1H, 13C, 17O NMR and quantum‐chemical study of the stereochemistry of the sulfoxide and sulfone derivatives of 3‐arylidene‐1‐thioflavan‐4‐one epoxides

The oxidation of the trans,cis‐( 2 ) and trans,trans‐epoxides ( 3 ) of differently substituted (Z)‐3‐arylidene‐1‐thioflavan‐4‐ones ( 1 ) with dimethyldioxirane (DMD) yielded the appropriate sulfoxides ( 4, 5 ) and sulfones ( 6, 7 ). The structures were elucidated by the extensive application of one‐ and two‐dimensional ¹H, ¹³C and ¹⁷O NMR spectroscopy. The conformational analysis was achieved by the application of ³J(C,H) coupling constants, NOESY responses and ab initio calculations. The preferred ground‐state conformers (twisted envelope‐A, twisted envelope‐B for 6 and twisted envelope‐A, envelope‐B for 7 ) were obtained as global minima of the theoretical ab initio MO study and also the examination of the ¹⁷O and ¹³C chemical shifts, calculated for the global minima structures of the sulfone isomers by the GIAO method. Analogous results, obtained for the sulfoxide isomers ( 4, 5 ), not only led to the preferred conformers but also gave evidence for the trans arrangement of the 2‐Ph group and the oxygen atom of the S?O group. Chemical shift differences between the isomers, sulfoxides and sulfones were corroborated by ab initio calculations of the anisotropic effects of the oxirane ring and the S?O and SO₂ groups. Copyright © 2003 John Wiley & Sons, Ltd.     

可积鞅测度的弱收敛(英语)

本文引入了可积鞅测度弱收敛的概念,并给出了可积鞅测弱收敛的一系列条件     

等谱和非等谱TD族,Lax表示与零曲率表示

首先，推广文「１」的结果，建立了等谱和非等谱ＴＤ族，并给出相应的Ｌａｘ表示，再用文「２」的方法得到了相应的零曲率表示。     

(1)H and (13)C NMR studies of asymmetrically substituted bis- and tris-Tröger's bases

The (1)H and (13)C NMR spectra of two stereoisomeric bis-Tr?ger's bases and four stereoisomeric tris-Tr?ger's bases asymmetrically substituted on the external aromatic rings were recorded and the corresponding signals assigned. The relative configuration of the stereogenic units has been unequivocally determined on the basis of homoallylic couplings and NOE experiments.     

Demixing of severely overlapped H NMR resonances and interpretation of anomalous intensity pattern of dipolar coupled A3 spins in a weakly aligning medium

The increasing scientific and industrial interest towards metabonomics takes advantage from the high qualitative and quantitative information level of nuclear magnetic resonance (NMR) spectroscopy. However, several chemical and physical factors can affect the absolute and the relative position of an NMR signal and it is not always possible or desirable to eliminate these effects a priori. To remove misalignment of NMR signals a posteriori, several algorithms have been proposed in the literature. The icoshift program presented here is an open source and highly efficient program designed for solving signal alignment problems in metabonomic NMR data analysis. The icoshift algorithm is based on correlation shifting of spectral intervals and employs an FFT engine that aligns all spectra simultaneously. The algorithm is demonstrated to be faster than similar methods found in the literature making full-resolution alignment of large datasets feasible and thus avoiding down-sampling steps such as binning. The algorithm uses missing values as a filling alternative in order to avoid spectral artifacts at the segment boundaries. The algorithm is made open source and the Matlab code including documentation can be downloaded from www.models.life.ku.dk.     

Integrable Rosochatius Deformations for an Integrable Couplings of CKdV Equation Hierarchy

We propose a method to construct the integrable Rosochatius deformations for an integrable couplings equations hierarchy. As applications, the integrable Rosochatius deformations of the coupled CKdV hierarchy with self-consistent sources and its Lax representation are presented.     

Integrable perturbations of the N-dimensional isotropic oscillator

Two new families of completely integrable perturbations of the N-dimensional isotropic harmonic oscillator Hamiltonian are presented. Such perturbations depend on arbitrary functions and N free parameters and their integrals of motion are explicitly constructed by making use of an underlying h₆-coalgebra symmetry. Several known integrable Hamiltonians in low dimensions are obtained as particular specializations of the general results here presented. An alternative route for the integrability of all these systems is provided by a suitable canonical transformation which, in turn, opens the possibility of adding (N−1) ‘Rosochatius’ terms that preserve the complete integrability of all these models.