A Rechargeable Hydrogen Battery Based on Ru Catalysis

Apart from energy generation, the storage and liberation of energy are among the major problems in establishing a sustainable energy supply chain. Herein we report the development of a rechargeable H₂ battery which is based on the principle of the Ru‐catalyzed hydrogenation of CO₂ to formic acid (charging process) and the Ru‐catalyzed decomposition of formic acid to CO₂ and H₂ (discharging process). Both processes are driven by the same catalyst at elevated temperature either under pressure (charging process) or pressure‐free conditions (discharging process). Up to five charging–discharging cycles were performed without decrease of storage capacity. The resulting CO₂/H₂ mixture is free of CO and can be employed directly in fuel‐cell technology.     

Chromatographic separation simulation of metal‐chelating peptides from surface plasmon resonance binding parameters

Some metal‐chelating peptides have antioxidant properties, with potential nutrition, health, and cosmetics applications. This study aimed to simulate their separation on immobilized metal ion affinity chromatography from their affinity constant for immobilized metal ion determined in surface plasmon resonance, both technics are based on peptide‐metal ion interactions. In our approach, first, the affinity constant of synthetic peptides was determined by surface plasmon resonance and used as input data to numerically simulate the chromatographic separation with a transport‐dispersive model based on Langmuir adsorption isotherm. Then, chromatographic separation was applied on the same peptides to determine their retention time and compare this experimental t_R with the simulated t_R obtained from simulation from surface plasmon resonance data. For the investigated peptides, the relative values of t_R were comparable. Hence, our study demonstrated the pertinence of such numerical simulation correlating immobilized metal ion affinity chromatography and surface plasmon resonance.     

Growth of anisotropic domains in a Langmuir monolayer

We studied the growth of solid anisotropic domains in a monolayer made of pure NBD-stearic acid spread on water. These domains have a needle-like shape. We found that the growth process is limited by the interface kinetics, and not by the diffusion of impurities. Moreover the longitudinal growth velocity of these needles is simply proportional to the overpressure, as for a rough interface. No such law was found for the width of the needles.     

Chain conformation in polymer melts during flow as measured by small angle neutron scattering

The anisotropic form factor of polystyrene (PS) chains during tensile and simple shear flows in the melt has been measured by small angle neutron scattering (SANS) on quenched samples containing deuterium labeled chains. For all tensile experiments, carried out in a wide range of strain rates, including linear viscoelastic behaviour, the chain conformation is well predicted by a temporary network model involving the recoverable strain. For binary blends of two PS with different molecular weight, the technique allows to characterize the chain conformation of either species. The scattering patterns of sheared samples show that the principal directions of molecular orientation depend on the magnitude of the scattering vector q: At high q (local level on the chain) the orientation is close to 45° with respect to the shear axis, whereas at low q the chains appear to be almost aligned with the stream lines.     

TSC defect level in silicon produced by irradiation with muons of GeV-energy

Deep level transient spectroscopy has been used to observe the reduced concentrations of vacancy-related defects in γ-irradiated n-type Si containing hydrogen atoms. Data are presented on the efficiency and depth of this damage reduction as a function of the duration and temperature of the exposure to the plasma used to introduce the atomic hydrogen. A 3-hour exposure in an H plasma at 300°C prior to irradiation reduced the concentrations of the O-V, V-V and P-V centres by half or more to a depth of ～20 μm, compared to the control samples.     

Monte Carlo simulations of star-branched polyelectrolyte micelles

The concentration profiles of monomers and counterions in star-branched polyelectrolyte micelles are calculated through Monte Carlo simulations, using the freely jointed chain model. We have investigated the onset of different regimes corresponding to the spherical and Manning condensation of counterions as a function of the strength of the Coulomb coupling. The Monte Carlo results are in fair agreement with the predictions of Self-Consistent-Field analytical models. We have simulated a real system of diblock copolymer micelles of (sodium-polystyrene-sulfonate)(NaPSS)-(polyethylene-propylene)(PEP) with f = 54 hydrophilic branches of N = 251 monomers at room temperature in salt-free solution. The calculated form factor compares nicely with our neutron scattering data. Received 18 July 2002 and Received in final form 11 October 2002 RID="a" ID="a"e-mail: roger@drecam.saclay.cea.fr     

A new organic nanoporous architecture: dumb-bell-shaped molecules with guests in parallel channels

A new type of dumb-bell-shaped host molecule (6-8) has been synthesised, of which 1,8-bis((1)-adamantyl)-1,3,5,7-octatetrayne (8 = BAOT) forms an open porous architecture when cocrystallised with a number of typical solvent molecules. Adamantyl substituents attached to a tetraalkyne spacer build up the walls of parallel channels wherein guest molecules are aligned. Surprisingly, the tetraalkyne unit is significantly bent. Desolvation experiments provide evidence for a reversible inclusion of guests. In the case of the inclusion of 2-butanone, a partial substitution by symmetrical and asymmetrical long-chain chromophores during crystallisation was possible. Stained crystals showed optical frequency doubling. The crystal structure analysis revealed a centric space group, although considerable translational and orientational disorder was present. Application of scanning pyroelectric microscopy revealed that the growth of inclusion compounds with 2-butanone produced polar ordering of guest molecules, which were aligned in two macro-domains of opposing polarity. The resulting orientation of the carbonyl dipoles is in agreement with the theoretical prediction of a Markov model of spontaneous polarity formation based on molecular recognition processes on growing crystal faces. The present case represents a new example of a property-driven supramolecular synthesis.     

Symmetries of Surface Singularities

The study of reductive group actions on a normal surface singularityX is facilitated by the fact that the group Aut X of automorphismsof X has a maximal reductive algebraic subgroup G which containsevery reductive algebraic subgroup of Aut X up to conjugation.If X is not weighted homogeneous then this maximal group G isfinite (Scheja, Wiebe). It has been determined for cusp singularitiesby Wall. On the other hand, if X is weighted homogeneous butnot a cyclic quotient singularity then the connected componentG₁ of the unit coincides with the C* defining the weighted homogeneousstructure (Scheja, Wiebe, Wahl). Thus the main interest liesin the finite group G/G₁. Not much is known about G/G₁. Ganterhas given a bound on its order valid for Gorenstein singularitieswhich are not log-canonical. Aumann-Körber has determinedG/G₁ for all quotient singularities. We propose to study G/G₁ through the action of G on the minimalgood resolution of X. If X is weightedhomogeneous but not a cyclic quotient singularity, let E₀ bethe central curve of the exceptional divisor of . We show that the natural homomorphism GAut E₀ haskernel C* and finite image. In particular, this re-proves therest of Scheja, Wiebe and Wahl mentioned above. Moreover, itallows us to view G/G₁ as a subgroup of Aut E₀. For simple ellipticsingularities it equals (Z_bxZ_b)Aut₀ E₀ where –b is theself-intersection number of E₀, Z_bxZ_b is the group of b-torsionpoints of the elliptic curve E₀ acting by translations, andAut₀ E₀ is the group of automorphisms fixing the zero elementof E₀. If E₀ is rational then G/G₁ is the group of automorphismsof E₀ which permute the intersection points with the branchesof the exceptional divisor while preserving the Seifert invariantsof these branches. When there are exactly three branches weconclude that G/G₁ is isomorphic to the group of automorphismsof the weighted resolution graph. This applies to all non-cyclicquotient singularities as well as to triangle singularities.We also investigate whether the maximal reductive automorphismgroup is a direct product GG₁xG/G₁. This is the case, for instance,if the central curve E₀ is rational of even self-intersectionnumber or if X is Gorenstein such that its nowhere-zero 2-form has degree ±1. In the latter case there is a ‘natural’section G/G₁G of GG/G₁ given by the group of automorphisms inG which fix . For a simple elliptic singularity one has GG₁xG/G₁if and only if –E₀ · E₀ = 1.