A protein molecule in an aqueous mixed solvent: fluctuation theory outlook

In the present paper a procedure to calculate the properties of proteins in aqueous mixed solvents, particularly the excesses of the constituents of the mixed solvent near the protein molecule and the preferential binding parameters, is suggested. Expressions for the Kirkwood-Buff integrals in ternary mixtures and for the preferential binding parameter were derived and used to calculate various properties of infinitely dilute proteins in aqueous mixed solvents. The derived expressions and experimental information regarding the partial molar volumes and the preferential binding parameters were used to calculate the excesses (deficits) of water and cosolvent (in comparison with the bulk concentrations of protein-free mixed solvent) in the vicinity of ribonuclease A, ribonuclease T1, and lysozyme molecules. The calculations showed that water was in excess in the vicinity of ribonuclease A for water/glycerol and water/trehalose mixtures, and the cosolvent urea was in excess in the vicinity of ribonuclease T1 and lysozyme. The derivative of the activity coefficient of the protein with respect to the mole fraction of water was also calculated. This derivative was negative for the water/glycerol and water/trehalose mixed solvents and positive for the water/urea mixture. The mixture of lysozyme in the water/urea solvent is of particular interest, because the lysozyme at pH 7.0 is in its native state up to 9.3M urea, while at pH 2.0 it is denaturated between 2.5 and 5M and higher concentrations of urea. Our results demonstrated a striking similarity in the hydration of lysozyme at both pHs. It is worthwhile to note that the excesses of urea were only weakly composition dependent on both cases.     

Solvation of lithium chloride in aqueous and mixed solutions of an aprotic solvent

The dynamic hydration and solvation numbers of lithium chloride are estimated on the basis of experimental data on the limiting electrodialysis concentration of an electrolyte from aqueous and aqueousorganic solutions containing aprotic solvent N,N-dimethylacetamide. It is established that the dependence of the hydration numbers of the salt on the volume fraction of the aprotic solvent is of an extreme character, and its solvation number on N,N-dimethylacetamide does not depend on the composition of the mixed solution.     

Local composition in solvent + polymer or biopolymer systems

The focus of this paper is on the application of the Kirkwood-Buff (KB) fluctuation theory to the analysis of the local composition in systems composed of a low molecular weight solvent and a high molecular weight polymer or protein. A key quantity in the calculation of the local composition is the excess (or deficit) of any species i around a central molecule j in a binary mixture. A new expression derived by the authors (J. Phys. Chem. B 2006, 110, 12707) for the excess (deficit) is used in the present paper. First, the literature regarding the local composition in such systems is reviewed. It is shown that the frequently used Zimm cluster integral provides incorrect results because it is based on an incorrect expression for the excess (or deficit). In the present paper, our new expression is applied to solvent + macromolecule systems to predict the local composition around both a solvent and a macromolecule central molecule. Five systems (toluene + polystyrene, water + collagen, water + serum albumin, water + hydroxypropyl cellulose, and water + Pluronic P105) were selected for this purpose. The results revealed that for water + collagen and water + serum albumin mixtures, the solvent was in deficit around a central solvent molecule and that for the other three mixtures, the opposite was true. In contrast, the solvent was always in excess around the macromolecule for all mixtures investigated. In the dilute range of the solvent, the excesses are due mainly to the different solvent and macromolecule sizes. However, in the dilute range of the macromolecule, the intermolecular interactions between solvent and macromolecule are mainly responsible for the excess. The obtained results shed some light on protein hydration.     

Anion-exchange studies of metal thiocyanates in aqueous and mixed solvent systems

The anion-exchange behaviour of metal ions in aqueous NH(4)CNS and aqueous NH(4)CNS-organic solvent mixtures has been studied. The effect of the pH and the concentrations of thiocyanate and organic solvent on the distribution coefficients has been investigated. Fifteen binary metal ion separations are reported.     

Dispersion stability in mixed solvent (aqueous/organic) media

The dependence of critical coagulation concentrations and zeta potentials on composition for polystyrene latex particles in n-alkanol/water and urea/water mixtures are compared. Similar data from other authors are also reviewed.     

Free energy of binding of a small molecule to an amorphous polymer in a solvent

Crystallization is a commonly used purification process in industrial practice. It usually begins with heterogeneous nucleation on a foreign surface. The complicated mechanism of heterogeneous nucleation is not well understood, but we hypothesize that a possible correlation between binding affinity to a surface and nucleation enhancement might exist. Amorphous polymers have been used in controlling crystallization. However, to our knowledge, no attempt has been made to calculate the free energy of binding of a small molecule to an amorphous polymer in a solvent, and to characterize the binding sites/conformations of this system at a molecular level. We developed a two-step approach, first using Adsorption Locator to identify probable binding sites and molecular dynamics to screen for the best binding sites and then using the Blue-Moon Ensemble method to compute the free energy of binding. A system of ethylene glycol, polyvinyl alcohol (PVA), and heavy water (D(2)O) was used for validation, since experimental data exists on a related system. Looking at four independently constructed surfaces, we found that ethylene glycol binds to an indentation on the surface or in a hole beneath the surface. We focused on the indentation binding sites because they are easily accessible and do not have large free energy barriers. The closest system for which experimental data on binding energetics exists is ethylene glycol on PVA in aqueous solutions/gels, and the magnitudes of the free energy of binding to the three best indentation binding sites are close to the experimental value, 0.4-3.7 kcal/mol higher. Our approach offers a way to compute the free energy of binding and characterize the binding sites/conformations, and is general enough to apply to other small molecule/amorphous polymer/solvent systems.     

Effect of binary solvent composition on phenol extraction from aqueous solutions

Partition factors D between an apolar solvent-ketone or ketone-ketone binary mixture and water have been determined for a series of p-alkylphenols. The effects of the composition of a binary solvent and phenol hydrophobicity on the partition factor have been studied. Empirical relationships adequately describing the partition factor isotherms versus the mole fraction of the active component of the binary organic solvent have been found and discussed.     

Dielectric relaxation of a short molecule in a liquid-crystalline solvent

Abstract

Dielectric relaxation measurements of 5 mole % 4-n-hexyloxycyanobenzene (I) dissolved in 4-n-pentyloxyphenyl-trans-4-n-octylcyclohexylcarboxylate (II) were carried out from 1 kHz to 10 MHz in the nematic, smectic A and smectic B phases. The relaxation frequency of I parallel to the director is about 05 MHz in the S_Bphase and increases rapidly at the transition from S_B to S_A.     

Dielectric relaxation of a short molecule in a liquid-crystalline solvent

Dielectric relaxation measurements of 5 mole % 4-n-hexyloxycyanobenzene (I) dissolved in 4-n-pentyloxyphenyl-trans-4-n-octylcyclohexylcarboxylate (II) were carried out from 1 kHz to 10 MHz in the nematic, smectic A and smectic B phases. The relaxation frequency of I parallel to the director is about 05 MHz in the S_Bphase and increases rapidly at the transition from S_B to S_A.     

Electrochemistry of cytochrome C in aqueous and mixed solvent solutions: thermodynamics, kinetics, and the effect of solvent dielectric constant

The solvent dielectric constant is considered an important factor in determining the redox potential of the heme-containing protein cytochrome c in solution. In this study, we investigate the electrochemical response of cytochrome c in aqueous/organic solvent mixtures (100% aqueous buffer, 30% acetonitrile, 40% dimethyl sulfoxide, and 50% methanol), reporting the redox potential (E degrees'), enthalpy, and entropy of reduction. The temperature dependence of the solvent dielectric constant (epsilon) was also measured. The results show that epsilon alone cannot regulate the E degrees' of cytochrome c in mixed solvent systems. The implications of the temperature dependence of epsilon on the validity of the thermodynamic data are also discussed. The effect of solvent and temperature on the electron-transfer rate constant, k(s), was determined in each solvent mixture. A substantial increase in the activation energy for electron transfer was observed in 40% DMSO.     

Studies on the liquid junction potential corrections of electrolytes at aqueous + mixed solvent boundaries

Liquid junction potentials (E_J) generated at the boundaries of various salt bridge/mixed aqueous + organic solutions, have been determined by comparing the measured emf of silver cells with the calculated emf using literature values of transfer activity coefficients γ_t (Ag⁺) and γ_t (Cl⁻) based on the tetraphenylarsonium-tetraphenylborate (TATB) assumption.The E_J values have been analyzed in terms of the ion-solvent interaction, determined by ionic transfer Gibbs energies, and the so-called solvent-solvent interaction. The effect of varying the cation, anion, and concentration of bridge electrolyte, is assessed in aqueous acetonitrile (AN), ethanol (EtOH), and dimethylsulfoxide (DMSO). It is concluded that the previously reported solvent-solvent contribution to E_J is merely a correction factor to the ion-solvent interaction contribution due to solvent mixing at the boundary. Four salt bridges (sat. K₂SO₄ 3.5 M KCl, 3.5 M NaClO₄, and 0.1 M Et₄N-picrate) are compared on the basis of E_J.The recommended salt bridge for use with mixed aqueous + organic solutions is 3.5 M NaClO₄ in water. Appropriate E_J correction factors are presented for emf measurements in mixtures of AN + H₂O, EtOH + H₂O, and DMSO + H₂O.     

Hydrophobic effect for anionic dye - cationic surfactant interaction in aqueous and mixed solvent

Abstract

The interaction between anionic dyes [Reactive Orange 122 (R.O 122), Reactive Blue 19 (R.B 19), Reactive Violet 5 (R.V 5) and Acid Green 20 (A.G 20)] with cationic surfactant cetyltrimethylammoniun bromide (CTAB) has been investigated by spectrophotometry and conductance technique. The used dyes are characterized by tautomeric behavior which affects the mechanism of the interaction. Various parameters such as dye structure, surfactant composition, solvent composition, temperature and pH of the medium were studied. The spectral data were applied for calculating the binding constant between dye and surfactant (K_b), fraction of micellization (?_mic), and standard free energy change of binding (ΔG°_b) in 0,10,20 and 30 v/v % acetonitile (AN). Conductance technique was constructed to estimate the ion pairing constant (K_a) at different temperatures and v/v % AN. Thermodynamic parameters (ΔG°, ΔH° and ΔS°) for ion pair formation were evaluated. The role of hydrophobic and electrostatic effect on dye-surfactant interaction was discussed.     

Comparative study of titanium(IV)-based exchangers in aqueous and mixed solvent systems

The antimonate, arsenate, tungstate, molybdate and selenite of titanium have been synthesized. Their composition and chemical and thermal stability have been determined. Effects of pH and temperature on ion-exchange capacity have been studied. Titanium antimonate was found to be the most stable. The utility of these ion-exchangers for analytical separations was examined by determining the distribution coefficients for 26 metal ions in some aqueous, non-aqueous and mixed solvent systems. Quantitative separations of HgCd, PbCu and PbZn have been achieved on titanium tungstate columns, and LaBa mixtures have been separated on a titanium arsenate column.     

Anion-exchange in mixed solvent systems

A quantitative separation scheme for 15 radionuclides is presented. The scheme is based on group separation by means of anion-exchange resins using mixed solvent systems and subsequent separation of the groups into individual components by means of change of both eluting agent and resin type. The optimum working conditions for separation are established. Separation procedures are of good reproducibility and practically quantitative.     

Potential energy of the smoothed surface of a molecule in its interaction with a solvent

A procedure was developed for calculating the potential of the smoothed surface of a solute molecule in its interaction with the solvent. The potential map of the smoothed surface was calculated for a series of molecules, including those containing various heteroatoms. A method was suggested for calculating the averaged potential of the solute molecule surface, taking into account the dynamics of solvation. The total energy of interaction of a solute molecule with the surrounding solvent was estimated.     

溶剂气浮法分离水中的Zn离子的研究

以双硫腙为配体,溴化十六烷基三甲基铵（CTAB）为表面活性剂。对Zn离子在无机相中形成的Zn-双硫腙-CTAB体系的溶剂气浮进行了研究。研究表明表面活性剂与Zn离子的物质的量之比为5：1,约1h水中的锌离子去除率可达98％。0．5mol／L NaCl大大提高体系的溶剂气浮的去除率,溶剂气浮的速率随着气流速率的增加而增加,共存溶质乙醇存在会使去除率降低,有机溶剂的量对溶剂气浮影响较小,溶剂气浮过程遵从假一级动力学。考察了不同温度下溶剂气浮的回收速率,计算了该过程中的气浮表观活化能为9．037kJ／mol。     

Dependence of the enthalpies of formation of glycylglycinate complexes of nickel(II) on the composition of a mixed water-dimethylsulfoxide solvent

The heat effects of the complexation reactions of nickel(II) with a glycylglycinate ion in a water-dimethylsulfoxide solvent in a range of compositions of 0.00–0.60 molar parts of dimethylsulfoxide (DMSO) (an ionic strength of 0.1 was maintained using sodium perchlorate) were determined by means of calorimetry at 298.15 K. It is established that the exothermicity of complexation reactions rises by the first two steps and falls upon the addition of a third glycylglycinate anion with an increase in the concentration of DMSO. It is shown that the formation of mono- and bis-glycylglycinate complexes of nickel(II) in a water-DMSO solvent is determined mostly by the enthalpic contribution. It is concluded that the formation of tris-ligand complexes is more associated with the entropic contribution.     

Anion exchange in mixed solvent systems

The diffusion of chlorocomplexes of some corrosion and fission products in anion exchange beads has been studied in mixed solvent media. The effects of variables on the kinetics of the exchange process by the batch and flow technique were examined. The strongly basic anion exchanger Dowex 2X8 in its Cl⁻ form was used in organic solvent—water—hydrochloric acid solutions. The dependence of the exchange rate on temperature, the viscosity of the solution, the mean resin particle diameter and the composition of the solution was studied. Film and particle diffusion coefficients were calculated from the experimental data. The results provide valuable data for the design of separation procedures.     

Indole fluorescence in mixed solvent solutions

This work is a contribution to spectroscopic studies of indole in polar and non-polar solvents. Alcohols and paraffins have been used as solvents. Solutions have been prepared by two different methods: a) putting paraffin drops in alcoholic solutions of indole and b) adding alcohol to indole paraffin solutions. Results show that the height of the firs fluorescence maximum depends on the method through which solution was made. Solutions of the a) class show a more intense maximum than b) type at equal solvent concentration, This fact can be related with hydrogen bond formation between indole and alcohol molecules.     

SnCl2/TiCl3-mediated deoximation of oximes in an aqueous solvent

A simple procedure for SnCl(2)/TiCl(3)-mediated deoximation of ketoximes in an aqueous solvent is reported. Under the conditions developed in this effort, various ketones and aldehydes are produced in good to excellent yields.