稀土离子在多孔阳离子交换剂内的扩散动力学

研究了稀土离子在Amberlyst15、D001、XN1010多孔树脂内的自扩散。结果表明,扩散过程遵循二级分散扩散机制。用粒内扩散方程求算了有效粒内扩散系数e,将e分解为树脂孔道扩散系数p及树脂固相扩散系数s,p与该离子在外部溶液中的自扩散系数相近,而s接近于与实验用的多孔树脂交联度相同的凝胶树脂内的自扩散系数值。     

茂锆载体催化剂下的乙烯／辛烯共聚及聚合物的^13C NMR研究

茂锆载体催化剂下的乙烯／辛烯共聚及聚合物的~（１３）ＣＮＭＲ研究刘胜生，于广谦，黄葆同（中国科学院长春应用化学研究所长春１３００２２）关键词茂锆载体催化剂，共聚，序列分布，~（１３）ＣＮＭＲ由于茂锆催化剂具有高活性，单一活性中心等特点［１，２］，并且能...     

气液色谱法研究Ni[(C8H17)O)2PS2]2与脂肪胺加合反应的热力学性质

The equilibium constants of acid-base interaction between Mi(Octyl_dtp)_2 and alkylamine were determined by GLC method at several temperatures. Thermodynamic parameters △H and △S were evaluted as follows:ethylamine: △H=-11.5kJ mol~(-1) △S=-22.7J K~(-1) mol~(-1)diethylamine: △H=-18.1kJ mol~(-1) △S=-42.1J K~(-1) mol~(-1)The variations of logK versus temperature fit following equations:ethylamine: lgK=-1.19+598.9/Tdiethylamine: lgK=-2.20+945.6/T     

HMS和NaY固载酒石酸钛配合物的研究

利用化学键合和“瓶中造船”方法,成功地将酒石酸钛配合物接枝到HMS(heragonal mesoporous silicas)上或包络合于微孔NaY内.FT-IR表征表明酒石酸钛在HMS上是通过与载体表面羟基发生交换作用而被固载的;在NaY载体上则是通过包络合被封装在载体的超笼内.UV-Vis可见漫反射表征表明两类固载型催化剂有着相似的钛配位环境.在催化肉桂醇环氧化反应中,HMS键合型催化剂的反应转化率比NaY包络型催化剂的高;但后者在环氧化选择性上要高于前者.回收样品的重复使用实验结果表明,两类固载型催化剂在重复使用过程中均存在不同程度的失活.     

Why is the partial molar volume of CO2 so small when dissolved in a room temperature ionic liquid? Structure and dynamics of CO2 dissolved in [Bmim+] [PF6(-)

When supercritical CO2 is dissolved in an ionic liquid, its partial molar volume is much smaller than that observed in most other solvents. In this article we explore in atomistic detail and explain in an intuitive way the peculiar volumetric behavior experimentally observed when supercritical CO2 is dissolved in 1-butyl-3-methylimidazolium hexafluorophosphate ([Bmim+] [PF6(-)]). We also provide physical insight into the structure and dynamics occurring across the boundary of the CO2 ionic liquid interface. We find that the liquid structure of [Bmim+] [PF6(-)] in the presence of CO2 is nearly identical to that in the neat ionic liquid (IL) even at fairly large mole fractions of CO2. Our simulations indicate, in agreement with experiments, that partial miscibilities of one fluid into the other are very unsymmetrical, CO2 being highly soluble in the ionic liquid phase while the ionic liquid is highly insoluble in the CO2 phase. We interpret our results in terms of the size and shape of spontaneously forming cavities in the ionic liquid phase, and we propose that CO2 occupies extremely well-defined locations in the IL. Even though our accurate prediction of cavity sizes in the neat IL indicates that these cavities are small compared with the van der Waals radius of a single carbon or oxygen atom, CO2 appears to occupy a space that was for the most part a priori "empty".     

Conduction stability of high-density polyethylene/carbon black composites due to electric field action

Conduction stability of high-density polyethylene/carbon black (HDPE/CB) composites with a CB volume fraction slightly above the percolation threshold is studied in relation to electric field action at various ambient temperatures below the melting point of HDPE. It is found that resistance of the composites shows considerable changes after the electric field is switched off. Influence of irradiation crosslinking of HDPE on the conduction stability is also discussed.     

Broadly effective enantioselective Diels-Alder reactions of 1-amino-substituted-1,3-butadienes

[reaction: see text] A broad range of substituted 1-amino-1,3-butadienes undergo enantioselective Diels-Alder reactions with methacrolein in the presence of 5 mol % of Cr(III)-salen complex 1. The reactions are carried out conveniently, at room temperature, and they afford the cycloadducts in high yields and excellent ee's.     

Molecular and nanoscale materials and devices in electronics

Over the past several years, there have been many significant advances toward the realization of electronic computers integrated on the molecular scale and a much greater understanding of the types of materials that will be useful in molecular devices and their properties. It was demonstrated that individual molecules could serve as incomprehensibly tiny switch and wire one million times smaller than those on conventional silicon microchip. This has resulted very recently in the assembly and demonstration of tiny computer logic circuits built from such molecular scale devices. The purpose of this review is to provide a general introduction to molecular and nanoscale materials and devices in electronics.     

Copper phosphonates with dinuclear and layer structures: a structural and magnetic study

Hydrothermal reactions of copper (II) nitrate with 1-hydroxycyclohexanephosphonic acid [C₆H₁₀(OH)PO₃H₂] or Δ¹-cyclohexenephosphonic acid [C₆H₉PO₃H₂] have resulted in three new copper phosphonates, namely, Cu(C₆H₁₀(OH)PO₃)(H₂O)₂ (1), Cu(C₆H₁₀(OH)PO₃) (2) and Cu(C₆H₉PO₃)(H₂O) (3). Compound 1 has a dinuclear structure in which two {CuO₅} square pyramids are bridged by two {CPO₃} tetrahedra through corner sharing. The dimers are connected through intermolecular hydrogen bonds, forming supramolecular layers. Both compounds 2 and 3 show layer structures typical for metal mono-phosphonates, in which the inorganic metal-containing layers are separated by cyclohexane or cyclohexene groups. The magnetic studies show that ferromagnetic interactions are mediated between copper centers in compound 1. In compounds 2 and 3, antiferromagnetic interactions are dominant.     

Solvent-mediated folding of a doubly charged anion

The microsolvation of the suberate dianion, -O2C(CH2)6CO2-, with two separate charge centers was studied by photoelectron spectroscopy and molecular dynamics simulation one solvent molecule at a time for up to 20 waters. It is shown that the two negative charges are solvated in the linear suberate alternately. As the solvent number increases, the negative charges are screened and a conformation change occurs at 16 waters, where the cooperative hydrogen bonding of water is large enough to overcome the Coulomb repulsion and pull the two negative charges closer through a water bridge. This conformation change, revealed both from the experiment and from the simulation, is a manifestation of the hydrophilic and hydrophobic forces at the molecular level.