Molecular design based on 3D-pharmacophore. Application to 5-HT subtypes receptors

A first definition of a pharmacophore for the serotonin reuptake inhibitors was carried out by considering a three-dimensional model which correlates the chemical structures of series of reuptake inhibitors with their biological affinities. A molecular design was described by analyzing two different 3D serotonin pharmacophores. This successful approach enabled us to consider the design of new serotonin ligands by the same method.     

Luminescence Properties of New Fused Benzothiophene Derivatives and Their Conductive Oligomers Structural and Solvent Effects

The structural and solvent effects on the electronic absorption and fluorescence spectra, and fluorescence quantum yields, of four new fused benzothiophene derivatives, including benzothieno[3,2b]-thiophene (BTT), benzothieno[3,2-b]benzothiophene (BTBT), 6-methoxy[1]benzothieno[3,2b]-thiophene (MeOBTT), and benzothieno[3,2-b]indole (BTI) were investigated at 295 K. The luminescence properties of the corresponding conductive oligomers, poly(BTT) and poly (MeOBTT), electrosynthesized in acetonitrile, were also studied. Satisfactory McRae, Suppan, and Kawski-Chamma-Viallet solvatochromic correlations were established for the four monomers in most solvents. A weak negative solvatochromic behavior was found for these compounds, indicating that their dipole moments are slightly lower in the excited singlet state than in the ground state. Kamlet-Abboud-Taft multiparametric correlations were also obtained for absorption and fluorescence wave numbers and quantum yields, demonstrating the existence of specific solute-solvent interactions. In the case of the oligomers, important red-shifts of the fluorescence emission maxima ( 90–110 nm) relative to the corresponding monomers were observed, which shows the extent of conjugated segments in the oligomer chains.     

Energy-filtered electron microscopy for imaging core–shell nanostructures

CuAg core–shell nanoparticles are synthesized by ultra-high vacuum thermal evaporation. We show on this system how the Energy-Filtered Transmission Electron Microscopy (EFTEM) technique allows one to improve the characterization by precisely pointing out the formation of core–shell arrangements in bimetallic nanoparticle assemblies. A criterion to measure the shell thickness from EFTEM images on unique core–shell nanoparticles is defined, that can be used for core–shell nanoparticles of any sizes, with shell thicknesses over 1 nm. It is based on the intensity variation along a line drawn across a core–shell nanoparticle on a EFTEM image. This criterion has been validated by a close comparison of the shell thickness measurements performed in this work and the ones obtained by acoustic micro-Raman spectroscopy. Using this criterion, we report a strong correlation between the size of the Cu cores and the formation of the core–shell arrangements in the nanoparticle assembly studied in this work. The influence of the Cu core shape is also evidenced. The characterisation of such systems using High Resolution TEM (HRTEM) is also discussed.     

Synthesis of 5-aroylamino-3H-1,3,4-thiadiazole-2-thiones and their tautomerism

5-Aroylamino-3H-1,3,4-thiadiazole-2-thiones 2 have been synthesized by acylation of 5-amino-3H-1,3,4-thiadiazole-2-thione 1 . 5-Aroylamino-3H-1,3,4-thiadiazole-2-thiones can exist in two tautomeric forms — a thiol form and a thione form. On the basis of the ¹³C nmr spectra and additional experimental information, it has been established that the thione form is the stable form in which these compounds exist.     

Intermittency of velocity time increments in turbulence

We analyze the statistics of turbulent velocity fluctuations in the time domain. Three cases are computed numerically and compared: (i) the time traces of Lagrangian fluid particles in a (3D) turbulent flow (referred to as the dynamic case); (ii) the time evolution of tracers advected by a frozen turbulent field (the static case); (iii) the evolution in time of the velocity recorded at a fixed location in an evolving Eulerian velocity field, as it would be measured by a local probe (referred to as the virtual probe case). We observe that the static case and the virtual probe cases share many properties with Eulerian velocity statistics. The dynamic (Lagrangian) case is clearly different; it bears the signature of the global dynamics of the flow.     

Statistics of Fourier modes of velocity and vorticity in turbulent flows: intermittency and long-range correlations

We perform a statistical analysis of experimental fully developed turbulence longitudinal velocity data in the Fourier space. We address the controversial issue of statistical intermittency of spatial Fourier modes by acting on the finite spectral resolution. We derive a link between velocity structure functions and the flatness of Fourier modes thanks to cascade models. Similar statistical behaviors are recovered in the analysis of spatial Fourier modes of vorticity obtained in an acoustic scattering experiment. We conclude that vorticity is long-range correlated and found more intermittent than longitudinal velocity.     

Test of the Wiedemann-Franz law in an optimally doped cuprate

We present a study of heat and charge transport in Bi(2+x)Sr(2-x)CuO(6+delta) focused on the size of the low-temperature linear term of the thermal conductivity at optimal-doping level. In the superconducting state, the magnitude of this term implies a d-wave gap with an amplitude close to what has been reported. In the normal state, recovered by the application of a magnetic field, measurement of this term and residual resistivity yields a Lorenz number L=kappa(N)rho(0)/T=1.3+/-0.2L(0). The departure from the value expected by the Wiedemann-Franz law is thus slightly larger than our estimated experimental resolution.     

Oxidative stress effects on erythrocytes determined by FT-IR spectrometry

This study was designed to evaluate changes in erythrocyte contents during endurance moderate intensity exercise, a model of physiological oxidative stress. 16 endurance-trained subjects cycled 2 h at 55% of maximal aerobic capacity and blood was collected every 15 min. Transmission FT-IR spectrometry was used to analyze separately plasma and erythrocyte content changes during oxidative stress. Erythrocyte FT-IR spectra were corrected for hemoconcentration (Hc) before spectral areas integration of main IR absorbances belonging to phospholipids [nu(as)(CH(3)), [nu(as)(CH(2)), and nu(P=O)], proteins [nu(C=O) and delta(N-H)], and lactate [nu(C-O)] were used to determine erythrocyte content changes. Changes in nu(as)(CH(2)) and nu(P=O) absorbances while nu(as)(CH(3)) remained stable showed the magnitude of free radical attacks on phospholipids bilayer. Decrease in nu(C=O) and delta(N-H) absorbances while plasma and intracellular lactate, O(2) consumption, and Hc rose were linked to hemoglobin, and possibly spectrin, denaturation. Finally, the synergistic changes found between physiological, plasmatic and erythrocyte parameters showed that FT-IR spectrometry was a sufficiently accurate and sensitive method to determine acute changes in erythrocytes during moderate, physiological, oxidative stress.     

Organic cross-linked electropolymers as supported oxidation catalysts: poly((tetrakis(9,9'-spirobifluorenyl)porphyrin)manganese) films

Anodic oxidation of free base and manganese complexes of tetraspirobifluorenylporphyrins leads to the coating of the working electrode by insoluble electroactive poly(9,9'-spirobifluorene-free and manganese porphyrin) films which electrochemical behavior and physicochemical properties are described. After removal from the electrode, the manganese-complexed polymers were evaluated as catalysts for the oxidation of alkenes by iodobenzene diacetate or iodosylbenzene. The results show that the reactions proceeded very efficiently at room temperature with good yields. The electrosynthesized polymer catalysts can be recycled by simple filtration and reused even up to the eighth cycle without loss of activity and selectivity. These results represent an important improvement over those previously described for manganese-porphyrin-catalyzed epoxidation reactions.