Negatively Charged Metallacarborane Redox Couples with Both Members Stable to Air

The metallacarborane [3,3′‐Co(1,2‐closo‐C₂B₉H₁₁)₂]^? has been synthesized. This species allows the formation of redox couples in which both partners are negatively charged. The E_1/2 potential can be tuned by adjusting the nature and number of substituents on B and C. The octaiodinated species [3,3′‐Co(1,2‐closo‐C₂B₉H₇I₄)₂]^? is the most favorable, as it is isolatable and stable in air. A DFT study on stability and redox potentials of complexes has been performed.     

Vector potential theory on nonsmooth domains in R<Superscript>3</Superscript> and applications to electromagnetic scattering

We study boundary value problems for the time-harmonic form of the Maxwell equations, as well as for other related systems of equations, on arbitrary Lipschitz domains in the three-dimensional Euclidean space. The main goal is to develop the corresponding theory for L^p-integrable bounday data for optimal values of p's. We also discuss a number of relevant applications in electromagnetic scattering.     

From monomeric to polymeric ferroelectric liquid crystals A comparative study of ferroelectric properties

Two new ferroelectric oligosiloxanes, a cyclic tetramer and a twin, have been synthesized. By a comparative study with their corresponding monomer and side chain polysiloxanes, the influence of oligo- and polymerization on the liquid crystalline and ferroelectric properties have been investigated. Polymerization leads to a stabilization of LC phases through increase of the clearing temperatures and suppression of crystallization. Oligomerization also leads to mesophase broadening, but, due to the low degree of polymerization, the effect is inferior to the linear polysiloxanes. The low viscosity of the oligosiloxanes ensures response times in the microsecond region, thus being comparable with their monomer and conventional LMWFLCs. It is found that polymerization increases the spontaneous polarization P_s. This is attributed to the density increase after polymerization, enhancing the inter-mesogenic interactions. The collective and local dynamics of the OFLCs are influenced differently with respect to their molecular structures. Each oligomer is already a good model for its corresponding polymer concerning the soft mode dynamics. For the local β-relaxation a similar temperature dependence of the relaxation times τ for the cyclic tetramer and for the side chain polysiloxanes is observed. The long axial rotation of the twin, having a very efficient decoupling, is significantly faster, thus resembling the monomer.     

Organocatalysis: quantum chemical modeling of nucleophilic addition to α,β‐unsaturated carbonyl compounds

One of the successful transformations within the field of organocatalysis, the organocatalytic asymmetric addition of nitromethane to α,β‐unsaturated aldehydes and ketones, has been studied by quantum chemical modeling. The level of accuracy of the hybrid density functional theory method B3LYP/6‐31G(d) was compared to a high level ab initio benchmark for this reaction. It is concluded that B3LYP/6‐31G(d) performs very well for this reaction type, giving good estimates of critical energies. The reaction between acrolein and nitromethane was studied in detail. The reaction mechanism revealed an intermediate oxazolidin structure, which is currently unknown. Alkyl substitution in various positions on the amine catalyst or α,β‐unsaturated carbonyl compound influences the reactivity in a predictive fashion. The iminium ion, prop‐2‐en‐iminium, is less activated towards nucleophilic attack compared to protonated acrolein. Copyright © 2007 John Wiley & Sons, Ltd.     

Hardy type inequalities with exponential weights for a class of convolution operators

In this paper we consider operators of the form H=λ(-i∇), with λ analytic in a strip and with some specific growth conditions at infinity, and prove Hardy type estimates in L ²(ℝ ⁿ ) with exponential weights. In fact we extend our previous results [19] from bounded analytic functions on a strip to analytic functions with polynomial growth in that strip.     

Sur quelques problèmes de probabilités géométriques pour des réseaux irréguliers dans l'espace euclidienE 2 etE n

Dans ce travail on détermine quelques probabilités géométriques concernant des réseaux irréguliers dans le plan euclidienE ₂ et dans l'espace euclidienE _n . Les propriétés généralisent certains résultats de Buffon, Deltheil et Stoka. Travail effectué avec l'aide du MURST (40%, 60%).     

RECURSIVE BAIRE CLASSIFICATION AND SPEEDABLE FUNCTIONS

Using recursive variants of Baire notions of nowhere dense and meagre sets we study the topological size of speedable and infinitely often speedable functions in a machine-independent framework. We show that the set of speedable functions is not “small” whereas the set of infinitely often speedable functions is “large”. In this way we offer partial answers to a question in [4].     

Synthesis,properties, and crystal structure of a novel 3-hydroxy-(4<Emphasis Type="Italic">H</Emphasis>)-benzopyran-4-one containing copper(II) complex,and its oxygenation and relevance to quercetinase

The preparation, spectroscopic properties, and crystal structure of [Cu(ind)(mco)] [ind is the anion of 1,3-bis(2-pyridylimino)isoindoline and mco is the anion of 3-hydroxy-(4H)-benzopyran-4-one] are reported. The complex exhibits a distorted square pyramidal geometry. The oxygenation of the title compound results in oxidative cleavage of the heterocyclic ring to give the (acetylsalicylato)copper(II) complex [Cu(asp)(ind)] (asp is the anion of acetylsalicylic acid) and CO as primary products, which reaction resembles the enzymatic reaction of quercetinase.