Exact results for a generalized classicalO(n) matrix spin model

A generalizedO(n) matrix version of the classical Heisenberg model, introduced by Fuller and Lenard as a classical limit of a quantum model, is solved exactly in one dimension. The free energy is analytic and the pair correlation functions decay exponentially for all finite temperatures. It is shown, however, that even for a finite number of spins the model has a phase transition in then limit. The transition features a specific heat jump, zero long-range order at all temperatures, and zero correlation length at the critical point. The Curie-Weiss version of the model is also solved exactly and shown to have standard mean-field type behavior for all finiten and to differ from the one-dimensional results in then limit.     

Sampling and local models for multivariate image analysis

Local models are a very important concept for microscopic and macroscopic imaging. Different methods of sub-sampling a multivariate image are described both in general and for three examples. The need for sub-sampling and its influence on multivariate image analysis and visualization are studied. Examples from MRI (256 × 256), satellite imaging (7 × 512 × 512) and biofuel studies (6 × 512 × 512) are used to illustrate some of the principles involved.     

Insecticidal Activity and Free Radical Scavenging Properties of Isolated Phytoconstituents from the Saudi Plant Nuxia oppositifolia (Hochst.)

Chromatographic purification of the alcoholic extract from the aerial parts of the Saudi plant Nuxia oppositifolia (Hochst.), Benth., resulted in five isolated phenolic compounds. Two flavones, hispidulin (1) and jaceosidin (2), and the phenylethanoid glycosides, verbascoside (3), isoverbascoside (4), and conandroside (5), were identified and their chemical structures were determined by spectroscopic analyses. The insecticidal activity of compounds 1 and 2, in addition to 11 compounds isolated in a previous research (6–16), was evaluated against the Yellow Fever mosquito, Aedes aegypti. Four compounds displayed adulticidal activity with LD₅₀ values of 2–2.3 μg/mosquito. Free radical scavenging properties of the plant extracts and compounds (1–5) were evaluated by measuring the 1,1-diphenyl-2-picrylhydrazyl radical (DPPH) and 2,2′-azino-bis (3-ethylbenzothiazoline-6-sulfonate radical cation (ABTS^•+) scavenging activity. All compounds exhibited notable activity, compared with the positive control, l-Ascorbic acid. This study suggests that N. oppositifolia could be a promising source of secondary metabolites, some with lethal adulticidal effect against Ae. aegypti.     

UO22＋•nH2O和PuO22＋•nH2O (n＝2, 4, 5, 6)密度泛函理论研究

首先用密度泛函理论(DFT)方法研究了铀酰和钚酰离子的几何与电子结构, 计算结果与实验基本符合, 表明DFT方法也能用于含铀和钚重原子的化合物计算. 然后对铀酰和钚酰水合离子的几何构型、Mulliken集居数分布以及铀酰(钚酰)与配体水分子的结合能进行计算, 计算结果表明UO₂^2＋•5H₂O和PuO₂^2＋•5H₂O分别为铀酰和钚酰系列水合离子中最稳定的配合物.     

Photoelectron Spectra of Nonmetal Compounds and Their Interpretation by MO Models

The results of (low energy) photoelectron spectroscopy render possible a better appreciation of the “Nature of the Chemical Bond”. The application of this new experimental method is demonstrated utilizing representative compounds of the nonmetal elements, and a close symbiosis delineated with molecular orbital models. In particular, general consequences are discussed concerning electron deficiency, σ- and π-interactions, electron pair delocalization, and substituent effects or geometric perturbations. Photoelectron spectroscopic ionization energies permit evaluation of parameters for specified molecular groups, allow correlation with numerous other experimental data, and are didactically valuable in the teaching of general chemistry.     

Relative stability of major types of beta-turns as a function of amino acid composition: a study based on Ab initio energetic and natural abundance data

Folding properties of small globular proteins are determined by their amino acid sequence (primary structure). This holds both for local (secondary structure) and for global conformational features of linear polypeptides and proteins composed from natural amino acid derivatives. It thus provides the rational basis of structure prediction algorithms. The shortest secondary structure element, the beta-turn, most typically adopts either a type I or a type II form, depending on the amino acid composition. Herein we investigate the sequence-dependent folding stability of both major types of beta-turns using simple dipeptide models (-Xxx-Yyy-). Gas-phase ab initio properties of 16 carefully selected and suitably protected dipeptide models (for example Val-Ser, Ala-Gly, Ser-Ser) were studied. For each backbone fold most probable side-chain conformers were considered. Fully optimized 321G RHF molecular structures were employed in medium level [B3LYP/6-311++G(d,p)//RHF/3-21G] energy calculations to estimate relative populations of the different backbone conformers. Our results show that the preference for beta-turn forms as calculated by quantum mechanics and observed in Xray determined proteins correlates significantly.     

A density functional study of propylene glycol conversion to propanal and propanone of various acid-catalyzed reaction models: a water-addition effect

The acid-catalyzed models on reaction mechanisms of pinacol rearrangement of propylene glycol conversion to propanal and propanone have been investigated using the density functional method at 298.15 K. Thermodynamic quantities of activation steps of four water-addition models were obtained. The number of added water interacting with the transition states of three concerted pathways has obviously affected the product ratio. The relative energetic profiles of the conversion reactions of all solvation models have been comparatively displayed. Estimation of the percent ratio of product composition computed from activation free energies of each acid-catalyzed reaction model was carried out. The percent ratios of propanal and propanone were decreased as the number of added water increased.     

Markov processes in single molecule fluorescence

This article examines the current status of Markov processes in single molecule fluorescence. For molecular dynamics to be described by a Markov process, the Markov process must include all states involved in the dynamics and the first-passage time (FPT) distributions out of those states must be describable by a simple exponential law. The observation of non-exponential FPT distributions or other evidence of non-Markovian dynamics is common in single molecule studies and offers an opportunity to expand the Markov model to include new dynamics or states that improve understanding of the system.     

MENTHOR,a database system for the storage and retrieval of three-dimensional molecular structures and associated data searchable by substructural,biologic, physical,or geometric properties

Summary MENTHOR is a database system for the storage and retrieval of three-dimensional coordinate and charge information on molecules as well as of traditional biological and physical properties. Our molecular graphics system retrieves from MENTHOR structural information in individual molecules and receptor map/macromolecular binding site hypotheses. Substructural searches of MENTHOR are used to find starting coordinates for molecular modeling and traditional database searches of MENTHOR identify compounds for which modeling is needed. It also forms the data to be searched with ALLADDIN, our substructure/geometric search program. MENTHOR expedites molecular modeling by organizing previous work and facilitating transmission of information between individuals. Examples from modeling of D-2 receptor agonists are shown.     

Molar mass distributions by gradient liquid chromatography: predicting and tailoring selectivity

Interactive liquid chromatography (iLC) for polymer analysis is usually applied to the characterisation of distributions other than molar mass. In particular, its use for the determination of chemical-composition, functionality-type and tacticity distributions has been demonstrated. The application of iLC for the determination of molar mass distributions (MMDs), however, has not yet been fully explored. An expanded version of the reversed-phase liquid chromatography model has been developed to describe and predict how the retention behaviour of polydisperse polystyrene samples changes with molar mass. The relationship between molar mass and the parameters of the model has been investigated in some detail and non-linear correlations were found. From the model and the relationships between the model parameters and molar mass, calibration curves (retention time versus molar mass) were constructed to predict changes in chromatographic selectivity across a given molar mass range. These calibration curves were compared to experimentally obtained curves and, in most cases, excellent agreement was found. The dramatic enhancement in selectivity that can be obtained with iLC in comparison to size-exclusion chromatography (SEC) was illustrated by measuring matrix-assisted laser desorption ionisation (MALDI) MS spectra of fractions collected during a gradient-LC separation. In the low-molar mass range, essentially monodisperse fractions were obtained. Calibration curves, predicted by the model and validated experimentally using narrow-dispersity standards and MALDI-MS spectra of fractions, were used to determine the molar mass distribution of some narrowly distributed polystyrene samples. Molar mass distributions for such standards were found to be somewhat lower than the values reported by the manufacturers. The results also deviated from those obtained by MALDI-MS.