Furanosyl Oxocarbenium Ion Conformational Energy Landscape Maps as a Tool to Study the Glycosylation Stereoselectivity of 2-Azidofuranoses, 2-Fluorofuranoses and Methyl Furanosyl Uronates

The 3D shape of glycosyl oxocarbenium ions determines their stability and reactivity and the stereochemical course of S_N1 reactions taking place on these reactive intermediates is dictated by the conformation of these species. The nature and configuration of functional groups on the carbohydrate ring affect the stability of glycosyl oxocarbenium ions and control the overall shape of the cations. We herein map the stereoelectronic substituent effects of the C2-azide, C2-fluoride and C4-carboxylic acid ester on the stability and reactivity of the complete suite of diastereoisomeric furanoses by using a combined computational and experimental approach. Surprisingly, all furanosyl donors studied react in a highly stereoselective manner to provide the 1,2-cis products, except for the reactions in the xylose series. The 1,2-cis selectivity for the ribo-, arabino- and lyxo-configured furanosides can be traced back to the lowest-energy ³E or E₃ conformers of the intermediate oxocarbenium ions. The lack of selectivity for the xylosyl donors is related to the occurrence of oxocarbenium ions adopting other conformations.     

Time-resolved photoluminescence study of excited states in nanostructured melanin

Abstract

Time resolved emission spectra (TRES), 3D maps of photoluminescence excitation-emission (PLE maps), 3D maps of TRES, and kinetics of photoluminescence (PL) spectra of natural and synthetic melanin, as well as melanin composites with surfactant, sodium dodecyl benzenesulfonate, have been studied. The kinetics of PL and TRES for the melanin and the composites were investigated at low temperatures that allowed to discuss melanin’s intermolecular complexation, nano-aggregation and formation of charge transfer states. Particularly, the radiation of Frenkel excitons from fragments of different degrees of conjugation that are the parts of molecular nanodisks of melanin is observed. Furthermore, charge transfer excitons (CT-excitons) can be formed and observed at both room and helium temperatures. Some bands in the PL spectra of melanin, depending on temperature, behave like excimer radiation. The studies are aiming to understand the electronic properties of various melanins, particularly natural ones.     

Commuting traces of multilinear maps on invertible elements

Let R be a unital simple ring. Under some technical restrictions, we characterize m-linear mappings G:R^m→R satisfying [G(u,…,u),u]?=?0 for all unit u∈R.     

Characterization of derivations on B(X) by local actions

Let A be a unital algebra and M be a unital A-bimodule. A linear map δ : A →M is said to be Jordan derivable at a nontrivial idempotent P ∈ A if δ(A) ? B + A ? δ(B) =δ(A ? B) for any A, B ∈ A with A ? B = P, here A ? B = AB + BA is the usual Jordan product. In this article, we show that if A = Alg N is a Hilbert space nest algebra and M = B(H), or A = M = B(X), then, a linear map δ : A → M is Jordan derivable at a nontrivial projection P ∈ N or an arbitrary but fixed nontrivial idempotent P ∈ B(X) if and only if it is a derivation. New equivalent characterization of derivations on these operator algebras was obtained.     

集值映射多目标半定规划问题的epsilon-弱有效性

对于集值映射多目标半定规划问题, 在近似锥-次类凸的框架下, 建立了含矩阵和向量的择一性定理, 给出了问题的epsilon-弱有效解的epsilon-Lagrange乘子定理及标量化定理和epsilon-弱鞍点定理．     

Spatial chaos in boundary layer transition

Experiments have been performed on a laminar flat plate boundary layer undergoing transition to turbulence. Reproducible disturbances were introduced via a loudspeaker embedded at some upstream location and their evolution over the plate measured using hot-wire anemometry. A new technique has been used to estimate the number of nonlinearly independent modes in the reconstructed phase portraits. Nonlinear maps were then fitted that explicitly model the spatial evolution of disturbances. These maps are consistent with classical linear stability theory for small disturbances, and give rise to Smale horse-shoe like behaviour for larger amplitude distrubances. Thus a mechanism for generating chaos has been uncovered.     

Perturbation methods for nonlinear autonomous discrete-time dynamical systems

Two perturbation methods for nonlinear autonomous discrete-time dynamical systems are presented. They generalize the classical Lindstedt-Poincaré and multiple scale perturbation methods that are valid for continuous-time systems. The Lindstedt-Poincaré method allows determination of the periodic or almost-periodic orbits of the nonlinear system (limit cycles), while the multiple scale method also permits analysis of the transient state and the stability of the limit cycles. An application to the discrete Van der Pol equation is also presented, for which the asymptotic solution is shown to be in excellent agreement with the exact (numerical) solution. It is demonstrated that, when the sampling step tends to zero the asymptotic transient and steady-state discrete-time solutions correctly tend to the asymptotic continuous-time solutions.