Determination of microtacticity of poly(vinylketones) and their derivatives by NMR spectroscopies of carbon-13 and proton

Sequence distribution of atactic poly(phenylvinylketone) (PPVK) has been determined by [¹³C]-[¹H]NMR spectroscopy. Quantitative analysis of the carbonyl pattern allows resolution into pentads with intensities fitting a first order Markov process. The carbonyl pattern of highly isotactic PPVK, initiated by diethylzinc, deviates strongly from Bernoullian statistics, as in the case of highly isotactic polymethylvinylketone (PMVK). For n-butyl-lithium initiated poly(isopropenylphenylvinylketone) (PIPK), the carbonyl pattern practically agrees with a Bernoullian distribution. Atactic PMVK, analyzed from the methylene and the carbonyl pattern in [¹³C] or [¹H]NMR, shows that the polymerization process is purely Bernoullian and quite different from that for poly(isopropenylmethylketone). Except for poly(methylallylalcohol) for which the tacticity can be determined, the resolution is too poor to allow a quantitative sequence distribution of poly(allylalcohols) or poly(allyltrifluoroacetates). [¹H] and [¹⁹F]NMR spectroscopies of these compounds do not give better results.     

Synthesis of new 7-aminosterol squalamine analogues with high antimicrobial activities through a stereoselective titanium reductive amination reaction

A series of 7-amino- and polyaminosterol analogues of squalamine and trodusquemine were synthesized involving a new stereoselective titanium reductive amination reaction in high chemical yields of up to 95% in numerous cases. These derivatives were evaluated for their in vitro antimicrobial properties against human pathogens. All the compounds present excellent activities against Gram-positive bacteria exhibiting similar results against Staphylococcus aureus and Streptococcus faecalis with minimum inhibitory concentrations (MICs) varying from 2.5 to 10 μg/mL. Numerous derivatives possess also MICs against Gram-negative Escherichia coli bacteria (MICs varying from 2.5 to 10 μg/mL) suggesting that nature of the amino group attached to the sterol moiety plays an important role on the activities of such products.     

The Linear Rational Pseudospectral Method with Preassigned Poles

We present a linear rational pseudospectral (collocation) method with preassigned poles for solving boundary value problems. It consists in attaching poles to the trial polynomial so as to make it a rational interpolant. Its convergence is proved by transforming the problem into an associated boundary value problem. Numerical examples demonstrate that the rational pseudospectral method is often more efficient than the polynomial method.     

Convexes divisibles III

Let Δ₀ be a group of finite type and FΔ₀⊂Hom(Δ₀,PGL(Rm)) be the subset of faithful representations for which there exists a properly convex Δ₀-invariant open subset Ω in P(Rm) such that the quotient Δ₀\Ω is compact. Koszul has proved in [J.L. Koszul, Déformation des connexions localement plates, Ann. Inst. Fourier 18 (1968) 103-114] that this subset FΔ₀ is open. We describe the closure of FΔ₀. As a consequence, we show that this subset FΔ₀ is closed if and only if the virtual center of Δ₀ is trivial. This condition is satisfied if and only if FΔ₀ contains a strongly¹ irreducible representation.     

Transparent boundary conditions for a class of boundary value problems in some ramified domains with a fractal boundary

We consider some boundary value problems in self-similar ramified domains, with Laplace and Helmholtz equations. We discuss transparent boundary conditions. These conditions permit computing the restriction of the solutions to domains obtained by stopping the geometric construction after a finite number of steps. To cite this article: Y. Achdou et al., C. R. Acad. Sci. Paris, Ser. I 342 (2006).     

Autour de la conjecture de L. Markus sur les variétés affines

Summary For any subgroupG of (n), we introduce some integer discGn called thediscompacity ofG. This number measures to what extent the closure ofG is not compact. The Markus' conjecture says that a compact affinely flat unimodular manifold is complete. Our main result (called the discompact theorem) is that this conjecture is true under the assumption that the linear holonomy i.e. the parallel transport has discompacity 1. Because discSO(n–1, 1)=1, this ensures that a compact flat Lorentz manifoldM is geodesically complete. Hence, by a previous result of W. Goldman and Y. Kamishima [GK], such aM is, up to finite covering, a solvmanifold. This achieves the proof of a Bieberbach's theorem for compact Lorentz flat manifolds.     

The crystal structure of bis(triphenylphosphine)-(η-cyclohexa-1,3-diene)rhenium trihydride

Bis(triphenylphosphine)(η-cyclohexa-1,3-diene)rhenium trihydride, (Ph₃P)₂(η-C₆H₈)ReH₃ (I) crystallises in the space group C2/c with cell dimensions a 22.76(2), b 10.14(1) c 29.813(6) Å, β 97.69(8)°. The final refinement of 126 variables using 1580 non-zero reflections resulted in a final R value of 0.064. In spite of uncertainties in some of the atomic positions, the structure of I is compatible with a trihydrido diene compound with a distorted pentagonal bipyramidal configuration, rather than with a dihydrido cyclohexenyl compound having an “agostic” CH ? Re interaction. The factors which govern the structure of the complexes (Ph₃P)₂(η-1,3-diene)ReH₃ are discussed.     

Enzymatic synthesis of neopentylpolyol esters in organic media

Utilization of lipases for synthesis of esters of hydrophilic polyols has been investigated. The choice of a suitable solvent is crucial in this type of reaction. An interesting case is fatty acid esters from neopentylpolyols, such as trimethylolpropane, which are of great interest as high temperature lubricants. Enzymatic synthesis of trimethylolpropane tricaprylate was studied as an alternative to chemical manufacturing. Triester production occurred only if the water produced by esterification was continuously removed from the medium. In these condition, kinetics of appearance and transformation of mono-, di- and triesters were determined in order to define optimal conditions.