Kinetics of the plasmon optical response of Au nanoparticles/TiO<Subscript>2</Subscript> catalyst under O<Subscript>2</Subscript> and H<Subscript>2</Subscript> followed by differential diffuse reflectance spectroscopy

The changes in the optical properties of Au/TiO₂ powder catalyst, prepared by the deposition-precipitation method, are measured in the visible range by use of a home-made diffuse differential reflectance spectrometer, when the ambient atmosphere is switched between H₂ and O₂. Two main features are observed: (i) a short wavelength one, located between 400 and 600 nm, is shown to be related to the modifications of the plasmon resonance of the 3-dimensional metallic gold particles with mean size around 4 nm, induced by the exposure to oxygen or by its removal; (ii) a second feature, observed at long wavelengths between 600 and 1100 nm, is extremely sensitive to the exposure to oxygen. This optical feature could be due to the presence in the catalyst, either of Au⁰ clusters of several tens atoms, which are expected to display molecular-like transitions in this optical range, or to specific sites of the Au particles (edge atoms or peripheral atoms at the interface with the TiO₂ support), which could be highly reactive to oxygen.     

Photochirogenesis: photochemical models on the absolute asymmetric formation of amino acids in interstellar space

Proteins of all living organisms including plants, animals, and humans are made up of amino acid monomers that show identical stereochemical L-configuration. Hypotheses for the origin of this symmetry breaking in biomolecules include the absolute asymmetric photochemistry model by which interstellar ultraviolet (UV) circularly polarized light (CPL) induces an enantiomeric excess in chiral organic molecules in the interstellar/circumstellar media. This scenario is supported by a) the detection of amino acids in the organic residues of UV-photo-processed interstellar ice analogues, b) the occurrence of L-enantiomer-enriched amino acids in carbonaceous meteorites, and c) the observation of CPL of the same helicity over large distance scales in the massive star-forming region of Orion. These topics are of high importance in topical biophysical research and will be discussed in this review. Further evidence that amino acids and other molecules of prebiotic interest are asymmetrically formed in space comes from studies on the enantioselective photolysis of amino acids by UV-CPL. Also, experiments have been performed on the absolute asymmetric photochemical synthesis of enantiomer-enriched amino acids from mixtures of astrophysically relevant achiral precursor molecules using UV-circularly polarized photons. Both approaches are based on circular dichroic transitions of amino acids that will be highlighted here as well. These results have strong implications on our current understanding of how life's precursor molecules were possibly built and how life selected the left-handed form of proteinogenic amino acids.     

Phase characterization of the reflection on an extreme UV multilayer: comparison between attosecond metrology and standing wave measurements

We characterize the phase shift induced by reflection on a multilayer mirror in the extreme UV range (80-93?eV) using two techniques: one based on high order harmonic generation and attosecond metrology (reconstruction of attosecond beating by interference of two-photon transitions), and a second based on synchrotron radiation and measurements of standing waves (total electron yield). We find an excellent agreement between the results from the two measurements and a flat group delay shift (±40?as) over the main reflectivity peak of the mirror.     

Frameworks with forced symmetry II: orientation-preserving crystallographic groups

We give a combinatorial characterization of minimally rigid planar frameworks with orientation-preserving crystallographic symmetry, under the constraint of forced symmetry. The main theorems are proved by extending the methods of the first paper in this sequence from groups generated by a single rotation to groups generated by translations and rotations. The proof makes use of new families of matroids and submodular functions defined on crystallographic groups.     

Modal criteria for robust optimization of vibroacoustic systems

This work is an extension of the work done in previous papers (Besset and Jézéquel in Intern J Numer Method Eng 70(5):523–542, 2007; J Vib Acoust 130(1):011008, 2008; Intern J Numer Method Eng 73:1347–1373, 2008; J Vib Acoust 130(3):031009, 2008). It deals with modal criteria allowing to process optimization of structures including robustness. The system considered in the paper is a fluid-structure system. The aim of the paper is to use component mode synthesis methods to optimize the geometry of the structure and the robustness with respect to the design parameter variations of its vibroacoustic behaviour. Two criteria will be proposed. The first one is directly linked to the pressure level in the acoustic cavity. The second one is linked to the robustness of the methods. It comes from the polynomial chaos study of the considered system. A classical multiobjective optimization is then processed and Pareto graphics are proposed to represent the optimal solutions of the optimization problem.     

Efficient hydrogen-evolving cathodes based on proton and electron reservoir behaviors of the phosphotungstate [H7P8W48O184](33-) and the Co(II)-Containing Silicotungstates [Co(6)H2O)(30){Co(9)Cl(2)(OH)(3)(H(2)O)(9)(beta-SiW(8)O(31))(3)}](5-) and [{Co(3)(B-beta-SiW(9)O(33)(OH))(B-beta-SiW(8)O(29)OH)(2)}(2)](22-)

Original and simple procedures for glassy carbon electrode modification with polyoxometalates (POMs), phosphotungstate [H7P8W48O184]33-, and Co(II)-containing silicotungstates [Co6(H2O)30{Co9Cl2(OH)3(H2O)9(beta-SiW8O31)3}]5- and [{Co3(B-beta-SiW9O33(OH))(B-beta-SiW8O29OH)2}2]22- give stable and very active surfaces for the hydrogen-evolution reaction (HER). For this purpose, the selected POMs fixed on Vulcan XC-72 were adsorbed on the electrode surface or were directly entrapped in polyvinylpyridine films on the electrode. Cyclic voltammetry and confocal microscopy results converge to indicate that the activation is related to the proton and electron reservoir-like behaviors of these molecular oxides and not to any electrode surface area increase. However, the Tafel parameters of the HER process, which are different from one POM to the next, are in the range of those of the best metallic electrodes.     

Study of interactions of concentrated marine dissolved organic matter with copper and zinc by pseudopolarography

The interaction of dissolved organic matter (DOM) with copper and zinc in a concentrated seawater sample was characterised by pseudopolarography. Measurements performed at increased concentrations of copper(II) ions showed successive saturation of active DOM sites which indicate possible partition of copper between (i) free or labile complexes, (ii) reduced and released within the potential window of the method, and (iii) electroinactive copper complexes. Pseudopolarograms measured at pH 4 indicate a release of copper which was bound to the active sites of DOM that formed non-labile complexes. Variation of the peak position and half-peak width along the scanned deposition potentials and with the increasing concentration of copper bear the information about the complex electrochemical processes at the electrode surface and in the bulk of the solution. Pseudopolarograms of zinc showed a strong dependence of the peak current and the peak position along the scanned deposition potentials on pH values, indicating preferentially complexation of zinc with carboxylic-like active sites of DOM in the measured sample. Pseudopolarography is a valuable method in the trace metal complexation and speciation studies, serving as a fingerprint of the analysed sample.     

Comparative dielectric and thermotropic properties of liquid crystalline polyesters as a function of mesogen group and flexible thioether group length

Two polyesters containing rigid biphenyl and hydroquinone bisbenzoate groups and presenting flexible thioether moieties with different lengths (14 elements in the flexible group) have been carried out using a reaction of the Michaël type. The properties of these polyesters have been compared to those of polyesters of the same type presenting shorter flexible groups (11 elements). All these polymers present thermotropic properties: the biphenyl ones are smectic and the bisbenzoate ones are nematic. The biphenyl polyesters present two types of dielectric relaxations: α and β. The bisbenzoate ones show three relaxations, α and two β (β and β^′). The lengthening of the flexible group increases significantly the flexibility of the molecular chains.     

A novel ethylene-bridged spiro[3.2]Hexane

3,3-Dichlorotricyclo[5.1.0.0^1,4]oct-5-en-2-one ($\text{1}$) was prepared by addition of dichloroketene to 1,3-cyclohexadiene followed by allylic bromination and dehydrobromination.