Polarographic study of Tl+, Li+, Na+, K+, and Cs+ complexes with monensin anion in dipolar aprotic solvents

Summary The stability constants,K _sof monensin complexes with Li⁺, Na⁺, K⁺ and Cs⁺ ions were studied by a competitive polarographic method using the Tl⁺/Tl(Hg) redox couple as a sensitive electrochemical probe. TheK _svalues are strongly influenced by the solvents (acetonitrile, propionitrile, acetone, N,N-dimethylformamide, N-methyl pyrolidinone, N,N-dimethylacetamide, dimethylsulfoxide, N,N-diethylformamide and N,N-diethylacetamide were used in experiments) and vary inversely with the Gutmann donicity scale. Molecular mechanics computations revealed the probable structures of the complexes.

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Polarographische Untersuchung von Tl⁺-, Li⁺-, Na⁺- und Cs⁺-Komplexen mit Monesin-Anion in dipolaren aprotischen Lösungsmitteln

Zusammenfassung Es wurden die StabilitätskonstantenK _svon Monesin-Komplexen mit Li⁺-, Ma⁺- und Cs⁺-Ionen mittels einer competitiven polarographischen Methode unter Verwendung der Tl⁺/Tl(Hg)-Redoxelektrode als sensitiver elektrochemischer Sonde bestimmt. DieK _s-Werte werden stark vom Lösungsmittel (Acetonitril, Propionitril, Aceton, N,N-Dimethylformamid, N-Methylpyrrolidinon, N,N-Dimethylacetamid, Dimethylsulfoxid, N,N-Diethylformamid und N,N-Diethylacetamid) beeinflußt, wobei sie invers zurGutmann schen Donizitätsskala variieren. Die wahrscheinliche Struktur der Komplexe wurde mittels molekularmechanischer Berechnungen ermittelt.

     

Calix[4]arene-based ditopic receptor for dicarboxylates

Shape-selective recognition for the dicarboxylates in DMSO can be attained by a new calix[4]arene-based receptor 1 having two urea groups. Biologically active chorismate selectively bound in 1 over its dehydrated derivative. Molecular mechanics calculations gave a plausible explanation for the selective binding.     

A structural and energetics analysis of the binding of a series of N-acetylneuraminic-acid-based inhibitors to influenza virus sialidase

Summary A molecular dynamics/energy-minimisation protocol has been used to analyse the structural and energetic effects of functional group substitution on the binding of a series of C4-modified 2-deoxy-2,3-didehydro-N-acetylneuraminic acid inhibitors to influenza virus sialidase. Based on the crystal structure of sialidase, a conformational searching protocol, incorporating multiple randomisation steps in a molecular dynamics simulation was used to generate a range of minimum-energy structures. The calculations were useful for predicting the number, location, and orientation of structural water molecules within protein-ligand complexes. Relative binding energies were calculated for the series of complexes using several empirical molecular modelling approaches. Energies were computed using molecular-mechanics-derived interactions as the sum of pairwise atomic nonbonded energies, and in a more rigorous manner including solvation effects as the change in total electrostatic energy of complexation, using a continuum-electrostatics (CE) approach. The CE approach exhibited the superior correlation with observed affinities. Both methods showed definite trends in observed and calculated binding affinities; in both cases inhibitors with a positively charged C4 substituent formed the tightest binding to the enzyme, as observed experimentally.This paper is based on a presentation given at the 14th Molecular Graphics and Modelling Society Conference, held in Cairns, Australia, August 27–September 1, 1995.Presently on a visiting postdoctoral fellowship in the Department of Biomolecular Structure, Glaxo Research & Development Ltd, Greenford, Middlesex UB6 OHE, U.K.     

Charge calculations in molecular mechanics. Part 8 Partial atomic charges from classical calculations

Summary The CHARGE2 programme, which involves the classical calculation of both the inductive and resonance contributions to the partial atomic charges in molecules is described, and the charges and electrostatic potentials obtained presented for some illustrative examples.In substituted methanes (CH₃X, CF₃X, CCl₃X) the effects of varying the electronegativity of the substituents and the - and -substituent contributions are clearly illustrated for a variety of substituent groups X.The problems involved in the inclusion of silicon into this scheme are detailed, together with the methods of overcoming them. The partial atomic charges ( and contributions) and electrostatic potentials for some silicon oxygen compounds are presented and discussed.The partial atomic charges from CHARGE2 for all the natural amino acids as their N-acetyl, N-methyl-amides are given and compared with those obtained from the AMBER and ECEPP/2 force fields. Considerable differences in these figures are observed, with the AMBER charges consistently much larger than those from the other two methods.The CHARGE2 partial atomic charges and electrostatic potentials for the four common nucleic acids, adenine, cytosine, guanine and thymine, are given and compared with those derived from other calculations. Again there is general similarity but also there are considerable differences, with those from the AMBER force field somewhat larger than the other methods.For previous parts in this series, see Refs. 1-7.     

Thermodynamics for Coulomb systems: A problem at vanishing particle densities

In this paper I combine techniques recently developed by Charles Fefferman with the well-known methods of Joel Lebowitz and Elliott Lieb to resolve some technical problems left unsettled by Lebowitz and Lieb's fundamental 1972 paper The constitution of matter: Existence of thermodynamics for systems composed of electrons and nuclei.     

Fermionic perturbation theory for the statistical mechanics of the nonlinear Schrödinger model

A fermionic perturbation theory is developed for the statistical mechanics of the nonlinear Schrödinger model. The theory is based on an interacting-fermion picture of the Bethe wave function. The inner product of the Bethe wave function is explicitly evaluated, and a simple graphical representation of it is given. The basic equations obtained for the free energy agree with those of Yang and Yang. In particular, the present theory gives a clear-cut meaning to the function of Yang and Yang: It represents a fermion energy at finite temperatures.     

单核锌双卟啉配合物构象平衡的理论研究及光谱分析

合成了一系列以不同长度柔韧链相连的p/p型单核锌双卟啉配合物。选用Tripos力场,利用分子动力学模拟退火和分子力学构象搜索相结合的方法对该系列双卟啉进行了能量优化和构象分析。理论计算结果表明:该类双卟啉稳定存在的最低能量构象为叠合式,最高能量构象为伸展式,并存在一系列的中间能量构象;双卟啉分子内π-π作用和能量转移与双卟啉存在的两种主要构象密切相关;分析了分子内π-π作用的本质。运用不同光谱测试手段验证了理论计算结果: 利用可见和相应二阶导数吸收光谱研究了双卟啉主要存在的叠合式和伸展式构象,通过红外光谱观察了对双卟啉构象和卟啉环间π-π作用较为敏感的吸收谱带;利用荧光光谱计算了双卟啉的分子内能量转移效率。     

Solid state photoreactions occurring at the interface between crystallites of two different organic compounds

This paper deals with the solid state bimolecular photoreactions occurring at the interface between crystallites of two different organic compounds prepared as a polycrystalline mixture by melting-resolidification. The photoreactions include the photoaddition of NH compounds to aromatic and olefinic double bonds, hydrogen abstraction, condensation reaction via photoelectron transfer and [2+2] photoaddition. Particular attention is focused on the characterization of the polycrystalline mixture, the selectivity of the photoreactions in the solid state compared with those in the solution phase and the factors controlling the photoreactions.     

全二维液相色谱（NPLC×RPLC）接口及其应用

用内径为0．53mm的填充毛细管正相液相色谱为第一维，用4．6mm（i．d．）×50mmRP-18e整体柱反相色谱为第二维，建立了定量环一阀切换接口的全二维液相色谱系统（NPLC×RPLC）．第一维色谱分离洗脱出的组分交替存储在十通阀上的两个定量环中，同时定量环中前一个组分被转移到第二维进行反相分离．因为第一维的流动相流量仅是第二维的1／500，自然解决了流动相兼容问题．采用芳香族化合物的混合物和中药丹参正己烷提取液对该全二维液相系统的分离能力进行了评价．     

Applicability of polymer theories to the thermodynamics of proteins at the air/water interface: example of β-lactoglobulin

Knowledge of the equation of state of adsorbed or deposited layers of proteins at the air/water interface is of fundamental interest in the understanding of the surface activity of these molecules. Using scaling laws of current polymer theories, it has been shown that the equation of state of the interfacial layer in the semi-dilute regime should relate the surface pressure to the surface concentration through a power law. The exponent of this power law should reflect the quality of the solvent and the conformation of the adsorbed polypeptide chain. In the case of β-lactoglobulin layers, in the range of surface concentrations that should correspond to the semi-dilute regime, the relationship between surface pressure and surface concentration is expressed as a power law. The exponent of this power law is strongly influenced by the nature of the aqueous substrate and by the net charge of the protein molecule. The use of scaling laws gives a coherent view of the expansion of the polypeptide chain in the interfacial layer and of the relationship between surface concentration and surface pressure in the semi-dilute regime. This result favours a strong similarity between β-lactoglobulin and a polymer chain in the interfacial layer. It is concluded that current theories of polymer adsorption could be applied to interfacial protein layers.