A DFT study of lithium battery materials: application to the β-VOXO4 systems (X=P, As, S)

VOXO₄ systems have been considered as potential lithium battery electrodes. They mainly present two distinct structural types: the tetragonal “α” type with a two-dimensional framework, and the three-dimensional orthorhombic “β”. DFT calculations were performed on this latter system for several β-Li_xVOXO₄ compounds (x=0, 1; X=P, As, S). They allowed to propose structural models for VOAsO₄ and LiVOSO₄, not fully crystallographically well described yet. Based on an experimental model of two-phase processes, these calculations led also to a good simulation of electrochemical potential values. A density of states analysis put in evidence the “inductive effect” and the role played by (XO₄)ⁿ⁻ groups inside the host frameworks on these potentials.     

Regioselective electrophilic trifluoromethylation of indolines, oxindoles and indoles in superacid

Treatment of indolines and N-acylindoles with HF/SbF₅/CCl₄ yields 6-trifluoro derivatives (indole numbering) whereas indoles and oxindoles give the 5-trifluoro derivatives in good yield.     

Synthesis, biochemical properties and molecular modelling studies of organometallic specific estrogen receptor modulators (SERMs), the ferrocifens and hydroxyferrocifens: evidence for an antiproliferative effect of hydroxyferrocifens on both hormone-dependent and hormone-independent breast cancer cell lines

A series of ferrocene derivatives based upon the structure of the antiestrogenic drug tamoxifen or of its active metabolite hydroxytamoxifen has been prepared and named by analogy ferrocifens and hydroxyferrocifens. This series includes 1-[4-(O(CH(2))(n)NMe(2))phenyl]-1-phenyl-2-ferrocenyl-but-1-ene and 1-[4-(-O(CH(2))(n)NMe(2))phenyl]-1-(4-hydroxyphenyl)-2-ferrocenyl-but-1-ene, with n=2, 3, 5 and 8, and 1-[4-(-O(CH(2))(2)NMe(2))phenyl]-1-(4-hydroxyphenyl)-2-ferrocenylethene. Most of these molecules have been synthesised by McMurry cross-coupling of the appropriate ketones, except for the ethene complexes, which were prepared by a four-step reaction sequence starting from the ferrocenylacetic acid. All these compounds were obtained as mixtures of Z and E isomers. The isomers were separated in the cases of the ferrocenyl derivatives of tamoxifen and hydroxytamoxifen (n=2). No isomerisation of the Z and E isomers occurred in DMSO after one day, while a 50:50 mixture of the isomers was obtained within one hour in chloroform. The X-ray structure of (E)-1-[4-(-O(CH(2))(2)NMe(2))phenyl]-1-(4-hydroxyphenyl)-2-ferrocenyl-but-1-ene has been determined. The relative binding affinity (RBA) values of the hydroxyferrocifens for the estrogen receptor alpha (ERalpha) was good to moderate, with values decreasing progressively with the length of the basic chain. The RBA values found for the estrogen receptor beta (ERbeta) are equal to or slightly less than those found for the alpha form. The lipophilicity of the hydroxyferrocifens are superior to the values found for estradiol and increase with lengthening of the chain. The antiproliferative effects of the four hydroxyferrocifens with n=2, 3, 5 and 8 were studied on four breast cancer cell lines (MCF7, MDA-MB231, RTx6 and TD5) possessing different levels of ERalpha. On MCF7 cells containing high levels of ERalpha, hydroxyferrocifens behave as antiestrogens. At a molarity of 1 microM the effect is close to that of hydroxytamoxifen (used for reference) when n=2 or 5, more marked when n=3, and weaker when n=8. Ferrocene alone has no effect. For the MDA-MB231 cells, classed as a hormone-independent breast cancer cell line, on the other hand, the hydroxyferrocifens show remarkable antiproliferative behaviour while the hydroxytamoxifen is completely inactive. Hydroxyferrocifens therefore show the unique property of being active both on hormone-dependent and on hormone-independent breast cancer cell lines. The molecular modelling study provides some clues for understanding of the antagonist effect of these molecules, while an additional cytotoxic effect due to the vectorised ferrocenyl unit is revealed in some occasions.     

A Simple Electronic Analog of the Squid Axon Membrane: The NEUROFET

A simple electronic circuit is proposed as an analog of the excitable membrane. It is based on the Hodgkin-Huxley model and their squid axon voltage clamp data. The simulated potassium and sodium conductances are reproduced satisfactorily and the electronic action potentials are very similar to the experimentally recorded ones. Since this analog contains only a few electronic elements, it is small and inexpensive to build. It could be very useful as a means of simulating a wide variety of membrane conductances and different types of action potentials. Also, the simplicity of the circuit makes it an ideal unit to build complex neuron networks.     

Dynamique des lasers à fibre dopée à I’erbium

The dynamics of the erbium doped fiber laser is analysed both experimentally and theoretically. This laser operates spontaneously in self-pulsing, in sinusoidal or in CW regime. Experiments have allowed to determine the control parameters : the cavity losses, the pumping rate and the ion pairs concentration. An antiphase dynamics is observed when the laser operates simultaneously at 1.55 µn and 1.536 µm. The self-pulsing behavior is attributed to a fast energy transfer which occurs between two neighboring ions (pair induced quenching). A simple model considering the active medium as a mixture of isolated ions and ions pairs is developped and leads to a good qualitative agreement with the experimental results.     

On the stochastic timed Pétri nets model and its application to the DQDB protocol

The goal of this paper is twofold : at first, to present the stochastic timed Pétri nets model by emphasizing its ability to express the main characteristics of real time distributed systems (parallelism, synchronization by message exchange, time attributes and in particular time constraints) and to allow both qualitative and quantitative analysis (concept of randomized states graph); second, to show a modeling methodology based on this model that allows a rigorous modeling of theDqdb protocol (Qa access, bwb mechanism role,Pa access influence). A new contribution to theQa mechanism has been done (1).     

Diffractive production of charmed strange mesons by neutrinos and antineutrinos

The diffractive production of charmed strangeD _s ^* and possiblyD _s mesons by neutrinos and antineutrinos on nucleons in hydrogen, deuterium and neon targets is observed. The slope parameter of thet distribution is 3.3±0.8 (GeV)^?2. The production rate per charged current neutrino interaction with an isoscalar target times the D _s ⁺ →φτ⁺ branching fraction is (1.03±0.27)×10^?4.     

Caractérisation de la correspondance de Langlands locale par les facteursε de paires

Résumé SoitF un corps local non archimédien à corps résiduel fini. La conjecture de Langlands locale (prouvée par Laumon, Rapoport et Stuhler quandF est de caractéristique non nulle) associe à une classe d'isomorphisme de représentations irréductibles du groupe de Weil deF une classe d'isomorphisme () de représentations admissibles irréductibles supercuspidales d'un groupe linéaire surF, le groupe GL _n (F) si est de dimensionn. Nous prouvons dans cet appendice qu'il existe au plus une telle correspondance qui préserve les facteurs de paires et coïncide, en dimension 1, avec l'application donnée par la théorie du corps de classes.

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Summary LetF be a non-archimedean local field with finite residue field. The local Langlands conjecture (proved by Laumon, Rapoport and Stuhler when the characteristic ofF is positive) associates to an isomorphism class of irreducible representations of the Weil group ofF an isomorphism class () of admissible irreducible supercuspidal representations of some linear group overF, viz. GL _n (F) if dim ()=n. In this appendix we prove that there is at most one such correspondence which extends local class field theory in dimension 1, and preserves -factors for pairs.

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Oblatum 10 XII 1991

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Un complément à l'article -elliptic sheaves and the Langlands correspondence par G. Laumon, M. Rapoport et U. Stuhler.     

Charge calculations in molecular mechanics. Part 8 Partial atomic charges from classical calculations

Summary The CHARGE2 programme, which involves the classical calculation of both the inductive and resonance contributions to the partial atomic charges in molecules is described, and the charges and electrostatic potentials obtained presented for some illustrative examples.In substituted methanes (CH₃X, CF₃X, CCl₃X) the effects of varying the electronegativity of the substituents and the - and -substituent contributions are clearly illustrated for a variety of substituent groups X.The problems involved in the inclusion of silicon into this scheme are detailed, together with the methods of overcoming them. The partial atomic charges ( and contributions) and electrostatic potentials for some silicon oxygen compounds are presented and discussed.The partial atomic charges from CHARGE2 for all the natural amino acids as their N-acetyl, N-methyl-amides are given and compared with those obtained from the AMBER and ECEPP/2 force fields. Considerable differences in these figures are observed, with the AMBER charges consistently much larger than those from the other two methods.The CHARGE2 partial atomic charges and electrostatic potentials for the four common nucleic acids, adenine, cytosine, guanine and thymine, are given and compared with those derived from other calculations. Again there is general similarity but also there are considerable differences, with those from the AMBER force field somewhat larger than the other methods.For previous parts in this series, see Refs. 1-7.