New chiral organosulfur donors related to bis(ethylenedithio)tetrathiafulvalene

Six new enantiopure chiral organosulfur donors, with structures related to BEDT-TTF, have been synthesised for use in the preparation of organic metals, starting either by double nucleophilic substitutions on the bis-mesylate of 2R,4R-pentane-2,4-diol or by a cycloaddition with subsequent elimination of acetic acid on the enol acetate of (+)-nopinone. Crystal structures of some of their radical cation triiodides salts and TCNQ complexes are reported.     

Detection of human and rodent 5-HT3B receptor subunits by anti-peptide polyclonal antibodies

Background  

The 5-HT₃ receptor is a member of a neurotransmitter-gated ion channel family which includes nicotinic acetylcholine, GABA_A, and glycine receptors. While antibodies specific for the 5-HT_3A receptor subunit are plentiful, and have revealed a wealth of structural and functional information, few antisera exist for the detection of 5-HT_3B receptor subunits. Here we describe the generation and characterisation of a rabbit polyclonal antiserum that specifically recognises 5-HT_3B receptor subunits     

Menthyloxycarbonyl phosphonium chlorides: new derivatives for determining the enantiomeric excess of chiral tertiary phosphines

The direct alkoxycarbonylation of tertiary phosphines with alkyl chloroformates has been examined and the products characterised by NMR and X-ray crystallographic analysis. The derivatisation of representative chiral tertiary phosphines with enantiopure menthyl chloroformate allows the determination of the enantiomeric excess of scalemic mixtures by ³¹P NMR spectroscopic analysis.     

HETEROCYCLIC CATIONS WITH DELOCALISED PI-SYSTEMS AND SHORT INTRAMOLECULAR SULFUR… SULFUR CONTACTS: THE STRUCTURES OF TWO DERIVATIVES OF THE 2-(1,3-DITHIOL-2-YLIDENEMETHYL)-1,3-DITHIOLIUM CATION

Abstract

The effective size of bonded divalent sulfur in S…S contacts is a function of the orientation of the groups, with the shortest contacts occurring when the groups are coplanar. A lower limit for the loner is indicated by the structures of the 2-(1,3-benzodithiol-2-ylidenemethyl)-1,3-benzodithiolium and 2-(1,3-dithiolan-2-ylidenemethyl)-1,3-dithiolanium cations, 2 and 3. These show almost mm symmetry with all four sulfur atoms involved in stabilisation of the positive charge. Short intramolecular sulfur… sulfur contact distances, 0.5–0.7 Å within the sum of traditional van der Waals radii, and maximised by in-plane angular distortions, indicate a lower limit to the effective size of the bonded divalent sulfur atom of ca. 1.45 Å.     

Dibenzyl Structuresin a Macromolecular Chain. III. Dibenzyldiisocyanates Reactivity

The reactivity of the 2,2′-, 2,4′-, 4,4′-dibenzyldiisocyanate (2,2′-, 2,4′-, 4,4′-DBDI) with n-butanol in benzene has been studied. The concentrations of all species were monitored by using high performance liquid chromatography (HPLC). The reactivity of 4,4′-DBDI is similar to that of 4,4′-diphenylmethanediisocyanate (4,4′-MDI). Very strong intramolecular catalytic effects were noticed in the case of 2,2′-DBDI, probably due to the variable molecular geometry. These effects are responsible for the whole reaction pattern. The 2,4′-DBDI NCO ortho and para groups reactivities are different and comparable to that of 2,4-toluylenediisocyanate (2,4-TDI).     

Tracking accuracy of a semi‐Lagrangian method for advection–dispersion modelling in rivers

There is an increasing need to improve the computational efficiency of river water quality models because: (1) Monte‐Carlo‐type multi‐simulation methods, that return solutions with statistical distributions or confidence intervals, are becoming the norm, and (2) the systems modelled are increasingly large and complex. So far, most models are based on Eulerian numerical schemes for advection, but these do not meet the requirement of efficiency, being restricted to Courant numbers below unity. The alternative of using semi‐Lagrangian methods, consisting of modelling advection by the method of characteristics, is free from any inherent Courant number restriction. However, it is subject to errors of tracking that result in potential phase errors in the solutions. The aim of this article is primarily to understand and estimate these tracking errors, assuming the use of a cell‐based backward method of characteristics, and considering conditions that would prevail in practical applications in rivers. This is achieved separately for non‐uniform flows and unsteady flows, either via theoretical considerations or using numerical experiments. The main conclusion is that, tracking errors are expected to be negligible in practical applications in both unsteady flows and non‐uniform flows. Also, a very significant computational time saving compared to Eulerian schemes is achievable. Copyright © 2006 John Wiley & Sons, Ltd.     

Squares,clique graphs,and chordality

We study the squares and the clique graphs of chordal graphs and various special classes of chordal graphs. Chordality conditions for squares and clique graphs are given. Several theorems concering chordal graphs are generalized. © 1996 John Wiley & Sons, Inc.     

An in depth study of the formation of new tetrathiafulvalene derivatives from 1,8-diketones

A detailed study of the reactions of phosphorus pentasulfide and Lawesson's reagent with a series of 4,5-bis(RCOCH₂S)-1,3-dithiole-2-thiones (R=Ph, 4-MeOC₆H₄, 4-Br C₆H₄, Me) has been carried out. These reactions lead to fusion of either an unsaturated 1,4-dithiin ring or a thiophene to the dithiole; the former in higher yield, while the latter is a significant product in the reactions with Lawesson's reagent; as well as small amounts of minor products. A mechanistic rationalization of these products is discussed in some detail. The new fused dithioles have been converted to novel series of fused TTF derivatives.