Theoretical Study on the Reaction Mechanism between Dichlorocarbene and Armchair Single-walled Carbon Nanotubes

1 INTRODUCTION Carbon nanotubes have many potential applica- tions due to their unique structures and properties[1～4]. Physicists have been studying their electrical, me- chanical and other properties since their discove- ries[5, 6]. Recently, chemists are interested in carbon nanotubes because their properties can be altered by chemical functionalization[7～14], and these functiona- lized nanotubes can undergo further chemical trea- tment. So the potential application range of such na- …     

A theoretical study of the ion pair SN2 reaction between lithium isocyanates with methyl fluoride with inversion and retention mechanism

This paper is devoted to a detailed theoretical study of an ion pair S_N2 reaction LiNCO+CH₃F in the gas phase and in solution at the level of MP2(full)/6-31+G**//HF/6-31+G**. Two possible reaction mechanisms, inversion and retention, are discussed. There are eight possible reaction pathways. The inversion mechanism is more favorable no matter in the gas phase or in solution based on analyses of the transition structures. Methyl isocyanate should form preferentially in the gas phase and more stable methyl cyanate is the main product in solution. The retardation of the reaction in solvents was attributed to the difference in solvation in the separated reactants and in the transition state.     

Evidence of a Photo‐Radical Pathway Responsible of the Rearrangement of a Manganese(III)‐Schiff Base Complex in Solution

A new Mn^III‐Schiff base complex, [MnL(OH₂)](ClO₄) ( 1 ) (H₂L = N, N′‐bis‐(3‐Br‐5‐Cl‐salicylidene)‐1, 2‐diimino‐2‐methylethane), an inorganic model of the catalytic center (OEC, Oxygen Evolving Complex) in photosystem II (PSII), has been synthesized and characterized by elemental analysis, IR and EPR spectroscopy, mass spectrometry, magnetic susceptibility measurement and the study of its redox properties by cyclic and normal pulse voltammetry. This complex mimics reactivity (showing a relevant photolytic activity), and also some structural characteristics (parallel‐mode Mn^III EPR signal from partially assembled OEC cluster) of the natural OEC. The complex 1 was found to rearrange in solution into a crystallographically solved square‐pyramidal complex, [MnLL′] ( 2 ) (HL′ = 6‐bromo‐4‐chloro‐2‐cyanophenol), through a process, which probably liberates radical species (detected by EPR), and provokes a C—N bond cleavage in the ligand. A photo‐radical mechanism is discussed to explain this rearrangement.     

Dicyclopentadienyl complexes of titanium,niobium, and tungsten in the controlled synthesis of poly(methyl methacrylate)

Organometallic compounds Cp₂TiCl₂, (EtC₅H₄)₂NbCl₂, and (PrⁱC₅H₄)₂WCl₂ were assessed as additives that control polymer chain growth in the polymerization of methyl methacrylate. In the presence of compounds mentioned in amounts comparable with that of the initiator, a uniform process with no gel-effect occured and respective linear increase in the molecular weight of the polymer up to high degrees of the monomer conversion was observed.     

社会经济管理系统和谐性模型的构建与分析

本文从非线性自然观的视野。引用与分析了社会经济系统功能模型与效应模型。构建了系统和谐状态模型与和谐状态可信度模型，形象地说明了企业系统的和谐既是一个随机不确定状态。又是企业和谐力量与不和谐力量相互抗争干涉的过程。依据协同学原理提出了企业系统和谐演进的机制，表明企业系统的和谐发展是子系统和谐协同的过程。即子系统竞争合作的过程。文中所构建的模型，从理论上清晰地说明了企业系统和谐有序运行的机理，为如何构建和谐企业。提供了建设性的思考。     

Selective synthesis of dehydroamino acids from threonines

Dehydropeptides containing dehydroamino acid (ΔAA) are frequently found in natural resources with important biological activity. Herein, we report the selective synthesis of Z- and E-ΔAbu from l- and l-allo-threonine as starting materials through selenation and oxidative elimination. The detailed reaction mechanism of phosphine-assisted selenoether formation is also discussed.     

Kinetic Studies on the Reaction of Sodium Hexa-cyanoferrate(II) Complex with Peroxydisulfate Anion

Introduction In the previous studies on the oxidation reaction,peroxydisulfate was widely used as an oxidizingagent.1-5 One of the advantages of this oxidant lies in itsstability in a wide range of pH values. The reaction be-tween Fe(CN)5L3- (L=N-aromatic heterocyclic li-gands) and S2O8 2- has been proved to proceed throughan outer-sphere electron transfer mechanism.5 For a re-action [(Eq. (1)] to be under an outer-sphere mechanismthe steps involved are the formation of a reactant …     

绢纺生产用抗静电剂的研究——SS1与SS2绢纺抗静电剂

本文对绢纺生产用抗静电剂的配方进行了研究,研制出SS1及SS2绢纺抗静电剂。应用表明,采用此类抗静电剂,不但降低了生产中的静电,而且提高了梳折;在圆梳系统中提高了3.23％,在精梳系统中提高了3.1％;同时精绵的长度和强力也有所增加,从而提高了经济效益。     

PbI_2－PbBr_2－KCl系统玻璃的形成及其析晶行为

ＰｂＩ_２可以单独形成玻璃。ＰｂＩ_２－ＰｂＢｒ_２－ＫＣｌ三元系统玻璃具有良好的玻璃形成能力。通过恰当的热处理，不仅可获得透红外性能与原始玻璃一致的微晶玻璃，同时还可克服自发析晶倾向和大幅度地提高玻璃的显微硬度。以此三元系统为基础，有望开发出一类具有实用前景的透红外玻璃材料。     

基于微观渗流机理的宏观油藏数值模拟研究

处于高含水开发期油藏的剩余油分布主要受流体性质和岩石孔隙结构的影响，而经典数值模拟并没有考虑微观孔喉特征的影响。为此建立了描述微观孔喉特征的地层孔隙网络模型，并对构成网络的基本连线单元进行改进，使网络模型能更细致地描述油水分布特征和水驱油微观机理。利用逾渗理论计算了基于微观渗流机理的相对渗透率曲线，并将其应用到经典数值模拟计算中，实现了微观渗流机理与宏观数值模拟计算的结合。实例分析表明，利用该数值模拟计算方法得到的基于微观特征的剩余油分布更符合地下实际流体分布，其结果可为调剖堵水、化学驱提供技术参数。