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1.
The 3D shape of glycosyl oxocarbenium ions determines their stability and reactivity and the stereochemical course of SN1 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.  相似文献   
2.
In this paper, we present novel integrable symplectic maps, associated with ordinary difference equations, and show how they determine, in a remarkably diverse manner, the integrability, including Lax pairs and the explicit solutions, for integrable partial difference equations which are the discrete counterparts of integrable partial differential equations of Korteweg‐de Vries‐type (KdV‐type). As a consequence it is demonstrated that several distinct Hamiltonian systems lead to one and the same difference equation by means of the Liouville integrability framework. Thus, these integrable symplectic maps may provide an efficient tool for characterizing, and determining the integrability of, partial difference equations.  相似文献   
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Line-focus Raman microscope system was designed and constructed for high speed quantitative analysis of Raman spectral maps. Laser line generator lens was used for formation of homogeneous laser power distribution thought the line. Three-dimensional Raman maps of mouse skin were obtained using point and line illumination modes. It was shown that laser line illumination can provide Raman spectrum with signal to noise ratio comparable to point illumination mode. The speed of scanning in line-focus mode achieved is two orders of magnitude faster compared to the point illumination mode, which enables ex vivo measurements of large areas of skin surface during a few minutes. Non-negative least squares (NNLS) decomposition of mouse skin spectral maps was done using keratin, lipids, water, lactate, urea and natural moisture factor (NMF) components as library spectra. Fluorescence background of measured spectra was corrected using the fluorescence profile obtained from time-lapse Raman skin measurements, which was used as additional component in NNLS decomposition procedure. The lateral and depth distribution of major skin components obtained from Raman maps mainly correlates with histological information. High-quality line-focus Raman maps from large sample area expand the possibilities of studying skin chemical components distribution.  相似文献   
6.
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.  相似文献   
7.
The aim of this paper is to introduce a computational tool that checks theoretical conditions in order to determine whether a weighted graph, as a topological invariant of stable maps, can be associated to stable maps without cusps (ie, fold maps) from closed surfaces to the projective plan.  相似文献   
8.
Willian Franca 《代数通讯》2018,46(7):2890-2898
Let R be a unital simple ring. Under some technical restrictions, we characterize m-linear mappings G:RmR satisfying [G(u,…,u),u]?=?0 for all unit uR.  相似文献   
9.
The primary goal of this study was to describe and compare the criteria used to assess carcinogenic activity. The statistically-based predictive quantitative structure–activity relationship (QSAR) models based on the counter propagation artificial neural network (CPANN) algorithm, and knowledge-based expert systems based on a decision tree structural alert (SA) approach (Toxtree application), were considered. The integration of the QSAR (CPANN models) and SAR (Toxtree SA application) approach contributed to the mechanistic understanding of the QSAR model considered. The mapping technique inherent to CPANN Kohonen enables us to relate the similarities or dissimilarities within a congeneric set of chemicals with particular SAs for carcinogenicity. The focus of our investigations was the similarities and dissimilarities of the features used in the QSAR and SAR methods. Due to the complexity of the carcinogenic endpoint, the integration of different approaches allows the models to be improved and provides a valuable technique for evaluating the safety of chemicals.  相似文献   
10.
Let H ∈ C 2(? N×n ), H ≥ 0. The PDE system arises as the Euler-Lagrange PDE of vectorial variational problems for the functional E (u, Ω) = ‖H(Du)‖ L (Ω) defined on maps u: Ω ? ? n  → ? N . (1) first appeared in the author's recent work. The scalar case though has a long history initiated by Aronsson. Herein we study the solutions of (1) with emphasis on the case of n = 2 ≤ N with H the Euclidean norm on ? N×n , which we call the “∞-Laplacian”. By establishing a rigidity theorem for rank-one maps of independent interest, we analyse a phenomenon of separation of the solutions to phases with qualitatively different behaviour. As a corollary, we extend to N ≥ 2 the Aronsson-Evans-Yu theorem regarding non existence of zeros of |Du| and prove a maximum principle. We further characterise all H for which (1) is elliptic and also study the initial value problem for the ODE system arising for n = 1 but with H(·, u, u′) depending on all the arguments.  相似文献   
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