现代热力学的完整分类系统--非平衡非耗散热力学新领域

在同一体系中同时有多个不可逆过程时，不可逆过程之间会有相互影响，原来的非自发过程有可能在其他自发过程的影响下得以进行，这种现象就称为热力学耦合或反应耦合，长期以来，经典热力学把热力学第二定律的等式作为平衡体系的充分必要条件，其中隐含了一个前提性的假定，即经典热力学的对象只限于非耦合的体系，摈弃这一隐含的前提性假定以后，热力学自身就发展成为一个现代热力学的完整学术体系，适用于任何宏观体系（包括极其复杂的生命体系），现代热力学的完整学术体系中包含了一个崭新的非平衡非耗散热力学新领域，由于该领域属于热力学第二定律的等式部分，因此可以定量计算，并得到一系列理论计算的非平衡相图，与文献上报道的激尖低压金刚石合成等的大量实验数据相符。     

A supramolecular hydrogen‐bonded complex between 1,3,5‐tris(diisobutylhydroxysilyl)benzene and trans‐bis(4‐pyridyl)ethylene

The trisilanol 1,3,5‐(HOi‐Bu₂Si)₃C₆H₃ ( 7 ), prepared in three steps from 1,3,5‐tribromobenzene via the intermediates 1,3,5‐(Hi‐Bu₂Si)₃C₆H₃ ( 8 ) and 1,3,5‐(Cli‐Bu₂Si)₃C₆H₃ ( 9 ) forms an equimolar complex with trans‐bis(4‐pyridyl)ethylene (bpe), 7 ·bpe, whose structure was investigated by X‐ray crystallography. The hydrogen‐bonded network features a number of SiO? H(H)Si and SiO? H hydrogen bridges. Evidence was found for cooperative strengthening within the sequential hydrogen bonds. Copyright © 2007 John Wiley & Sons, Ltd.     

Controlled structure and density of “living” polystyrene brushes on flat silica surfaces

Thin layers of polystyrene were grown from surface-grafted nitroxide initiators via controlled “living” free radical polymerization. The “reactive” Langmuir-Blodgett deposition method allowed an effective control of the initiator layer density leading to PS brushes with different and high grafting density and stretching. The influence of the grafting density on the layer structure was studied. Comparison with theoretical predictions for monodispersed brushes in bad solvent was discussed. The thickness was found to vary linearly with molecular weight and the density dependence was shown using wetting measurements. Special features of controlled radical nitroxide polymerization from a surface were discussed. A direct comparison of the molecular weight and polydispersity between surface and bulk polymers was made by de-grafting the brushes into a toluene/HF solution. Finally, some evidence of a “surface Fischer” effect was shown from re-initiated layers. Received 20 December 2001     

不同方法制备的CO2-3替换磷灰石固溶体晶体化学的FTIR研究

采用不同方法制备了CO2-3替换的磷灰石固溶体,利用FTIR结合XRD对其进行了晶体化学研究,结果表明均相沉淀法制备的碳羟磷灰石(CHAP)属B型替换且替换方式是[CO3·OH]四面体替换[PO4]四面体;固相离子交换法制备的CHAP属A型替换且替换方式是[CO3]三角形配位体替换通道位置的OH-;固相反应法制备的碳氟磷灰石(CFAP)属B型替换,其替换方式是[CO3·F]四面体替换[PO4]四面体;sol-gel法制备的CHAP属AB混合型替换,其Ψ3分裂为Ψ3-1,Ψ3F,Ψ3-4.高斯函数法拟合表明Ψ3F峰是A型替换的Ψ3-2与B型替换的Ψ3-3的叠合.当WCO2-3＜3.34%时,随CO2-3含量增加,A型替换量增大,且当WCO2-3=3.34%时达最大值,当3.34%＜WCO2-3＜7.52%时,随CO2-3含量增加,B型替换量增大,且当WCO2-3= 7.52%时亦到饱和.     

Combinatorial computational chemistry approach of tight-binding quantum chemical molecular dynamics method to the design of the automotive catalysts

Recently, we have developed a new tight-binding quantum chemical molecular dynamics program “Colors” for combinatorial computational chemistry approach. This methodology is based on our original tight-binding approximation and realized over 5000 times acceleration compared to the conventional first-principles molecular dynamics method. In the present study, we applied our new program to the simulations on various realistic large-scale models of the automotive three-way catalysts, ultrafine Pt particle/CeO₂(111) support. Significant electron transfer from the Pt particle to the CeO₂(111) surface was observed and it was found to strongly depend on the size of the Pt particle. Furthermore, our simulation results suggest that the reduction of the Ce atom due to the electron transfer from the Pt particle to the CeO₂ surface is a main reason for the strong interaction of the Pt particle and CeO₂(111) support.     

Supramolecular chemistry

The article discusses molecular recognition and overviews the key concepts -storage and retrieval of chemical information by molecular structures, supramolecular reagents and catalysts, molecular transport, semiochemistry and self assembly. The prospects of controlling supramolecular architecture through engineered molecular recognition and design of ‘programmed systems’ controlled by molecular information are also discussed.     

High spin chemistry underlying organic molecular magnetism: Topological symmetry rule as the first principle of spin alignment in organic open-shell systems of π-conjugation and their ions

This review paper deals with an overview of molecule-based magnetism as a rapidly developing interdisciplinary field, topological symmetry rule as the first principle of spin alignment in organic open-shell systems in the ground state, the proposal of organic through-bond 1D and 2D ferro- and superparamagnets and the detection of the first organic high-spin molecule, m-phenylenebis(phenylmethylene) in the quintet ground state (S = 2), followed by extended organic high-spin systems with π-conjugation such as aromatic hydrocarbons having S = 3, 4, 5. The paper also describes a theoretical approach to the understanding of electronic spin structures of organic high-spin molecules by invoking both Heisenberg and Hubbard model Hamiltonians, weakly interacting intramolecular high-spin systems from both experimental and theoretical sides, the spin density distribution of the first organic high-spin molecule in terms of electron- nuclear multiple resonance spectroscopy and the detection and characterization of ionic high-spin hydrocarbons, emphasizing the establishment of high spin chemistry underlying organic molecular magnetism.     

A novel greener glycosidation using an acid-ionic liquid containing a protic acid

The glycosidations of glucopyranosyl diethyl phosphite and alcohols using an ionic liquid, 1-n-hexyl-3-methylimidazolium trifluoromethanesulfonimidide (C₆mim[NTf₂]) containing a protic acid, trifluoromethanesulfonimide (HNTf₂), as a novel solvent-catalyst system, effectively proceeded under mild conditions to give the corresponding glycosides in good to high yields. Furthermore, this acid-ionic liquid combination could be reused many times for the glycosidations without any loss in efficiency.