A resonant γ-ray study of iron (III) bis and tris dithio chelates

The Mössbauer spectra of iron (III) bis and tris dithiocarbamates containing the piperidylradical have been investigated at various temperatures. The tris chelate shows a quadrupole splitting decreasing when the sample is warmed up which indicates the presence of a Boltzmann spin equilibrium. The bis chelate yields a temperature-independent quadrupole splitting due to the lattice contribution.Work sponsored in part by G.N.S.M. and in part by C.N.R.     

Bioadhesive properties of a polyaminoacidic hydrogel: evaluation by ATR FT-IR spectroscopy

The bioadhesive properties of a novel chemical hydrogel based on a polymer of protein-like structure, have been investigated by using ATR FT-IR spectroscopy. In particular, the copolymer PHG obtained by partial derivatization of PHEA with GMA was chemically crosslinked by UV irradiation at 313 nm. Crosslinked PHG was treated with water to obtain a swelled sample, named PHG-UV gel, that was brought into contact with a phosphate buffer/citric acid solution at pH 7.0 in the absence or in the presence of mucin at various concentrations (0.01, 0.1 and 1 wt.-%). Preliminary dynamic swelling studies have evidenced the occurrence of an interaction between the PHG-UV gel and the glycoprotein. This result was confirmed by ATR FT-IR measurements. A diffusion model using a solution of Ficks' second law was employed to determine the diffusion coefficient of water into PHG-UV gel as a consequence of adsorption and/or interdiffusion which occur at the PHG-UV gel/mucin solution interface. Experimental results suggest a potential use of PHG-UV gel to prepare bioadhesive devices.     

Cholesterol oxidation in meat-based baby foods

Cholesterol oxidation in commercial meat-based homogenized and freeze-dried baby foods was examined. The 7 major products of this reaction were determined by gas chromatography coupled with mass spectrometry (GC-MS). As far as single cholesterol oxidation products (COP) are concerned, 7-ketocholesterol was the major product of direct cholesterol oxidation in the 2 groups of analyzed samples, and this study confirmed that it is a useful marker of the whole cholesterol oxidation process. Nevertheless, the amounts of cholesterol-5beta,6beta-epoxide were often similar to and sometimes higher than the amounts of 7-ketocholesterol, thus showing a strong development of both direct and indirect cholesterol oxidation pathways. Total COP content was significantly higher in freeze-dried than in homogenized products. Moreover, in freeze-dried samples, the COP content per serving was quite variable and, in 2 samples, it was close to or even higher than 500 microg. The greater development of cholesterol oxidation in the freeze-dried samples was confirmed by their highest total COP/cholesterol percent ratios. A constant correlation between the fatty acid composition and the development of cholesterol oxidation was not found, although a positive correlation between unsaturated fatty acid content and total COP content occasionally exists in samples of the same brand.     

Acetylene to vinylidene rearrangements on electron rich d6 metal centers: a density functional study

The acetylene to vinylidene isomerization on several Ru(II) d(6) metal fragments with different electron richness of the metal center has been investigated by means of density functional theory calculations. We considered the [(eta(5)-C(5)Me(5))Ru(dippe)](+), [(eta(5)-C(5)Me(5))Ru(dmpe)](+), [(eta(5)-C(5)H(5))Ru(PMe(3))(2)](+), [(eta(6)-C(6)Me(6))(PMe(3))ClRu](+), [(eta(5)-C(5)H(5))Ru(CO)(PPh(3))](+) and [eta(6)-C(6)H(6))(PMe(3))ClRu](+), species which are quite common in the chemistry of cationic Ru(II) complexes and span a wide range of electron-richness. For each of the considered fragments, the minima on the potential energy surfaces for the two possible isomerization mechanisms, i.e. through a direct 1,2-hydrogen shift or through a hydrido-alkynyl intermediate, have been localized. A linear correlation has been found between the C=C stretching frequencies of the vinylidene complexes, as an estimate of the electron richness, and the stability of the corresponding hydrido-alkynyl intermediates. For the most electron-rich among the considered fragments, [(Cp*)(dippe)Ru(HCCH)](+), the hydrido-alkynyl species has been found essentially isoenergetic with the alkyne complex (only 1.9 kcal mol(-1) higher), in agreement with the experimental evidence showing for this system an equilibrium between these two species. For the same [(Cp*)(dippe)Ru](+) fragment, a detailed analysis of the reaction profiles for the two possible acetylene rearrangement pathways has been performed. Our results show that once the eta(2)-C-H coordinated acetylene intermediate is accessed, the system can easily evolve towards a hydrido-alkynyl intermediate, this process being kinetically favored with respect to the direct 1,2-shift leading to the vinylidene product.     

Recycling asymmetric hydrogenation catalysts by their immobilisation onto ion-exchange resins

New systems based on cationic chiral phosphine-rhodium complexes anchored to a commercial cation-exchange gel-type resin showed high efficiency and easy recycling in the asymmetric hydrogenation of prochiral olefins.     

Hardy inequalities with optimal constants and remainder terms

We show that the classical Hardy inequalities with optimal constants in the Sobolev spaces and in higher-order Sobolev spaces on a bounded domain can be refined by adding remainder terms which involve norms. In the higher-order case further norms with lower-order singular weights arise. The case being more involved requires a different technique and is developed only in the space .

     

Integral cohomology of the Milnor fibre of the discriminant bundle associated with a finite Coxeter group

Let W be a finite Coxeter group generated by real reflections in a complex vector space. We compute the integral cohomology of the Milnor fibre of the discriminant bundle $\Delta :{\mathbb{C}}^n/W\to \mathbb{C}$, together with the action of the monodromy, for the whole list of exceptional groups. Here Δ is the map induced by the square of the polynomial defining the arrangement of reflection hyperplanes of W. The computation is equivalent to that of the cohomology, with suitable local coefficients, of the corresponding Artin group. These computations complete, for the exceptional cases, those performed by De Concini et al. for rational coefficients. To cite this article: F. Callegaro, M. Salvetti, C. R. Acad. Sci. Paris, Ser. I 339 (2004).     

Fixed points of commuting holomorphic mappings other than the Wolff point

Let be the unit disc of and let be such that . For 1$">, let . We study the behavior of on . In particular, we prove that . As a consequence, besides conditions for , we prove a conjecture of C. Cowen in case and are univalent mappings.