232 research outputs found

    Evaluation of Reduced-Graphene-Oxide Aligned with WO3-Nanorods as Support for Pt Nanoparticles during Oxygen Electroreduction in Acid Medium

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    Hybrid supports composed of chemically-reduced graphene-oxide-aligned with tungsten oxide nanowires are considered here as active carriers for dispersed platinum with an ultimate goal of producing improved catalysts for electroreduction of oxygen in acid medium. Here WO3 nanostructures are expected to be attached mainly to the edges of graphene thus making the hybrid structure not only highly porous but also capable of preventing graphene stacking and creating numerous sites for the deposition of Pt nanoparticles. Comparison has been made to the analogous systems utilizing neither reduced graphene oxide nor tungsten oxide component. By over-coating the reduced-graphene-oxide support with WO3 nanorods, the electrocatalytic activity of the system toward the reduction of oxygen in acid medium has been enhanced even at the low Pt loading of 30 microg cm-2. The RRDE data are consistent with decreased formation of hydrogen peroxide in the presence of WO3. Among important issues are such features of the oxide as porosity, large population of hydroxyl groups, high Broensted acidity, as well as fast electron transfers coupled to unimpeded proton displacements. The conclusions are supported with mechanistic and kinetic studies involving double-potential-step chronocoulometry as an alternative diagnostic tool to rotating ring-disk voltammetry.Comment: arXiv admin note: text overlap with arXiv:1805.0315

    Degradation of Serotonin N-Acetyltransferase, a Circadian Regulator, by the N-end Rule Pathway

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    Serotonin N-acetyltransferase (AANAT) converts serotonin to N-acetylserotonin (NAS), a distinct biological regulator and the immediate precursor of melatonin, a circulating hormone that influences circadian processes, including sleep. N-terminal sequences of AANAT enzymes vary among vertebrates. Mechanisms that regulate the levels of AANAT are incompletely understood. Previous findings were consistent with the possibility that AANAT may be controlled through its degradation by the N-end rule pathway. By expressing the rat and human AANATs and their mutants not only in mammalian cells but also in the yeast Saccharomyces cerevisiae, and by taking advantage of yeast genetics, we show here that two complementary forms of rat AANAT are targeted for degradation by two complementary branches of the N-end rule pathway. Specifically, the N-terminally acetylated (Nt-acetylated) Ac-AANAT is destroyed through the recognition of its Nt-acetylated N-terminal Met residue by the Ac/N-end rule pathway, whereas the non-Nt-acetylated AANAT is targeted by the Arg/N-end rule pathway, which recognizes the unacetylated N-terminal Met-Leu sequence of rat AANAT. We also show, by constructing lysine-to-arginine mutants of rat AANAT, that its degradation is mediated by polyubiquitylation of its Lys residue(s). Human AANAT, whose N-terminal sequence differs from that of rodent AANATs, is longer-lived than its rat counterpart and appears to be refractory to degradation by the N-end rule pathway. Together, these and related results indicate both a major involvement of the N-end rule pathway in the control of rodent AANATs and substantial differences in the regulation of rodent and human AANATs that stem from differences in their N-terminal sequences.1141Ysciescopu

    A rapidly-reversible absorptive and emissive vapochromic Pt(II) pincer-based chemical sensor

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    Selective, robust and cost-effective chemical sensors for detecting small volatile-organic compounds (VOCs) have widespread applications in industry, healthcare and environmental monitoring. Here we design a Pt(II) pincer-type material with selective absorptive and emissive responses to methanol and water. The yellow anhydrous form converts reversibly on a subsecond timescale to a red hydrate in the presence of parts-per-thousand levels of atmospheric water vapour. Exposure to methanol induces a similarly-rapid and reversible colour change to a blue methanol solvate. Stable smart coatings on glass demonstrate robust switching over 104 cycles, and flexible microporous polymer membranes incorporating microcrystals of the complex show identical vapochromic behaviour. The rapid vapochromic response can be rationalised from the crystal structure, and in combination with quantum-chemical modelling, we provide a complete microscopic picture of the switching mechanism. We discuss how this multiscale design approach can be used to obtain new compounds with tailored VOC selectivity and spectral responses

    The Flux-Line Lattice in Superconductors

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    Magnetic flux can penetrate a type-II superconductor in form of Abrikosov vortices. These tend to arrange in a triangular flux-line lattice (FLL) which is more or less perturbed by material inhomogeneities that pin the flux lines, and in high-TcT_c supercon- ductors (HTSC's) also by thermal fluctuations. Many properties of the FLL are well described by the phenomenological Ginzburg-Landau theory or by the electromagnetic London theory, which treats the vortex core as a singularity. In Nb alloys and HTSC's the FLL is very soft mainly because of the large magnetic penetration depth: The shear modulus of the FLL is thus small and the tilt modulus is dispersive and becomes very small for short distortion wavelength. This softness of the FLL is enhanced further by the pronounced anisotropy and layered structure of HTSC's, which strongly increases the penetration depth for currents along the c-axis of these uniaxial crystals and may even cause a decoupling of two-dimensional vortex lattices in the Cu-O layers. Thermal fluctuations and softening may melt the FLL and cause thermally activated depinning of the flux lines or of the 2D pancake vortices in the layers. Various phase transitions are predicted for the FLL in layered HTSC's. The linear and nonlinear magnetic response of HTSC's gives rise to interesting effects which strongly depend on the geometry of the experiment.Comment: Review paper for Rep.Prog.Phys., 124 narrow pages. The 30 figures do not exist as postscript file
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