Model studies of trialkyltin–protein interactions: 13C NMR analysis of solution equilibria of the complex between trimethyltin and methyl N-benzoyl-l-leucyl-l-histidinate

¹³C NMR spectra for the 1:1 complex between methyl N-benzoyl-l-leucyl-l-histidinate and the trimethyltin moiety in d-chloroform (CDC1₃), d₄-methanol (CD₃OD) dimethyl sulphoxide (DMSO) and d₆-DMSO/H₂O solvents are reported, and contrasted with those for the free ligand. The spectra are interpreted in terms of a variety of solution equilibria illustrating the nature of the interaction between the trimethyltin species and primarily the imidazole ring of the histidine residue. Evidence for the preferential stability of pentacoordinate solution structures about tin is presented.     

Fluorous phase transfer catalysts: From onium salts to crown ethers

Fluorous quaternary ammonium and phosphonium salts, as well as fluorous macrocyclic ligands, such as crown and aza-crown ethers, have been gradually emerging as viable alternatives to classical phase transfer catalysts. The major results thus far obtained in this burgeoning field will be the focus of this review.     

Prediction of vapor–liquid and liquid–liquid equilibria for polymer systems: Comparison of activity coefficient models

A large number of equations of state and activity coefficient models capable of describing phase equilibria in polymer solutions are available today, but only a few of these models have been applied to different systems. It is therefore useful to investigate the performance of existing thermodynamic models for complex polymer solutions which have not yet been widely studied. The present work studies the application of several activity coefficient models [P.J. Flory, Principles of Polymer Chemistry, Cornell University Press, New York, NY, 1953; T. Oishi, J.M. Prausnitz, Estimation of solvent activities in polymer solutions using a group-contribution method, Ind. Eng. Chem. Process Design Dev. 17 (1978) 333; H.S. Elbro, A. Fredenslund, P. Rasmussen, A new simple equation for the prediction of solvent activities in polymer solutions, Macromolecules 23 (1990) 4707; G.M. Kontogeorgis, A. Fredenslund, D. Tassios, Simple activity coefficient model for the prediction of solvent activities in polymer solutions, Ind. Eng. Chem. Res. 32 (1993) 362; C. Chen, A segment-based local composition model for the Gibbs energy of polymer solutions, Fluid Phase Equilib. 83 (1993) 301; A. Vetere, Rules for predicting vapor–liquid equilibria of amorphous polymer solutions using a modified Flory–Huggins equation, Fluid Phase Equilib. 97 (1994) 43; C. Qian, S.J. Mumby, B.E. Eichinger, Phase diagrams of binary polymer solutions and blends, Macromolecules 24 (1991) 1655; Y.C. Bae, J.J. Shim, D.S. Soane, J.M. Prausnitz, Representation of vapor–liquid and liquid–liquid equilibria for binary systems containing polymers: applicability of an extended Flory–Huggins equation, J. Appl. Polym. Sci. 47 (1993) 1193; G. Bogdanic, J. Vidal, A segmental interaction model for liquid–liquid equilibrium calculations for polymer solutions, Fluid Phase Equilibria 173 (2000) 241] and activity coefficient from equations of state [F. Chen, A. Fredenslund, P. Rasmussen, Group-contribution Flory equation of state for vapor–liquid equilibria en mixtures with polymers, Ind. Eng. Chem. Res. 29 (1990) 875; M.S. High, R.P. Danner, Application of the group contribution lattice—fluids EOS to polymer solutions, AIChE J. 36 (1990) 1625]. The evaluation of these models was carried out both at infinite dilution and at finite concentrations and the results compared to experimental data. Furthermore, liquid–liquid equilibrium predictions for binary polymer solutions using six activity coefficient models are compared in this work. The parameters were estimated for all the models to achieve the best possible representation of the reported experimental equilibrium behavior.     

Spectroscopic Study of Acid-base Equilibria and Ion Pairing in Supercritical Methanol

Acid-base equilibria between 2,5-dichlorophenol (DCP) and various bases (LiOH, NaOH, and KOH) were studied in ambient to supercritical methanol, by measuring the absorption spectrum of DCP at alkali metal hydroxide molalities ranging up to 10 mmol⋅kg⁻¹, at temperatures up to 250 °C and a pressure of 25.0 MPa. The spectrum was deconvoluted into contributions for the acidic (HA) and basic (A⁻) forms of DCP, taking into account a blue shift of the phenolate (A⁻) spectrum due to the effect of ion pairing with an alkali metal cation. Degrees of dissociation of DCP determined from the spectra suggested that the dissociation constant of DCP has a maximum around 150 °C, whereas that of KOH decreases with temperature. The phenolate-alkali metal ion pairing was examined from the peak shift of the phenolate spectrum in the presence of Li⁺, Na⁺, and K⁺. A smaller cation radius and higher temperature (thus a lower dielectric constant for methanol) give rise to stronger electrostatic interaction in the ion pair. The basicities of the alkali metal hydroxides in supercritical methanol were compared using DCP as an indicator, and were shown to follow the order LiOH < NaOH ≤ KOH. This order is the same as that for the catalytic effect of alkali metal hydroxides on the methylation of phenol in supercritical methanol (Takebayashi et al.: Ind. Eng. Chem. Res. 47:704–709, 2008). Electronic Supplementary Material  The online version of this article () contains supplementary material, which is available to authorized users.     

Topological KKM theorems and generalized vector equilibria on G-convex spaces with applications

In the present paper, slightly modifying the topological KKM Theorem of Park and Kim (1996), we obtain a new existence theorem for generalized vector equilibrium problems related to an admissible multifunction. We work here under the general framework of G-convex space which does not have any linear structure. Also, we give applications to greatest element, fixed point and vector saddle point problems. The results presented in this paper extend and unify many results in the literature by relaxing the compactness, the closedness and the convexity conditions.

     

多相高分子体系中的粘弹相分离行为

相分离广泛存在于各种凝聚态物质中.根据局部浓度的变化形式,可将相分离分为固体模型(model B)和流体模型(model H),这两种模型适用于动力学对称的体系.近年来,Tanaka发现在一些动力学不对称的多组分高分子体系里存在一种新的相分离模式,其相分离过程分为动力学过程可用一个普适的粘弹模型来进行描述.动力学不对称可由体系中两组分间大的尺寸差异或玻璃化温度差异引起.本文介绍了多相高分子体系中产生粘弹相分离的原理及其基本特征,并讨论了模量、粘度、填料等因素对粘弹相分离动力学过程及多相体系微观结构的影响.     

Efficiency of Classical and Quantum Games Equilibria

Nash equilibria and correlated equilibria of classical and quantum games are investigated in the context of their Pareto efficiency. The examples of the prisoner’s dilemma, battle of the sexes and the game of chicken are studied. Correlated equilibria usually improve Nash equilibria of games but require a trusted correlation device susceptible to manipulation. The quantum extension of these games in the Eisert–Wilkens–Lewenstein formalism and the Frąckiewicz–Pykacz parameterization is analyzed. It is shown that the Nash equilibria of these games in quantum mixed Pauli strategies are closer to Pareto optimal results than their classical counter-parts. The relationship of mixed Pauli strategies equilibria and correlated equilibria is also studied.     

ChemInform Abstract: Study of Phase Transformation in BaTe2O6 by in situ High‐Pressure X‐Ray Diffraction,Raman Spectroscopy,and First‐Principles Calculations.

The title compound is synthesized by solid state reaction of a stoichiometric mixture of BaCO₃ and TeO₂ (air, 550 °C for 6 h, and 650 °C for 12 h).     

A thermodynamic consistency test for the binary constant-temperature VLE data using numerically optimized binary parameters

A thermodynamic consistency (TC) test for the constant-temperature VLE data was investigated by numerically optimizing the binary parameters of the activity coefficient equations to satisfy the Gibbs–Duhem (GD) equation. It was shown that the one parameter Margules equation can best satisfy the GD equation, even if significant experimental errors are involved. A thermodynamic consistency (TC) criterion was defined using the one parameter Margules equation. The TC criterion showed that, of the 37 alkane–alkane, 18 methanol–water and 44 ethanol–water binaries, 36, 16 and 1 binaries are reliable, respectively. Simple liquid mixtures meet the TC criterion.