理论研究C8H80-（H2O）n（n=1～5）团簇

应用密度泛函B3LYP／6—31＋G（d，p）方法对C8H80-（H2O）n（n=1～5）团簇这种弱相互作用体系进行垒自由度能量梯度优化，得到该系列团簇的稳定蛄构．计算结果表明。在该系列二元团簇中，一方面水分子数目的多少对苯基丙酮分子的结构影响很小，另一方面由于苯基丙酮分子的存在，破坏了团簇中水分子的对称性结构，在团簇内部极力形成O—H—O这样弯曲的有方向性的氢键．对苯基丙酮-水这样结构复杂的团簇，指认光谱的难度非常大，本文只讨论了与C=O有关的振动峰和水分子的对称伸缩振动的最强峰．     

Synthesis of coumarins by Pt-catalyzed hydroarylation of propiolic acids with phenols

Synthesis of coumarins from phenols and propiolic acids was examined by using a Pt catalyst such as PtCl₂/AgOTf, K₂PtCl₄/AgOTf, and K₂PtCl₄/AgOAc. Propiolic acid reacted even with less reactive phenols in trifluoroacetic acid to give coumarins and dihydrocoumarins. In the case of substituted propiolic acids, phenylpropiolic acid and 2-octynoic acid, the reactions proceeded selectively to afford coumarins in good to high yields.     

Preparation, structure and properties of novel 1,3-dithiol-2-ylidene derivatives containing bis(ethynylpyridine) units

1,3-Dithiol-2-ylidene derivatives containing bis(ethynylpyridine) units were synthesized using a Pd-catalyzed reaction of the corresponding dibromide. X-Ray crystal analysis revealed unique crystal structures depending on the aromatic groups. The absorption spectra and redox properties indicated intramolecular charge-transfer interactions between the 1,3-dithiole unit and the pyridyl parts.     

Structure and electrochemical behaviour of 4,7-diazaheptyl-trimethoxy-silane and vinyl-trialkoxy-silane adsorbed at silver surface

Novel self-assembled monolayers were obtained on silver using 4,7-diazaheptyl-trimethoxy-silane (SiN) and vinyl-trialkoxy-silane (SiVA, where the alkyl group is 3,6,9,12,15,18,21,24,27,30,33,36,39,42,45,48,51,54,57,60-eicozaoxa- hexaheptaconan). It was shown that thus modified metal surface was protected against electrooxidation. A densely packed monolayer remained stable and did not desorb from the Ag electrode on the potential cycling. The structure of SiN and SiVA as well as their complexes with Li⁺ cations were calculated and visualised by the AM1d and PM5 semi-empirical methods.     

A remark on divisibility of definable groups

We show that if G is a definably compact, definably connected definable group defined in an arbitrary o‐minimal structure, then G is divisible. Furthermore, if G is defined in an o‐minimal expansion of a field, k ∈ ? and p_k : G → G is the definable map given by p_k (x ) = x^k for all x ∈ G , then we have |(p_k )^–1(x )| ≥ k^r for all x ∈ G , where r > 0 is the maximal dimension of abelian definable subgroups of G . (© 2005 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Structure of a poly(2,5‐benzimidazole)/phosphoric acid complex

As‐cast films of poly(2,5‐benzimidazole) exhibit uniplanar orientation in which the planes of the aromatic rings lie parallel to the film surface. Upon doping with phosphoric acid, the original crystalline order is lost, but the doped film can be stretched to produce films with uniaxial orientation. After thermal annealing at 540 °C, nine Bragg reflections are resolved in the fiber diagram, and these are indexed by an orthorhombic unit cell with the dimensions a = 18.1 Å, b = 3.5 Å, and c = 11.4 Å, containing four monomer units of two chains. The absence of odd‐order 00l reflections points to a 2₁ chain conformation, which is probably planar so that the aromatic units can be stacked along the b axis. The water and phosphoric acid contents of the crystalline structure cannot be determined exactly because of the presence of extensive amorphous regions that probably have different solvation. The best agreement between the observed and calculated intensities is for an idealized structure containing two phosphoric acids and two water molecules per unit cell. However, the phosphoric acid is probably present mainly in the form of pyrophosphoric acid and its higher oligomers. In addition, the X‐ray data are consistent with a more disordered structure containing chains with random (up and down) polarity and a lack of c‐axis registry. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2576–2585, 2004     

Non-protein amino acids in peptide design

An overview of the use of non-protein amino acids in the design of conformationally well-defined peptides, based on work from the author’s laboratory, is discussed. The crystal structures of several designed oligopeptides illustrate the useα-aminoisobutyric acid (Aib) in the construction of helices, D-amino acids in the design of helix termination segments and^DPro-Xxx segments for nucleating ofβ-hairpin structures.β- andγ-amino acid residues have been used to expand the range of designed polypeptide structures. Dedicated to Professor C N R Rao on his 70th birthday     

ΓD‐convergence for a class of quasilinear elliptic equations in thin structures

We study the asymptotic behaviour of the solution of a stationary quasilinear elliptic problem posed in a domain Ω^(ε) of asymptotically degenerating measure, i.e. meas Ω^(ε) → 0 as ε → 0, where ε is the parameter that characterizes the scale of the microstructure. We obtain the convergence of the solution and the homogenized model of the problem is constructed using the notion of convergence in domains of degenerating measure. Proofs are given using the method of local characteristics of the medium Ω^(ε) associated with our problem in a variational form. Copyright © 2005 John Wiley & Sons, Ltd.     

New efficient catalysts for the aerobic oxidation of ethers

Some nickel, copper, and silver salts or complexes are efficient catalysts for the oxidation of benzylic ethers with oxygen in 1,2-dimethoxyethane. Salts of the weakly coordinating anion trifluoroacetate are particularly efficient, approaching (and, in some cases, improving) the yields obtained with cobalt(II) chloride, the best catalyst so far reported.