In situ XPS investigation of Pt(Sn)/Mg(Al)O catalysts during ethane dehydrogenation experiments

Calcined hydrotalcite with or without added metal (Mg(Al)O, Pt/Mg(Al)O and Pt,Sn/Mg(Al)O) have been investigated with in situ X-ray Photoelectron Spectroscopy (XPS) during ethane dehydrogenation experiments. The temperature in the analysis chamber was 450oC and the gas pressure was in the range 0.3 – 1 mbar. Depth profiling of calcined hydrotalcite and platinum catalysts under reaction, oxidation and in hydrogen-water mixture was performed by varying the photon energy, covering an analysis depth of 10-21 Å. It was observed that the Mg/Al ratio in the Mg(Al)O crystallites does not vary significantly in the analysis depth range studied. This result indicates that Mg and Al are homogeneously distributed in the Mg(Al)O crystallites. Catalytic tests have shown that the initial activity of a Pt,Sn/Mg(Al)O catalyst increases during an activation period consisting of several cycles of reduction - dehydrogenation - oxidation. The Sn/Mg ratio in a Pt,Sn/Mg(Al)O catalyst was followed during several such cycles, and was found to increase during the activation period, probably due to a process where tin spreads over the carrier material and covers an increasing fraction of the Mg(Al)O surface. The results further indicate that spreading of tin occurs under reduction conditions. A PtSn2 alloy was studied separately. The surface of the alloy was enriched in Sn during reduction and reaction conditions at 450°C. Binding energies were determined and indicated that Sn on the particle surface is predominantly in an oxidized state under reaction conditions, while Pt and a fraction of Sn is present as a reduced Pt-Sn alloy

An outbreak caused by S. Typhimurium DT177, BTa in Bavaria characterized by an unusual antibiotic resistance and plasmid profile

Additional to the cases of S.Typhimurium infections due to the phage types DTI04 [1] and DTI20 an unusual high number of severe illness were observed in August/September 2000. Most of the cases came from Heiligenstadt, a town in n01thern Bavaria

Signatures of three-nucleon interactions in few-nucleon systems

Recent experimental results in three-body systems have unambiguously shown that calculations based only on nucleon-nucleon forces fail to accurately describe many experimental observables and one needs to include effects which are beyond the realm of the two-body potentials. This conclusion owes its significance to the fact that experiments and calculations can both be performed with a high accuracy. In this review, both theoretical and experimental achievements of the past decade will be underlined. Selected results will be presented. The discussion on the effects of the three-nucleon forces is, however, limited to the hadronic sector. It will be shown that despite the major successes in describing these seemingly simple systems, there are still clear discrepancies between data and the state-of-the-art calculations.Comment: accepted for publication in Rep. Prog. Phy

The Effect of Water on the 2-Propanol Oxidation Activity of Co-Substituted LaFe₁₋Co_xO₃ Perovskites

Perovskites are interesting oxidation catalysts due to their chemical flexibility enabling the tuning of several properties. In this work, we synthesized LaFe1−xCoxO3 catalysts by co-precipitation and thermal decomposition, characterized them thoroughly and studied their 2-propanol oxidation activity under dry and wet conditions to bridge the knowledge gap between gas and liquid phase reactions. Transient tests showed a highly active, unstable low-temperature (LT) reaction channel in conversion profiles and a stable, less-active high-temperature (HT) channel. Cobalt incorporation had a positive effect on the activity. The effect of water was negative on the LT channel, whereas the HT channel activity was boosted for x > 0.15. The boost may originate from a slower deactivation rate of the Co3+ sites under wet conditions and a higher amount of hydroxide species on the surface comparing wet to dry feeds. Water addition resulted in a slower deactivation for Co-rich catalysts and higher activity in the HT channel state

Failure analysis method for enhancing circularity through systems perspective

Recently, a circular economy has attracted global attention as an approach for addressing material security and resource-efficiency issues. As our societies shift toward a circular economy, manufacturers need to not only produce environmentally conscious products but to also realize reliable systems that will ensure the closure of the loops of the products, components, and materials. To do so, early-stage design is crucial to effectively and efficiently detect possible failures and then take adequate countermeasures against them. Although a few methods of failure analysis have been proposed to address environmental issues, these methods have failed to consider the cause–effect relationships among failures. This will hinder manufacturers from identifying core problems that should be addressed in a given system. Therefore, this study extends failure mode and effect analysis, which is an engineering technique used to address potential failures, by addressing the entire system reliability in relation to circularity. As a result of a case study of a manufacturer aiming to increase circularity with their products on the market, we revealed that the proposed method is useful in the early stage of design to (a) identify failure modes where effects are largely given to or received from other failures, (b) develop countermeasures effectively by addressing root causes of failures, and (c) find an opportunity to collaborate with external actors

Far-from-equilibrium quantum many-body dynamics

The theory of real-time quantum many-body dynamics as put forward in Ref. [arXiv:0710.4627] is evaluated in detail. The formulation is based on a generating functional of correlation functions where the Keldysh contour is closed at a given time. Extending the Keldysh contour from this time to a later time leads to a dynamic flow of the generating functional. This flow describes the dynamics of the system and has an explicit causal structure. In the present work it is evaluated within a vertex expansion of the effective action leading to time evolution equations for Green functions. These equations are applicable for strongly interacting systems as well as for studying the late-time behaviour of nonequilibrium time evolution. For the specific case of a bosonic N-component phi^4 theory with contact interactions an s-channel truncation is identified to yield equations identical to those derived from the 2PI effective action in next-to-leading order of a 1/N expansion. The presented approach allows to directly obtain non-perturbative dynamic equations beyond the widely used 2PI approximations.Comment: 20 pp., 6 figs; submitted version with added references and typos corrected

Membrane Association of the PTEN Tumor Suppressor: Molecular Details of the Protein-Membrane Complex from SPR Binding Studies and Neutron Reflection

The structure and function of the PTEN phosphatase is investigated by studying its membrane affinity and localization on in-plane fluid, thermally disordered synthetic membrane models. The membrane association of the protein depends strongly on membrane composition, where phosphatidylserine (PS) and phosphatidylinositol diphosphate (PI(4,5)P2) act pronouncedly synergistic in pulling the enzyme to the membrane surface. The equilibrium dissociation constants for the binding of wild type (wt) PTEN to PS and PI(4,5)P2 were determined to be Kd∼12 µM and 0.4 µM, respectively, and Kd∼50 nM if both lipids are present. Membrane affinities depend critically on membrane fluidity, which suggests multiple binding sites on the protein for PI(4,5)P2. The PTEN mutations C124S and H93R show binding affinities that deviate strongly from those measured for the wt protein. Both mutants bind PS more strongly than wt PTEN. While C124S PTEN has at least the same affinity to PI(4,5)P2 and an increased apparent affinity to PI(3,4,5)P3, due to its lack of catalytic activity, H93R PTEN shows a decreased affinity to PI(4,5)P2 and no synergy in its binding with PS and PI(4,5)P2. Neutron reflection measurements show that the PTEN phosphatase “scoots" along the membrane surface (penetration <5 Å) but binds the membrane tightly with its two major domains, the C2 and phosphatase domains, as suggested by the crystal structure. The regulatory C-terminal tail is most likely displaced from the membrane and organized on the far side of the protein, ∼60 Å away from the bilayer surface, in a rather compact structure. The combination of binding studies and neutron reflection allows us to distinguish between PTEN mutant proteins and ultimately may identify the structural features required for membrane binding and activation of PTEN

Electron-ion temperature relaxation in warm dense hydrogen observed with picosecond resolved X-Ray scattering

Angularly resolved X-ray scattering measurements from fs-laser heated hydrogen have been used to determine the equilibration of electron and ion temperatures in the warm dense matter regime. The relaxation of rapidly heated cryogenic hydrogen is visualized using 5.5 keV X-ray pulses from the Linac Coherent Light (LCLS) source in a 1 Hz repetition rate pump-probe setting. We demonstrate that the electron-ion energy transfer is faster than quasi-classical Landau-Spitzer models that use ad hoc cutoffs in the Coulomb logarithm

Roles of Electrostatics and Conformation in Protein-Crystal Interactions

In vitro studies have shown that the phosphoprotein osteopontin (OPN) inhibits the nucleation and growth of hydroxyapatite (HA) and other biominerals. In vivo, OPN is believed to prevent the calcification of soft tissues. However, the nature of the interaction between OPN and HA is not understood. In the computational part of the present study, we used molecular dynamics simulations to predict the adsorption of 19 peptides, each 16 amino acids long and collectively covering the entire sequence of OPN, to the {100} face of HA. This analysis showed that there is an inverse relationship between predicted strength of adsorption and peptide isoelectric point (P<0.0001). Analysis of the OPN sequence by PONDR (Predictor of Naturally Disordered Regions) indicated that OPN sequences predicted to adsorb well to HA are highly disordered. In the experimental part of the study, we synthesized phosphorylated and non-phosphorylated peptides corresponding to OPN sequences 65–80 (pSHDHMDDDDDDDDDGD) and 220–235 (pSHEpSTEQSDAIDpSAEK). In agreement with the PONDR analysis, these were shown by circular dichroism spectroscopy to be largely disordered. A constant-composition/seeded growth assay was used to assess the HA-inhibiting potencies of the synthetic peptides. The phosphorylated versions of OPN65-80 (IC50 = 1.93 µg/ml) and OPN220-235 (IC50 = 1.48 µg/ml) are potent inhibitors of HA growth, as is the nonphosphorylated version of OPN65-80 (IC50 = 2.97 µg/ml); the nonphosphorylated version of OPN220-235 has no measurable inhibitory activity. These findings suggest that the adsorption of acidic proteins to Ca2+-rich crystal faces of biominerals is governed by electrostatics and is facilitated by conformational flexibility of the polypeptide chain