Synthesis and reactivity of (C6F5)3B-N-heterocycle complexes. 1. Generation of highly acidic sp3 carbons in pyrroles and indoles

The reaction of pyrroles and indoles with B(C(6)F(5))(3) and BCl(3) produces 1:1 B-N complexes containing highly acidic sp(3) carbons, for example, N-[tris(pentafluorophenyl)borane]-5H-pyrrole (1) and N-[tris(pentafluorophenyl)borane]-3H-indole (2), that are formed by a new formal N-to-C hydrogen shift, the mechanism of which is discussed. With some derivatives, restricted rotation around the B-N bond and/or the B-C bonds was observed by NMR techniques, and some rotational barriers were calculated from experimental data. The acidity of the sp(3) carbons in these complexes is shown by their ability to protonate NEt(3), with formation of pyrrolyl- and indolyl-borate ammonium salts. The driving force for this reaction is given by the restoration of the aromaticity of the heterocycle.     

Pharmacophore modeling as an efficient tool in the discovery of novel noncompetitive AMPA receptor antagonists

A three-dimensional pharmacophore model for the binding of noncompetitive AMPA receptor antagonists was developed in order to map common structural features of highly active compounds. This hypothesis, which consists of two hydrophobic regions, one hydrogen bond acceptor and one aromatic region, was successfully used as framework for the design of a new class of allosteric modulators containing a tetrahydroisoquinoline skeleton and for in silico screening. The promising biological results suggested that the identified molecules might be useful "lead compounds" for future drug development.     

Cellulose beads: a new versatile solid support for microwave- assisted synthesis. Preparation of pyrazole and isoxazole libraries

The synthesis of libraries of substituted pyrazoles and isoxazoles has been developed via in situ generation of polymer-bound enaminones. The synthetic protocol makes use of commercially available aniline cellulose, a low-cost and versatile biopolymer, under very mild conditions. This new support allowed us to carry out reactions in polar solvents under both conventional heating and MW irradiation without degradation of the polymer. The reaction between cellulose-bound enaminone and hydroxylamine or hydrazines to afford the target heterocycles in high yields directly in solution is the key step. The support can be conveniently recycled.     

Structure of three-interval exchange transformations II: a combinatorial description of the tranjectories

Astract  We describe an algorithm for generating the symbolic sequences which code the orbits of points under an interval exchange transformation on three intervals. The algorithm has two components. The first is an arithmetic division algorithm applied to the lengths of the intervals. This arithmetic construction was originally introduced by the authors in an earlier paper and may be viewed as a two-dimensional generalization of the regular continued fraction. The second component is a combinatorial algorithm which generates the bispecial factors of the associated symbolic subshift as a function of the arithmetic expansion. As a consequence, we obtain a complete characterization of those sequences of block complexity 2n+1 which are natural codings of orbits of three-interval exchange transformations, thereby answering an old question of Rauzy. Partially supported by NSF grant INT-9726708.     

Porphyrin deposition induced by UV irradiation

Simple irradiation by UV light of porphyrin TpyP and its zinc(II) and manganese(III) metal derivatives in chlorinated solvents leads to the deposition on silica of mesoscale aggregates. The process is due to the photochemical decomposition of the solvent with generation of HCl, which causes the precipitation of a protonated form. The morphology of the resulting objects is driven by the nature of the inserted metal ion.     

The Boggess-Polking extension theorem for<Emphasis Type="Italic">CR</Emphasis> functions on manifolds with corners

We give the “boundary version” of the Boggess-PolkingCR extension theorem. LetM andN be real generic submanifolds of ℂ ⁿ withN ⊂M and letV be a “wedge” inM with “edge”N and “profile” Σ ⊂T _NM in a neighborhood of a pointz _o.We identify in natural manner and assume that for a holomorphic vector fieldL tangent toM and verifying we have that the Levi form takes a value . Then we prove thatCR functions onV extend ∀_ω to a wedgeV ₁ “attached” toV in direction of a vector fieldiV such that |pr(iV(z ₀))−iv ₀| < ε (where pr is the projection pr:T _NX →T _MX | _N ).We then prove that when the Levi cone “relative to Σ”iZ _Σ = convex hull is open inT _MX, thenCR functions extend to a “full” wedge with edgeN (that is, with a profile which is an open cone ofT _NX). Finally, we prove that iff is defined in a couple of wedges ±V with profiles ±Σ such thatiZ _Σ =T _MX, and is continuous up toN, thenf is in fact holomorphic atz _o.     

Experimental assessment of electrochemical processes in the remediation of atrazine contaminated soils

The electrochemical oxidation of an atrazine solution obtained from a flushing treatment of a contaminated soil was investigated. The influence of ethanol on atrazine oxidation was studied. Results show that the electrogenerated Fenton's reagent provides a complete degradation of atrazine and its main chlorinated by-products via N-dehalkylation and dechlorination. This process therefore presents an effective alternative to the chemical oxidation treatment which necessarily needs a further biological state.     

Analysis by the two-fluids model of the dynamical behavior of a viscoelastic fluid probed by dynamic light scattering

The dynamic properties of a model transient network have been studied by dynamic light scattering. The network is formed by microemulsion droplets linked by telechelic polymers (modified hydrophilic polymers with two grafted hydrophobic stickers). We compare the properties of two networks that are similar but for the residence time of the hydrophobic stickers in the droplets. The results are interpreted according to the so-called two-fluids model, which was initially developed for semidilute polymer solutions and which we extend here to any Maxwellian viscoelastic medium characterized by its elastic modulus and terminal time as measured by rheology. This model is found to describe consistently and quantitatively the experimental observations.     

The structure of acrolein in a liquid crystal phase

The (1)H NMR spectrum of a sample of acrolein dissolved in the nematic liquid crystal phase I52 has been analysed to yield 18 dipolar couplings between all the magnetic nuclei in the molecule; moreover, the (13)C and (13)C{(1)H} NMR spectra of a sample of acrolein in CDCl(3) were recorded and analysed to determine the indirect J(ij) couplings. The data were used to obtain the relative positions of the carbon and hydrogen atoms, assuming that these are independent of the conformations generated by rotation around the C--C bond through an angle phi, and to obtain a probability distribution P(phi). It has been found that in the liquid phase, the distribution is a maximum at the trans form whereas the abundance of the cis form is significantly smaller compared with that found by microwave spectroscopy or high level quantum mechanical calculations. Such calculations produced also a suitable force field needed to develop suitable strategies for vibrational correction procedure in the case of flexible molecules.