Potentiometric studies on sodium dehydrocholate micelles

The scarcely studied sodium dehydrocholate-water system was investigated at low concentration by using H⁺-, Na⁺- and dehydrocholate-ion-selective electrodes. The findings at concentrations below the critical micelle concentration are consistent with those of previous work. A dimeric chelate structure entrapping Na⁺ ions at very low concentration is proposed. The composition of the micelles and the degree of ionisation were studied and explained as the result of the possibility of a back-to-face mechanism of aggregation of this steroid salt. This mechanism also explains the possibility of formation of acid soaplike aggregates at intermediate concentrations.     

The aggregation of sodium dehydrocholate in water

 We used a battery of different methods to study the association in aqueous sodium dehydrocholate (NaDHC) solutions. This salt associates by a stepwise mechanism. Below (9.6 ± 4.2) × 10⁻⁴ mol dm⁻³ there is a molecular solution with some strongly insoluble dehydrocholic acid produced by hydrolysis. Between (9.6 ± 4.2) × 10⁻⁴ and (5.2 ± 2.2) × 10⁻³ mol dm⁻³, an aggregate similar to acid soap (NaDHC.HDHC) appears and its amount and the aggregate's size increase with concentration. At =(2.20 ± 0.85) × 10⁻² mol dm⁻³ the aggregates formed have properties usually associated with true micelles, such as solubilisation of water-insoluble dyes. These aggregates increase in size with concentration and change their shape at 8 × 10⁻² mol dm⁻³, giving nonsymmetrical aggregates. The changes in the solution physicochemical properties at these concentrations may be misinterpreted and this explains the different values of the critical micelle concentration reported in the literature for substances with similar structure, such as bile salts. Received: 14 May 2001 Accepted: 10 August 2001     

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.     

The interaction of Co ions and sodium deoxycholate micelles

To mimic the interaction between divalent metal ions and bile slats in vivo, two groups of coordination complex compounds, crystalline and gel-like, were synthesized in vitro by mixing the aqueous solutions of CoCl₂ with sodium deoxycholate (NaDC) at various concentrations. Structures and compositions of the compounds were investigated using FT-IR, EXAFS, XRD as well as elemental and ICP analysis, respectively. Then the interaction of Co²⁺ with deoxycholate in solution was observed by laser light scattering (LLS), Transmission electronic microscope techniques and ICP analysis. Conclusions are (1) the crystalline complexes, Co (DC)₂·3H₂O were obtained by reaction of Co²⁺ with mono-molecules of NaDC, and the gel-like complexes, Na_nCo_m(DC)_n+2m formed by reaction of Co²⁺ with NaDC micelles. The gel-like complexes exhibit the non-stoichiometric character; (2) the coordination structures of carboxyl groups with Co²⁺ were different between the crystalline and gel-like complexes. In Co(DC)₂·3H₂O complex, the carboxyl groups of deoxycholate coordinated with Co²⁺ in chelating and pseudo-chelating modes, but that in bridge mode in the case of Na_nCo_m(DC)_n+2m complexes. The non-stoichiometric complexes of Na_nCo_m(DC)_n+2m are formed with a macromolecular structure through the Co²⁺ bridges; (3) NaDC can increase the solubility of Co(DC)₂·3H₂O in aqueous solution, and larger micelles (30-80 nm diameter) formed in the supernate. It is a mixed micelle formed by Co²⁺ ions bridges connecting with NaDC simple micelles. So these micelles are a new kind of micelle containing two kinds of metal ions; (4) these results are in agreement with those formed under physiological conditions in that the different states such as gel, precipitate, micelles of various structures are present in bile of gallbladder. An ideal model of the interaction between Co²⁺ and bile salts in vivo has been proposed.     

Structure of sodium alkyl sulfate micelles

Apparent and partial molar volumes of aggregated sodium octyl-, decyl-, dodecyl-, and tetradecyl sulfate molecules have been determined rigorously in terms of the pseudophase separation model. Mass density inside the micellar core—a basic thermodynamic parameter in the research of micelles by nuclear techniques—has been derived from the partial molar volumes.Micellar aggregation numbers of the same surfactants, obtained from small-angle neutron scattering [SANS] by systematically varying the surfactant concentration and solution temperature are published. A survey is given of the physical models and evaluation algorithms applied in SANS, together with a critical comparison of available experimental data published by various research teams.By utilizing a new least-squares fitting algorithm based on a microscopic diffusion model, the formation and annihilation parameters of ortho-positronium Co-Ps) in the micellar pseudophase and in the aqueous solvent, as well as the o-Ps diffusion coefficient in the solvent are deduced by evaluating conventionally measured positron lifetime spectra. From the pickoff annihilation rate of o-Ps in micelles the surface tension of the micellar core around the solubilization site of o-Ps is calculated. SANS results are utilized to determine the diffusion coefficient of o-Ps in normal and in 99.85% heavy water as a function of temperature. A definite isotopic effect in the two solvents can be seen from the results obtained for the diffusion coefficient and its activation energy. The Arrhenius plot of o-Ps diffusion coefficients indicates that o-Ps diffuses in both media without tunnelling.     

Site-specific hydration status of an amphipathic peptide in AOT reverse micelles

Reverse micelles formed by sodium bis(2-ethylhexyl) sulfosuccinate (AOT) in isooctane (IO) and water have long been used as a means to provide a confined aqueous environment for various applications. In particular, AOT reverse micelles have often been used as a template to mimic membrane-water interfaces. While earlier studies have shown that membrane-binding peptides can indeed be incorporated into the polar cavity of AOT reverse micelles where they mostly fold into an alpha-helical structure, the underlying interactions leading to the ordered conformation are however not well understood. Herein, we have used circular dichroism (CD) and infrared (IR) spectroscopies in conjunction with a local IR marker (i.e., the CN group of a non-natural amino acid, p-cyano-phenylalanine) and a global IR reporter (i.e., the amide I' band of the peptide backbone) to probe the conformation as well as the hydration status of an antimicrobial peptide, mastoparan x (MPx), in AOT reverse micelles of different water contents. Our results show that at, w0=6, MPx adopts an alpha-helical conformation with both the backbone and hydrophobic side chains mostly dehydrated, whereas its backbone becomes partially hydrated at w0=20. In addition, our results suggest that the amphipathic alpha-helix so formed orients itself in such a manner that its positively charged, lysine-rich, hydrophilic face points toward the negatively charged AOT head groups, while its hydrophobic face is directed toward the polar interior of the water pool. This picture is in marked contrast to that observed for the binding of MPx to phospholipid bilayers wherein the hydrophobic surface of the bound alpha-helix is buried deeper into the membrane interior.     

Temperature effect on formation of sodium cholate micelles

The micellization of sodium cholate (NaC) at 293.2, 298.2, 303.2, 308.2, and 313.2 K by cholate anion concentration was studied over the pH range from 6.0 to 7.2. Using a stepwise association model of cholate anions without bound sodium counterions, the aggregation number (nmacr;) of the cholate micelles was evaluated and found to increase with the total concentration, indicating that the stepwise association model is applicable. The nmacr; values go up and down with increasing temperature; 17 at 298.2 and 12 at 313.2 K and at 60 mM of the sodium cholate. The fluorescence of pyrene was measured in sodium cholate solution to determine the critical micelle concentration (CMC), indicating a narrow concentration range for CMC. A sodium-ion-specific electrode was used to determine a relatively low degree of counterion binding to micelles, supporting the validity of the present association model of cholate anions. The aggregation numbers evaluated at a constant ionic strength of 0.15 and at lower but variable ionic strengths were similar except for higher cholate concentrations.     

Separation and selectivity of benzophenones in micellar electrokinetic chromatography using sodium dodecyl sulfate micelles or sodium cholate modified mixed micelles

The separation and selectivity of nine benzophenones in micellar electrokinetic chromatography (MEKC) using sodium dodecyl sulfate (SDS) micelles or sodium cholate (SC) modified mixed micelles were investigated in the pH range 6.5-8.0. The results indicate that the combined effects of buffer pH and SC concentration can greatly affect the separation and selectivity of benzophenones, particularly for benzophenones possessing a hydroxyl substituent at the 4-position of the aromatic ring with respect to the carbonyl moiety when using SDS-SC mixed micelles. Better separability can be obtained with SDS-SC mixed micelles than with SDS micelles. Complete separation of nine benzophenones in MEKC can be achieved with an appropriate choice of buffer pH and the concentration of SDS micelles or SC modified mixed micelles. The dependence of the migration order of those benzophenones based on their structures and solute-micelle interactions is discussed.     

Microscopic hydration of the sodium chloride ion pair

Hydration of ion pairs is an essential process in various physicochemical phenomena occurring in solutions. Isolated clusters of an ion pair solvated with finite number of waters have been considered as a model system for the critical evaluation of microscopic interactions involved in the process, and theoretical studies have contributed exclusively to the subject up to now. Here we report the first experimental characterization of structure and internal dynamics of hydrated ion pairs, NaCl-(H2O)n (n = 1-3). The measurements of their rotational spectra have proven that the clusters have cyclic forms, in which Na+ and Cl- ions are strongly interacted with the O and H atoms of the solvent molecules, respectively. The Na-Cl distance shows a pronounced increase with the successive addition of water molecules. The separation for n = 3 approaches the value predicted for the contact ion-pair state in aqueous solution by recent molecular dynamics simulations.     

The interaction of isomeric hexanediols with sodium dodecyl sulfate and dodecyltrimethylammonium bromide micelles

The micelle formation process for a typical anionic surfactant, sodium dodecyl sulfate, and a typical cationic surfactant, dodecyltrimethylammonium bromide, has been investigated in a series of mixed solvents consisting of different concentrations of isomeric hexanediols (1,2-hexanediol and 1,6-hexanediol) in water. The critical micelle concentrations and the degrees of counterion dissociation of the mixed micelles were obtained from conductance experiments. Luminescence probing experiments have been used to determine the concentration of micelles in solution and, hence, the micellar aggregation numbers of the surfactants in the mixed solvent systems. The alcohol aggregation numbers were determined by combining the partition coefficients (obtained using NMR paramagnetic relaxation enhancement experiments) with the micellar concentrations from the luminescence probing experiments. All these results are interpreted in terms of the difference in the interaction of the isomeric hexanediols with the surfactant as a function of the position of the hydroxyl groups on the six-carbon chain of the alcohol. Received: 28 June 2000/Accepted: 5 July 2000     

Rheological properties of wormlike micelles in sodium oleate solution induced by sodium ion

Aqueous solutions of anionic surfactant, sodium oleate (NaOA), have been studied by means of steady-state shear rheology and dynamic oscillatory technique. The micellar structure can be changed upon the addition of NaCl, Na₂CO₃ and NaCl/NaOH while NaOA concentration is maintained at 0.060 M. These systems except NaOA/NaCl show high viscosity and strong viscoelasticity. The hydroxide ion is very important for the formation of wormlike micelles. The anions of salts also have effect on the rheological properties of wormlike micelles. Three parameters: intersection frequency ω_i, plateau modulus G₀ and relaxation time τ are also discussed. The Maxwell model and Cole-Cole plot are applied to investigate the dynamic viscoelasticity of wormlike micelles. Variation in surfactant packing parameter R_P can be used to explain the change of rheology and microstructure of the micelles.     

Structure, stability, and hydration of a polypeptide in AOT reverse micelles

In this communication, we provide theoretical evidence that the folded structure of a simple peptide, alanine zwitterionic octapeptide, or A8, unstable in solution, becomes stable in a reverse micelle (RM) of appropriate size. Our molecular dynamics simulations were carried out for realistic models of sodium 2-ethylhexylsulfosuccinate RM in isooctane, simulated for an extended period of time. For the RM of the smaller size, we find that a helical structure is stable for the whole length of the simulation. On the contrary, the peptide very quickly takes an extended structure in larger micelles.     

Diffusion of sodium dodecyl sulfate micelles in agarose gels

The gradient diffusion of ionic sodium dodecyl sulfate micelles in agarose gel was investigated at moderate concentrations above the CMC. Of particular interest were the effects of micelle, gel, and sodium chloride concentration on the micelle diffusivity. Holographic interferometry was used to measure the gradient diffusion coefficient at three sodium chloride concentrations (0, 0.03, 0.10 M), three gel concentrations (0, 1, 2 wt%), and several surfactant concentrations. Time-resolved fluorescence quenching was used to measure aggregation numbers both in solution and gel. The micelle diffusivity increased linearly with surfactant concentration at the two larger sodium chloride concentrations and all gel concentrations. In general, the strength of this effect increased with decreasing sodium chloride concentration and increased with gel concentration. This behavior is evidence of decreasing micelle-micelle electrostatic interactions with increasing sodium chloride concentrations, and increasing excluded volume effects and hydrodynamic screening with increasing gel concentration, respectively. The only exception was at 0.1M sodium chloride and 2 wt% agarose, which showed a slight reduction in the slope compared to 1 wt% agarose. It was found that the concentration effect is quite strong for charged solutes: at a NaCl concentration of 0.03 M in a 2% agarose gel, in a solution with 3% SDS micelles by volume, the micelle diffusion coefficient is doubled relative to its value in the same gel at infinite dilution. The extrapolated, infinite-dilution diffusion coefficients and the rate at which the micelle diffusivity increased with surfactant concentration were compared with predictions of previously published theories in which the micelles are treated as charged, colloidal spheres and the gel as a Brinkman medium. The experimental data and theoretical predictions were in good agreement.     

The role of hydration water in isothermal step annealing of neutron irradiated sodium nitroprusside

A kinetic study of isothermal step annealing of neutron-irradiated sodium nitroprusside has been performed. The influence of water and -irradiation on the behaviour of the compound is analyzed and compared with previous results obtained with the analogous compound Na₂/Fe/CN/₅NO/.2H₂O. It is possible to characterize two different fundamental processes that, in spite of occurring at two different temperatures, present the same activation energy than the hydrated system.     

Bilirubin conformational enantiomer selection in sodium deoxycholate chiral micelles

Intramolecularly hydrogen-bonded, bichromophoric tetrapyrrole pigments, bilirubin-IX and mesobilirubin-XIII, adopt either of two enantiomeric conformations which are in dynamic equilibrium in solution. InpH 8 aqueous sodium deoxycholate solutions, chiral micelles preferentially select one conformational enantiomer, and the solutions exhibit a bisignate circular dichroism Cotton effect in the vicinity of the bilirubin long wavelength electronic transition. Exciton coupling theory indicates a predominance of the left-handed (or negative) chirality bilirubin conformational enantiomer.     

Ionic quenching of naphthalene fluorescence in sodium dodecyl sulfate micelles

Micellar effects on luminescense of organic compounds or probes are well established, and here we show that quenching is highly favored in aqueous sodium dodecyl sulfate (SDS) micelles, which concentrate a naphthalene probe and cations of lanthanides, transition metals, and noble metals. Interactions have been studied by steady state and time-resolved fluorescence in examining the fluorescence suppression of naphthalene by metal ions in anionic SDS micelles. The quenching is collisional and correlated with the unit charge and the reduction potential of the metal ion. The rate constants, calculated in terms of local metal ion concentrations, are close to the diffusion control limit in the interior of SDS micelles, where the microscopic viscosity decreases the transfer rate, following the Stokes-Einstein relation.     

Characterisation of chlorophyll a solubilised in sodium lauryl sulphate micelles

Poisson statistics has been applied to the problem of solubilisation of chlorophyll a in sodium lauryl sulphate micelles. Dilution experiments have been carried out to support the finding that each unit of chlorophyll a contributing to the 740 nm band contains just one chlorophyll a molecule.     

Neutron scattering study of pentanol solubilization in sodium octanoate micelles

We extend a previous small-angle neutron scattering study of sodium octanoate (NaC₈) micelles to the ternary system sodium octanoate/pentanol/water. The use of contrast variation through selective deuteration of individual components together with explicit computation of interference effects, permits us to deduce the location of pentanol (C₅OH) in the micelles. Our main conclusion is that, although the micelles grow as (C₅OH) is solubilised, there is no concomitant variation in the NaC₈ aggregation number. At low alcohol concentrations, the C₅OH is located near the NaC₈ polar heads, while at higher concentration the -OH groups are distributed throughout the micellar core.     

Temperature effect on solubilization of n-alkylbenzenes into sodium cholate micelles

The solubilization of n-alkylbenzenes (benzene, toluene, ethylbenzene, n-propylbenzene, n-butylbenzene, n-pentylbenzene, n-hexylbenzene) into an aqueous micellar solution of sodium cholate was carried out. Solubilizate concentrations at equilibrium were determined spectrophotometrically at 293.2, 298.2, 303.2, 308.2, and 313.2 K. The first stepwise association constants (K(1)) between solubilizate monomers and vacant micelles were evaluated from the equilibrium concentrations and found to increase with increasing hydrophobicity of the solubilizate molecules. From the Gibbs energy change for solubilization at different micelle aggregation numbers and from the molecular structure of the solubilizates, the function of sodium cholate micelles as solubilizer was discussed. Enthalpy and entropy changes of solubilization were calculated from the temperature dependence of the K(1) values, and the solubilization was found to be enthalpy-driven for the solubilizates with shorter alkyl chains. The results obtained were also compared with those for conventional aliphatic micelles.