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Sulfamethoxazol (SMX),a sulfonamide, is a widely used bacteriostatic antibiotic and therefore a promising marker for the entry of anthropogenic Pollution in the environment. SMX is frequently found in wastewater and surface water. This study presents the production of high affinity and selective polyclonal antibodies for SMX and the development and Evaluation of a direct competitive enzyme-linked immunosorbent assay(ELISA)for the quantification of SMX in environmental watersamples. The crystal structures of the cross-reacting compounds sulfamethizole, N4-acetyl-SMX andsuccinimidyl-SMX were determined by x-ray diffraction aiming to explain their high cross-reactivity. These crystal structures are described for the first time. The quantification range of the ELISA is 0.82–63 µg/L. To verify our results, the SMX concentration in 20 environmental samples,including wastewater and surfacewater,was determined by ELISA and tandem mass spectrometry(MS/MS).A good Agreement of the measured SMX concentrations was found with average recoveries of 97–113%for the results of ELISA compared to LC-MS/MS.
The present work shows results on elemental distribution analyses in Cu(In,Ga)Se2 thin films for solar cells performed by use of wavelength-dispersive and energy-dispersive X-ray spectrometry (EDX) in a scanning electron microscope, EDX in a transmission electron microscope, X-ray photoelectron, angle-dependent soft X-ray emission, secondary ion-mass (SIMS), time-of-flight SIMS, sputtered neutral mass, glow-discharge optical emission and glow-discharge mass, Auger electron, and Rutherford backscattering spectrometry, by use of scanning Auger electron microscopy, Raman depth profiling, and Raman mapping, as well as by use of elastic recoil detection analysis, grazing-incidence X-ray and electron backscatter diffraction, and grazing-incidence X-ray fluorescence analysis. The Cu(In,Ga)Se2 thin films used for the present comparison were produced during the same identical deposition run and exhibit thicknesses of about 2 µm. The analysis techniques were compared with respect to their spatial and depth resolutions, measuring speeds, availabilities, and detection limits.
The development of fluorescence applications in the life and material sciences has proceeded largely without sufficient concern for the measurement uncertainties related to the characterization of fluorescence instruments. In this first part of a two-part series on the state-of-the-art comparability of corrected emission spectra, four National Metrology Institutes active in high-precision steady-state fluorometry performed a first comparison of fluorescence measurement capabilities by evaluating physical transfer standard (PTS)-based and reference material (RM)-based calibration methods. To identify achievable comparability and sources of error in instrument calibration, the emission spectra of three test dyes in the wavelength region from 300 to 770 nm were corrected and compared using both calibration methods. The results, obtained for typical spectrofluorometric (0°/90° transmitting) and colorimetric (45°/0° front-face) measurement geometries, demonstrated a comparability of corrected emission spectra within a relative standard uncertainty of 4.2% for PTS- and 2.4% for RM-based spectral correction when measurements and calibrations were performed under identical conditions. Moreover, the emission spectra of RMs F001 to F005, certified by BAM, Federal Institute for Materials Research and Testing, were confirmed. These RMs were subsequently used for the assessment of the comparability of RM-based corrected emission spectra of field laboratories using common commercial spectrofluorometers and routine measurement conditions in part 2 of this series (subsequent paper in this issue).
The performance of glow discharge mass spectrometry (GD-MS) is investigated for the accurate quantification of metallic impurities and oxygen in solid samples using the fast flow source GD-MS instrument ELEMENT GD.
Different quantification approaches based on relative and absolute sensitivity factors are evaluated for the determination of metallic impurities using three sample matrixes (Al, Cu and Zn). The effect of the discharge conditions (voltage, current, discharge gas pressure/flow) on the sensitivity is investigated and the parameters are optimized to favour matrix independent calibrations. Improved standard relative sensitivity factors (StdRSFs) are calculated under optimal conditions based on multi-matrix calibrations. The sputtering rate corrected calibration is also presented as a multi-matrix calibration approach.
The capabilities of GD-MS for oxygen determination are also investigated using a set of new conductive samples containing oxygen with mass fractions in the percent range in three different matrices (Al, Mg and Cu) produced by a sintering process. Poor limits of detection (in the order of g/kg) were obtained as consequence of the reduced sensitivity of oxygen in GD-MS and high oxygen background signal intensity as well as its variations. The absolute sensitivity procedure is shown as a matrix-independent approach, which provides quantitative values consistent with those obtained by carrier gas hot extraction (CGHE).
One of the challenges of high-temperature polymer electrolyte membrane fuel cells is the poisoning of the Pt catalyst with H3PO4. H3PO4 is imbibed into the routinely used polybenzimidazole-based membranes, which facilitate proton conductivity in the temperature range of 120−200 °C. However, when leached out of the membrane by water produced during operation, H3PO4 adsorbs on the Pt catalyst surface, blocking the active sites and hindering the oxygen reduction reaction (ORR).
The reduction of H3PO4 to H3PO3, which occurs at the anode due to a combination of a low potential and the presence of gaseous H2, has been investigated as an additional important contributing factor to the observed poisoning effect. H3PO3 has an affinity toward adsorption on Pt surfaces even greater than that of H2PO4 −. In this work, we investigated the poisoning effect of both H3PO3 and H3PO4 using a half-cell setup with a gas diffusion electrode under ambient conditions. By means of in situ X-ray absorption spectroscopy, it was possible to follow the signature of different species adsorbed on the Pt nanoparticle catalyst (H, O, H2PO4 −, and H3PO3) at different potentials under ORR conditions in various electrolytes (HClO4, H3PO4, and H3PO3). It was found that H3PO3 adsorbs in a pyramidal configuration P(OH)3 through a Pt−P bond. The competition between H3PO4 and H3PO3 adsorption was studied, which should allow for a better understanding of the catalyst poisoning mechanism and thus assist in the development of strategies to mitigate this phenomenon in the future by minimizing H3PO3 generation by, for example, improved catalyst design or adapted operation conditions or changes in the electrolyte composition.
“Fluxomics” refers to the systematic analysis of metabolic fluxes in a biological system and may uncover novel dynamic properties of metabolism that remain undetected in conventional metabolomic approaches. In labeling experiments, tracer molecules are used to track changes in the isotopologue distribution of metabolites, which allows one to estimate fluxes in the metabolic network. Because unidentified compounds cannot be mapped on pathways, they are often neglected in labeling experiments. However, using recent developments in de novo annotation may allow to harvest the information present in these compounds if they can be identified. Here, we present a novel tool (HiResTEC) to detect tracer incorporation in high-resolution mass spectrometry data sets. The software automatically extracts a comprehensive, nonredundant list of all compounds showing more than 1% tracer incorporation in a nontargeted fashion. We explain and show in an example data set how mass precision and other filter heuristics, calculated on the raw data, can efficiently be used to reduce redundancy and noninformative signals by 95%. Ultimately, this allows to quickly investigate any labeling experiment for a complete set of labeled compounds (here 149) with acceptable false positive rates. We further re-evaluate a published data set from liquid chromatography-electrospray ionization (LC-ESI) to demonstrate broad applicability of our tool and emphasize importance of quality control (QC) tests. HiResTEC is provided as a package in the open source software framework R and is freely available on CRAN.
In the second part of this two-part series on the state-of-the-art comparability of corrected emission spectra, we have extended this assessment to the broader community of fluorescence spectroscopists by involving 12 field laboratories that were randomly selected on the basis of their fluorescence measuring equipment. These laboratories performed a reference material (RM)-based fluorometer calibration with commercially available spectral fluorescence standards following a standard operating procedure that involved routine measurement conditions and the data evaluation software LINKCORR developed and provided by the Federal Institute for Materials Research and Testing (BAM). This instrument-specific emission correction curve was subsequently used for the determination of the corrected emission spectra of three test dyes, X, QS, and Y, revealing an average accuracy of 6.8% for the corrected emission spectra. This compares well with the relative standard uncertainties of 4.2% for physical standard-based spectral corrections demonstrated in the first part of this study (previous paper in this issue) involving an international group of four expert laboratories. The excellent comparability of the measurements of the field laboratories also demonstrates the effectiveness of RM-based correction procedures.
To date, in the textile manufacturing process of warp knitting, trouble-shooting and process optimization mainly rely on empirical knowledge and experiments. This factor limits the achievable increase in productivity and quality. On the other hand, using simulations, different phenomena that affect the quality of the knitted fabric and the knitting process can be clarified in the run-up of the experiments. Consequently, an increase in quality and flexibility can be reached with reduced experimental effort. This paper presents a process simulation of the warp thread dynamics in the thread feeding system of a warp knitting machine. For this purpose, a continuum model of the warp thread that includes the spatial dynamics of the thread and the axial transport movement has been developed.
Metal-based gas diffusion electrodes are utilized in chlor-alkali electrolysis or electrochemical reduction of carbon dioxide, allowing the reaction to proceed at high current densities. In contrast to planar electrodes and predominantly 2D designs, the industrially required high current densities can be achieved by intense contact between the gas and liquid phase with the catalytically active surfaces. An essential asset for the knowledge-based design of tailored electrodes is therefore in-depth information on electrolyte distribution and intrusion into the electrode’s porous structure. Lab-based and synchrotron radiography allow for monitoring this process operando. Herein, we describe the development of a cell design that can be modularly adapted and successfully used to monitor both the oxygen reduction reaction and the electrochemical reduction of CO2 as exemplary and currently very relevant examples of gas-liquid reactions by only minor modifications to the cell set-up. With the reported cell design, we were able to observe the electrolyte distribution within the gas diffusion electrode during cell operation in realistic
conditions.
The conventional hybridoma screening and subcloning process is generally considered to be one of the most critical steps in hapten-specific antibody production. It is time-consuming, monoclonality is not guaranteed, and the number of clones that can be screened is limited. Our approach employs a novel hapten-specific labeling technique of hybridoma cells. This allows for fluorescence-activated cell sorting (FACS) and single-cell deposition and thereby eliminates the above-mentioned problems. A two-step staining approach is used to detect antigen specificity and antibody expression: in order to detect antigen specificity, hybridoma cells are incubated with a hapten−horseradish peroxidase conjugate (hapten−HRP), which is subsequently incubated with a fluorophore-labeled polyclonal anti-peroxidase antibody (anti-HRP−Alexa Fluor 488). To characterize the expression of membrane-bound immunoglobulin G (IgG), a fluorophore-labeled anti-mouse IgG antibody (anti-IgG−Alexa Fluor 647) is used. Hundreds of labeled hybridoma cells producing monoclonal antibodies (mAbs) specific for a hapten were rapidly isolated and deposited from a fusion mixture as single-cell clones via FACS. Enzyme-linked immunosorbent assay (ELISA) measurements of the supernatants of the sorted hybridoma clones revealed that all hapten-specific hybridoma clones secrete antibodies against the target. There are significant improvements using this high-throughput technique for the generation of mAbs including increased yield of antibody-producing hybridoma clones, ensured monoclonality of sorted cells, and reduced development times.
For many heterogeneous sensor applications as well as the synthesis of hapten antigens to produce antibodies, protein conjugates of the target substance are essential. A requirement is that the target substance already offers or is modified to contain a functionality that allows for coupling to a protein, that is, an amino acid residue. Ideally, to avoid shielding of the compound by the carrier protein, a sufficient distance to the protein surface should be provided. With its carboxyl function diclofenac (DCF) allows for direct binding to lysine residues after in situ synthesis of the NHS ester. One problem is that diclofenac as free acid tends to autocondensation, which results in low yields. Here we describe the 'insertion' of a C6 spacer via synthesis of the amide with 6-aminohexanoic acid. To carry out the reaction in solution, first the methyl ester of the amino acid had to be produced. Due to otherwise low yields and large cleaning efforts, solid-phase synthesis on Fmoc Ahx Wang resin is recommended. The crude product is mainly contaminated by cleavage products from the resin which were removed by chromatography. The structure of the highly pure hapten was completely determined by nuclear magnetic resonance (NMR) spectroscopy.
Small-scale variations in mineral chemistry, textures, and platinum group element (PGE) mineralization were investigated in the Lower and Middle Group chromitite layers LG6, LG6a, MG1, MG2, and MG2 II from vertical drill core profiles at the Thaba mine in the northwestern limb of the Bushveld Complex. We present detailed geochemical profiles of chromite composition and chromite crystal size distribution curves to shed light on the processes of chromite accumulation and textural modification as well as mineralization. Multiple samples within each layer were assayed for PGE concentrations, and the respective platinum group mineral association was determined by mineral liberation analysis (MLA).
There is strong evidence for postcumulus changes in the chromitites. The crystal size distribution curves suggest that the primary chromite texture was coarsened by a combination of adcumulus growth and textural equilibration, while compaction of the crystal mush played only a minor role. Mineral compositions were also modified by postcumulus processes, but because of the very high modal amount of chromite and its local preservation in orthopyroxene oikocrysts, that phase retained much primary information. Vertical variations of chromite composition within chromitite layers and from one layer to another do not support the idea of chromite accumulation from crystal-rich slurries or crystal settling from a large magma chamber. Instead, we favor a successive buildup of chromitite layers by repeated injections of relatively thin layers of chromite-saturated magmas, with in situ crystallization occurring at the crystal mush-magma interface. The adcumulus growth of chromite grains to form massive chromitite required addition of Cr to the layers, which we attribute to downward percolation from the overlying magma.
The PGE concentrations are elevated in all chromitite layers compared to adjacent silicate rocks and show a systematic increase upward from LG6 (avg 807 ppb Ir + Ru + Rh + Pt + Pd + Au) to MG2 II (avg 2,062 ppb).
There are also significant internal variations in all layers, with enrichments at hanging and/or footwalls. The enriched nature of chromitites in PGEs compared to host pyroxenites is a General feature, independent of the layer thickness. The MLA results distinguish two principal groups of PGE mineral associations: the LG6, LG6, and MG1 are dominated by the malanite series, laurite, and PGE sulfarsenides, while the MG2 and MG2 II layers are characterized by laurite and PGE sulfides as well as Pt-Fe-Sn and PGE-Sb-Bi-Pb alloys. Differences in the PGE associations are attributed to postcumulus alteration of the MG2 and MG2 II layer, while the chromitites below, particularly LG6 and LG6a, contain a more pristine association.
3-Bromopyruvic acid (3BP) is a potential anticancer drug, the action of which on cellular metabolism is not yet entirely clear. The presence of a bromine atom suggests that it is also reactive towards low-energy electrons, which are produced in large quantities during tumour Radiation therapy. Detailed knowledge of the interaction of 3BP with secondary electrons is a prerequisite to gain a complete picture of the effects of 3BP in different forms of Cancer therapy. Herein, dissociative electron attachment (DEA) to 3BP in the gas phase has been studied both experimentally by using a crossed-beam setup and theoretically through scattering and quantum chemical calculations. These results are complemented by a vacuum ultraviolet absorption spectrum.
The main fragmentation channel is the formation of Br@ close to 0 eV and within several resonant features at 1.9 and 3–8 eV. At low electron energies, Br@ formation proceeds through s* and p* shape resonances, and at higher energies through core-excited resonances. It is found that the electron-capture cross-section is clearly increased compared with that of non-brominated pyruvic acid, but, at the same time, fragmentation reactions through DEA are significantly altered as well. The 3BP transient negative ion is subject to a lower number of fragmentation reactions than those of pyruvic acid, which indicates that 3BP could indeed act by modifying the electron-transport chains within oxidative phosphorylation. It could also act as a radio-sensitiser.
Limited data exist on the pharmacokinetic profile of novel direct acting antivirals in kidney transplant recipients. Daclatasvir is primarily eliminated via the biliary route and sofosbuvir via the renal route; here we report the pharmacokinetic profile of combined treatment with these compounds in a prospective study of hepatitis C virus positive kidney transplant recipients (EudraCT: 2014-004551-32). In this study plasma samples of 16 HCV positive kidney transplant recipients receiving daclatasvir and sofosbuvir were collected at 4 time points at day 1, 7, 14, 21, 56, and 84 after start of treatment. Inclusion criteria were stable graft function and an estimated GFR (eGFR) > 30mL/min/1.73m. Daclatasvir, sofosbuvir and GS-331007 (inactive metabolite of sofosbuvir) plasma concentrations were determined using ultra-performance liquid chromatography quadrupole time of flight mass spectrometry. All patients showed a rapid virological response with HCV RNA below the detection limit 21 days after the start of therapy (medium time to viral clearance). No difference of the areas under the concentration-time curve (AUC) of daclatsavir, sofosbuvir and GS-331007 was observed between patients with an eGFR below or ≥ 60mL/min. For GS-331007, no relevant changes of trough levels were observed over time. Mean GS-331007 trough levels were 339.5±174.9 ng/mL in patients with an eGFR ≥ 60mL/min and 404.3±226 ng/mL in patients with an eGFR < 60mL/min at day 7 (p=0.52). At day 84, GS-331007 trough levels were 357.8±200.8 ng/mL and 404.2±70.2 ng/mL in patients with an eGFR ≥ 60 mL/min and in patients with an eGFR < 60 mL/min, respectively (p=0.51). The accumulation ratios of renally eliminated GS-331007 for AUC and Cmax did not significantly differ between the two eGFR groups at day 7. An impaired eGFR (30-60 mL/min) does not lead to a dose accumulation of daclatasvir, sofosbuvir and GS-331007. This study provides the rationale for future studies investigating the pharmacokinetic profile of sofosbuvir based HCV treatment in kidney transplant recipients with an eGFR < 30 mL/min.
An interlaboratory comparison (ILC)was organised to characterise 87Sr/86Sr isotope ratios in geological and industrial reference materials by applying the so-called conventional method for determining 87Sr/86Sr isotope ratios. Four cements (VDZ 100a,VDZ 200a, VDZ 300a, IAG OPC-1), one limestone (IAG CGL ML-3) and one slate (IAG OU-6) reference materials were selected, covering a wide range of naturally occurring Sr isotopic signatures. Thirteen laboratories received aliquots of these six reference materials together with a detailed technical protocol. The consensus values for the six reference materials and their associated measurement uncertainties were obtained by applying a Gaussian, linear mixed effects model fitted to all the measurement results. By combining the consensus values and their uncertainties with an uncertainty contribution for potential heterogeneity, reference values ranging from 0.708134 mol mol-1 to 0.729778 mol mol-1 were obtained with relative expanded uncertainties of ≤ 0.007 %. This study represents an ILC on conventional 87Sr/86Sr isotope ratios, within which metrological principles were considered and the compatibility of measurement results obtained by MC-ICP-MS and by MC-TIMS is demonstrated. The materials characterised in this study can be used as reference materials for validation and quality control purposes and to estimate measurement uncertainties in conventional 87Sr/86Sr isotope ratio measurement.
During the mineralisation of metal carbonates MCO3 (M = Ca, Sr, Ba, Mn, Cd, Pb) liquid-like amorphous intermediates emerge. These intermediates that form via a liquid/liquid phase separation behave like a classical emulsion and are stabilized electrostatically. The occurrence of these intermediates is attributed to the formation of highly hydrated networks whose stability is mainly based on weak interactions and the variability of the metal-containing pre-critical clusters. Their existence and compositional freedom are evidenced by electrospray ionization mass spectrometry (ESI-MS). Liquid intermediates in non-classical crystallisation pathways seem to be more common than assumed.