分子内Diels-Alder反应在有机合成方面的新进展

本文按合成产物的结构类型,综述分子内 Diels-Alder 反应在有机合成方面的新进展。     

Coulombic Basis for Relative Hydrogen-Bonding Basicities and Conformational Energies of Tertiary Amine Oxides and Phosphine Oxides

The structures, energies, and natural atomic charges of 2-dimethylaminophenol oxide, 2-Me₂N-(O)C₆H₄OH, and 2-dimethylphosphinylphenol, 2-Me₂P(O)C₆H₄OH, in three different conformations were computed at the ab initio MP2/6-31G* level. Computed natural charges indicate distributions of electron density in amine oxides and phosphine oxides that are quite different from what is normally assumed on the basis of the formal charges in the usual representations of these compounds. The charges on nitrogen and phosphorus in these compounds are typically computed to be approximately zero on nitrogen and +2 on phosphorus, and the oxygen is considerably more negative in the phosphine oxide than in the amino oxide. Electronegativity differences thus play a larger role and formal charges a smaller one in determining atomic charges in these compounds than is generally believed. Despite the more negative oxygen in phosphine oxides, amine oxides are computed to be considerably more basic when participating in hydrogen bonding. Calculations treating the computed natural charges on these six conformations as point charges for classical approximations of the coulombic energies support the idea that the quantum mechanically computed relative energies are largely determined by coulombic interactions.     

Fermentation characteristics and the dynamic trend of chemical components during fermentation of Massa Medicata Fermentata

As a representative of traditionally fermented Chinese medicine, Massa Medicata Fermentata (MMF) shows the functions of invigorating the spleen and stomach and promoting digestion, which plays an important role in the treatment of gastrointestinal diseases. The fermentation mechanism and the key factors that affect the quality of MMF have not been revealed yet, which has become an urgent issue that limits its clinical application. This article aims to systematically and comprehensively reveal the transformation of physical properties and the dynamic trend of chemical components including substrate components, volatile components, and lactic acid as anaerobic fermentation product during MMF fermentation. Along with obvious hyphae growth observed for MMF, the weight of MMF decreased, and the moisture and temperature increased. Through the quantified 14 components from substrate, ferulic acid increased from 45.53 ± 6.94 to 141.89 ± 78.40 μg/g, while glycosides and phenolic acids declined except caffeic acid. Also, within the 66 volatile components analyzed, alcohols and acids increased, while aldehydes and ketones decreased. Lactic acid was not detected in the fermentation substrate, but an apparent increase in lactic acid content was observed along with the increased fermentation days, resulting in 2.54 ± 0.15 mg/g on day 8. Based on the tested components, the fermentation process of MMF was discriminated into three distinct stages by principal component analysis, and an optimal fermentation time of four days was proposed. The results of this study will be of great significance to clarify the characteristics of fermentation and conduce to improving quality standards of MMF.     

空间机器人组装超大型结构的动力学分析北大核心CSCD

超大型航天结构具有超大柔性、超低固有频率的特点,空间机器人在轨组装时应尽可能避免激起超大型结构的柔性振动.空间机器人组装超大型结构模块的过程分成抓捕阶段、位姿调整与稳定阶段、安装阶段和爬行阶段.通过对安装阶段的动力学与控制研究,提出共线安装的轨迹规划方法,有效避免了柔性结构振动.首先,采用自然坐标法和绝对节点坐标法建立主结构-空间机器人-待组装结构的在轨组装系统动力学模型.然后,将共线安装的要求转化为空间机器人的轨迹规划约束,要求空间机器人质心到主结构/待组装结构的距离保持不变,实现共线安装的轨迹规划.数值仿真表明:提出的组装方法在组装过程中可有效避免超大型结构的横向运动,降低夹持力矩.最后,分析了系统参数对组装过程动力学响应的影响,为超大型航天器的在轨组装提供了参考.     

The diagnonal multivariate natural exponential families and their classification

A natural exponential family (NEF)F in ? ⁿ ,n>1, is said to be diagonal if there existn functions,a ₁,...,a _n , on some intervals of ?, such that the covariance matrixV _F (m) ofF has diagonal (a ₁(m ₁),...,a _n (m _n )), for allm=(m ₁,...,m _n ) in the mean domain ofF. The familyF is also said to be irreducible if it is not the product of two independent NEFs in ? ^k and ? ^n-k , for somek=1,...,n?1. This paper shows that there are only six types of irreducible diagonal NEFs in ? ⁿ , that we call normal, Poisson, multinomial, negative multinomial, gamma, and hybrid. These types, with the exception of the latter two, correspond to distributions well established in the literature. This study is motivated by the following question: IfF is an NEF in ? ⁿ , under what conditions is its projectionp(F) in ? ^k , underp(x ₁,...,x _n )∶=(x ₁,...,x _k ),k=1,...,n?1, still an NEF in ? ^k ? The answer turns out to be rather predictable. It is the case if, and only if, the principalk×k submatrix ofV _F (m ₁,...,m _n ) does not depend on (m _k+1,...,m _n ).     

Spectrum of positive entropy multidimensional dynamical systems with a mixed time

It is shown that if an abelian countable group is such that is a finite group and every aperiodic positive entropy action of on a Lebesgue probability space has a countable Haar spectrum in the subspace , where denotes the Pinsker -
algebra of , then every aperiodic positive entropy action of on has the same property. A positive answer to the question of J.P. Thouvenot is obtained as a corollary.

     

Cocycle d'Euler etK2

In this paper we construct a canonical 2-cocycle on the groupP SL(2,k) with values in the Witt groupW(k) of the fieldk. This allows us to produce anatural homomorphism :H ₂(SL(2,k); Z)I ²(k), whereI ²(k) is the square of the fundamental ideal. We prove that this homomorphism is in fact a lift of Milnor's symbol.

     

An aldol approach to the total synthesis of (+)-brefeldin A

A convergent selective route to (+)-brefeldin A (BFA) and 7-epi-BFA was developed, with the crucial C-4/C-5 stereogenic centers were established using Crimmins asymmetric aldolization.