Palladium-platinum powder catalysts manufactured by colloid synthesis II. Characterization and catalytic tests after oxidizing and reducing treatment

Unsupported Pd, Pt and PdPt bimetallic catalysts were prepared in different atomic ratios using methods of colloid chemistry. They were characterized by XPS, UPS and TEM. Four subsequent treatments with O2 and H2 up to T = 603K were applied in the preparation chamber of the electron spectrometer and before the catalytic runs. Platinum strongly hindered the oxidation of palladium in the bimetallic samples indicating an alloying of the two components. The H2 treatment after O2 led to rather clean metals. These treatments up to 603K decreased the Pt enrichment near to the surface found by XPS, destroying presumably the Pt islands on the surface of a Pd-rich matrix. The particle composition approached thus a homogeneous metal mixture. The catalytic behavior was tested in the hydrogenative ring opening reaction of cis- and trans-methyl-ethyl-cyclopropane (MECP) at 373 K. The product ratios 2-methylpentane/3-methylpentane (2MP/3MP) and 2-methylpentane/n-hexane (2MP/nH) were used to characterize the ring-opening pattern of the samples. The bimetallic catalysts revealed higher activity and completely different selectivities than the monometallic Pt and Pd. Moreover, the 2MP/3MP ratio from trans-MECP and 2MP/nH ratio from cis-MECP increased as the surface Pt enrichment decreased. PdPt catalysts were cleaner than Pd or Pt, their activity higher and selectivity closer to random C C rupture, due, very likely, to the presence of active Pd-Pt ensembles

SoxAX cytochromes, a new type of heme copper protein involved in bacterial energy generation from sulfur compounds

SoxAX cytochromes are essential for the function of the only confirmed pathway for bacterial thiosulfate oxidation, the so-called "Sox pathway," in which they catalyze the initial formation of a S-S bond between thiosulfate and the SoxYZ carrier protein. Our work using the Starkeya novella diheme SoxAX protein reveals for the first time that in addition to two active site heme groups, SoxAX contains a mononuclear Cu(II) center with a distorted tetragonal geometry and three to four nitrogen ligands, one of which is a histidine. The Cu(II) center enhanced SoxAX activity in a newly developed, glutathione-based assay system that mimics the natural reaction of SoxAX with SoxYZ. EPR spectroscopy confirmed that the SoxAX CuII center is reduced by glutathione. At pH 7 a K(m app) of 0.19 +/- 0.028 mM and a k(cat app) of 5.7 +/- 0.25s(-1) were determined for glutathione. We propose that SoxAX cytochromes are a new type of heme-copper proteins, with SoxAX-mediated S-S bond formation involving both the copper and heme centers

A & B model approaches to surface operators and Toda theories

It has recently been argued by Alday et al that the inclusion of surface operators in 4d N=2 SU(2) quiver gauge theories should correspond to insertions of certain degenerate operators in the dual Liouville theory. So far only the insertion of a single surface operator has been treated (in a semi-classical limit). In this paper we study and generalise this proposal. Our approach relies on the use of topological string theory techniques. On the B-model side we show that the effects of multiple surface operator insertions in 4d N=2 gauge theories can be calculated using the B-model topological recursion method, valid beyond the semi-classical limit. On the mirror A-model side we find by explicit computations that the 5d lift of the SU(N) gauge theory partition function in the presence of (one or many) surface operators is equal to an A-model topological string partition function with the insertion of (one or many) toric branes. This is in agreement with an earlier proposal by Gukov. Our A-model results were motivated by and agree with what one obtains by combining the AGT conjecture with the dual interpretation in terms of degenerate operators. The topological string theory approach also opens up new possibilities in the study of 2d Toda field theories.Comment: 43 pages. v2: Added references, including a reference to unpublished work by S.Gukov; minor changes and clarifications

Virtual Reality Based Simulation of Hysteroscopic Interventions

Virtual reality based simulation is an appealing option to supplement traditional clinical education. However, the formal integration of training simulators into the medical curriculum is still lacking. Especially, the lack of a reasonable level of realism supposedly hinders the widespread use of this technology. Therefore, we try to tackle this situation with a reference surgical simulator of the highest possible fidelity for procedural training. This overview describes all elements that have been combined into our training system as well as first results of simulator validation. Our framework allows the rehearsal of several aspects of hysteroscopy—for instance, correct fluid management, handling of excessive bleeding, appropriate removal of intrauterine tumors, or the use of the surgical instrument

Al₂Pt für die Sauerstoffentwicklungsreaktion bei der Wasserspaltung: eine Strategie zur Erzeugung von Multifunktionalität in der Elektrokatalyse

Die Herstellung von Wasserstoff durch Wasserelektrolyse ist nur möglich, wenn wirksame und stabile Katalysatoren für die Sauerstoffentwicklungsreaktion (Oxygen Evolution Reaction, OER) verfügbar sind. Intermetallische Verbindungen mit genau definierter Kristallstruktur und elektronischen Eigenschaften sowie besonderer chemischer Bindung werden als Vorstufe für neue Werkstoffe vorgeschlagen, die interessante katalytische Eigenschaften aufweisen. Al2Pt kristallisiert im Anti‐Fluorit‐Kristallstrukturtyp und zeigt eine stark polare chemische Bindung. Platin ist hierbei katalytisch aktiv und wird auch unter den Bedingungen der Sauerstoffentwicklungsreaktion vergleichsweise wenig aus der Katalysatoroberfläche herausgelöst. Im Folgenden wird die unerwartete Leistungsfähigkeit einer Oberflächen‐Nanokomposit‐Architektur beschrieben, die aus der selbstorganisierten Umwandlung der intermetallischen Vorstufe Al2Pt resultiert. Hierbei wird insbesondere das Langzeitverhalten der katalytischen Aktivität und Stabilität unter den Bedingungen der Sauerstoffentwicklungsreaktion untersucht

Challenges of beta-deformation

A brief review of problems, arising in the study of the beta-deformation, also known as "refinement", which appears as a central difficult element in a number of related modern subjects: beta \neq 1 is responsible for deviation from free fermions in 2d conformal theories, from symmetric omega-backgrounds with epsilon_2 = - epsilon_1 in instanton sums in 4d SYM theories, from eigenvalue matrix models to beta-ensembles, from HOMFLY to super-polynomials in Chern-Simons theory, from quantum groups to elliptic and hyperbolic algebras etc. The main attention is paid to the context of AGT relation and its possible generalizations.Comment: 20 page

M5-branes, toric diagrams and gauge theory duality

In this article we explore the duality between the low energy effective theory of five-dimensional N=1 SU(N)^{M-1} and SU(M)^{N-1} linear quiver gauge theories compactified on S^1. The theories we study are the five-dimensional uplifts of four-dimensional superconformal linear quivers. We study this duality by comparing the Seiberg-Witten curves and the Nekrasov partition functions of the two dual theories. The Seiberg-Witten curves are obtained by minimizing the worldvolume of an M5-brane with nontrivial geometry. Nekrasov partition functions are computed using topological string theory. The result of our study is a map between the gauge theory parameters, i.e., Coulomb moduli, masses and UV coupling constants, of the two dual theories. Apart from the obvious physical interest, this duality also leads to compelling mathematical identities. Through the AGTW conjecture these five-dimentional gauge theories are related to q-deformed Liouville and Toda SCFTs in two-dimensions. The duality we study implies the relations between Liouville and Toda correlation functions through the map we derive.Comment: 58 pages, 17 figures; v2: minor corrections, references adde

Human Iron−Sulfur Cluster Assembly, Cellular Iron Homeostasis, and Disease†

ABSTRACT: Iron-sulfur (Fe-S) proteins contain prosthetic groups consisting of two or more iron atoms bridged by sulfur ligands, which facilitate multiple functions, including redox activity, enzymatic function, and maintenance of structural integrity. More than 20 proteins are involved in the biosynthesis of iron-sulfur clusters in eukaryotes. Defective Fe-S cluster synthesis not only affects activities of many iron-sulfur enzymes, such as aconitase and succinate dehydrogenase, but also alters the regulation of cellular iron homeostasis, causing both mitochondrial iron overload and cytosolic iron deficiency. In this work, we review human Fe-S cluster biogenesis and human diseases that are caused by defective Fe-S cluster biogenesis. Fe-S cluster biogenesis takes place essentially in every tissue of humans, and products of human disease genes, including frataxin, GLRX5, ISCU, and ABCB7, have important roles in the process. However, the human diseases, Friedreich ataxia, glutaredoxin 5-deficient sideroblastic anemia, ISCU myopathy, and ABCB7 sideroblastic anemia/ataxia syndrome, affect specific tissues, while sparing others. Here we discuss the phenotypes caused by mutations in these different disease genes, and we compare the underlying pathophysiology and discuss the possible explanations for tissue-specific pathology in these diseases caused by defective Fe-S cluster biogenesis. HUMAN CELLULAR IRON HOMEOSTASI

Antiinflammatory Therapy with Canakinumab for Atherosclerotic Disease

Background: Experimental and clinical data suggest that reducing inflammation without affecting lipid levels may reduce the risk of cardiovascular disease. Yet, the inflammatory hypothesis of atherothrombosis has remained unproved. Methods: We conducted a randomized, double-blind trial of canakinumab, a therapeutic monoclonal antibody targeting interleukin-1β, involving 10,061 patients with previous myocardial infarction and a high-sensitivity C-reactive protein level of 2 mg or more per liter. The trial compared three doses of canakinumab (50 mg, 150 mg, and 300 mg, administered subcutaneously every 3 months) with placebo. The primary efficacy end point was nonfatal myocardial infarction, nonfatal stroke, or cardiovascular death. RESULTS: At 48 months, the median reduction from baseline in the high-sensitivity C-reactive protein level was 26 percentage points greater in the group that received the 50-mg dose of canakinumab, 37 percentage points greater in the 150-mg group, and 41 percentage points greater in the 300-mg group than in the placebo group. Canakinumab did not reduce lipid levels from baseline. At a median follow-up of 3.7 years, the incidence rate for the primary end point was 4.50 events per 100 person-years in the placebo group, 4.11 events per 100 person-years in the 50-mg group, 3.86 events per 100 person-years in the 150-mg group, and 3.90 events per 100 person-years in the 300-mg group. The hazard ratios as compared with placebo were as follows: in the 50-mg group, 0.93 (95% confidence interval [CI], 0.80 to 1.07; P = 0.30); in the 150-mg group, 0.85 (95% CI, 0.74 to 0.98; P = 0.021); and in the 300-mg group, 0.86 (95% CI, 0.75 to 0.99; P = 0.031). The 150-mg dose, but not the other doses, met the prespecified multiplicity-adjusted threshold for statistical significance for the primary end point and the secondary end point that additionally included hospitalization for unstable angina that led to urgent revascularization (hazard ratio vs. placebo, 0.83; 95% CI, 0.73 to 0.95; P = 0.005). Canakinumab was associated with a higher incidence of fatal infection than was placebo. There was no significant difference in all-cause mortality (hazard ratio for all canakinumab doses vs. placebo, 0.94; 95% CI, 0.83 to 1.06; P = 0.31). Conclusions: Antiinflammatory therapy targeting the interleukin-1β innate immunity pathway with canakinumab at a dose of 150 mg every 3 months led to a significantly lower rate of recurrent cardiovascular events than placebo, independent of lipid-level lowering. (Funded by Novartis; CANTOS ClinicalTrials.gov number, NCT01327846.