Oxygen reduction in acid media: influence of the activity of CoNPc(1,2) bilayer deposits in relation to their attachment to the carbon black support and role of surface groups as a function of heat treatment

O2 reduction was investigated using rotating disk electrode and voltammetry techniques on NPcCo(1,2) impregnations deposited onto two kinds of carbon black support. They were selected on the basis of their similar pH and dibuthylphthalate (DBP) adsorption values. Samples were also characterized by IR and X-ray photoelectron spectroscopy techniques. An optimized thermal treatment yielded an improvement in the O2 reducibility and identical activities (with N = 3.8) on both supports. These spectroscopic methods revealed a bilayer structure and suggested the presence of two sorts of site (active and inactive) which differed in their attachment of the substrate via surface groups which were characterized

Oxygen reduction in acid media: effect of iron substitution by cobalt on heat-treated naphthalocyanine impregnations supported on preselected carbon blacks

FeNPc(1.2) impregnations were investigated at various loadings using a rotating-disk electrode, voltammetry and X-ray photoelectron spectroscopy (XPS) techniques. Optimal activity takes place at monolayer coverage, and major demetallation occurs after prolonged exposure to acid solution. The substitution of Fe by Co enables the electrochemical performances to reach those presented by 10% Pt on Vulcan and stops the demetallation process. The application of fast atomic bombardment secondary ion mass spectrometry (FABS) together with XPS sheds light on the detrimental role of some electrophilic groups attached to the carbon black-catalyst interface

Oxygen reduction in acid media: influence of the heat treatment on the FeNPc(1–20 isomer mixture impregnated on carbon blacks and active charcoals

Oxygen reduction with the aid of a number of FeNPc(1–2) impregnated carbon supports in sulphuric acid solutions has been investigated.\ud \ud Loading of the carbon samples amounted to about 10 wt.%. After a 10 day stay in the aerated solutions the samples were investigated with rotating disk electrode and X-ray photoelectron spectroscopy techniques. The most active and stable samples correspond to mono- or submonolayers of FeNPc deposited on high dibutylphthalate adsorption carbon blacks. Comparison with data obtained previously on Norit BrX impregnations emphasizes the rôle of the electron density on the inner nitrogen atoms rather than that on the iron centres

Oxygen reduction in acid media on supported iron naphthalocyanine: Effect of isomer configuration and pyrolysis

O2 reduction in H2SO4 medium has been investigated on FeNPc impregnations on Norit BrX by the rotating disk electrode technique. Important differences in activity and stability were found between the 1,2- and 2,3-FeNPc isomers (pyrolysed or not). XPS analyses show, for the most inactive sample, strong demetallation and nitrogen losses. This phenomenon can be attributed to the differences in flexibility between the FeNPc isomers, which influences their stabilization on the substrate

Mechanical probing of liquid foam aging

We present experimental results on the Stokes experiment performed in a 3D dry liquid foam. The system is used as a rheometric tool : from the force exerted on a 1cm glass bead, plunged at controlled velocity in the foam in a quasi static regime, local foam properties are probed around the sphere. With this original and simple technique, we show the possibility of measuring the foam shear modulus, the gravity drainage rate and the evolution of the bubble size during coarsening

Oxygen reduction in an acid medium : electrocatalysis by CoNPc(1,2) impregnated on a carbon black support; effect of loading and heat treatment

O2 reduction in an acid medium has been investigated on a transition metal macrocycle, CoNPc(1,2), impregnated on a carbon black support with a high dibutylphthalate adsorption value, using a rotating disk electrode and voltammetry techniques described previously, combined with X-ray photoelectron spectroscopy measurements. Optimal activity was found for a bilayer coverage (n = 2) at 17%-18% w/w loading. Heat treatment seems to be beneficial for n 3: it increases the overall number N of exchanged electrons and improves the electrode wetting. For the most active samples, mixed Co(II)/Co(III) valencies were displayed

Three new potent cytotoxic macrolides closely related to sphinxolide from the New Caledonia sponge Neosiphonia superstes

Three new macrolides 2-4 have been isolated with sphinxolide 1 from the marine sponge #N. superstes$ collected off New Caledonia. The structures of the new compounds were determined by interpretation of NMR spectral data as well as comparison of spectral data with those of 1. These compounds were highly cytotoxic against various human carcinoma cells. (Résumé d'auteur

Bipolaron Binding in Quantum Wires

A theory of bipolaron states in quantum wires with a parabolic potential well is developed applying the Feynman variational principle. The basic parameters of the bipolaron ground state (the binding energy, the number of phonons in the bipolaron cloud, the effective mass, and the bipolaron radius) are studied as a function of sizes of the potential well. Two cases are considered in detail: a cylindrical quantum wire and a planar quantum wire. Analytical expressions for the bipolaron parameters are obtained at large and small sizes of the quantum well. It is shown that at $R\gg 1$ [where $R$ means the radius (halfwidth) of a cylindrical (planar) quantum wire, expressed in Feynman units], the influence of confinement on the bipolaron binding energy is described by the function $\sim 1/R^{2}$ for both cases, while at small sizes this influence is different in each case. In quantum wires, the bipolaron binding energy $W(R)$ increases logarithmically with decreasing radius. The shapes and the sizes of a nanostructure, which are favorable for observation of stable bipolaron states, are determined.Comment: 17 pages, 6 figures, E-mail addresses: [email protected]; [email protected]

Does Free Cell Area Influence the Outcome in Carotid Artery Stenting?

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The double Caldeira-Leggett model: Derivation and solutions of the master equations, reservoir-induced interactions and decoherence

In this paper we analyze the double Caldeira-Leggett model: the path integral approach to two interacting dissipative harmonic oscillators. Assuming a general form of the interaction between the oscillators, we consider two different situations: i) when each oscillator is coupled to its own reservoir, and ii) when both oscillators are coupled to a common reservoir. After deriving and solving the master equation for each case, we analyze the decoherence process of particular entanglements in the positional space of both oscillators. To analyze the decoherence mechanism we have derived a general decay function for the off-diagonal peaks of the density matrix, which applies both to a common and separate reservoirs. We have also identified the expected interaction between the two dissipative oscillators induced by their common reservoir. Such reservoir-induced interaction, which gives rise to interesting collective damping effects, such as the emergence of relaxation- and decoherence-free subspaces, is shown to be blurred by the high-temperature regime considered in this study. However, we find that different interactions between the dissipative oscillators, described by rotating or counter-rotating terms, result in different decay rates for the interference terms of the density matrix.Comment: 42 pages, 7 figures, new discussion added, typos adde