(XN)4R4簇合物的结构与化学键

用密度泛函理论,在B3LYP/6-311G水平上,对(XN)4R4 (X=C,Si,Ge;R=H,CH3,NH2,OH)及合成的先驱化合物(XN)2R2进行几何构型、电子结构、振动频率和化学反应焓变等进行了研究.结果表明,(RCN)4比(CNR)4更稳定.所有簇合物的零点能EZP值,R=H时最小,R=CH3时最大,R配位原子依次为C、N和O时,EZP值逐渐减小.     

The chemical synthesis of conductive polyaniline doped with dicarboxylic acids

The chemical polymerization of aniline was carried out in media containing different linear dicarboxylic acids with the use of oxidants such as K₂Cr₂O₇, KMnO₄, K₂S₂O₈, KIO₃ and FeCl₃. The highest yield and the conductivity were observed with K₂Cr₂O₇. The yield and the conductivity of the polyaniline (PAn) synthesized were observed to decrease in the order of oxalic acid > malonic acid > succinic acid > glutaric acid > adipic acid > phthalic acid. The solubility tests carried out in solvents such as DMF, DMSO and NMP showed that the larger the dopant molecule, the higher is the solubility of polyaniline. The PAn synthesized was characterized by measurements of conductivity, intrinsic viscosity, density and FTIR, UV-VIS and TGA techniques.     

(ClAlNH)n簇合物的结构与稳定性

用量子化学从头算方法（HF／6－31G）和密度泛函理论（DFT）的B3LYP方法，以6－31G标准基组加一个极化函数，对（ClAlNH)n(n=1-10)簇合物的几何构型，电子结构和红外光谱进行了优化，并讨论了聚合反应（ClAlNH)m→(ClAlNH)n的热力学效应，结果表明，（ClAlNH)n系列簇合物的基态稳定结构为Cs(n=1),D2h(n=2),D3h(n=3),Td(n=4),Cs(n=5),D3d(n=6),Cs(n=7),S4(n=8),D3h(n=9),C2h(n=10,n=2,4,6,8,10等偶数对应的（ClAlNH)n簇化合物的结构比n等于奇数量更稳定。     

Concerning the Thermal Diastereomerization of the Green Fluorescent Protein Chromophore

Summary. Two model compounds for the green fluorescent protein chromophore were prepared. One of them incorporates the natural 4-hydroxybenzylidene group of the natural tyrosin derived chromophore, the other one bears a methyl group instead of the hydroxy group. Whereas the photochemically prepared (E)-diastereomer of the first compound very effectively reverted thermally (room temperature) to the thermodynamically stable (Z)-diastereomer, the (E)-diastereomer of the second derivative proved to be stable even at elevated temperatures for more than a day. This finding can be rationalized by constructing the appropriate resonance structures showing that only in the first case an effective delocalization enables partial single bond character of the benzylidene double bond. From the standpoint of chemical etiology, only Nature’s choice of the tyrosin derived chromophore of the green fluorescent protein provides an efficient radiationless thermal relaxation channel for the unwanted photo-diastereomerization product formed after excitation besides the dominating fluorescence channel of its chromophore.     

Molecular potential-energy surfaces for chemical reaction dynamics

This paper reviews the construction of molecular potential-energy surfaces by an interpolation method which has been developed over the last several years. The method uses ab initio quantum chemistry calculations of the molecular electronic energy in an automated procedure to construct global potential- energy surfaces which can be used to simulate chemical reactions with either classical or quantum dynamics. The methodology is explained and several applications are presented to illustrate the approach. Received: 22 February 2002 / Accepted: 2 May 2002 / Published online: 6 November 2002 Correspondence to: M. A. Collins e-mail: collins@rsc.anu.edu.au Acknowledgements. The methods described in this overview are the result of collaborations with former members of my group, in particular with Josef Ischtwan, Meredith Jordon, Keiran Thompson and Ryan Bettens. I am also indebted for inspiration gained from many discussions with my colleagues Leo Radom and Donghui Zhang (National University of Singapore). This work has been supported by the Supercomputer Facility of the Australian National University and the Australian Partnership for Advanced Computing.     

A thorough study of the surface wax of apple fruits

The composition of the surface waxes of three apple ( Malus domestica L.) cultivars ("Florina", "Golden B" and "Ozark Gold") has been studied by means of spectroscopic and GC–MS analysis of the class-fractionated mixture of components. Odd n -alkanes, mainly C₂₇ and C₂₉ molecules, are prevalent in the saturated fraction. Small concentrations of alkenes were also found; the C_28:1 component is strongly (72%) in excess over the other 1-alkenes. Straight-chain esters (mainly of palmitic acid) of saturated primary alcohols (C₁₈–C₃₀) were also detected; whereas the acyl moiety is made up essentially of an even number of carbons, the alcohol counterpart does not exhibit this characteristic. Aldehydes are present (C₂₀–C₃₀) with the homologue patterns C₂₆–C₃₀ most strongly represented. Straight-chain free secondary alcohols characterize the waxes of "Florina" and "Ozark Gold"; the hydroxy function is located far from the extremity of the carbon framework. Outstanding is the presence of three alcohols with 29 carbon centres. These alcohols are accompanied by free straight-chain primary alcohols, mainly with even-numbered carbon chains in the range C₂₆–C₃₀. Free fatty acids are present; all of have a framework of even-numbered carbon chains mainly in the range C₁₆–C₂₀. C_18:1 (oleic acid) is well represented.     

2D metal slabs in new nickel-tin chalcogenides Ni7−δSnQ2 (QSe, Te): average crystal and electronic structures, chemical bonding and physical properties

A systematic search for mixed low-valence, nickel-tin chalcogenides performed by establishing phase relations in the parts of Ni-Sn-Se and Ni-Sn-Te ternary systems resulted in the discovery of two new compounds, Ni_5.62SnSe₂ and Ni_5.78SnTe₂. Single crystals of both compounds were prepared by chemical transport with iodine and crystal structures were determined by single crystal X-ray investigation. The ED patterns for Ni_5.78SnTe₂ showed the presence of satellite reflections, which indicate a modulated structure with q≈0.4a^*. Average crystal structures of both compounds were determined to be of tetragonal symmetry (Sp.gr. I4/mmm, Z=2) with a=3.6890(8) Å, c=18.648(3) Å, R_w=0.0716 and a=3.7680(5) Å, c=19.419(4) Å, R_w=0.0832, correspondingly, and are isostructural to known Ni_5.72SbSe₂ and Ni_5.66SbTe₂. Measurements were carried out for both compounds with respect to thermal, electrical and magnetic properties. Ab initio band structure calculations were also performed to take a first glance into the electronic structure of such type compounds. The anisotropy of their band structure was found. Physical property measurements showed both compounds to be the anisotropic metallic conductors and paramagnetics. Calculated difference charge density maps revealed pairwise covalent and multicenter metallic nature of the d-metal—chalcogen and d-metal—p-metal interactions, respectively.     

Applicability of glass fiber as a support material for generation of gaseous standard mixtures using thermal decomposition of the surface compound. Calibration of analytical equipment

The use of glass fiber as a support material for a surface compound serving to generate gaseous standard mixtures of ethene is described. The technique is based on the process of thermal decomposition of the surface compound in a desorber connected on‐line via a multi‐port valve to the calibrated device. The surface compound undergoes thermal decomposition at 245°C, yielding known amounts of ethene. The method enables on‐line preparation of a standard mixture immediately before the calibration step. Consequently, it can be also applied for the generation of standard mixtures containing volatile, malodorous, unstable, and toxic compounds.     

Comparison between potentiostatic and galvanostatic intermittent titration techniques for determination of chemical diffusion coefficients in ion-insertion electrodes

Using well-cycled, thin composite graphite electrodes we analyze carefully the limitations of potentiostatic and galvanostatic intermittent titration techniques (PITT and GITT, respectively) for determination of the differential (incremental) intercalation capacitance, C_dif, and the chemical diffusion coefficient, D, of Li ions in these ion-insertion electrodes (IIEs). We demonstrate the superiority of the GITT over PITT to determine these quantities as the former technique allows for a more accurate determination of C_dif and hence D which closely approach to the spinodal domain related to the first-order phase transition during ion-insertion. We show that GITT is also more effective in eliminating the parasitic contributions of background currents to the total measured response. A pronounced difference in the initial, intrinsic kinetics of formation of a new phase in the bulk of the old one has been observed depending on the direction of titration (phases less saturated with Li are formed faster during deintercalation than the Li-rich phases in the course of intercalation).     

活性酚醛树脂中羟甲基含量的测定

本文提出一种酚醛树脂中羟甲基含量的化学分析法，分别以＾１３ＣＮＭＲ和化学分析法测定酚醛树脂的羟甲基含量。将两种测试结果与已知的投料量进行比较，证明所建立的化学分析法可行。