A1 - Deistung, A. A1 - Reichenbach, J. R. A1 - Trampel, R. A1 - Geyer, S. A1 - Müller, Larissa A1 - Jakubowski, Norbert A1 - Arendt, T. A1 - Bazin, P.-L. A1 - Weiskopf, N. T1 - Superficial white matter imaging: Contrast mechanisms and whole-brain in vivo mapping N2 - Superficial white matter (SWM) contains the most cortico-cortical white matter connections in the human brain encompassing the short U-shaped association fibers. Despite its importance for brain connectivity, very little is known about SWM in humans, mainly due to the lack of noninvasive imaging methods. Here, we lay the groundwork for systematic in vivo SWM mapping using ultrahigh resolution 7 T magnetic resonance imaging. Using biophysical modeling informed by quantitative ion beam microscopy on postmortem brain tissue, we demonstrate that MR contrast in SWM is driven by iron and can be linked to the microscopic iron distribution. Higher SWM iron concentrations were observed in U-fiber–rich frontal, temporal, and parietal areas, potentially reflecting high fiber density or late myelination in these areas. Our SWM mapping approach provides the foundation for systematic studies of interindividual differences, plasticity, and pathologies of this crucial structure for cortico-cortical connectivity in humans. KW - Magnetic resonance imaging KW - Laser ablation KW - ICP-MS KW - Brain KW - Imaging PY - 2020 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-514430 DO - https://doi.org/10.1126/sciadv.aaz9281 SN - 2375-2548 VL - 6 IS - 41 SP - eaaz9281 PB - American Association for the Advancement of Science (Science/AAAS) CY - Washington, DC, USA AN - OPUS4-51443 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 - 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 - Meermann, Björn T1 - The future of elemental analytical chemistry – the sixth special issue dedicated to young analytical scientists N2 - Editorial for a special issue KW - Editorial KW - Special issue, young analytical scientists KW - Elemental analysis PY - 2021 DO - https://doi.org/10.1039/d1ja90038b VL - 36 IS - 9 SP - 1794 EP - 1796 PB - RSC AN - OPUS4-53086 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Sargent, M A1 - Goenaga-Infante, H A1 - Inagaki, K A1 - Ma, L A1 - Meija, J A1 - Pramann, A A1 - Rienitz, O A1 - Sturgeon, R A1 - Vogl, Jochen A1 - Wang, J A1 - Yang, L T1 - The role of ICP-MS in inorganic chemical metrology N2 - ICP-MS has played a key role in inorganic chemical metrology for 25 years, from the 1993 CIPM feasibility study which led to establishment of the CCQM. Since that time, the Inorganic Analysis Working Group of the CCQM has organised 56 international comparisons involving measurements by ICP-MS and, in a recent comparison, 16 different national institutes submitted their results using the technique. Metrological applications of ICP-MS currently address an enormous range of measurements using a wide variety of instrumentation, calibration strategies and methodologies. This review provides an overview of the ICP-MS field with an emphasis on developments which are of particular relevance to chemical metrology. Examples from CCQM comparisons and the services available from the participants are used to illustrate how the capability and scope of ICP-MS methods have expanded far beyond the expectations of 1993. This is due in part to the research and development Programmes of the national institutes which participate in the CCQM. They have played a key role in advancing new instrumentation and applications for elemental analysis, isotope dilution mass spectrometry, determination of isotopic ratio or composition, and speciation of organometallic compounds. These developments are continuing today, as demonstrated by work in new fields such as heteroatom quantitation of proteins, characterisation and counting of nanoparticles using spICP-MS, and LA-ICP-MS analysis of solid materials. KW - CCQM KW - Metrology KW - Interlaboratory comparison KW - ICP-MS KW - Mass spectrometry KW - Hyphenated KW - Isotope ratio PY - 2019 DO - https://doi.org/10.1088/1681-7575/ab0eac VL - 56 IS - 3 SP - 034005 PB - IOP Publishing AN - OPUS4-47929 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Coplen, T. B. A1 - Holden, N. E. A1 - Ding, T. A1 - Meijer, H. A. J. A1 - Vogl, Jochen A1 - Zhu, X. T1 - The Table of Standard Atomic Weights—An exercise in consensus N2 - The present Table of Standard Atomic Weights (TSAW) of the elements is perhaps one of the most familiar data sets in science. Unlike most parameters in physical science whose values and uncertainties are evaluated using the “Guide to the Expression of Uncertainty in Measurement” (GUM), the majority of standard atomic weight values and their uncertainties are consensus values, not GUM-evaluated values. The Commission on Isotopic Abundances and Atomic Weights of the International Union of Pure and Applied Chemistry (IUPAC) regularly evaluates the literature for new isotopic-abundance measurements that can lead to revised standard atomic-weight values, Ar(E) for element E. The Commission strives to provide utmost clarity in products it disseminates, namely the TSAW and the Table of Isotopic Compositions of the Elements (TICE). In 2016, the Commission recognized that a guideline recommending the expression of uncertainty listed in parentheses following the standard atomic-weight value, for example, Ar(Se) = 78.971(8), did not agree with the GUM, which suggests that this parenthetic notation be reserved to express standard uncertainty, not the expanded uncertainty used in the TSAW and TICE. In 2017, to eliminate this noncompliance with the GUM, a new format was adopted in which the uncertainty value is specified by the “±” symbol, for example, Ar(Se) = 78.971 ± 0.008. To clarify the definition of uncertainty, a new footnote has been added to the TSAW. This footnote emphasizes that an atomic-weight uncertainty is a consensus (decisional) uncertainty. Not only has the Commission shielded users of the TSAW and TICE from unreliable measurements that appear in the literature as a result of unduly small uncertainties, but the aim of IUPAC has been fulfilled by which any scientist, taking any natural sample from commerce or research, can expect the sample atomic weight to lie within Ar(E) ± its uncertainty almost all of the time. KW - Atomic weight KW - Standard atomic weight KW - Uncertainty PY - 2022 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-551299 DO - https://doi.org/10.1002/rcm.8864 SN - 1097-0231 VL - 36 IS - 15 SP - 1 EP - 15 PB - Wiley AN - OPUS4-55129 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Vogl, Jochen T1 - The triple-isotope calibration approach: a universal and standard-free calibration approach for obtaining absolute isotope ratios of multi-isotopic elements N2 - The theory of a new calibration approach for obtaining absolute isotope ratios of multi-isotopic elements without the use of any standard has been developed. The calibration approach basically uses the difference in the instrumental isotope fractionation of two different types of mass spectrometers, leading to two different fractionation lines in a three-isotope diagram. When measuring the same sample with both mass spectrometers, the different fractionation lines have one point in common: this is the ‘true’ logarithmized isotope ratio pair of the sample. Thus, the intersection of both fractionation lines provides us with the absolute isotope ratios of the sample. This theory has been tested in practice by measuring Cd and of Pb isotope ratios in the certified reference materials BAM-I012 and NIST SRM981 by thermal ionization mass spectrometry and by inductively coupled plasma mass spectrometry while varying the ionization conditions for both mass spectrometers. With this experiment, the theory could be verified, and absolute isotope ratios were obtained, which were metrologically compatible with the certified isotope ratios. The so-obtained absolute isotope ratios are biased by − 0.5% in average, which should be improved with further developments of the method. This calibration approach is universal, as it can be applied to all elements with three or more isotopes and it is not limited to the type of mass spectrometers applied; it can be applied as well to secondary ion mass spectrometry or others. Additionally, this approach provides information on the fractionation process itself via the triple-isotope fractionation exponent θ. KW - Triple isotope fractionation KW - Absolute isotope ratio KW - Mass spectrometry KW - Calibration KW - Uncertainty PY - 2020 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-516364 DO - https://doi.org/10.1007/s00216-020-03050-4 VL - 413 IS - 3 SP - 821 EP - 826 PB - Springer Verlag AN - OPUS4-51636 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Pramann, A. A1 - Vogl, Jochen A1 - Rienitz, O. T1 - The Uncertainty Paradox: Molar Mass of Enriched Versus Natural Silicon Used in the XRCD Method N2 - The X-ray crystal density method uses silicon spheres highly enriched in 28Si as a primary method for the dissemination of the SI base unit kilogram yielding smallest possible uncertainties associated with the mass m within a few parts in 10-8. This study compares different available and newly developed analytical methods and their results for the determination of the molar mass M of silicon highly enriched in 28Si (Me) and of silicon (Mx) with an almost natural isotopic distribution. While for Me relative uncertainties urel(Me) in the lower 10-9 range are obtained routinely, it was not possible to fall below a value of urel(Mx) < 4 x 10-6 in the case of natural silicon, which is approximately three orders of magnitude larger. The application of the state-of the-art isotope ratio mass spectrometry accompanied with sophisticated thoroughly investigated methods suggests an intrinsic cause for the large uncertainty associated with the molar mass of natural silicon compared to the enriched material. KW - silicon KW - Molar mass KW - Isotope ratios KW - SI KW - Kilogram KW - Mole KW - XRCD method PY - 2020 DO - https://doi.org/10.1007/s12647-020-00408-y VL - 35 SP - 499 EP - 510 PB - Springer Verlag AN - OPUS4-51637 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 - Tatzel, Michael A1 - Vogl, Jochen A1 - Rosner, M. A1 - Henehan, M. J. A1 - Tütken, T. T1 - Triple Isotope Fractionation Exponents of Elements Measured by MC-ICP-MS - An Example of Mg N2 - In most chemical reactions, stable isotopes are fractionated in a mass-dependent manner, yielding correlated isotope ratios in elements with three or more stable isotopes. The proportionality between isotope ratios is set by the triple isotope fractionation exponent θ that can be determined precisely for, e.g., sulfur and oxygen by IRMS, but not for metal(loid) elements due to the lower precision of MC-ICP-MS analysis and smaller isotopic variations. Here, using Mg as a test case, we compute a complete metrologically robust uncertainty budget for apparent θ values and, with reference to this, present a new measurement Approach that reduces uncertainty on θ values by 30%. This approach, namely, direct educt-product bracketing (sample−sample bracketing), allows apparent θ values of metal(loid) isotopes to be determined precisely enough to distinguish slopes in three-isotope space. For the example of Mg, we assess appropriate quality Control standards for interference-to-signal ratios and Report apparent θ values of carbonate−seawater pairs. We determined apparent θ values for marine biogenic carbonates, where the foraminifera Globorotalia menardii yields 0.514 ± 0.005 (2 SD), the coral Porites, 0.515 ± 0.006 (2 SD), and two specimens of the giant clam Tridacna gigas, 0.508 ± 0.007 (2 SD) and 0.509 ± 0.006 (2 SD), documenting differences in the uptake pathway of Mg among marine calcifiers. The capability to measure apparent θ values more precisely adds a new dimension to metal(loid) δ values, with the potential to allow us to resolve different modes of fractionation in industrial and natural processes. KW - Isotope fractionation KW - Delta value KW - Biogenic carbonates KW - Calcification KW - Magnesium isotope ratios KW - Measurement uncertainty KW - Sample-sample bracketing PY - 2019 DO - https://doi.org/10.1021/acs.analchem.9b02699 VL - 91 IS - 22 SP - 14314 EP - 14322 PB - ACS Publications AN - OPUS4-49818 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 - Kader, A. A1 - Brangsch, J. A1 - Reimann, C. A1 - Kaufmann, Jan Ole A1 - Mangarova, D. B. A1 - Moeckel, J. A1 - Adams, L. C. A1 - Zhao, J. A1 - Saatz, Jessica A1 - Traub, Heike A1 - Buchholz, R. A1 - Karst, U. A1 - Hamm, B. A1 - Makowski, M. R. T1 - Visualization and Quantification of the Extracellular Matrix in Prostate Cancer Using an Elastin Specific Molecular Probe N2 - One of the most commonly diagnosed cancers in men is prostate cancer (PCa). Understanding tumor progression can help diagnose and treat the disease at an early stage. Components of the extracellular matrix (ECM) play a key role in the development and progression of PCa. Elastin is an essential component of the ECM and constantly changes during tumor development. This article visualizes and quantifies elastin in magnetic resonance imaging (MRI) using a small molecule probe. Results were correlated with histological examinations. Using an elastin-specific molecular probe, we were able to make predictions about the cellular structure in relation to elastin and thus draw conclusions about the size of the tumor, with smaller tumors having a higher elastin content than larger tumors. Human prostate cancer (PCa) is a type of malignancy and one of the most frequently diagnosed cancers in men. Elastin is an important component of the extracellular matrix and is involved in the structure and organization of prostate tissue. The present study examined prostate cancer in a xenograft mouse model using an elastin-specific molecular probe for magnetic resonance molecular imaging. Two different tumor sizes (500 mm3 and 1000 mm3) were compared and analyzed by MRI in vivo and histologically and analytically ex vivo. The T1-weighted sequence was used in a clinical 3-T scanner to calculate the relative contrast enhancement before and after probe administration. Our results show that the use of an elastin-specific probe enables better discrimination between tumors and surrounding healthy tissue. Furthermore, specific binding of the probe to elastin fibers was confirmed by histological examination and laser ablation–inductively coupled plasma–mass spectrometry (LA-ICP-MS). Smaller tumors showed significantly higher signal intensity (p > 0.001), which correlates with the higher proportion of elastin fibers in the histological evaluation than in larger tumors. A strong correlation was seen between relative enhancement (RE) and Elastica–van Gieson staining (R2 = 0.88). RE was related to inductively coupled plasma–mass spectrometry data for Gd and showed a correlation (R2 = 0.78). Thus, molecular MRI could become a novel quantitative tool for the early evaluation and detection of PCa. KW - Magnetic resonance imaging KW - MRI KW - Molecular imaging KW - Cancer KW - LA-ICP-MS PY - 2021 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-538410 DO - https://doi.org/10.3390/biology10111217 VL - 10 IS - 11 SP - 1 EP - 14 PB - MDPI CY - Basel AN - OPUS4-53841 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Golusda, L. A1 - Kühl, A. A. A1 - Lehmann, M. A1 - Dahlke, K. A1 - Mueller, S. A1 - Boehm-Sturm, P. A1 - Saatz, Jessica A1 - Traub, Heike A1 - Schnorr, J. A1 - Freise, C. A1 - Taupitz, M. A1 - Biskup, K. A1 - Blanchard, V. A1 - Klein, O. A1 - Sack, I. A1 - Siegmund, B. A1 - Paclik, D. T1 - Visualization of inflammation in experimental colitis by magnetic resonance imaging using very small superparamagnetic iron oxide particles N2 - Inflammatory bowel diseases (IBD) comprise mainly ulcerative colitis (UC) and Crohn´s disease (CD). Both forms present with a chronic inflammation of the (gastro) intestinal tract, which induces excessive changes in the composition of the associated extracellular matrix (ECM). In UC, the inflammation is limited to the colon, whereas it can occur throughout the entire gastrointestinal tract in CD. Tools for early diagnosis of IBD are still very limited and highly invasive and measures for standardized evaluation of structural changes are scarce. To investigate an efficient non-invasive way of diagnosing intestinal inflammation and early changes of the ECM, very small superparamagnetic iron oxide nanoparticles (VSOPs) in magnetic resonance imaging (MRI) were applied in two mouse models of experimental colitis: the dextran sulfate sodium (DSS)-induced colitis and the transfer model of colitis. For further validation of ECM changes and inflammation, tissue sections were analyzed by immunohistochemistry. For in depth ex-vivo investigation of VSOPs localization within the tissue, Europium-doped VSOPs served to visualize the contrast agent by imaging mass cytometry (IMC). VSOPs accumulation in the inflamed colon wall of DSS-induced colitis mice was visualized in T2* weighted MRI scans. Components of the ECM, especially the hyaluronic acid content, were found to influence VSOPs binding. Using IMC, colocalization of VSOPs with macrophages and endothelial cells in colon tissue was shown. In contrast to the DSS model, colonic inflammation could not be visualized with VSOP-enhanced MRI in transfer colitis. VSOPs present a potential contrast agent for contrast-enhanced MRI to detect intestinal inflammation in mice at an early stage and in a less invasive manner depending on hyaluronic acid content. KW - Inflammation KW - Imaging KW - Immunohistochemistry KW - MRI KW - Nanoparticle KW - Extracellular matrix KW - Laser ablation KW - ICP-MS PY - 2022 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-555395 DO - https://doi.org/10.3389/fphys.2022.862212 SN - 1664-042X VL - 13 IS - July 2022 SP - 1 EP - 15 PB - Frontiers Research Foundation CY - Lausanne AN - OPUS4-55539 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - 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 -