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.     

High resolution 2D 1H-13C correlation of cholesterol in model membrane

High resolution 2D NMR MAS spectra of liposomes, in particular 1H-13C chemical shifts correlations have been obtained on fluid lipid bilayers made of pure phospholipids for several years. We have investigated herein the possibility to obtain high resolution 2D MAS spectra of cholesterol embedded in membranes, i.e. on a rigid molecule whose dynamics is characterized mainly by axial diffusion without internal segmental mobility. The efficiency of various pulse sequences for heteronuclear HETCOR has been compared in terms of resolution, sensitivity and selectivity, using either cross polarization or INEPT for coherence transfer, and with or without MREV-8 homonuclear decoupling during t1. At moderately high spinning speed (9 kHz), a similar resolution is obtained in all cases (0.2 ppm for 1H(3,4), 0.15 ppm for 13C(3,4) cholesterol resonances), while sensitivity increases in the order: INEPT < CP(x4) < CP + MREV. At reduced spinning speed (5 kHz), the homonuclear dipolar coupling between the two geminal protons attached to C(4) gives rise to spinning sidebands from which one can estimate a H-H dipolar coupling of 10 kHz which is in good agreement with the known dynamics of cholesterol in membranes.     

On the use of x-ray-excited optical luminescence (XEOL) for the analysis of multisite rare-earth systems

The realization of a XEOL (X-ray-excited optical luminescence) spectrometer is reported. The aim of the present paper is to show that a comparison between UV-excited emission spectra and XEOL spectra can be helpful in the assignment of some weak transitions for multiple site rare-earth compounds. The case of c-Y₂O₃ doped with Eu³⁺ cations is considered in some detail, as in the XEOL spectrum three lines to be assigned to transitions occurring at the centrosymmetrical Eu³⁺ (C_3i) site are strongly enhanced. Additional site-selective UV-excited emission spectra are also reported supporting the present discussion.     

Induction asymétrique et réaction des α-hydroxy-oximes avec le bromure de phenylmagnésium. Synthéses stéreoselectives d'alcools aziridiniques et d'aza-bicyclo[3.1.0]oxo-2 oxaisothiazolidines-1,2,3

A facile synthesis of aziridine is describe. It is the reaction between Grignard regents and α-hydroxoximes in toluene. The aziridine alchohols are cyclised into 2-oxo-oxathiazolidines. The use of the nuclear Overhauser effect allows the assignment of the relative configurations of these latter compounds and also the configuration of the aziridine alcohols. A proof of the Grignard reagent complex with the alcoolate id given by action of methylmagensium bromide with 2-phenyl 3-methanol azirine. The asymetrie insuction observed is discussed with a transition state involving this complex.     

Electronically ‘atypical’ a 15-type compounds based on chromium and molybdenum

The superconducting transition temperature has been investigated as a function of composition and degree of long-range order in a number of binary and ternary A 15-type phases on Cr and Mo. It is concluded that these compounds are unlike the typical Nb- or V- based phases with the same structure. The maximum T_c does usually not occur at the ideal composition. Nevertheless, a correlation has been found between T_c and the degree of order.     

A theoretical study of the difference in the behavior ofl- andd-alanine toward the two inverse forms of kaolinite

The adsorption ofl- andd-alanine on kaolinite is studied by means of the self-consistent field method, the field created by the crystal being simulated by that of 230 point charges, corresponding to two layers. The absolute structure we have adopted for kaolinite is that for whichthe ( ) trihedron is direct. Indeed, it has been shown that, owing to the nuclear weak interactions, this structure is more stable than the inverse structure. On the adopted structure, the l forms of the positive ion and of the zwitterion are more easily adsorbed than the d forms. The difference between the adsorption energies of thel andd forms are 0.14 and 0.04 kJ mol^–1 for the positive ion and the zwitterion, respectively. These differences are considerably larger than those arising from the weak interactions (ca. 10^–17 kJ mol^–1) so that the asymmetrical adsorption on kaolinite seems to be one of the causes of thel homochirality observed for the amino acids of proteins.