A New Synthesis of Methyl 3-Amino-3,4-dideoxy-β-D-xylo-hexopyranoside

Abstract

Benzylidenation of methyl β-D-glucopyranoside, followed by selective 3-O-tosylation, reductive acetal opening, chlorination, radical deoxygenation and transesterification, afforded methyl 2,3-anhydro-6-O-benzyl-4-deoxy-β-D-ribo-hexopyranoside 8. Subsequent epoxide opening with NaN₃ and catalytic hydrogenation led to the title compound.     

Stereoselective photoinduced electrocyclic ring closure of aromatic enehydrazides. Asymmetric synthesis of 3-aryl dihydroisoquinolones and tetrahydroisoquinolines

A flexible route for the stereoselective synthesis of a variety of 3-aryl dihydroisoquinolones and tetrahydroisoquinolines has been developed. The key step is a diastereoselective photoinduced 6π-electrocyclic ring closure of enantiopure aromatic enehydrazides via a 1,4-remote asymmetric induction. N–N bond cleavage to release the chiral appendage from the preliminary annulated compounds and/or concomitant reduction of the lactam carbonyl group completed the synthesis of the title compounds.     

Low generation PEGylated phosphorus-containing dendrons with phosphonate anchors

We present a simple strategy to obtain non-symmetrical polyethylene glycols equipped with telechelic phosphorus-containing dendrimeric moieties having adhesive phosphonate surface functions. The dendronized PEG tails were characterized by means of multi-nucleus NMR. The grafting abilities of model symmetrical PEG compounds equipped with telechelic amino-bis(methylene-dimethylphosphonates) and amino-bis(methylenephosphonic acids) were rapidly screened on plasma treated silicon wafers and activated silica.     

X-ray photoemission spectra measurements of CeNi2Sb2 and CeCu2Sb2

X-ray photoemission spectra, resistivity and susceptibility of CeNi₂Sb₂ and CeCu₂Sb₂ were measured and are discussed. The results indicate that these alloys are Kondo systems. For comparison of the valence band properties, the spectra of the isostructural alloys of RT₂X₂-type with R = La, Gd, T = Cu, Ni and X = Sn, Sb were investigated, too.     

On the spectral function of the Poisson–Voronoi cells

Denote by (t)=∑_n1e^−λ_nt, t>0, the spectral function related to the Dirichlet Laplacian for the typical cell of a standard Poisson–Voronoi tessellation in . We show that the expectation E(t), t>0, is a functional of the convex hull of a standard d-dimensional Brownian bridge. This enables us to study the asymptotic behaviour of E(t), when t→0⁺,+∞. In particular, we prove that the law of the first eigenvalue λ₁ of satisfies the asymptotic relation lnP{λ₁t}−2^dω_dj_(d−2)/2^d·t^−d/2 when t→0⁺, where ω_d and j_(d−2)/2 are respectively the Lebesgue measure of the unit ball in and the first zero of the Bessel function J_(d−2)/2.     

Newton's method on Riemannian manifolds: covariant alpha theory

In this paper, Smale's theory is generalized to the contextof intrinsic Newton iteration on geodesically complete analyticRiemannian and Hermitian manifolds. Results are valid for analyticmappings from a manifold to a linear space of the same dimension,or for analytic vector fields on the manifold. The invariant is defined by means of high-order covariant derivatives. Boundson the size of the basin of quadratic convergence are given.If the ambient manifold has negative sectional curvature, thosebounds depend on the curvature. A criterion of quadratic convergencefor Newton iteration from the information available at a pointis also given.     

Convergence rates for steady-state derivative estimators

We describe various derivative estimators for the case of steady-state performance measures and obtain the order of their convergence rates. These estimatorsdo not use explicitly the regenerative structure of the system. Estimators based on infinitesimal perturbation analysis, likelihood ratios, and different kinds of finite-differences are examined. The theoretical results are illustrated via numerical examples.     

Confined dynamics, forms and transitions in colloidal systems: from clay to DNA

Colloidal suspensions are a classic example of confining systems developing large specific surfaces, presenting a rich variety of shapes and exhibiting complex organization on a length scale ranging from 1 nm to several micrometers. Two distinct confined dynamics are generally considered in such systems: (1) the embedded fluid dynamics entrapped in the pore network with two main contributions, surface interaction and long-range connectivity, and (2) the dynamics of the host matrix, associated with a time evolution of the interfacial geometry. This last contribution is particularly important during dynamic and structural transitions of colloidal suspensions such as jamming, glass transition, phase separations and flocculation. It is generally believed that the characteristic time scale needed to describe colloidal movement and interfacial geometrical reorganization is much slower than the dynamics of the embedded fluid (except in the trivial situation where the fluid molecule is irreversibly adsorbed to a colloidal surface). Thus, few connections are made between these two distinct dynamics. In this presentation, we show how the slow and confined water dynamics at proximity of a colloidal surface provides an original way to probe colloidal shape and colloidal orientation dynamics. Two topics are presented. First of all, water field-cycling NMR relaxometry is used to probe the glass transition and the strong rotational slowing down of a colloidal system made of plate-like particles, a synthetic clay (laponite). Second, we analyze the case of long colloidal thin rods (either mineral or biologic such as DNA cylinders) dispersed in very diluted suspensions. At large distance and/or long time, these particles appear as a portion of a line. We discuss how the embedded fluid dynamics can be sensitive to this morphological crossover and may provide information about the particle shape. Some comparisons with recent experiments are presented.     

A Consistent BGK-Type Model for Gas Mixtures

We introduce a relaxation collision operator for a mixture of gases which satisfies several fundamental properties. Different BGK type collision operators for gas mixtures have been introduced earlier but none of them could satisfy all the basic physical properties: positivity, correct exchange coefficients, entropy inequality, indifferentiability principle. We show that all those properties are verified for our model, and we derive its Navier–Stokes limit by a Chapman–Enskog expansion.