The effect of the solvents on the specific intramolecular C-H...N interactions studied by1H NMR spectroscopy

The analysis of the effect of the solvents on the proton chemical shifts in¹H NMR spectra of 2-vinyloxypyridine indicates that the C—H...N interaction of weak intramolecular hydrogen bond type hinders the formation of intermolecular hydrogen C—H...X and C-H... bonds. The protonating solvents reduce the intramolecular C—H...N interaction due to association with the N atom of the pyridine cycle.Translated fromIzvestiya Akademii Nauk. Seriya Khimieheskaya, No. S, pp. 1202–1204, May, 1996.     

Influence of quaternary onium salts,crown ethers and cryptands on olefin epoxidations promoted by HOCl/ClO− in the Presence of Mn(III)-tetrakis(2,6-dichlorophenyl)porphyrin chloride

Reaction rates of alkene epoxidations, promoted by aqueous NaOCl and catalyzed by Mn(III)-tetrakis(2,6-dichlorophenyl)porphyrin chloride1 (P) in the presence of a lipophilic axial ligand (L) (e.g.N-hexylimidazole) and carried out under H₂O/CH₂Cl₂ two phase conditions at 0°C, are strongly enhanced by lowering the pH of the aqueous phase from 12.7 to 9.5. Under these conditions, a further relevant increase in the reaction rates can be achieved by adding phase-transfer catalysts (PT), e.g. quaternary ammonium salt 3, lipophilic crown ether4 or cryptand5, provided that the amount of L is very small (L/P=1 for very reactive alkenes, e.g. cyclooctene, and 10 for poorly reactive ones, e.g. 1-dodecene). In the case of cyclooctene epoxidation, the use of 0.006–0.03 mol. equiv. of PT completes the reaction in 1–10 min., the initial rates being up to 600 turnovers/min. with (2.2.2,C₁₀) cryptand. In the absence of the axial ligand, the quaternary ammonium salt3 and cryptand5 show an inhibitory effect. Such an effect is due to the formation of the poorly reactive Mn(P)CI species, by Cl– extraction to the organic phase. However, dibenzo crown ether 4 does not show this effect. In the presence of 4, and with L/P =1, the 1-dodecene epoxidation reaches 94% in 1 min. The unique behavior of crown ethers can be explained by their ineffectiveness in extracting alkali chlorides, providing a very low concentration of Cl– in the organic phase and thus avoiding the Mn(III)-porphyrin deactivation.This paper is dedicated to the memory of the late Dr C. J. Pedersen.     

Structure and dynamics of liquid water with different long-range interaction truncation and temperature control methods in molecular dynamics simulations

We have used molecular dynamics simulations to study the physical properties of modified TIP3P water model included in the CHARMM program, using four different methods-the Ewald summation technique, and three different spherical truncation methods-for the treatment of the long-range interactions. Both the structure and dynamics of the liquid water model were affected by the methods used to truncate the long-range interactions. For some of the methods artificial structuring of the model liquid was observed around the cutoff radius. The model liquid properties were also affected by the commonly applied temperature control methods. Four different methods for controlling the temperature of the system were studied, and the effects of these methods on the bulk properties for liquid water were analyzed. The system size was also found to change the dynamics of the model liquid water. Two control simulations with the SPC/E water model were carried out. The self-diffusion coefficient (D), the radial distribution function (g(OO)), the distance dependent Kirkwood G-factor [G(k)(r)] and the intermolecular potential energy (E(pot)) were determined from the different trajectories and compared with the experimental data.     

农民外出务工对义务教育的影响

农民工收入的增加及观念的转变有利于义务教育的完全普及,同时,农民外出务工又带来了留守生和流动子女的教育问题;要解决农民外出务工对义务教育的负面影响,国家、政府及学校都要采取补救措施。     

运动对自由基代谢影响的研究

根据有关文献资料,综合分析总结出剧烈运动使自由基增加的几个因素,阐述了体内过多的自由基对机体造成的几种损伤,并就清除体内过多自由基论述了相关的基本原理与方法.     

企业在成本竞争中的约束因素

分析了企业在成本竞争中的约束因素,阐述了同质成本与异质成本的概念及内涵,指出异质成本对总成本的影响弹性一定大于同质成本对总成本的影响弹性。     

艺术院校新生焦虑状况及其影响因素初探

运用贝克焦虑量表及影响因素量表对某艺术院校新生进行调查,结果表明:有14%的新生存在一定程度的焦虑,引起新生焦虑的主要因素有学习适应、人际交往、经济压力等.因此有必要对艺术院校新生的心理健康状况加以分析、研究,使学生正确认识这些矛盾冲突及所产生的原因,并有针对性地进行调适,使之尽快适应新的环境.     

在华外商直接投资对我国产业结构的双重影响与对策研究

近几年,在华外商直接投资迅速增加,掀起了新一轮在华投资热潮。我国三次产业结构日趋合理,在华外商直接投资在其中起到了积极和消极两方面的作用。本文分析了在华外商直接投资的现状及其对我国产业结构影响的正负效应,并提出了相关对策。     

Left-lateral shear deformation found in southern part of the Gaoligong range in west Yunnan and its tectonic implications

It is generally understood that the Tertiary structural deformation in the Gaoligong range in west Yunnan was under the control of right-lateral shear, resulting from the northward movement of Indian relative to Eurasian. In the southern part of Gaoligong range, however, we have recently found many pieces of evidence of left-lateral shear deformation, featuring a 10 km wide shear zone cutting through all tectonic elements of the range in N-S direction, which possibly occurred in late Tertiary time, and postdated the right-lateral shear. This is a significant discovery for revealing characteristics of the Tertiary intracontinental deformation of the Gaoligong range and the interaction between the Indian and the Eurasian continents.     

自动量程转换电路设计

介绍了双积分式 A/D转换器 CC1 44 3 3在宽范围电压测量中自动量程转换电路的设计及工作原理 .通过多路模拟开关与运放的组合设置了多个电压量程 ,应用 CC1 44 3 3的超欠量程信息控制双向移位寄存器的移位操作 ,获得了合适的量程标志 .通过量程标志对多路模拟开关及显示器小数点位置的控制 ,实现了量程的自动切换及表示 .应用辅助门电路及数据选择器解决了量程标志中边界问题及无效量程标志问题 .设计的电路具有测量电压范围宽、工作稳定可靠、显示直观等优点 .