A versatile electrophoresis system for the analysis of high- and low-molecular-weight proteins

A new, versatile, multiphasic buffer system for high-resolution sodium dodecyl sulfate-polyacrylamide gel electrophoresis of proteins in the relative molecular weight range of 300 000-3000 Da is described. The system, based on the theory of multiphasic zone electrophoresis, allows complete stacking and destacking of proteins in the above M(r) range. The buffer system uses taurine and chloride as trailing and leading ion, respectively, and Tris, at a pH close to its pK(a), as the buffering counterion. Coupled with limited variation in the acrylamide concentration, this electrophoresis system allows to tailor the resolution in the 6-200 kDa M(r) range, with minimal difficulties in the post electrophoretic identification processes.     

Sterically encumbered diphosphaalkenes and a bis(diphosphene) as potential multiredox-active molecular switches: EPR and DFT investigations

The reduction products of two diphosphaalkenes (1 and 2) and a bis(diphosphene) (3) containing sterically encumbered ligands and corresponding to the general formulas Ar-X=Y-Ar'-Y=X-Ar, have been investigated by EPR spectroscopy. Due to steric constraints in these molecules, at least one of the dihedral angles between the CXYC plane and either the Ar plane or the Ar' plane is largely nonzero and, hence, discourages conformations that are optimal for maximal conjugation of P=X (or P=Y) and aromatic pi systems. Comparison of the experimental hyperfine couplings with those calculated by DFT on model systems containing no cumbersome substituents bound to the aromatic rings shows that addition of an electron to the nonplanar neutral systems causes the X=Y-Ar'-Y=X moiety to become planar. In contrast to 1 and 2, 3 can be reduced to relatively stable dianion. Surprisingly the two-electron reduction product of 3 is paramagnetic. Interpretation of its EPR spectra, in the light of DFT calculations on model dianions, shows that in [3](2)(-) the plane of the Ar' ring is perpendicular to the CXYC planes. Due to interplay between steric and electronic preferences, the Ar-X=Y-Ar'-Y=X-Ar array for 3 is therefore dependent upon its redox state and acts as a "molecular switch".     

Hydrosilylation of allyl carbamates by poly(methylhydrosiloxane) and related side-reactions

Hydrosilylation of allyl carbamates by poly(methylhydrosiloxane) (PMHS) catalyzed by platinum- or rhodium-based complexes was investigated. About 10% of the carbamate molecules decompose during the hydrosilylation reaction through the cleavage of the carbamate bond. A redistribution process also takes place among the polysiloxane chains resulting in the formation of branched polymers but no crosslinking occurs. A mechanism for this side-reaction is proposed. © 1993 John Wiley & Sons, Inc.     

Electrical behaviour of catalytic nanostructured CeO2/CuOx composites under air-methane gas impulses

Nanostructured composites based on copper oxide and cerium dioxide phases [CuO-CeO₂] were elaborated from sol-gel route, with weight fractions of CuO phase ranging between 0 and 0.4. They are interesting potential catalysts allowing conversion of CH₄ and CO into CO₂ and H₂O and might be used in miniaturized gas sensors. An electrical study of this nanostructured system was carried out to determine catalytic behaviours under air-methane impulses at 350 °C. The electrical analysis was based on a specific homemade electronic device. Time dependent interactions between gas pulses and solid catalyst (CuO/CeO₂) were analyzed from a frequency modification of the electronic device. Kinetic parameters were determined from a model describing adsorption and desorption of gases adapted to short interaction time between gas and solid. These time dependent electrical behaviours were then correlated with infrared spectroscopy analyses allowing time dependent analysis of methane conversion into CO₂ gas, for long interaction time between gas and solid.     

Renormalised Chern–Weil forms associated with families of Dirac operators

We provide local expressions for Chern–Weil type forms built from superconnections associated with families of Dirac operators previously investigated in [S. Scott, Zeta–Chern forms and the local family index theorem, Trans. Amer. Math. Soc. (in press). arXiv: math.DG/0406294] and later in [S. Paycha, S. Scott, Chern–Weil forms associated with superconnections, in: B. Booss-Bavnbeck, S. Klimek, M. Lesch, W. Zhang (Eds.), Analysis, Geometry and Topology of Elliptic Operators, World Scientific, 2006].     

Analysis of hemoglobin adducts of acrylamide and glycidamide by liquid chromatography-electrospray ionization tandem mass spectrometry, as exposure biomarkers in French population

The determination of biomarkers of acrylamide exposure in humans from general French population by measurement of hemoglobin adduct levels of acrylamide (AA) and glycidamide (GA) is presented. The analytical procedure included modified Edman degradation and LC-ESI-MS/MS analysis of the final derivatives using deuterated internal standards. Method performances were evaluated in terms of linearity, precision, accuracy, and sensitivity. The method was firstly assessed on rat blood samples and then applied to the study of background adducts levels of AA and GA in 68 human hemoglobin samples, showing mean levels of 33 and 23 pmol/g globin for AA and GA adducts, respectively.