二十面体准晶对非晶形成影响的模拟

采用分子动力学模拟技术,以液态金属Ni为例,研究了在不同冷却条件下形成晶体及非晶的过程.模拟采用镶嵌原子法(EAM)作用势,得到了不同温度、不同冷却速度下Ni的径向分布函数以及原子组态变化的重要信息,利用键对分析技术探讨了二十面体准晶对非晶形成的影响.     

Linear Monodisperse π-Conjugated Oligomers: Model Compounds for Polymers and More

The development of structure–property relationships for monodisperse oligomers has been extremely useful to rationalize the properties of high molecular weight linear π-conjugated polymers. A great variety of spectacular molecular architecture has been generated, culminating in the recent preparation of molecular wires such as 1 with lengths exceeding 10 nm that have potential applications in molecular electronics.     

Calculation of the regions of solid phase precipitations in the metal ion-water-complexing agent systems

The calculation the regions of solid phase precipitations with the different compositions by use of solubility product and molecular solubility expressions has been suggested. Advantage of use of molecular solubility expression has been showed, consisting in insignificant difference of values of the molecular solubility constant for metal ions, having same oxidation level and same counter ion. A value determination task of the system parameters, which composition of the solid phases is changed on, has been decided.     

超分子化学发展简介

本文综述了超分子化学的定义 , 范围及内容. 着重介绍了分子识别, 分子自组装, 超分子催化, 超分子器件及超分子材料等概念. 对由此可能形成的新的前沿科学如分子电子学, 分子离子学, 分子光子学及超分子工艺学等作了扼要介绍 .     

Polyelectrolyte complexes of soluble poly-2-[(methacryloyloxy)ethyl]trimethylammonium chloride and its hydrogels with poly(acrylic acid)

The complex formation of poly-2-[(methacryloyloxy)-ethyl]trimethylammonium chloride (PMADQUAT) with poly(acrylic acid) (PAA) of different molecular weights has been studied in aqueous solutions by potentiometric, viscometric, turbidimetric and FTIR spectroscopic methods. The formation of insoluble non-stoichiometric polyelectrolyte complexes has been shown. The stability of polyelectrolyte complexes in solutions of different pH and ionic strength has been evaluated. The formation of polyelectrolyte complexes between hydrogels of PMADQUAT and linear PAA of different molecular weights has been studied. It was shown that the molecular weight of PAA considerably affects the kinetics of interaction as well as the final state of gel-polymer complex.     

Cyclic macromolecules. Synthesis and characterization of ring-shaped polystyrenes

A method has been developed to synthesize cyclic polystyrene molecules, by reacting bifunctional “living” polystyrene with α,α′ dibromo-p-xylene. The ability of the method to yield cyclic polymers over a molecular weight range from 7000 to 250,000 has been thoroughly investigated and discussed. Characterization of the cyclic macromolecules with respect to linear homologues of the same molecular weight has been performed by means of viscometry. The effect of cyclization tends to decrease as the molecular weight increases.     

Molecular structure and electronic spectrum of ellagic acid: Semiempirical molecular orbital calculations

The molecular structure of ellagic acid has been optimized by using PM3 semiempirical MO method. Ellagic acid has been calculated to be planar with the molecular symmetry of C_2h. The lactone carbonyl groups are not tilted from the molecular plane. CNDO/S MO method has been used to interpret the experimental uv-vis spectroscopic data. The results of the PM3 and CNDO/S calculations have been in good agreement with the experimental data.     

Chitosans: Thermochemical Study

The physical and phase transitions of a series of chitosans differing in molecular weight and deacetylation degree have been revealed by means of differential scanning calorimetry, thermogravimetry, and mass spectrometry. The temperature ranges corresponding to the dehydration and thermolysis of the considered polymers have been determined. The devitrification temperature of the polymers has been recorded, and its two-parametric regression on the chitosans molecular weight and deacetylation degree has been found. The molecular weight of the polymer revealed stronger effect on the devitrification temperature in comparison with the deacetylation degree.     

Concentration effect in hyaluronan analysis by size exclusion chromatography

Summary The concentration effect in size-exclusion chromatographic analysis of hyaluronans of various relative molecular masses (RMM) has been studied. A critical concentration has been found that is negatively dependent on the hyaluronan molecular mass; the higher the biopolymer molecular mass, the smaller the injected sample where the concentration effect should be taken into account for accurate evaluation of molecular mass distribution. At higher temperatures, however, the concentration effect diminishes significantly.     

Refractometric studies of mesogenic molecules in isotropic solutions

The Lorenz-Lorentz equation for binary isotropic mixtures, consisting of anisotropic molecules, has been derived using the point-dipole approximation taking into account only pair molecular correlations. This permits the calculation of the effect of molecular correlations on the refractive index. Special attention has been paid to the case of infinite dilution in the solvents consisting of isotropic molecules, where an experimental check of the equations is possible. The specific refraction of some solutes with different molecular polarizability anisotropy and polarity has been studied in various solvents. It has been shown, that the main theoretically predicted features are observed in these experiments, but for a quantitative comparison information on the two-particle distribution function is needed.     

The structure and spontaneous orientational order in surface layers of water-soluble methyl- and hydroxypropylmethyl cellulose films

The structure of the surface layers of thin films cast from water-soluble derivatives of cellulose—methyl cellulose and hydroxypropyl methylcellulose—has been studied by the methods of an oblique polarized beam and molecular hydrodynamics. It has been demonstrated that the molecular chains of the polymers under study are characterized by a high degree of order in surface film layers. The orientational order of molecular chains demonstrates a strong molecular mass dependence. This effect is associated with the concentration of terminal segments whose orientational order parameter relative to the film surface differs from the corresponding value of internal segments composing the molecular chain. The quantitative estimates of the orientational order parameter of terminal and internal segments have been performed.     

X-ray characterisation of local molecular orientation in the electroclinic effect of surface-stabilised SmA liquid crystals

The local molecular orientation in the electroclinic effect of the chiral smectic A phase in a surface-stabilised cell has been determined using a time-resolved synchrotron X-ray microbeam diffraction technique. Space- and time-resolved X-ray wide-angle halo scattering under an electric field reveals the static and dynamic intralayer molecular orientation. The molecular orientation varies spatially in accordance with the stripe texture and is dependent on the applied voltage. It has been found that the deviation of the molecular orientation from the rubbing direction depends strongly on the sample history. The relation between the apparent molecular orientation and the layer structure is discussed.     

Molecular recognition of aminoglycoside antibiotics by bacterial defence proteins: NMR study of the structural and conformational features of streptomycin inactivation by Bacillus subtilis aminoglycoside-6-adenyl transferase

The molecular recognition of streptomycin by Bacillus subtilis aminoglycoside-6-adenyl transferase has been analysed by a combination of NMR techniques and molecular dynamic simulations. This protein inactivates streptomycin by transferring an adenyl group to position six of the streptidine moiety. Our combined approach provides valuable information about the bioactive conformation for both the antibiotic and ATP and shows that the molecular recognition process for streptomycin involves a conformational selection phenomenon. The binding epitope for both ligands has also been analysed by 1D-STD experiments. Finally, the specificity of the recognition process with respect to the aminoglycoside and to the nucleotide has been studied.     

Synthesis,characterization, and curing of well-defined allyl ether-maleate functional ester oligomers: Linear versus nonlinear structures

A series of allyl ether-maleate functional star-shaped esters with from one to four arms has been synthesized. The structures that have been made are an analogous series with increasing molecular weight and functionality where the increase in molecular weight has been made nonlinear, i.e., star-shaped. The resins are monodisperse in the sense that each arm has a well-defined structure and that, within a certain sample, only one type of molecule exists. The viscosity and rheological behavior of the resins have been studied. The curing kinetics of the star-shaped (branched) resins and the properties of the films formed have also been studied. These properties have been related to differences in functionality and to differences in the molecular architecture of the resins. © 1992 John Wiley & Sons, Inc.     

Liquid structure of vanadium tetrachloride from neutron diffraction study

Assuming the separation of the intermolecular scattering function into the radial and angular parts and using Egelstaffet al’s orientational model for tetrachlorides, the structure of liquid vanadium tetrachloride has been studied. It has been observed that such a separation is approximate for this liquid and the introduction of a third correction term is required to account for the molecular structure function. The chlorine-chlorine partial structure and effective angleaveraged intermolecular chlorine-chlorine potential in the liquid has been evaluated. Without taking the third correction term, introduced to generate theoretically the molecular structure function, the centre structure function has been obtained in an approximate way from the experimentally observed molecular structure function and from it the centre radial distribution function, centre direct correlation function and the angle-averaged vanadium-vanadium effective potential has been evaluated.     

Interesting anion-inclusion behavior of cucurbit[5]uril and its lanthanide-capped molecular capsule

The selective encapsulation behavior of cucurbit [5]uril and its lanthanide-capped molecular capsule toward nitrate and chloride ions has been investigated. Using fluorescence spectroscopy, the metal-free host has been demonstrated to selectively include nitrate ion. In contrast, the lanthanide-capped molecular capsule showed preference toward the inclusion of chloride ion. Solid-state structures of the nitrate and chloride inclusion complexes with the La(III)-capped molecular capsule have been crystallographically determined.     

cis-Glyco-fused benzopyran compounds as new amyloid-β peptide ligands

A small library of glyco-fused benzopyran compounds has been synthesised. Their interaction features with Aβ peptides have been characterised by using STD-NMR and trNOESY experiments. The conformational analysis of the compounds has also been carried out through molecular mechanics (MM) and molecular dynamics (MD) simulations.     

Theoretical calculation of the coiled-coil stability in water in the context of its possible use as a molecular rack

The coiled-coil stability and rigidity may be of importance for molecular electronics (electronically bistable molecules). The coiled-coil binding free energy has been calculated using molecular dynamics (MD). The energy has been computed as a difference of the appropriate free energies; derived for the coiled-coil and isolated alpha-helices separately. All MD simulations have been performed using an explicit model of the solvent, whereas the continuum solvent approach has been applied to analyze the MD trajectories. The computed stability of the coiled-coil is of the order of -87 kcal/mol, i.e., about -1.2 kcal/mol per amino acid residue, and arises mainly from the electrostatic interactions and hydrophobic effect. The entropy term has been roughly estimated to be of the order of -22 kcal/mol. This assures that coiled-coil polypeptides may be used as a stable molecular scaffolding.     

Comparison of Ethene Diffusion Characteristics in H[Al]ZSM‐5 at 300 K and 400 K by Molecular Dynamics

The ethene diffusion characteristics in the framework of H[Al]ZSM‐5 at 300 K and 400 K have been studied by molecular dynamics (MD) simulation. The data have been obtained for the molecular kinetic, potential and total energies, mean square displacement and self‐diffusion coefficient, interaction and beat of adsorption. The dependence of molecular diffusion on temperature has been explored.     

The atom assignment problem in automated de novo drug design. 5. Tests for envelope-directed fragment placement based on molecular similarity

Summary The fragment placement method has been successfully extended to the problem of envelope-directed design. The atom assignment paradigm was based on molecular similarity between two molecular structures. A composite supersurface is defined to form the surface onto which the molecular fields are projected. The assignment process is then determined by using molecular similarity in the objective function to be optimized. In principle, this procedure is closely similar to that outlined in the previous paper for site-directed design. The rationale has been extensively tested on two benzodiazepine antagonists believed to bind to the same site.