ParaHydrogen Polarized Ethyl-[1-13C]pyruvate in Water,a Key Substrate for Fostering the PHIP-SAH Approach to Metabolic Imaging

An efficient synthesis of vinyl-[1-¹³C]pyruvate has been reported, from which ¹³C hyperpolarized (HP) ethyl-[1-¹³C]pyruvate has been obtained by means of ParaHydrogen Induced Polarization (PHIP). Due to the intrinsic lability of pyruvate, which leads quickly to degradation of the reaction mixture even under mild reaction conditions, the vinyl-ester has been synthesized through the intermediacy of a more stable ketal derivative. ¹³C and ¹H hyperpolarizations of ethyl-[1-¹³C]pyruvate, hydrogenated using ParaHydrogen, have been compared to those observed on the more widely used allyl-derivative. It has been demonstrated that the spin order transfer from ParaHydrogen protons to ¹³C, is more efficient on the ethyl than on the allyl-esterdue to the larger J-couplings involved. The main requirements needed for the biological application of this HP product have been met, i. e. an aqueous solution of the product at high concentration (40 mM) with a good ¹³C polarization level (4.8 %) has been obtained. The in vitro metabolic transformation of the HP ethyl-[1-¹³C]pyruvate, catalyzed by an esterase, has been observed. This substrate appears to be a good candidate for in vivo metabolic investigations using PHIP hyperpolarized probes.     

Hydrodynamical limit for a drift-diffusion system modeling large-population dynamics

In this paper we study the stability of the following nonlinear drift-diffusion system modeling large population dynamics ∂_tρ+div(ρU−ε∇ρ)=0, divU=±ρ, with respect to the viscosity parameter ε. The sign in the second equation depends on the attractive or repulsive character of the field U. A proof of the compactness and convergence properties in the vanishing viscosity regime is given. The lack of compactness in the attractive case is caused by the blow-up of the solution which depends on the mass and on the space dimension. Our stability result is connected, depending of the character of the potentials, with models in semiconductor theory or in biological population.     

Asymptotically balanced schemes for non-homogeneous hyperbolic systems – application to the Shallow Water equations

In this work we introduce a class of balanced numerical schemes, up to second order, for the solution of general non-homogeneous hyperbolic systems of conservation laws. We give a general technique to build such schemes. We also prove that they balance up to second order a large class of steady solutions in the whole domain but some subset whose measure tends to zero as the grid size decreases to zero. We finally present an application to Shallow Water equations that exhibit the good performances of some of the schemes introduced. To cite this article: T. Chacón Rebollo et al., C. R. Acad. Sci. Paris, Ser. I 338 (2004).     

AFM, SEM and GIXRD studies of thin films of red polycarbazolyldiacetylenes

In this paper we report the results of a morphological and structural investigation on film properties of a soluble polydiacetylene, the poly[1,6-bis(3,6-dihexadecyl-N-carbazolyl)-2,4-hexadiyne] (polyDCHD-HS). The red films of this polymer, prepared by standard spin-coating techniques, revealed absence of linear dichroism and birefringence in contrast with the ordered mesophases detected by powder X-ray studies. In order to interpret the optical behavior of this polymer, we performed AFM and SEM studies of polyDCHD-HS films spun on hydrophylic and hydrophobic glass substrates. We found the presence of surfaces organized in rod-like particles, more regularly oriented on the hydrophylic substrate. GIXRD studies, carried out on films sufficiently thick to allow the observation of the diffraction pattern, reveled the presence of a lamellar structure with a spacing of 3.22 nm. The low intensity of the diffraction peaks and the isotropic linear optical properties of the films show that the lamellar mesophases are not extended over large areas. These findings were compared with the data obtained from AFM and SEM studies on films of two other polydiacetylenes, the poly[1-(3,6-dihexadexyl-N-carbazolyl)-6-(N-carbazolyl)-2,4-hexadyine] (polya-DCHD) and the poly[1,6-bis(3,6-dipalmitoyl-N-carbazolyl)-2,4-hexadyine] (polyDPCHD), spun on hydrophylic glass substrate. The results confirmed the presence of nodular morphologies which seem to be a general characteristic of this class of materials. The particles organization appears instead related to the chemical nature of the substituents on the carbazolyl rings.     

Sharply 1-transitive subsets of certain permutation groups

In this paper we give a method for constructing sharply 1-transitive permutation sets inside a finite permutation group with certain properties and we apply this method to obtain a family of sharply 1-transitive permutation subsets of the sharply 3-transitive permutation group M(p ^2f ) on PG(1, p ^2f ) for p ^f 1 (mod 4).Work supported by G.N.S.A.G.A. and M.P.I.     

Effects of substrate relaxation in regular chemisorption. Hydrogen on graphite

Substrate relaxation is shown to play an important role in the 1 : 2 regular chemisorption of hydrogen atoms above alternate carbon atoms in a graphite monolayer. Binding energy, population analysis and electron density maps show that the direct HC bond is strengthened on relaxation.