Apparent Molar Volumes of Multicharged Cations in Dimethyl Sulfoxide Solutions at 25°C

Densities for DMSO solutions of iron(III), aluminium(III), beryllium(II) and magnesium(II) perchlorates and silver nitrate are reported. Densities for DMSO solutions of tetraethylammonium perchlorate and nitrate and tetrabutylammonium perchlorate and tetraphenylborate are also presented. The partial molar volumes of the DMSO-solvated cations are derived and discussed in terms of variation with the charge number.     

The Gibbs Energies of Activation of Lysozyme for Viscous Flow in Water + Dimethyl Sulfoxide Solutions at 298.15 K

Gibbs energies of activation for viscous flow of binary water (1) + dimethyl sulfoxide (2) mixtures, Δμ ₁₂^○, and of lysozyme (3) in corresponding ternary mixtures, Δμ ₃^○, were determined at 298.15 K. The binary mixtures have a maximum in the value of the excess quantity for Δμ ₁₂^○ at a dimethyl sulfoxide mole fraction of x ₂≈0.31. The values of Δμ ₃^○ are larger than Δμ ₁₂^○ at all values of x ₂, even when normalized by their molar volumes, suggesting that the solvents interact more strongly with lysozyme than with themselves. The values of Δμ ₃^○ significantly increased in the range of x ₂=0.3 to 0.4 because of an increase in solvent-lysozyme interactions, which resulted from an increase in the accessible surface area of lysozyme that was exposed by its unfolding. The mean value obtained for Δμ ₃^○ per amino acid of lysozyme at x ₂=0.2 is greater than that for hydrophobic amino acids, indicating that the solvent interacts with hydrophilic amino acids more strongly than with hydrophobic ones.     

Diffusion Mechanism of As‐spun Polyacrylonitrile Fiber in a Dimethyl Sulfoxide‐Water Coagulation Bath

In this paper, the diffusion mechanism of as‐spun PAN fiber was investigated in dimethyl sulfoxide‐water by determining the dynamic compositions of the fibers and the diffusion coefficients of solvent and nonsolvent during coagulation. The diffusion process could be divided into two stages. Results showed that the first stage of the diffusion process was the most important during the whole process, which was fundamental to further study on the formation mechanism. Also, compared with wet spinning, the dry‐jet wet spinning method had the advantage of mild coagulating at a high jet‐stretch. At high concentrations, the diffusion coefficients increased and the ratio of solvent diffusion coefficient to nonsolvent diffusion coefficient decreased; an increasing temperature resulted in the increase of both diffusion coefficients with a decrease in their ratios. To some extent, for the PAN‐DMSO‐water system, the more the ratios D_s*/D_n* tended to 1, the more the cross‐section shapes of as‐spun PAN fiber tended to be circular.     

Dielectric Relaxation in Glycine–Water and Glycine–Ethanol–Water Solutions Using Time Domain Reflectometry

Dielectric relaxation measurements on water–ethanol–glycine ternary system were carried out using time domain reflectometry (TDR) at 25, 30, 35, and 40°C in the frequency range from 10 MHz to 10 GHz. Glycine–ethanol–water solutions are prepared with different concentrations of ethanol (0, 5, 10, 15, 20, and 30%) and also for different glycine molar concentrations (0, 0.2, 0.4, 0.6, 0.8, and 1 M). The dielectric relaxation parameters are measured for aqueous glycine solutions also to compare the results with those for the glycine–ethanol–water ternary system. For all the mixtures considered, only one relaxation peak was observed in this frequency range. All the mixtures display a Cole–Davidson dispersion. The relaxation peaks shift to lower frequency with an increase in glycine concentration and also with ethanol concentration. The logarithm of the relaxation time log() shows a nonlinear relation with glycine concentration which implies a change of relaxation mechanism with glycine concentration. The dielectric strength for these mixtures shows a nearly linear relation with glycine molar concentration.     

Solubility of Adenine and Kinetin in Water–Ethanol Solutions

We have measured the solubility of adenine and kinetin in water–ethanol solutions. Various models of cosolvency have been taken into account in the analysis of the experimental data. The results are interpreted in terms of hydrophobic interactions.     

Magnetic Circularly Polarized Luminescence in the Photoexcited States of Racemic [n]Helicenes (n=3–5,7) in Tetrahydrofuran and Dimethyl Sulfoxide Solutions

This paper reports the first magnetic circularly polarized luminescence (MCPL) characteristics of racemic helicenes, including four unsubstituted [n]helicenes (n=3,4,5,7) and two [4]helicene derivatives bearing methoxy substituents, in tetrahydrofuran (THF) and dimethyl sulfoxide (DMSO) solutions. The value of |g_MCPL| was calculated to be of the order of 10⁻³ T⁻¹ within 350–430 nm under the north-up (N-up) and south-up (S-up) Faraday geometries in an external magnetic field of 1.6 T. The [n]-dependent MCPL signs were altered by the N-up and S-up geometries.     

Nonelectrolyte Solvation in Aqueous Dimethyl Sulfoxide—A Calorimetric and Infrared Spectroscopic Study

We report enthalpies of solution of formamide, N,N-dimethylformamide,N,N-dimethylacetamide, acetic acid, methyl acetate, and acetonitrile in water +dimethylsulfoxide mixed solvents. These, along with literature data for additional solutes,are analyzed in terms of the extended coordination model of solvation. We alsoanalyze infrared data for several of these solutes. These analyses show thatN,N-dimethylformamide and N,N-dimethylacetamide are preferentially hydrated,while the other solutes appear to be preferentially solvated by dimethylsulfoxide.In all cases, the extent of preferential solvation is relatively small. It is also foundthat the degrees of preferential solvation recovered from analyses of the enthalpydata correspond closely to those recovered from the infrared data, although thelatter refer only to the polar chromophores on the solute molecules. It is foundthat the extent to which the solutes disrupt the solvent-solvent interactions variessystematically with the area of the nonpolar surfaces of the solute molecules.     

Conductance Determination of the Ion Association of Tris-(ethylenediamine)chromium(III) Chloride in Dimethyl Sulfoxide–Water Mixtures at Various Temperatures

The electrical conductances of tris-(ethylenediamine)chromium chloride, ([Cr(en)₃]Cl₃; en = ethylenediamine) were measured as functions of temperature and concentration in 20–80 wt% dimethyl sulfoxide (DMSO)–water mixtures. Conductance data were analyzed by the Kraus–Bray and Shedlovsky models. Also, density and viscosity values for 20–80 wt% DMSO–water mixtures have been determined experimentally at temperatures varying from (288.15 to 318.15) K. The limiting molar conductance, Λ ⁰, and the association constant, K _A, for ([Cr(en)₃]Cl₃ were computed by using Shedlovsky’s equation. The Λ ⁰ values decrease with increase in the percentage of DMSO in the mixed solvent. The K _A values increase with increasing temperature and increasing percentage of DMSO in the mixed solvent at all temperatures. This may be attributed to the increase in association constant with the decrease in the relative permittivity of the mixed solvent. Thermodynamic parameters (Gibbs energy, enthalpy and entropy changes) were determined from the temperature dependence of K _A for ([Cr(en)₃]Cl₃. The results of the study have been interpreted in terms of ion–solvent interactions and solvent properties.     

Potentiometric Studies on Some α-Amino Acid-Schiff Bases and Their Manganese(III) Complexes in Dimethyl Sulfoxide–Water Mixtures at 25°C

In this study the stoichiometric protonation constants were determined for some -amino acids (glycine, L-alanine, L-methionine, L-phenylalanine, and L-threonine), the Schiff bases derived from them and 2-hydroxy-1-naphthaldehyde, along with the stoichiometric stability constants of Schiff base–Mn(III) complexes. These equilibrium constants were determined potentiometrically using a combined pH electrode system calibrated in concentration units of the hydrogen ion at 25°C, and at an ionic strength of 0.10 mol-dm^–3 NaCl in 30 and 50% dimethyl sulfoxide–water mixtures. The calculations of these constants were carried out using the PKAS and the BEST computer programs. In addition, the effects of solvent composition and structures on the protonation and the complex formation constants were investigated. The mole ratio of Mn(III) to amino acid-Schiff bases was also determined and it was found that the complexes were of the MnL₂ type.     

Structural Inhomogeneity in Electrolyte Solutions: The Calcium Perchlorate–Water System

A new approach has been proposed to study the structure of aqueous electrolyte solutions. NIR, Raman and attenuated total reflectance, Fourier transform infra-red (ATR FTIR) spectra have been measured for aqueous calcium perchlorate solutions in the 0.22–4.3 mol·L^?1 (0.22–7.46 mol·kg^?1) concentration range at 25 °C. By the methods of principal component analysis (PCA) and multivariate curve resolution—alternating least squares (MCR-ALS) the number, spectra and concentration profiles have been determined for spectroscopically distinguishable forms of water and ClO ₄ ^? ion in solutions. The results have been analyzed using a phenomenological model, establishing thereby: concentration ranges for structural rearrangements of the solution, the nature of structural microirregularities and different states of the ClO ₄ ^? ion in the areas of domination of the natural water structure, and of cybotactic groups of calcium perchlorate hexa and tetra hydrates.     

Stability Constants of Copper(II) Glycylglycinate Complexes in Water–Dimethylsulfoxide Solutions

Russian Journal of Physical Chemistry A - Stability constants of normal and copper(II) bis-glycylglycinate complexes in water–dimethylsulfoxide solutions of variable composition are...     

Ion–Water Cooperative Interactions in Aqueous Solutions of MgCl2 by Dielectric Spectroscopy

The dielectric constant of aqueous MgCl₂ solution has been determined in the frequency range 0.2 MHz to 20 GHz at 298 K using the dielectric relaxation spectroscopy method. The behavior is well described according to four Cole-Cole terms whose evolution with composition is analyzed. The static dielectric constant and relaxation times decreases with the increasing aqueous MgCl₂ solution concentrations. Only one H-bonded water cluster with the aqueous MgCl₂ solution relaxes is reported during the cutoff relaxation time. A distinct ion–water cooperative interaction is observed, and water molecules perturbed by ion contribution on dielectric constant beyond the first hydration shell are obtained.     

Influence of Excitation of the Lanthanide 4 fShell on Complexation with Organic Substrates in Solutions: 2. Isotope Effects in Complexation of Tris(heptafluorodimethyloctanedionato)europium(III) with Dimethyl Sulfoxide in Benzene Solutions

The effect of deuteration of dimethyl sulfoxide on the fluorescence quantum yield, temperature quenching of fluorescence, and its complexation with tris(heptafluorodimethyloctanedionato)europium(III) (Eu(fod)₃) in the ground and excited states was studied. It was found that excitation of f–ftransitions in Eu(III) increases the stability of Eu(fod)₃complexes with sulfoxides but has a very insignificantly influence on isotope effects. The deuterium effect is displayed to a small extent in altering the quantum yield and is accompanied by a decrease in the efficiency of temperature quenching of Eu(fod)^* ₃fluorescence.     

Effect of the Composition of the Water–Dimethyl Sulfoxide Solvent on the Thermodynamics of the Formation of the [Ag(18-Crown-6)]+Complex

The effect of a water–dimethyl sulfoxide solvent (X _DMSO= 0–0.97, where X _DMSOis the mole fraction of DMSO) on the thermodynamics of complexation between Ag⁺and 18-crown-6 and the solvation of all reagents involved in this equilibrium were studied. In aqueous solutions, the complex is stable mainly because of the enthalpy contribution to _r G°. For X _DMSO> 0.3, the contributions from entropy and enthalpy become comparable in magnitude, but they are opposite in sign. In the binary solvent, the complex is most stable at X _DMSO= 0.2 to 0.3. Analysis of the enthalpy characteristics of reagent solvation showed that this solvent effect was due to the superposition of two opposite solvation contributions occurring with an increase in the DMSO concentration in the binary solvent, namely, the destabilization of the ligand solvate sphere and the formation of stable Ag⁺complexes with DMSO.     

Dimethyl Sulfoxide: A Bio-Friendly or Bio-Hazard Chemical? The Effect of DMSO in Human Fibroblast-like Synoviocytes

The effect of dimethyl sulfoxide (DMSO) in rheumatoid arthritis (RA) human fibroblast-like synoviocytes (FLSs) has been studied on five different samples harvested from the joints (fingers, hands and pelvis) of five women with RA. At high concentrations (>5%), the presence of DMSO induces the cleavage of caspase-3 and PARP-1, two phenomena associated with the cell death mechanism. Even at a 0.5% concentration of DMSO, MTT assays show a strong toxicity after 24 h exposure (≈25% cell death). Therefore, to ensure a minimum impact of DMSO on RA FLSs, our study shows that the concentration of DMSO has to be below 0.05% to be considered safe.     

Dielectric Studies of Glycine–Ethylene Glycol–Water Solutions Using Time Domain Reflectometry

Time domain reflectometry (TDR) has been used for dielectric relaxation measurements on the glycine–ethylene glycol–water ternary system (TDR) at 25, 30, 35, and 40°C in the frequency range from 10 MHz to 10 GHz. Glycine–ethylene glycol–water solutions are prepared with different concentrations of ethylene glycol (0, 5, 10, 15, 20, and 30%) and also for different glycine molar concentrations (0, 0.2, 0.4, 0.6, 0.8, and 1 M). The dielectric relaxation parameters are measured for aqueous glycine solutions also to compare the results with those for the glycine–ethylene glycol–water ternary system. For all the solutions considered, only one relaxation peak was observed in this frequency range. The complex permittivity spectra for the aqueous glycine solutions can be well described by the Cole–Davidson expression, whereas that for the ternary system can be well described by the Havriliak–Negami expression. The logarithm of the relaxation time log() shows a nonlinear relation with the glycine molar concentration that implies a change in the relaxation mechanism with glycine concentration. The dielectric strength increases with an increase in glycine molar concentration, whereas it decreases with an increase in ethylene glycol concentration.     

Is “Water in Salt” Electrolytes the Ultimate Solution? Achieving High Stability of Organic Anodes in Diluted Electrolyte Solutions Via a Wise Anions Selection

The introduction of the water-in-salt (WIS) electrolytes concept to prevent water splitting and widen the electrochemical stability window, has spurred extensive research efforts toward development of improved aqueous batteries. The successful implementation of these electrolyte solutions in many electrochemical systems shifts the focus from diluted to WIS electrolyte solutions. Considering the high costs and the tendency of these nearly saturated solutions to crystallize, this trend can be carefully re-evaluated. Herein we show that the stability of organic electrodes comprising the active material perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA), is strongly influenced by the solvation character of the anions rather than the concentration of the electrolyte solution. Even though the charging process of PTCDA involves solely insertion of cations (i.e., principal counter-ions), surprisingly, the dominant factor influencing its electrochemical performance, including long-term electrode stability, is the type of the co-ions (i.e., electrolytic anions). Using systematic electrochemical analysis combined with theoretical simulations, we show that the selection of kosmotropic anions results in fast fading of the PTCDA anodes, while a selection of chaotropic anions leads to excellent stability, even at electrolytes concentrations as low as 0.2 M. These findings provide a new conceptual approach for designing advanced electrolyte solutions for aqueous batteries.