Analytic Atomic Screening Parameters for Slater Type Orbitals

Screening parameters to be used in Slater Type Orbitals were obtained in analytic form. The values compared well with the numerical results given by Clementi and Roetti (after a laborious process of optimization) and with the phenomenological values of Jung and Gould. The analytic formulation is based on the splitting of the two-body operator 1/r_st as the sum of effective one-body operators.     

A thermodynamic framework to model thixotropic materials

Thixotropic materials are widely used in a variety of industrial applications. The constitutive relations to describe these materials are based on one-dimensional experiments in which the material is subjected to a shear motion and there is no unique methodology to obtain proper three-dimensional models. The path towards generalization to a three-dimensional framework is invariably carried out in a ad hoc manner. Here we propose a three-dimensional model that stems from a general thermodynamic framework that has proved to be quite robust in the development of constitutive relations, namely the application of the second law of thermodynamics together with the maximization of the entropy production. This leads to a constitutive equation that has the same form of a generalized Upper Convected Maxwell equation, if we require that changes of microstructure due to the deformation of each Maxwell element that comprises the model are reversible. Changes in microstructure are governed by a potential that is a measure of the difference between the current structure and the equilibrium structure associated with it. The equilibrium structure associated with the current structure is determined by the current value of stress, considered the main break up agent. We assume that the state of equilibrium would be achieved in a Motion With Constant Stress History, starting from the current stress state, until a steady state where the kinematics is not changing.     

Imine Oligomers and Polymers

Abstract

In the last few years, polymers with highly conjugated chains have attracted much attention because of their wide variety of applications in the field of electronics, opto‐electronics, and photonics. Polyimines (PIs) (polymeric Schiff bases) is a class of polymer family, which has been less reviewed. In this paper, we focus on the synthesis methods of PIs by polycondensation, using diamines or hydrazine and dialdehydes, diketones or quinone compounds, or by chemical and electrochemical polymerization of imine oligomers containing terminal oxidable groups (pyrrole, thiophene, furan, naphthalene, etc). PIs with liquid crystalline behavior or having rotaxane and dendrimer architectures are also discussed. Structure, thermal, opto‐electronic, electrical, and mechanical properties and some potential applications of this class of polymers are presented in the last chapters.     

光谱法研究水团簇结构对AlCl3溶液与血清白蛋白作用的影响

研究了冷冻-解冻处理对A1CI₃溶液团簇结构和AICl₃与血清白蛋白相互作用的影响。测定了AICl₃溶液冷冻-解冻处理前后电导率的变化,发现AICI₃溶液经冷冻处理后,电导率有明显增加。采用紫外分光光度法和荧光光谱法对冷冻前后AICI₃溶液与血清白蛋白相互作用的研究表明,A1C1₃溶液经冷冻-解冻处理后,与血清白蛋白的相互作用变弱,配位诱导作用降低,静态猝灭作用变小,这种相互作用变弱的效应是由于水的分子团簇结构变化引起的。     

An integrative in silico approach to the structure of Omp33-36 in Acinetobacter baumannii

Omp33-36 in A. baumannii, a bacterium causing serious nosocomial infections, is a virulence factor associated with the pathogen metabolic fitness as well as its adherence and invasion to human epithelial cells. This protein is also involved in interaction of the bacteria with host cells by binding to fibronectin. Moreover, Omp33-36 renders cytotoxicity to A. baumannii in addition to inducing apoptosis and modulation of autophagy. In the present study, an integrated strategy is launched to pierce into the 3D structure of Omp33-36 protein. The signal peptide within the sequence was determined, then, topology as well as secondary and tertiary structures of the protein were predicted. The mature protein assigned as a 14-stranded barrel in which residues 1–19 is removed as signal peptide. The obtained 3D models were evaluated in terms of quality; and then, served as queries to find similar protein structures. The hits were analyzed regarding topology among which 14-stranded were considered. The most qualified model was refined and then its sequence aligned to its counterpart similar structure protein (CymA from Klebsiella oxytoca). The determined structure of Omp33-36 could justify its porin function and carbapenem-resistance associated with the loss of this protein.     

Shear-induced nonisothermal crystallization of two grades of PLA

Shear-induced nonisothermal crystallization of two commercial polylactides (PLAs) differing in optical purity was studied. The molten polymers were sheared at selected temperatures (T_s) and subsequently cooled. The crystallization was followed by a light depolarization method, whereas the specimens were analysed ex-situ by DSC, 2D-WAXS and SEM after etching. It was found that the effect of shear, especially on the crystallinity developed during post-shearing cooling, intensified with a decrease of T_s from 160 to 146 ^°C, and with increasing shear rate and strain. Moreover, the effect of shear on PLA1.5 with d-lactide content of 1.5% was stronger than PLA2.8 with 2.8% of d-lactide, although maximum crystallinity of both polymers was practically the same. A decrease of cooling rate from 30 to 10 ^°C/min increased crystallinity of both PLAs, except for those shearing conditions which induced high crystallinity even during faster cooling. Although SEM examination revealed some row-nucleated forms, no significant crystal orientation was detected by 2D-WAXS, indicating that, under the experimental conditions, the shear induced predominantly point-like nuclei.     

Analyses of lepidopteran sex pheromones by mass spectrometry

Lepidoptera, including about 150,000 species in the world, comprise the second largest insect group, and sex pheromones have been identified from virgin female moths of more than 600 species. The chemical structures are simple, but diverse, because species-specific pheromones play an important role in the reproductive isolation of each species. The pheromone content in each female is quite low, and gas chromatography coupled to mass spectrometry (GC-MS) is most frequently utilized to reveal the chemical structure. Almost all pheromone components are straight-chain compounds and are classified into two major groups [i.e. unsaturated C₁₀-C₁₈ fatty alcohols and their derivatives (Type I) and C₁₇-C₂₃ polyenyl hydrocarbons and their epoxides (Type II)]. In addition to the unbranched compounds, some species secrete methyl-branched compounds (e.g., 2-ketones). For the identification of these compounds, determining the positions of the double bond, the epoxy ring, and the methyl group is an important key step. Copious spectral information measured by electron-impact ionization (70 eV) has been accumulated for these compounds. This review therefore deals with their spectral characteristics, namely, diagnostic ions, to apply them to pheromone studies on new target insects.     

Influence of crystal polymorphism on mechanical and barrier properties of poly(l-lactic acid)

The effect of crystal polymorphism on barrier and mechanical properties of PLLA is detailed in this contribution. PLLA films containing different amounts of α and α′ crystal forms were prepared by annealing quenched PLLA at different temperatures. The polymorphic structure of the films was analyzed by X-ray diffraction. Mechanical properties and permeability to water vapor were investigated as a function of degree of crystallinity (w_C) and related to crystal polymorphism developed during annealing. The polymorphic structure of PLLA significantly affects mechanical and barrier properties. The α crystal modification provides a better barrier to water vapor and a higher Young’s modulus, compared to films containing the α′ modification, but a lower elongation at break. The varied barrier and mechanical properties were correlated to the different packing of PLLA chains in the two analyzed polymorphs. The conformational disorder of the α′ form makes this structure a mesophase (condis crystal), with remarkable effects on material properties.