Interaction between Metal in Metallo Enzyme and Small Biological Molecules

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液相色谱中一个新的表征参数Z：Ⅱ.反相液相色谱中小分子极性溶质体系

反相高效液相色谱（ＲＰＬＣ）中小分子极性溶质的极性是可以用液相色谱中溶质计量置换保留模型中的Ｚ值（１ｍｏｌ溶质被固定相吸附时，在固定相与溶质子间释放出置换剂的ｍｏｌ数）来表征的，其大小可用带有该极性端基的同系物的Ｚ值对碳原子数线性作图的截距求得。这些检性基的Ｚ测量定值与疏水性片段指数１ｇｆ间有极好的线性关系。依此关系还可测出一些用其他实验方法无法测得的某些基团的１ｇｆ值。     

Permutation representations in molecular symmetry

The reducible representations of the point groups are generally studied because of their relevance to molecular orbital and vibration theory. Triple correlations within the polyhedra are described by group-theoretical invariants that are related to the permutation representations and termed polyhedral isoscalar factors. These invariants are applied in theorems on matrix elements referring to the symmetry-adapted bases at different centres. Further invariants or geometrical weight factors inter-relate different types of reduced matrix elements of irreducible tensors (generalization of the Wigner-Eckart theorem to the polycentric case). As a demonstration a complete tabulation is given for the point group C ₄.     

Theoretical Definition of a Functional Group and the Molecular Orbital Paradigm

It is the purpose of this review to demonstrate that the empirical classification of the observations of chemistry in terms of the properties assigned to functional groups is a consequence of and is predicted by physics. This is accomplished by showing that the atoms and functional groups of chemistry can be identified with bounded space-filling objects whose properties are defined by quantum mechanics. The quantum mechanical definition of a group is combined with a new pictorial representation of its form to obtain a unified picture which should make it eminently recognizable to chemists. This picture, when combined with the demonstrated ability of these groups to recover the measured properties of atoms in molecules, is offered as one which meets the expectations a chemist associates with the concept of a functional group. The manner in which this physical definition of a group differs fundamentally from models of functional groups based upon molecular orbital theory is discussed.     

The temperature-induced denaturation of small globular proteins as a first-order phase transition of ‘crystal molecules’

A general feature of temperature-induced reversible denaturation of small globular proteins is its all-or-none character. This strong cooperativity leads to think that protein molecules, possessing only two accessible thermodynamic states, the native and the denatured one, resemble ‘crystal molecules’ that melt at raising temperature. An analysis, grounded on mean field theory, allows to conclude that the two-state transition is a first-order phase transition. The implication of this conclusion are briefly discussed.     

Calculation of harmonic force constants,vibrational frequencies and integrated intensities of some organic molecules using the MINDO—Forces method

The harmonic force constants, vibrational frequencies and integrated intensity ratios of CH₂, H₂O, CH₂O, C₂H₂, CO₂, HCN, CH₃, CH₄, and C₂H₄ have been calculated using the MINDO—FORCES program and the Pulay method for the calculation of the molecular force constants. The results obtained are in general quite satisfactory when compared with available literature values. The results are, however, not as satisfactory in case of molecules containing heteroatoms, due to the neglect of some dipolar repulsion integrals for the heteroatoms by the MINDO/3 method. Calculated integrated intensities for CH₃ and C₂H₄ agree well with experimental results. The calculated integrated intensities for other molecules are obtained for the first time and no comparison with published data is therefore possible.Part of the M.Sc. Thesis of K. H. A. 1978.     

On the Criteria of Instability for Electrochemical Systems

Both cyclic-voltammetry-based and impedance-based experimental criteria that have been developed recently for the oscillatory electrochemical systems are critically appraised with two typical categories of oscillators.Consistent conclusions can be drawn by the two criteria for the category of oscillators that involve the coupling of charge transfer mainly with surface steps(e.g.ad-and desorption)such as in the electrooxidation of C1 organic molecules.Whereas,impedance-based criterion is not applicable to the category of oscillators that involve the coupling of charge transfer mainly with mass transfer(e.g.diffusion and convection) such as in the Fe(CN)6^3- reduction accompanying periodic hydrogen evolution.The reason is that the negative impedance cannot include the feedback information of convection mass transfer induced by the hydrogen evolution.However,both positive and negative nonlinear feedbacks,i.e., the diffusion-limited depletion and convection-enhanced replenishment of the Fe(CN)6^3- surface concentration,that coexist between the bistability,i.e.,Fe(CN)6^3- reduction with and without hydrogen evolution at lower and higher potential sides respectively,are all reflected in the crossed cyclic voltammogram(CCV).It can be concluded that the voltammetry-based criterion(in time domain)is more intuitive,less time-consuming and has a wider range of applications than the impedancebased one (in frequency domain).     

New crystal structures of β-[Ni(NCS)2(4-methylpyridine)4] clathrates with furan,tetrahydrofuran, methylene chloride,benzene + ethanol and methylcellosolve as guest molecules

Single crystal X-ray structures of clathrates of -[Ni(NCS)₂(4-methylpyridine)₄] with furan, tetrahydrofuran, benzene + ethanol, methylene chloride, and methylcellosolve as guests molecules are reported. The location of the guest molecule in the partially decomposed clathrate with methylene chloride was defined by X-ray diffraction and compared with the fully occupied one. The host lattices of all clathrates studied are tetragonal (I4₁/a) and do not differ significantly from typical -phase clathrates of [M(NCS)₂(4-methylpyridine)₄] (M = divalent metal cation). Arrangements of guest molecules represent different types of packing: one type of guest molecule occupies both possible types of positions, two different guest molecules occupy different positions, with only one type of positions occupied by one type of guest molecule. Possible stoichiometries of clathrates with -type lattices are discussed.Presented at the Sixth International Seminar on Inclusion Compounds, Istanbul, Turkey, 27–31 August 1995.     

On the interpretation of fluorescence anisotropy decays from probe molecules in lipid vesicle systems

Measurements of fluorescence depolarization decays are widely used to obtain information about the molecular order and rotational dynamics of fluorescent probe molecules in membrane systems. This information is obtained by least-squares fits of the experimental data to the predictions of physical models for motion. Here we present a critical review of the ways and means of the data analysis and address the question how and why totally different models such as Brownian rotational diffusion and wobble-in-cone provide such convincing fits to the fluorescence anistropy decay curves. We show that while these models are useful for investigating the general trends in the behavior of the probe molecules, they fail to describe the underlying motional processes. We propose to remedy this situation with a model in which the probe molecules undergo fast, though restricted local motions within a slowly rotating cage in the lipid bilayer structure. The cage may be envisaged as a free volume cavity between the lipid molecules, so that its position and orientation change with the internal conformational motions of the lipid chains. This approach may be considered to be a synthesis of the wobble-in-cone and Brownian rotational diffusion models. Importantly, this compound motion model appears to provide a consistent picture of fluorescent probe behavior in both oriented lipid bilayers and lipid vesicle systems.     

有机链状分子的定域分子轨道的研究

利用Foster-Boys定域化程序和STO-3G ab initio方法,对含有C、H、O、N原子的100多个有机链状分子进行了研究,得到定域分子轨道能量及其相互作用参数。应用这些参数和定域分子轨道模型,对于众多的含有C、H、O、N原子的有机链状分子,可得到相应的正则分子轨道能量及其与定域分子轨道的关系。以此预测它们的电离能,结果与实验值符合较好。