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Organisationseinheit der BAM
Ananion-dopedaluminiumchlorofluoride AlCl0.1F2.8(OTeF5)0.1(ACF-teflate) was synthesized.The material contains pentafluor-oorthotellurate(teflate)groups, which mimic fluoride ions electronically, but are sterically more demanding. They are embedded into the amorphous structure. The latter was studied by PDF analysis, EXAFS data and MAS NMR spectroscopy. The mesoporous powder is a Lewis superacid, and ATR-IR spectra of adsorbed CD3CN reveal a blue-shift of the adsorption band by73 cm-1, which is larger than the shift for SbF5. Remarkably,ACF-teflate catalyzes dehydrofluorination reactions of mono-fluoroalkanes to yield olefins in C6D6. In these cases,no Friedel-Crafts products were formed.
FAU membranes of type NaX and MFI membranes of type silicalite-1 which contain adsorbed azobenzene (AZB), have photoswitchable permeation properties due to the transcis photoisomerization of AZB. The change of gas permeation through these hostguest composite membranes depends on the irradiation wavelength, the quality of the membranes and the amount of adsorbed AZB. The permeances of the gases in the trans-form of the zeolite-encapsulated AZB were higher than those in the cis-form. The separation factors of equimolar mixtures of N2/CO2 and CH4/CO2 fed through the FAUAZB membrane were higher at trans-switching than at cis-switching. The changes of the permeances of single gases and of the separation factors of equimolar gas mixtures by photoinduced transcis switching were found to be reversible over numerous switching cycles. The experimental results are in agreement with predictions made by Monte Carlo simulations for passing of permeant gases through these hostguest systems with the zeolite-hosted AZB in the trans- and in the cis-configuration.
Clear evidence of the effects caused by hydrogen, introduced in different forms in an analytical glow discharge source (GDS) operated with argon, is presented for the different matrix elements copper, stainless steel, titanium, aluminium and silicon. When hydrogen is present even in small quantities in argon, not only are there significant changes in the emission line intensities of most elements (analyte and plasma species), but also new spectral features, such as emission bands of new compounds (hydrides of sputtered sample constituents) and a continuous background in the range ~220440 nm. Moreover, the discharge current (the dependent parameter in our experiments) decreases with increasing hydrogen concentration. Different modes of hydrogen introduction, externally in gaseous form or sputtered as a sample constituent, cause very similar effects in terms of discharge current, line intensity (of analyte and plasma gas) and emission continua, which implies similar changes in the discharge processes in the two cases. The excitation of the hydrogen continuum appears to quench the population of the argon metastables (11.55 and 11.72 eV) and, consequently, other elementary processes in the plasma in which the argon metastables take part, but to a different extent for each analyte.
The influence of hydrogen contained in a sample or otherwise introduced into a glow discharge source (GDS) is here extensively experimentally presented for the case of copper as a sample by means of the addition of small quantities of molecular hydrogen (<1% relative partial pressure) to the argon carrier gas. The progressive addition of molecular hydrogen causes different intensity changes particular to the individual lines of different species such as atomic (Cu I) and ionic (Cu II) copper, and also atomic (Ar I) and ionic (Ar II) argon. Some interesting features of the emission spectrum of hydrogen such as its line, band and even continuum spectrum are observed. It was also found that the depth resolution becomes worse even at very low concentrations of hydrogen.
The analysis of thin layers of thickness 100 nm has become a new field of application for glow discharge optical emission spectroscopy (GDOES). In this paper an overview is given of the experiences and possibilities gained by the authors in later years at their research, development and application of GDOES.
During GDOES analysis of a multilayer system the depth resolution was determined using the inverse maximal slope method. Under optimized discharge conditions a depth resolution of 25 nm at 100 nm depth was achieved. The gas flow in a Grimm-type source for glow discharge mass spectrometry (GDMS) was simulated and a correlation between calculated pressure and crater shape was found. Cleanness of the sample and source turned out to be essential for a fast stabilization time and reduction of the influence of light elements and molecules. Thereby, a 10 nm layer at the top surface of a sample could be quantified. Apart from the influence of density, the reflectivity of the sample surface is discussed. It is shown that a high sample reflectivity can cause up to 100% more light to be measured by the spectrometer.
Depth profiling of electrically non-conductive layered samples by RF-GDOES and HFM plasma SNMS
(2001)
The work is intended to compare the capabilities of two similar depth profiling techniques to analyse electrically non-conductive samples. In order to get a better evaluation of the depth resolution, various multilayer sandwiches, such as SiO2/TiO2 and Si3N4/SiO2 deposited on glass substrates have been investigated. Optimised depth profiles are presented for both methods, glow discharge optical emission spectrometry (GDOES) and radiofrequency mode (known as HFM in the SNMS literature) of plasma secondary neutral mass spectrometry (SNMS). The optimisation procedure, necessary to get the best set of plasma parameters, which result in the optimal depth resolution, is also described for one selected sample. Additionally, sputtering crater profilometry was carried out in order to check out the flatness of the sputtered crater. The influence of the thickness of the sample substrate on the sputtering rate is discussed. Finally, advantages and disadvantages of the use of these two depth profiling methods, especially for the non-conductive samples, are concluded from this comparative study. Time-of-flight secondary ion mass spectrometry (ToF-SIMS) analysis of a cross-sectioned sample was carried out in order to get supplementary information.
In order to gain an insight into the numerous effects caused by the addition of hydrogen to an argon glow discharge, comparison experiments have been made with neon as carrier gas. In some cases the effects are diminished or even disappear. Using various bulk samples, such as copper, steel and titanium, sputtered in a neon glow discharge, the intensities of the analytical lines are affected by the presence of hydrogen in different ways from argon; the dependent parameter (the discharge current in this work) and the sputtering rate vary less than in argon. The crater shape and roughness are also affected and these effects are discussed qualitatively. Probably the most important spectral feature caused by hydrogen in the case of a discharge in argon is the emission of a continuous background. This does not appear in neon under similar discharge conditions and only weakly at high hydrogen concentrations. This supports the suggestion, made in previous work, that an effective quenching process of the argon metastables (11.55 and 11.72 eV) is Penning excitation of the hydrogen molecules, and subsequent decay to a repulsive state with emission of the continuum; in neon the energy match does not occur. It was found with neon, as with argon, that similar features occur as when hydrogen is introduced in different ways into the glow discharge: as a molecular gas contamination or as a constituent of the sample. Glow discharge mass spectrometry (GD-MS) experiments carried out with both argon and neon support the results obtained by optical emission spectrometry (OES) and provide further relevant information.
Objective: The utilization of fluorescein-guided biopsies and resection has been recently discussed as a suitable strategy to improve and expedite operative techniques for the resection of central nervous system (CNS) tumors. However, little is known about the optical properties of sodium fluorescein (NaFl) in human tumor tissue and their potential impact on ex vivo analyses involving fluorescence-based methods.
Methods: Tumor tissue was obtained from a study cohort of an observational study on the utilization of fluorescein-guided biopsy and resection (n=5). The optical properties of fluorescein-stained tissue were compared to the optical features of the dye in vitro and in control samples consisting of tumor tissue of high-grade glioma patients (n=3) without intravenous (i.v.) application of NaFl. The dye-exposed tumor tissues were used for optical measurements to confirm the detectability of NaFl emission ex vivo. The tissue samples were fixed in 4%PFA, immersed in 30% sucrose, embedded in Tissue-Tek OCT compound, and cut to 10 mm cryosections. Spatially resolved emission spectra from tumor samples were recorded on representative slides with a Confocal Laser Scanning Microscope FV1000 (Olympus GmbH, Hamburg, Germany) upon excitation with lexc = 488 nm.
Results: Optical measurements of fluorescein in 0.9% sodium chloride (NaCl) under in vitro conditions showed an absorption maximum of lmax abs = 479 nm as detected with spectrophotometer Specord 200 and an emission peak at lmax em = 538 nm recorded with the emCCD detection system of a custom-made microscope-based single particle setup using a 500 nm long-pass filter. Further measurements revealed pH- and concentration-dependent emission spectra of NaFl. Under ex vivo conditions, confocal laser scanning microscopy of fluorescein tumor samples revealed a slight bathochromic shift and a broadening of the emission band.
Conclusion: Tumor uptake of NaFl leads to changes in the optical properties – a bathochromic shift and broadening of the emission band – possibly caused by the dye’s high pH sensitivity and concentration-dependent reabsorption acting as an innerfilter of the dye’s emission, particularly in the short wavelength region of the Emission spectrum where absorption and fluorescence overlap. Understanding the ex vivo optical properties of fluorescein is crucial for testing and validating its further applicability as an optical probe for intravital microscopy, immunofluorescence localization studies, and flow cytometry analysis.
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.
Between Aromatic and Quinoid Structure: A Symmetrical UV to Vis/NIR Benzothiadiazole Redox Switch
(2020)
Reversibly switching the light absorption of organic molecules by redox processes is of interest for applications in sensors, light harvesting, smart materials, and medical diagnostics. This work presents a symmetrical benzothiadiazole (BTD) derivative with a high fluorescence quantum yield in solution and in the crystalline state and shows by spectroelectrochemical analysis that reversible switching of UV absorption in the neutral state, to broadband Vis/NIR absorption in the 1st oxidized state, to sharp band Vis absorption in the 2nd oxidized state, is possible.
For the one-electron oxidized species, formation of a delocalized radical is confirmed by electron paramagnetic resonance spectroelectrochemistry. Furthermore, our results reveal an increasing quinoidal distortion upon the 1st and 2nd oxidation, which can be used as the leitmotif for the development of BTD based redox switches.
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.
A novel method that optimizes the screening for antibody-secreting hapten-specific hybridoma cells by using flow cytometry is described. Cell clones specific for five different haptens were analyzed. We selectively double stained and analyzed fixed hybridoma cells with fluorophore-labeled haptens to demonstrate the target-selectivity, and with a fluorophore-labeled anti-mouse IgG antibody to characterize the level of surface expression of membrane-bound IgGs. ELISA measurements with the supernatants of the individual hybridoma clones revealed that antibodies from those cells, which showed the highest fluorescence intensities in the flow cytometric analysis, also displayed the highest affinities for the target antigens. The fluorescence intensity of antibody-producing cells corresponded well with the produced antibodies' affinities toward their respective antigens. Immunohistochemical staining verified the successful double labeling of the cells. Our method makes it possible to perform a high-throughput screening for hybridoma cells, which have both an adequate IgG production rate and a high target affinity.