Quantitative depth profiling of Ce 3+ in Pt/CeO 2 by in situ high-energy XPS in a hydrogen atmosphere

The redox property of ceria is a key factor in the catalytic activity of ceria-based catalysts. The oxidation state of well-defined ceria nanocubes in gas environments was analysed in situ by a novel combination of near-ambient pressure X-ray Photoelectron Spectroscopy (XPS) and high-energy XPS at a synchrotron X-ray source. In situ high-energy XPS is a promising new tool to determine the electronic structure of matter under defined conditions. The aim was to quantitatively determine the degree of cerium reduction in a nano-structured ceria-supported platinum catalyst as a function of the gas environment. To obtain a non-destructive depth profile at near-ambient pressure, in situ high-energy XPS analysis was performed by varying the kinetic energy of photoelectrons from 1 to 5 keV, and, thus, the probing depth. In ceria nanocubes doped with platinum, oxygen vacancies formed only in the uppermost layers of ceria in an atmosphere of 1 mbar hydrogen and 403 K. For pristine ceria nanocubes, no change in the cerium oxidation state in various hydrogen or oxygen atmospheres was observed as a function of probing depth. In the absence of platinum, hydrogen does not dissociate and, thus, does not lead to reduction of ceria.

Reconstruction and electrochemical oxidation of Au(110) surface in 0.1 M H2SO4

Variations of the surface structure and composition of the Au(110) electrode during the formation/lifting of the surface reconstruction and during the surface oxidation/reduction in 0.1 M aqueous sulfuric acid were studied by cyclic voltammetry, scanning tunneling microscopy and shell-isolated nanoparticle enhanced Raman spectroscopy. Annealing of the Au(110) electrode leads to a thermally-induced reconstruction formed by intermixed (1×3) and (1×2) phases. In a 0.1 M H2SO4 solution, the decrease of the potential of the atomically smooth Au(110)-(1×1) surface leads to the formation of a range of structures with increasing surface corrugation. The electrochemical oxidation of the Au(110) surface starts by the formation of anisotropic atomic rows of gold oxide. At higher potentials we observed a disordered structure of the surface gold oxide, similar to the one found for the Au(111) surface.

CO Oxidation on Pt(100): New Insights based on Combined Voltammetric, Microscopic and Spectroscopic Experiments

We present an experimental study of the CO electro-oxidation on Pt(100)-(1 × 1) electrodes employing electrochemical methods in combination with in situ scanning tunneling microscopy (STM) and shell-isolated nanoparticle enhanced Raman spectroscopy (SHINERS). We discussed the nature and stability of the active sites in the preignition region in the presence of dissolved CO (COb) and monitored substrate structure changes during the COb electro-oxidation process. We corroborated that the electro-oxidation kinetics is determined decisively by the history of CO adlayer formation. A new mechanism was proposed for Pt(100) electrode deactivation in the preignition region after excursion of electrode potential to COb ignition region. We believe that this mechanism takes place on Pt surfaces independently on their crystallographic orientation.

Prediction of Post-Weaning Fibrinogen Status during Cardiopulmonary Bypass: An Observational Study in 110 Patients.

BACKGROUND After cardiac surgery with cardiopulmonary bypass (CPB), acquired coagulopathy often leads to post-CPB bleeding. Though multifactorial in origin, this coagulopathy is often aggravated by deficient fibrinogen levels. OBJECTIVE To assess whether laboratory and thrombelastometric testing on CPB can predict plasma fibrinogen immediately after CPB weaning. PATIENTS / METHODS This prospective study in 110 patients undergoing major cardiovascular surgery at risk of post-CPB bleeding compares fibrinogen level (Clauss method) and function (fibrin-specific thrombelastometry) in order to study the predictability of their course early after termination of CPB. Linear regression analysis and receiver operating characteristics were used to determine correlations and predictive accuracy. RESULTS Quantitative estimation of post-CPB Clauss fibrinogen from on-CPB fibrinogen was feasible with small bias (+0.19 g/l), but with poor precision and a percentage of error >30%. A clinically useful alternative approach was developed by using on-CPB A10 to predict a Clauss fibrinogen range of interest instead of a discrete level. An on-CPB A10 ≤10 mm identified patients with a post-CPB Clauss fibrinogen of ≤1.5 g/l with a sensitivity of 0.99 and a positive predictive value of 0.60; it also identified those without a post-CPB Clauss fibrinogen <2.0 g/l with a specificity of 0.83. CONCLUSIONS When measured on CPB prior to weaning, a FIBTEM A10 ≤10 mm is an early alert for post-CPB fibrinogen levels below or within the substitution range (1.5-2.0 g/l) recommended in case of post-CPB coagulopathic bleeding. This helps to minimize the delay to data-based hemostatic management after weaning from CPB.

Ms. hebr. oct. 110 - Pene levanah

Vorbesitzer: Eljāqīm Carmoly; Abraham Merzbacher

Chemical compositions of solid particles present in the Greenland NEEM ice core over the last 110,000 years

This study reports the chemical composition of particles present along Greenland’s North Greenland Eemian Ice Drilling (NEEM) ice core, back to 110,000 years before present. Insoluble and soluble particles larger than 0.45 μm were extracted from the ice core by ice sublimation, and their chemical composition was analyzed using scanning electron microscope and energy dispersive X-ray spectroscopy and micro-Raman spectroscopy. We show that the dominant insoluble components are silicates, whereas NaCl, Na₂SO₄, CaSO ₄, and CaCO₃ represent major soluble salts. For the first time, particles of CaMg(CO₃)₂ and Ca(NO₃)₂ 4H₂O are identified in a Greenland ice core. The chemical speciation of salts varies with past climatic conditions. Whereas the fraction of Na salts (NaCl + Na₂SO₄) exceeds that of Ca salts (CaSO₄+ CaCO₃) during the Holocene (0.6–11.7 kyr B.P.), the two fractions are similar during the Bølling-Allerød period (12.9–14.6 kyr B.P.). During cold climate such as over the Younger Dryas (12.0–12.6 kyr B.P.) and the Last Glacial Maximum (15.0–26.9 kyr B.P.), the fraction of Ca salts exceeds that of Na salts, showing that the most abundant ion generally controls the salt budget in each period. High-resolution analyses reveal changing particle compositions: those in Holocene ice show seasonal changes, and those in LGM ice show a difference between cloudy bands and clear layers, which again can be largely explained by the availability of ionic components in the atmospheric aerosol body of air masses reaching Greenland.

Adsorption of biomedical coating molecules, amino acids, and short peptides on magnetite (110)

Superparamagnetic iron oxide nanoparticles for biomedical applications are usually coated with organic molecules to form a steric barrier against agglomeration. The stability of these coatings is well established in the synthesis medium but is more difficult to assess in physiological environment. To obtain a first theoretical estimate of their stability in such an environment, we perform density functional theory calculations of the adsorption of water, polyvinyl alcohol (PVA) and polyethylene glycol (PEG) coating molecules, as well as the monomer and dimer of glycine as a prototype short peptide, on the (110) surface of magnetite (Fe3O4) in vacuo. Our results show that PVA binds significantly stronger to the surface than both PEG and glycine, while the difference between the latter two is quite small. Depending on the coverage, the wateradsorption strength is intermediate between PVA and glycine. Due to its strongly interacting OH side groups, PVA is likely to remain bound to the surface in the presence of short peptides. This stability will have to be further assessed by molecular dynamics in the solvated state for which the present work forms the basis.

Ms. Barth. 110 - Metamorphoseon Libri XV

Vorbesitzer: Bartholomaeusstift Frankfurt am Main

Subunit composition of VRAC channels determines substrate specificity and cellular resistance to Pt-based anti-cancer drugs

Although platinum-based drugs are widely used chemotherapeutics for cancer treatment, the determinants of tumor cell responsiveness remain poorly understood. We show that the loss of subunits LRRC8A and LRRC8D of the heteromeric LRRC8 volume-regulated anion channels (VRACs) increased resistance to clinically relevant cisplatin/carboplatin concentrations. Under isotonic conditions, about 50% of cisplatin uptake depended on LRRC8A and LRRC8D, but neither on LRRC8C nor on LRRC8E. Cell swelling strongly enhanced LRRC8-dependent cisplatin uptake, bolstering the notion that cisplatin enters cells through VRAC. LRRC8A disruption also suppressed drug-induced apoptosis independently from drug uptake, possibly by impairing VRAC-dependent apoptotic cell volume decrease. Hence, by mediating cisplatin uptake and facilitating apoptosis, VRAC plays a dual role in the cellular drug response. Incorporation of the LRRC8D subunit into VRAC substantially increased its permeability for cisplatin and the cellular osmolyte taurine, indicating that LRRC8 proteins form the channel pore. Our work suggests that LRRC8D-containing VRACs are crucial for cell volume regulation by an important organic osmolyte and may influence cisplatin/carboplatin responsiveness of tumors.

Contrasting PT paths within the Barchi-Kol UHP terrain (Kokchetav Complex): Implications for subduction and exhumation of continental crust

The Barchi-Kol terrain is a classic locality of ultrahigh-pressure (UHP) metamorphism within the Kokchetav metamorphic belt. We provide a detailed and systematic characterization of four metasedimentary samples using dominant mineral assemblages, mineral inclusions in zircon and monazite, garnet zonation with respect to major and trace elements, and Zr-in-rutile and Ti-in-zircon temperatures. A typical diamond-bearing gneiss records peak conditions of 49 ± 4 kbar and 950–1000 °C. Near isothermal decompression of this rock resulted in the breakdown of phengite associated with a pervasive recrystallization of the rock. The same terrain also contains mica schists that experienced peak conditions close to those of the diamond-bearing rocks, but they were exhumed along a cooler path where phengite remained stable. In these rocks, major and trace element zoning in garnet has been completely equilibrated. A layered gneiss was metamorphosed at UHP conditions in the coesite field, but did not reach diamond-facies conditions (peak conditions: 30 kbar and 800–900 °C). In this sample, garnet records retrograde zonation in major elements and also retains prograde zoning in trace elements. A garnet-kyanite-micaschist that reached significantly lower pressures (24 ± 2 kbar, 710 ± 20 °C) contains garnet with major and trace element zoning. The diverse garnet zoning in samples that experienced different metamorphic conditions allows to establish that diffusional equilibration of rare earth element in garnet likely occurs at ~900–950 °C. Different metamorphic conditions in the four investigated samples are also documented in zircon trace element zonation and mineral inclusions in zircon and monazite. U-Pb geochronology of metamorphic zircon and monazite domains demonstrates that prograde (528–521 Ma), peak (528–522 Ma), and peak to retrograde metamorphism (503–532 Ma) occurred over a relatively short time interval that is indistinguishable from metamorphism of other UHP rocks within the Kokchetav metamorphic belt. Therefore, the assembly of rocks with contrasting P-T trajectories must have occurred in a single subduction-exhumation cycle, providing a snapshot of the thermal structure of a subducted continental margin prior to collision. The rocks were initially buried along a low geothermal gradient. At 20–25 kbar they underwent near isobaric heating of 200 °C, which was followed by continued burial along a low geothermal gradient. Such a step-wise geotherm is in good agreement with predictions from subduction zone thermal models.

Frau Minna Klausner-Exin [Illustration] : geb. 1764 - gest. 1874 (110 Jahr alt)

Scan von Monochrom-Mikroform

Psalm 110

Hermann Baneth