Weak chemiluminescence emission during base induced rearrangement of G-factors

A rearrangement in basic medium of the natural endoperoxide G3-factor extracted from Eucalyptus grandis is described. Evidence to support a 1,2-dioxetane intermediate that decomposes with weak luminescence emission (quantum yield) is presented.     

Square versus tetrahedral iron clusters with polyoxometalate ligands

Two new insoluble transition metal substituted phosphotungstates, (C2N2H10)11[{(B-alpha-PW9O34)Fe3(OH)3}4(PO4)4Fe].38H2O(1) and K4(C2N2H10)12[(alpha-PW10Fe2O39)4].30H2O(2), have been isolated by the hydrothermal reaction of [A-alpha-PW9O34]9-, Fe(III) ions and ethylenediamine. Compound 1 has a tetrahedral symmetry and contains a Fe13 core built from the assembly of four Fe(III) trisubstituted [B-alpha-PW9O34]9- anions around a central disordered iron ion via four phosphato ligands. The anion in 2 can be described as a square of disubstituted [PW10O37]9- anions linked by Fe(III)-O-Fe(III) bridges. Magnetic measurements performed on 1 and 2 have shown the occurrence of antiferromagnetic interactions between the iron ions and have allowed the coupling constants between the magnetic centers to be determined.     

One-electron reduction of superoxide radical-anions by 3-alkylpolyhydroxyflavones in micelles. Effect of antioxidant alkyl chain length on micellar structure and reactivity

In micellar solutions, one-electron reduction of (*)O 2 (-) radical-anions by 3-alkylpolyhydroxyflavones (FnH) with alkyl chains of n = 1, 4, 6, 10 carbons produces phenoxyl radicals ( (*)Fn) identical to those obtained by one-electron oxidation by (*)Br 2 (-) radical-anions or by repair of tryptophan radicals. In cetyltrimethylammonium bromide (CTAB), F1H localizes in the Stern layer, and alkyl chains of other FnH solubilize in the hydrophobic interior, interacting with cetyl tails. This interaction produces more compact micelles with lower intramicellar fluidity, as suggested by the increase in the pseudo-first-order rate constant of (*)Fn formation ( k 1) from approximately 390 s (-1) for n = 1 to 610 s (-1) for n = 10, leading to an intramicellar bimolecular rate constant of 1 x 10 (5) M (-1) s (-1). Additionally, (*)F1 and (*)F4 decay by intermicellar bimolecular reaction (2 k = 20 and 2 x 10 (5) M (-1) s (-1), respectively) whereas other (*)Fn radicals are stable over seconds due to increased localization with regards to the Stern layer. In contrast, the thick uncharged hydrophilic palisade layer and the compact hydrophobic core of Triton X100 micelles are responsible for a much higher microviscosity resulting in a decrease in k 1 from approximately 15.6 s (-1) for n = 1 to 9.6 s (-1) for n = 10.     

A stereodivergent synthesis of beta-hydroxy-alpha-methylene lactones via vinyl epoxides

A catalytic diastereoselective sulfonium ylide epoxidation of aldehydes furnished original vinyl epoxides, having an MBH backbone. These highly functionalized building blocks were used for a formal synthesis of the antibiotic conocandin, and opened up a stereodivergent route towards beta-hydroxy-alpha-methylene lactones, core units of naturally occurring compounds. Under acidic conditions, the oxiranes were mainly transformed, with moderate to good yields, into trans beta-hydroxy-alpha-methylene lactones. On the other hand, a user-friendly palladium-catalysed CO2 insertion and cyclisation sequence gave the cis beta-hydroxy-alpha-methylene lactone counterparts along with an interesting cis-trans equilibration of the pi-allyl intermediates.     

Modelling NiFe hydrogenases: nickel-based electrocatalysts for hydrogen production

NiFe hydrogenases are unique enzymes that catalyze the H+/H2 interconversion with remarkable efficiency. The determination of the tridimensional structure of their active site (a sulfur-rich dinuclear nickel-iron cluster with diatomic cyanide and carbonyl ligands) has stimulated the synthesis of a variety of nickel-based complexes as potential electrocatalysts for hydrogen production. These catalysts may provide an adequate alternative to platinum. This paper gives an historical perspective of this biomimetic structural approach and then focusses on recently reported bio-inspired functional mimics displaying electrocatalytic activity for hydrogen production.     

Alkylammonium-based protic ionic liquids. II. Ionic transport and heat-transfer properties: fragility and ionicity rule

The physicochemical characterization of six alkylammonium-based protic ionic liquids (PILs) is presented. These compounds were prepared through a simple and atom-economic neutralization reaction between a tertiary amine and a Br?nsted acid, HX, where X- is HCOO-, CH3COO-, HF2-. The temperature dependency and the effect of added water on properties such as density, viscosity, ionic conductivity, and the thermal comportment of these PILs were measured and investigated. The results allowed us to classify them according to a classical Walden diagram and to appreciate their great "fragility". PILs have applicable perspectives in replacements of conventional inorganic acids for fuel cell devices and thermal transfer fluids.     

Analysis of high molecular mass proteins larger than 150 kDa using cyanogen bromide cleavage and conventional 2-DE

Proteomic approaches including high-resolution 2-DE are providing the tools needed to discover disease-associated biomarkers in complex biological samples. Although 2-DE is an extremely powerful approach to analyze the proteome, the separation of proteins with extreme molecular masses still remains an issue requiring improvement. Because high molecular mass (HMM) proteins larger than 150 kDa have already been observed to be differentially expressed in several pathologies such as cancer, we developed an original strategy to analyze this part of the proteome that is not easily separated by 2-DE in polyacrylamide gels. This strategy is based on the 2-DE separation of cyanogen bromide (CNBr) fragments of purified HMM protein fractions, and combines techniques including SEC fractionation, TCA precipitation, CNBr cleavage, 2-DE and MS analysis. The method was first tested on a model protein, the BSA. Preliminary results obtained using colonic tissues led to the identification of six HMM proteins with M(r) comprised between 163 and 533 kDa in their reduced state. These results demonstrated that our CNBr/2-DE approach should provide a powerful tool for identification of new biomarkers larger than 150 kDa.     

Multi-residue analysis of pharmaceutical compounds in aqueous samples

Pharmaceutical compounds are nowadays an emerging group of organic pollutants in aquatic systems. Several methodologies have already been published to measure these pollutants in the environment, showing the difficulties to take into account the various compounds belonging to numerous therapeutical and chemical groups. In order to develop environmental monitoring, there is a need for a less costly and time-consuming multi-component procedure. The work presented here deals with the development of an extraction procedure which enables the measurement of a wide spectrum of pharmaceuticals at trace levels (ng 1(-1)) with quite simple equipment (i.e. GC-MS with single quadruple as analyzer). The analyzed compounds comprise anti-inflammatories, antidepressants and hypolipidic drugs. The reliability and sensitivity have been tested on 18 different compounds (7 basic compounds and 11 acidic drugs) extracted simultaneously and analyzed by GC-MS. The optimized procedure has been successfully applied to the analysis of wastewaters, surface waters and drinking waters from the following areas: first the Cortiou rocky inlet, in the Mediterranean Sea (South coast of France), highly impacted by the Marseilles wastewater treatment plant effluent and secondly the Hérault watershed by studying drinking water, surface water and wastewater. In both cases, the level of pharmaceuticals was totally unknown. Results obtained have demonstrated the suitability of the method for multi-residue analysis of different types of water matrices.