用能量转移探测萘-蒽二元分子体系的构象变化

合成了一个带有末端取代的能量给体-萘和能量受体-蒽的开链冠醚（DSA）.吸收光谱表明两个发色团之间在基态时没有相互作用.选择性激发萘观察到萘的荧光强度下降, 同时伴随着蒽的发射增强, 表明发生了从萘至蒽的单重态-单重态能量转移.能量转移效率受溶剂极性的影响.可以认为在极性小的溶剂如苯中－OCH2CH2O－单元中的中心C－C键主要以反式存在,而在极性大的溶剂如乙腈中则以邻交叉式为主.因此,开链冠醚末端取代的萘和蒽之间的距离随着溶剂极性的增大,能量转移效率却随之降低.表明能量转移可以用于探测以柔性配体键连接的给体-受体体系在不同极性溶剂中的构象变化特性.     

Conformational and structural studies of 1-chloropropane and 1-bromopropane from temperature-dependant FT-IR spectra of rare gas solutions and ab initio calculations

Variable temperature (−55 to −150°C) studies of the infrared spectra (3500–400 cm⁻¹) of 1-chloropropane (CH₃CH₂CH₂Cl) and 1-bromopropane (CH₃CH₂CH₂Br) dissolved in liquid krypton and xenon, respectively, have been recorded. Utilizing two conformer pairs in krypton solution for chloride and three conformer pairs in xenon solution for bromide, enthalpy differences of 52±3 cm⁻¹ (0.62±0.06 kJ/mol) and 72±7 cm⁻¹ (0.86±0.08 kJ/mol) were obtained for the chloride and bromide, respectively, with the gauche form being the more stable conformer for both molecules. From these data, it is estimated that 28 and 26% of trans form are present at ambient temperature for the chloride and bromide, respectively. The conformation stabilities, harmonic force constants, fundamental frequencies, infrared intensities and Raman activities have been obtained from RHF/6-31G(d) and/or MP2/6-31G(d) ab initio calculations for both halopropanes and these quantities have been compared to the experimental values when appropriate. The optimized geometries have also been obtained with several different ab initio basis sets with full electron correlation by the perturbation method up to MP2/6-311+G(2d,2p). The r₀ structural parameters of both halopropanes have been obtained by combining the ab initio data with the previously reported microwave rotational constants for both conformers. The quantities are compared to the corresponding results for some similar molecules.     

Influence of ligand binding on the conformation of Torpedo californica acetylcholinesterase

With the aim of identifying structural changes in acetylcholinesterase, induced by ligand binding, we use a completely automatic procedure to analyse the differences between the backbone conformation of the free enzyme and those in eight complexes of Torpedo californica acetylcholinesterase, with various quaternary ammonium ligands, and with the protein inhibitor fasciculin. In order to discriminate between structural changes due to ligand binding and those arising from model imprecision, we also examine protein–ligand and protein–water contacts. Except for the peptide flip in the complex with huperzine A, the backbones of other complexes with quaternary ammonium ligands display negligible changes relative to the free enzyme. Another exception is the complex with the bisquaternary ammonium ligand decamethonium, where several loops display above average deformations, but only two, those spanning residues 334–348 and residues 277–304, seem to move as a result of ligand binding. Movement of the ω loop (residues 61–95) is detected only in the complex with the protein fasciculin. Received: 21 July 2000 / Accepted: 18 September 2000 / Published online: 28 February 2001     

Modeling Variability Order: A Semiparametric Bayesian Approach

In comparing two populations, sometimes a model incorporating a certain probability order is desired. In this setting, Bayesian modeling is attractive since a probability order restriction imposed a priori on the population distributions is retained a posteriori. Extending the work in Gelfand and Kottas (2001) for stochastic order specifications, we formulate modeling for distributions ordered in variability. We work with Dirichlet process mixtures resulting in a fully Bayesian semiparametric approach. The details for simulation-based model fitting and prior specification are provided. An example, based on two small subsets of time intervals between eruptions of the Old Faithful geyser, illustrates the methodology.     

聚乙烯型尾形链构象统计的Monte Carlo研究

以聚乙烯型尾形链为例 ,根据链的实际键长、键角和Θ条件下每一链段处于不同旋转异构态的条件概率 ,用MonteCarlo模拟方法生成样本链分子 ,计算了尾形链的均方末端矩及其分量、构象数 ,并与完全计算法及理论推导值作了比较 ,讨论了尾形链构象数和沿边界方向及法线方向均方末端矩分量随链段数n及键角Φ的变化 .     

Correlation-induced spectral changes dependent upon spatiotemporal interference effects

A wave-front folded interferometer consisting of a Kösters prism and an image forming lens provides an excellent way to make a precision measurement of correlation-induced spectral changes. Experiments are successfully made by incorporating a primary spectral source of super-luminescent diodes. The diode emits a Gaussian-like spectrum. Theoretical background for the measurement is given in the framework of geometric optics. It is shown theoretically and experimentally that the spectral changes are induced by two causes: one is the complex degree of spectral coherence of the secondary source, and the other the time delay between the interfering optical waves. No spectral change takes place if the secondary source satisfies a spatially incoherent condition at particular optical frequency, whereas the spectrum changes most clearly if a spatially coherent condition is satisfied.     

Estimation of time-varying ARMA models with Markovian changes in regime

In this paper, we consider the estimation of time-varying ARMA models subject to Markovian changes in regime. We give explicit conditions ensuring consistency and asymptotic normality, as well as the limiting covariance matrix, of least squares and quasi-generalized least-squares estimators.     

Conformational Analysis of Epiquinine and Epiquinidine

The conformational potential energy surfaces for the epiquinine and epiquinidine molecules were analyzed in gas phase and water solution using semiempirical and ab initio levels of theory. The results obtained showed that the main conformation of the nonactive threo epimers is distinct from those observed for the active parent compounds quinine and quinidine. This result might be used, on a qualitative way, to understand the loss of activity of the threo epimers and allow selecting important conformations to be considered in molecular modeling quantitative studies addressing the drug–receptor interactions.     

Stereoselective Synthesis of 1,3-Disaccharides through Diels-Alder Reactions: Part 2[ 1 ]: Convenient Protecting Groups for Heterodienes and Conformational Evaluations

Improved synthesis of 1,3-disaccharides, obtained diastereomerically pure by [4+2] hetero cycloadditions between glycals and α -thiono-β -keto-δ -lactones, has been reported. The choice of appropriate protecting groups for β -keto-δ -lactones, stable under cycloaddition conditions employed, sensibly shortened the synthesis of heterodienic precursors. The first example of a β -oxy-imino-δ -lactone synthesized from β -keto-δ -lactones was also reported. Molecular modeling and conformational evaluations about the cycloaddition features allowed tentatively rationalizing the experimental results.     

Temperature effects in capillary electrophoresis. 1: Internal capillary temperature and effect upon performance

Summary In isothermal CE the migration velocity of analytes and the number of theoretical plates delivered are expected to be proportional to the field strength. In reality ohmic heating of the capillary causes distortions: the migration velocity increases more rapidly while the plate count increases less rapidly, and may even fall at high values of the field. These distortions are worse the larger the bore of the capillary and the higher the concentration of buffer. A detailed investigation of these effects using capillaries cooled by natural convection has confirmed that self heating of the capillary is indeed largely responsible. The extent of self heating has been determined by three independent methods and to a first approximation is proportional to the power dissipation in the capillary. Decreasing viscosity with temperature is responsible for the nonlinearity of the dependence of velocity upon field strength while increase in the diffusion coefficient of analytes is responsible for the poorer than expected performance at high field strengths.