The influence of the ionic medium on the behaviour of sodium glycocholate and cholate aqueous solutions

In the framework of research on the sodium bile salts, solutions of sodium cholate and glycocholate had been studied only at three ionic medium concentrations. In this paper, experiments in two other concentrations of ionic medium are carried out both to verify the behaviour dependence on the ionic medium and to apply the results of this paper to a future investigation on solutions containing contemporary sodium cholate and glycocholate. To this aim, solubility, protonation constants, lead (II) salts solubility products at 25 degrees C and in 0.300 and 0.750 mol dm(-3) N(CH3)4Cl were determined. The formed species in solutions containing lead (II) together with the selected bile salts and the behaviour of the sodium salts in micellar and premicellar solutions were investigated, too. The obtained results were compared with those obtained at the other ionic medium concentrations.     

Properties of aqueous solution of sodium glycocholate and a nonionic surfactant,and their mixtures

The micellar properties of aqueous binary mixed solutions of sodium glycocholate, NaGC, and octa-oxyethylene glycol mono-n-decyl ether, C₁₀E₈, have been studied on the basis of surface tensions, the mean aggregation number and the polarity of the interior of the micelles. The mean aggregation number, measured by steady state quenching method, decreased with the increase of the mole fraction of NaGC in the mixed system. The polarity of the interior, estimated by the ratio of first and third vibronic peak in a monomeric pyrene fluorescence emission spectrum, suggested that the hydrophobicity of intramicelles increased with the increase of the mole fraction of NaGC in the mixed system. These are considered to be caused by the differences in the chemical structure and the hydrophobic nature between NaGC and C₁₀E₈. The mean aggregation number and the polarity of the interior for each micelle near the CMC in lower total concentration of surfactants showed the tendency approaching those of pure micelle of the nonionic surfactant. This suggests that the ratio of NaGC in the initial micelles in the range of lower total concentration near the CMC is lower than that of the corresponding prepared mole fraction in the mixed system. This lower value was confirmed also from theoretical calculation of the ratio of NaGC at the CMC in the mixed micelle by regular solution treatment of Rubingh in the solution.     

Free energy relationships in aqueous amino acid and peptide solutions containing sodium chloride

Three systems of the type amino acid or peptide-sodium chloride-water have been investigated over wide solute molality ranges using the isopiestic vapor pressure method. The amino acid employed was L--alanine, while the peptides were diglycine and triglycine. Equations were obtained for the activity coefficients of these compounds in the salt solutions in terms of the molalities of the solutes. The trace activity coefficients of the peptides were negative at low salt molality and became positive as the salt molality was increased. The limiting interaction parameters were calculated for the systems using the Kirkwood ion-dipole expression and empirical quantities derived from previous work to obtain the salt effect on the nonpolar and amide portion of the molecule. Good agreement was obtained between the calculated values and the experimental results in the case of diglycine, but they diverged in the case of triglycine. The calculated value for L--alanine is in poorer agreement with the experimental value than for the other amino acids studied previously.Presented in part at the Second International Conference on Calorimetry and Thermodynamics, Orono, Maine, July 1971.     

Dynamic light scattering and rheology studies of aqueous solutions of amphiphilic sodium maleate containing copolymers

Light scattering techniques, video particle‐tracking microrheology, and bulk rheology were employed to examine the structure and dynamics of a series of alternating sodium maleate copolymers with moderately hydrophobic comonomers (diisobutylene, styrene, and isobutylene) in aqueous solutions. The scaling dependence of the specific viscosity (η_sp) on the polyelectrolyte concentration (c) was studied with and without added salt; similar trends were found in both conventional rheology and particle‐tracking microrheology measurements, showing good performance of the technique with flexible polyelectrolytes. Furthermore, with dynamic light scattering performed in high added salt conditions, we examined the behavior of the amplitude of the fast mode, which is in agreement with scaling predictions. In contrast, the slow modes are not understood and display three separate behaviors for the wavevector q dependence of the decay rate (Γ), depending on the comonomer; superdiffusive (Γ ～ q^2.7, isobutylene) possibly because of sticky aggregates, wavevector independent (Γ ～ q⁰, styrene) most likely because of coupled polyion‐ion diffusion and diffusive (Γ ～ q^2.0, diisobutylene) presumably because these aggregates are not sticky. The hydrophobicity of the comonomer appears to switch the aggregation process between “open,” “closed,” and “non” association for isobutylene, diisobutylene, and styrene respectively. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 774–785, 2007     

Effective extractants for the extraction of lithium from aqueous solutions containing sodium and potassium compounds

The extraction power of newly obtained pure methoxy-1,3-diketones in diluents and in their mixtures with electron-donating additives during the extraction of lithium from aqueous solutions containing sodium and potassium was investigated. High separation factors were obtained; no appreciable amounts of sodium and potassium were found in the extract after total extraction of the lithium.Institute of Chemical Kinetics and Combustion, Siberian Branch, Russian Academy of Sciences, 630090 Novosibirsk. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 6, pp. 1304–1310, June, 1992.     

Structure of aqueous sodium perchlorate solutions

Salt solutions have been the object of study of many scientists through history, but one of the most important findings came along when the Hofmeister series were discovered. Their importance arises from the fact that they influence the relative solubility of proteins, and solubility is directly related to one of today's holy grails: protein folding. In this work we characterize one of the more-destabilizing salts in the series, sodium perchlorate, by studying it as an aqueous solution at various concentrations ranging from 0.08 to 1.60 mol/L. Molecular dynamics simulations at room temperature permitted a detailed study of the organization of solvent and cosolvent, in terms of its radial distribution functions, along with the study of the structure of hydrogen bonds in the ions' solvation shells. We found that the distribution functions have some variations in their shape as concentration changes, but the position of their peaks is mostly unaffected. Regarding water, the most salient fact is the noticeable (although small) change in the second hydration shell and even beyond, especially for g(O(w)***O(w)), showing that the locality of salt effects should not be restricted to considerations of only the first solvation shell. The perturbation of the second shell also appears in the study of the HB network, where the difference between the number of HBs around a water molecule and around the Na(+) cation gets much smaller as one goes from the first to the second solvation shell, yet the difference is not negligible. Nevertheless, the effect of the ions past their first hydration shell is not enough to make a noticeable change in the global HB network. The Kirkwood-Buff theory of liquids was applied to our system, in order to calculate the activity derivative of the cosolvent. This coefficient, along with a previously calculated preferential binding, allowed us to establish that if a folded AP peptide is immersed in the studied solution, becoming the solute, then increasing the salt concentration will make the helix more stable.     

Composition of sodium cholate micellar solutions

To study the composition of sodium cholate solutions, an investigation was carried out at 25 degrees C and in N(CH3)4Cl, as a constant ionic medium, at three different concentrations (W = 0.100; 0.500 and 0.800 mol dm(-3)). Electromotive force measurements of three different galvanic cells, the first involving a glass electrode for hydrogen ions, the second an electrode for sodium ions and the third a lead amalgam electrode, were performed. Independently, lead (II) cholate solubility measurements in the presence of sodium ions were performed, as well. The experimental results obtained from both approaches were explained by assuming the formation of aggregates in cholate and sodium of different composition depending on W and on the cholate concentration. The maximum aggregation found number for cholate was 24 and even aggregation numbers were markedly predominant. Only two species with odd aggregation number were found, but at a low percentage. The assumed species and the relative constants were compared with those found for the other sodium salt of cholanic acids.     

A potentiometric multisensor system for determining lysine in aqueous solutions containing potassium and sodium chloride

A potentiometric multisensor system has been developed for the determination of lysine in aqueous solutions containing sodium and potassium chlorides. The sensor array includes a cross-sensitive sensor, the response of which is the Donnan potential at the ion-exchange polymer/test solution interface, a set of ion-selective electrodes, and a silver-silver chloride reference electrode. Multidimensional regression analysis has been employed for the calculation of component concentrations. The relative error of determining lysine, potassium, and sodium did exceed 10% in the tested solutions.     

Aggregation of sodium dodecyl sulfate in aqueous sodium chloride solutions

Summary Aqueous solutions of sodium dodecyl sulfate with added sodium chloride (0–0.3 mol kg^–1) were studied at 298.2 K in order to calculate the molar standard free energy of micelle formationG _m . The following properties were measured: (i) aggregation number by membrane osmometry, (ii) counter-ion binding and sodium ion activities by electromotive force, (iii) critical micelle concentration by electromotive force and fluorescence spectrophotometry. The results indicate thatG _m . is independent of the NaCl concentration.     

Effect of bicarbonate ions on photodecomposition of sodium dodecyl sulfate in aqueous solutions containing hydrogen peroxide

Effect exerted by bicarbonate ions on decomposition of sodium dodecyl sulfate in the presence of hydrogen peroxide under the action of UV light was studied.     

Protolytic equilibria in aqueous sodium deoxycholate solutions

Protolytic equilibria taking place in aqueous solutions of sodium deoxycholate (DCNa) have been studied at 25°C using 0.5M NaCl as ionic medium. Electromotive force measurements of a galvanic cell were carried out by means of a glass electrode.The reagent necessary to change the acidity of the solutions was produced in situ by supplying a constant small current.Solubility and acid constant of deoxycholic acid (HDC) have been determined for the chosen experimental conditions. Experimental data obtained in less acid solutions have been explained by assuming the presence of the species H(DC)₂. The relative stability constant has been determined. At higher deoxycholate concentration the presence of a polymeric micellar species has been assumed.

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Protolytische Gleichgewichte in wäßrigen Natriumdesoxycholat-Lösungen

Zusammenfassung Die Protonierung von Natrium-Desoxycholat (DCNa) in wäßrigen Lösungen mit 0.5M NaCl wurde bei 25°C mit Hilfe von E.M.K. Messungen mit einer Glaselektrode untersucht.Das notwendige Reagens für die Umwandlung der Säure in den untersuchten Lösungen wurde in situ durch einen konstanten schwachen Strom erzeugt.Löslichkeit und Dissoziationkonstante von Desoxycholsäure (HDC) wurden unter den gewählten experimentellen Bedingungen bestimmt. Die experimentellen Daten in schwach sauren Lösungen konnten mit der Annahme der Existenz von H(DC)₂ erklärt werden. Die entsprechende Konstante wurde bestimmt. Zur Erklärung der Daten in stärker konzentrierten Lösungen von Desoxycholat ist die Annahme einer polynuklearen Spezies nötig.

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Symbols H analytical excess of hydrogenions, if negative it corresponds to OH^–; - h free concentration of hydrogen ions; - A total concentration of deoxycholate; - a free concentration of deoxycholate; - K _a acid constant of deoxycholic acid (HDC) defined as follows: [HDC]K _a =ha; - _q,p stability constant of a speciesH _p (DC) _q defined as follows: [H _p (DC) _q ]= _q,p h ^p a ^q ; - C ⁰ solubility of HDC; - formation function representing the average number of H⁺ bonded to deoxycholate.     

Evaporation studies on sodium dehydrocholate aqueous solutions

The evaporation through the air/solution interface of sodium dehydrocholate (NaDHC) aqueous solutions was studied by surface tension and microbalance measurements. The evaporation rate was related to the aggregation processes in the bulk, but not with the adsorption monolayer compactness. Except for very dilute solutions the air/solution interface was saturated by NaDHC molecules, giving rise to a strongly nonideal monolayer. At very low concentration, the adsorbed monolayer behaved as an ideal two-dimensional gas. The results were in agreement with previous research results.     

Low-concentration aqueous solutions of undecenoic acid and sodium undecenoate

The behaviors of low-concentration aqueous solutions of 10-undecenoic acid and its sodium salt were studied by several techniques. The acid does not have a critical micelle concentration, but gives an emulsion of very small droplets at (0.8–1) ×  10⁻⁴ mol dm⁻³. The emulsion was clearly visible by eye at 0.002 mol dm⁻³. The sodium salt has a stepwise aggregation process, giving premicellar aggregates at 0.023 ± 0.008 mol dm⁻³, which grow to form micelles at 0.117 ± 0.007 mol dm⁻³. The compositions of the solution and the micelles were also studied. Received: 25 February 1999 Accepted in revised form: 21 June 1999     

Heat capacities of aqueous solutions containing diethanolamine and N-methyldiethanolamine

In this work, we present new results for heat capacities of aqueous mixtures of diethanolamine with N-methyldiethanolamine over the temperature range (303.2 to 353.2) K with a differential scanning calorimeter. For mole fractions of water ranging from 0.2 to 0.8, 16 concentrations of the (DEA + MDEA + water) systems were investigated. For the binary system, (DEA + MDEA), heat capacities of nine concentrations were also measured. A Redlich–Kister-type equation for representing excess molar heat capacity was applied to correlate the measured C_p of aqueous alkanolamine solutions. For a total of 176 data points for the (DEA + MDEA + water) system, the overall average absolute percentage deviation of the calculations are 16.5% and 0.2% for the excess molar heat capacity and the molar heat capacity, respectively. The heat capacities presented in this study are, in general, of sufficient accuracy for most engineering-design calculations.     

Transport numbers of sodium polyacrylate in aqueous solutions

The moving boundary technique has been used to measure independently the transference numbers of macroion and counterions in water solutions of sodium polyacrylate at 25° and in the concentration range 0·050-0·8 eq/l. The experimental results allow us to compute, without any arbitrary assumption, the fraction of counterions which contribute to the transport of current towards the cathode and which may be called the “fraction of free ions”.     

Solubility of sodium soaps in aqueous salt solutions

The solubility of sodium soaps in dilute aqueous salt solutions has been systematically investigated by direct visual phase behavior observations. The added electrolytes, including simple inorganic salts and bulky organic salts, influence the solubility of sodium soaps in water, as represented by the varied soap Krafft point. Two inorganic salts, sodium chloride and sodium perchlorate, demonstrate a "salting-out" property. On the other hand, tetraalkylammonium bromides show an excellent ability to depress the soap Krafft point and enhance the soap solubility in water. With increasing the tetraalkylammonium ionic size, the degree of "salting-in" of soaps in water increases. However, solubility of pure tetraalkylammonium bromide in water decreases as the length of the alkyl chains increases. Furthermore, in the ternary water-tetrapentylammonium bromide (TPeAB)-sodium myristate (NaMy) system, we observed an upper cloud point phenomenon, which greatly shrinks the 1-phase micellar solution region in the phase diagram. This miscibility gap, together with the organic salt solubility limitation, restricts the use of tetraalkylammonium bromides with alkyl chains longer than 4 carbon atoms as effective soap solubility enhancement electrolytes. We also found that for sodium soap with a longer hydrocarbon chain, more tetrabutylammonium salt is required to reduce the soap Krafft point to room temperature.     

The unusual importance of activity coefficients for micelle solutions illustrated by an osmometry study of aqueous sodium decanoate and aqueous sodium decanoate + sodium chloride solutions

Freezing-point and vapor-pressure osmometry data are reported for aqueous sodium decanoate (NaD) solutions and aqueous NaD + NaCl solutions. The derived osmotic coefficients are analyzed with a mass-action model based on the micelle formation reaction qNa(+) + nD(-) = (Na(q)D(n))(q-n) and Guggenheim equations for the micelle and ionic activity coefficients. Stoichiometric activity coefficients of the NaD and NaCl components and the equilibrium constant for micelle formation are evaluated. Illustrating the remarkable but not widely appreciated nonideal behavior of ionic surfactant solutions, the micelle activity coefficient drops to astonishingly low values, below 10(-7) (relative to unity for ideal solutions). The activity coefficients of the Na(+) and D(-) ions, raised to large powers of q and n, reduce calculated extents of micelle formation by up to 15 orders of magnitude. Activity coefficients, frequently omitted from the Gibbs equation, are found to increase the calculated surface excess concentration of NaD by up to an order of magnitude. Inflection points in the extent of micelle formation, used to calculate critical micelle concentration (cmc) lowering caused by added salt, provide unexpected thermodynamic evidence for the elusive second cmc.