A comparison between electrokinetic capillary chromatography and absorption spectroscopy for the analysis of peptide-micelle association by weak hydrophobic interactions

Micellar electrokinetic capillary chromatography (MEKC) was compared to absorption spectroscopy to estimate equilibrium association constans (K(as)) for peptide-micelle systems involving three peptides (leucine-enkephalin, methionine-enkephalin and leucine-phenylalanine (LF)) and two surfactant micelles (sodium dodecyl sulfate (SDS) and cetyltrimethylammonium bromide (CTAB)). Buffer pH was chosen to minimize purely electrostatic interactions between peptides and micelles that could not be interrogated by absorption spectroscopy. Viscosity-corrected MEKC mobilities gave reasonably similar estimates of K(as) between the two methods for all three peptide-SDS micelle systems, with K(as) values ranging from 13.7 +/- 0.3 to 49 +/- 1 M(-1). For CTAB, estimates of K(as) for LF-CTAB micelle association were of the same order of magnitude as the SDS micelle by the two methods of estimation. On the other hand, enkephalin-CTAB micelle binding was about 10 times stronger (K(as) = 122 +/- 3 M(-1) to 311 +/- 9 M(-1)) than the enkephalin-SDS micelle binding. In addition, MEKC underestimated the K(as) values relative to spectroscopy by a factor of 2-3 for the enkephalin-CTAB system.     

Study of valsartan interaction with micelles as a model system for biomembranes

In this study, the interaction of valsartan (VAL), an angiotensin II receptor antagonist, with cationic surfactant cetyltrimethylammonium bromide (CTAB) was investigated. The effect of cationic micelles on spectroscopic and acid-base properties of VAL was carried out using UV spectrophotometry at physiological conditions (pH 7.4). The binding of VAL to CTAB micelles implied a shift in drug acidity constant (pK(a)(water)-pK(a)(micelle)=1.69) proving the great affinity of VAL dianion for the positively charged CTAB micelle surface. To quantify the degree of VAL/CTAB interaction, two constants were calculated by using mathematical models: micelle/water partition coefficient (K(x)) and drug/micelle binding constant (K(b)). The decrease of K(x) with VAL concentration, obtained by using pseudo-phase model, is consistent with an adsorption-like phenomenon. From the dependence of differential absorbance at lambda=295 nm on CTAB concentration, by using mathematical model that treats the solubilization of VAL dianion as its binding to specific sites in the micelles (Langmuir adsorption isotherm), the binding constant (K(b)=(2.50+/-0.49)x10(4)M(-1)) was obtained. Binding constant VAL/CTAB was also calculated using micellar liquid chromatography (MLC).     

Micelle formation of Tyr-Phe dipeptide and Val-Tyr-Val tripeptide in aqueous solution and their influence on the aggregation of SDS and PEO-PPO-PEO copolymer micelles

The aggregation properties of Tyr-Phe dipeptide and Val-Tyr-Val tripeptide were studied in aqueous solution and in the presence of SDS and SDS-polymer environments using UV-visible, surface tension, fluorescence and circular dichroism (CD) techniques. Both the peptides formed micelles. The cmc values obtained for dipeptide and tripeptide are 2×10(-5) and 4×10(-5) M, respectively in aqueous solution at 25°C. The presence of additives (SDS and polymer) hindered the micelle formation of peptides. The cmc values obtained by various methods are in good agreement with each other. Effect of peptides on the aggregation properties of SDS also was investigated. The cmc of SDS was decreased in presence of peptides and were reduced with increase in temperature. Using monophasic micellization concept, the association constant (K(A)) for the SDS-peptide mixed micellar systems was determined. Using biphasic model, the thermodynamic parameters viz; ΔG°(m), ΔH°(m) and ΔS°(m) for SDS-water and SDS-peptide-water mixed micellar systems, the standard free energy for transfer of SDS from aqueous to peptide additive environments were estimated at various temperatures. These results suggest that the SDS is more stable in micellized form in the SDS-water-peptide ternary systems compared to the situation in the corresponding SDS-water binary systems.     

The electrical double layer of micelles in ionic surfactant solutions in the presence of a background electrolyte: 1. Diluted micellar solutions of sodium dodecyl sulfate

The structure of the electrical double layer (EDL) of micelles in dilute micellar solutions in the presence of a background electrolyte is studied within the framework of the Gouy-Chapman-Stern theory. On the basis of the Stern isotherm for counterion adsorption, conditions of electroneutrality, and the Gauss condition at the interface between the diffuse and dense parts of EDL, three equations are derived for the electrostatic potentials of the surface of micelle cores and the diffuse part of EDL as well as for the potential of the specific adsorption of counterions. Model parameters are verified by the example of sodium dodecyl sulfate (SDS). Potentials of the diffuse part of EDL, the degree of binding of counterions with micelles, and the specific adsorption potential are calculated from the experimental data on the potential of the surface of SDS micelle cores and their sizes, critical micellization concentration, aggregation numbers, and the constants of premicellar association. The specific adsorption potential of SDS is found to be ?(4.6 ± 0.1)?, where ? is the product of Boltzmann’s constant and absolute temperature. The specific adsorption potential is independent of the background electrolyte concentration, remains constant within the determination error of the parameters, and substantially contributes to the formation of EDL of micelles.     

Reactions within association complexes: the reaction of imidazole with substituted phenyl acetates in the presence of detergents in aqueous solution

The bimolecular rate constants for reaction of imidazole with phenyl acetates complexed with sodium dodecyl sulfate (SDS) or cetyltrimethylammonium bromide (CTAB) micelles obey Bronsted equations with beta 1g similar to that of the reaction in aqueous solution. The dissociation constants of ester (Ks) and the hypothetical dissociation constant (KTS) of the transition state of the micelle complexes obey Hansch equations with similar sensitivities (p) to pi (-0.66 and -0.589 for KS and -0.735 and -0.495 for KTS, respectively). The slopes also indicate that the microsolvation environments associated with the transition state and the complexed ester have aqueous character. The relative values of KTS and KS indicate that the transition state of the reaction of imidazole with ester is more weakly complexed to both micelles than is the reactant ester. Log KTS values are linear functions of log KS for reactions with both CTAB and SDS; the slopes are, respectively, -0.893 and -1.19 consistent with a slightly more "water-like" medium for the transition state than for the site of binding of ester with CTAB-micelle and slightly less for the SDS-micelle. The results for ester and transition state are consistent with the location of the phenyl residue in a hydrophobic region that possesses water molecules. It is concluded that the acetyl group in the complexed transition state is located in an aqueous part of the Stern region, whereas the phenyl residue is in a part of the Stern region that possesses alkane components. The derived kinetic and complexation parameters in these experiments refer to micelles with Stern regions that have been maintained at constant ionic compositions.     

Interaction of UO2 2+ with sodium dodecyl sulfate micelles: association of phenols to micelles through fluorescence quenching data

Time-resolved laser-induced fluorescence (TRLIF) has been used to study the interaction of uranyl ion with sodium dodecyl sulfate (SDS) micelles in H(3)PO(4) 1 M. The titration curve consists of two curved regions with different slopes, one of them more pronounced at low concentration of SDS and the other, with a less pronounced positive slope at larger [SDS] until a plateau is reached. The fluorescence quenching of uranyl ion by para-substituted phenol compounds was studied by TRLIF and steady-state emission intensity measurements. The results were interpreted in terms of binding of phenolic compounds to the micelle. The binding constant (K(Q)) as well as the entrance and exit rate constants were determined for all the quenchers used.     

Geminate proton recombination at the surface of SDS and CTAC micelles probed with a micelle-anchored anthocyanin

The functionalized flavylium salt 6-hexyl-7-hydroxy-4-methyflavylium chloride (HHMF) was employed to probe some of the fundamental features of proton transfer reactions at the surface of anionic sodium dodecyl sulfate (SDS) and cationic hexadecyltrimethylammonium chloride (CTAC) micelles. In contrast to most ordinary flavylium salts, HHMF is insoluble in water, but readily incorporates into SDS and CTAC micelles. In the ground state, the rate constant for deprotonation of the acid form (AH+) of HHMF decreases 100-fold upon going from CTAC (kd = 3.0 x 10(6) s(-1)) to SDS (kd = 1.4 x 10(4) s(-1)), consistent with the presence of an activation barrier for proton transfer in the ground state and reflecting, respectively, stabilization or destabilization of the AH+ cation by the micelle. Reprotonation of A is diffusion-controlled in both micelles (kp(SDS) = (2.1 x 10(11))[H+]aq s(-1) and kp(CTAC) = (3.7 x 10(8))[H+]aq s(-1)), the difference reflecting the rate of proton entry into the micelles. In the excited singlet state, the rate constants for deprotonation of the AH+* form of HHMF are similar in the two micelles (2.4 x 10(10) s(-1)), consistent with activationless proton transfer. Reprotonation of the excited A is dominated by fast geminate recombination of the photogenerated (A*-H+) pair at the micelle surface (k(rec)(SDS) = 6.1 x 10(9) s(-1) and k(rec)(CTAC) = 3.4 x 10(10) s(-1)) and the net efficiencies of geminate recombination are quite similar in SDS (0.89) and CTAC (0.86).     

Micellar effects on dediazoniation and on azo coupling reactions

The effects of a sodium dodecyl sulfate, SDS, micellar solution on the coupling rates of two arenediazonium ions, ArN(2)(+), with the hydrophobic 1-naphthylamine, 1NA and N-(1-naphthyl) ethylenediamine, NED, coupling agents and with the hydrophilic Na salt of 2-naphthol-6-sulfonic acid, 2N6S, have been studied. First, we explored the micellar effects on the thermal decomposition of the arenediazonium ions. The observed rate constants are slightly depressed or increased, depending on the nature of ArN(2)(+), compared to those in pure water upon increasing [SDS]. Estimations of the corresponding association constant to the micelle indicate that a significant fraction of the arenediazonium ions are incorporated into the micelles even at low surfactant concentrations. The sulfonate group in 2N6S prevents its incorporation into the micellar aggregate due to the electrostatic barrier imposed by the micelles and, in consequence, the coupling reaction is inhibited. In contrast, when employing the naphthylamine derivatives, the observed rate constant increase rapidly up to a maximum at [SDS]相似文献   

Interaction of a tripeptide with cesium perfluorooctanoate micelles

The interaction of alanyl-phenylalanyl-alanine (Ala-Phe-Ala) with the micelles formed by cesium perfluorooctanoate (CsPFO) in water was studied in the isotropic phase by means of 1H NMR and by molecular dynamics (MD) simulations. Information on the location of the peptide was experimentally obtained from selective variations in Ala-Phe-Ala chemical shifts and from differential line broadening in the presence of the paramagnetic ion Mn2+. The peptide-micelle association constant was estimated analyzing the chemical shift variations of the most sensitive Ala-Phe-Ala resonances with the peptide concentration. MD simulations of Ala-Phe-Ala in the micellar environment confirmed the experimental observations, identifying the hydrogen bonding interactions of the different peptide moieties with the micelle, yielding a binding constant close to the experimental one. NOESY experiments suggest that the peptide in the micellar environment does not adopt a preferred conformation but is mainly unstructured. Details on the conformational behavior of the peptide in the micellar solution observed through MD were consistent with a different conformational equilibrium in the proximity of the micelle. Information on Ala-Phe-Ala dynamics was obtained from 1H T1 data and compared to MD simulation results on the overall tumbling motion.     

Diffusion of alpha-tocopherol in membrane models: probing the kinetics of vitamin E antioxidant action by fluorescence in real time

The new fluorescent membrane probe Fluorazophore-L, a lipophilic derivative of the azoalkane 2,3-diazabicyclo[2.2.2]oct-2-ene, is employed to study the quenching of alpha-tocopherol (alpha-Toc) by time-resolved fluorescence in the microheterogeneous environments of Triton XR-100 and SDS micelles, as well as POPC liposomes. Fluorazophore-L has a small nonaromatic fluorescent polar headgroup and an exceedingly long-lived fluorescence (e.g., 140 ns in aerated SDS micelles), which is efficiently quenched by alpha-Toc (3.9 x 10(9) M(-1) s(-1) in benzene). Based on solvatochromic effects and the accessibility by water-soluble quenchers, the reactive headgroup of Fluorazophore-L, along with the chromanol group of alpha-Toc, resides at the water-lipid interface, which allows for a diffusion-controlled quenching in the lipidic environments. The quenching experiments represent an immobile or stationary case; that is, interparticle probe or quencher exchange during the excited-state lifetime is insignificant. Different quenching models are used to characterize the dynamics and antioxidant action of alpha-Toc in terms of diffusion coefficients or, where applicable, rate constants. The ideal micellar quenching model is suitable to describe the fluorescence quenching in SDS micelles and affords a pseudo-unimolecular quenching rate constant of 2.4 (+/- 0.4) x 10(7) s(-1) for a single quencher per micelle along with a mean aggregation number of 63 +/- 3. In Triton micelles as well as in unilamellar POPC liposomes, a two-dimensional (lateral) diffusion model is most appropriate. The mutual lateral diffusion coefficient D(L) for alpha-Toc and Fluorazophore-L in POPC liposomes is found to be 1.8 (+/- 0.1) x 10(-7) cm(2) s(-1), about a factor of 2 larger than for mutual diffusion of POPC, but more than 1 order of magnitude lower than a previously reported value. The comparison of the different environments suggests a quenching efficiency in the order benzene > SDS micelles > Triton micelles > POPC liposomes, in line with expectations from microviscosity. The kinetic measurements provide important benchmark values for the modeling of oxidative stress in membranes and other lipidic assemblies. The special case of small lipidic assemblies (SDS micelles), for which the net antioxidant efficacy of alpha-Toc may be lower than expected on the grounds of its diffusional behavior, is discussed.     

Quantitating the association of charged molecules with ionic micelles

We have studied micelles comprised of cationic (CTAB) and anionic (SDS) surfactants through the interactions of solution phase anionic disodium fluorescein (DSF) and cationic rhodamine 110 (R110) dyes with perylene sequestered within the micelles. Fluorescence lifetime measurements monitor energy transfer between the nonpolar optical donor within the micelle and ionic probes in the surrounding solution. The efficiency of this process is mediated by the extent to which the ionic dyes interact with the micelle palisade layer, and our fluorescence lifetime data allow us to determine the association constants for acceptor-micelle interactions.     

Gallium(III)/4-(2-pyridylazo)resorcinol system in water and SDS solution: kinetics and thermodynamics

The equilibria and kinetics of the complex formation and dissociation reaction between gallium(III) and PAR [4-(2-pyridylazo)resorcinol] have been investigated in water and in the presence of SDS micelles. The reactive form of Ga(III) is GaOH2+ in both cases. The addition of SDS results in an increase of both the binding affinity and velocity, the maximum accelerating effect being observed just above the cmc value of SDS that, under the conditions of the experiments, is 5.6 x 10-3 M. At pH = 3.2, the maximum value of the equilibrium constant ratio Kapp(SDS)/Kapp(H2O) is 27.4, whereas that of the binding rate constants kf(SDS)/kf(H2O) is 16. The results are interpreted in terms of increased concentrations of the reactants on the micelle surface and on competition of PAR and SDS for GaOH2+.     

Solubilization of Polycyclic Aromatic Compounds into n-Decyltrimethylammonium Perfluorocarboxylate Micelles

Solubilization of polycyclic aromatic compounds in aqueous dilute solutions of three cationic amphiphiles was studied. The maximum additive concentrations (MACs) of the aromatic compounds were constant below their critical micelle concentrations (cmcs) and monotonically increased above the cmcs. The first stepwise association constants (K(1)) between a solubilizate monomer and a vacant micelle were evaluated from the MACs for the solubilizates using the mass action model for solubilization into micelles in the dilute solution. The standard Gibbs energy changes of solubilization (DeltaG degrees ) were calculated from K(1), and the enthalpy and entropy changes of solubilization were estimated from the temperature dependence. MACs of each surfactant at the same surfactant concentration above the cmc were different depending on the cmc, but there was little difference in the DeltaG degrees values. Some differences appeared in the enthalpy and entropy values in accordance with their micellar size or degrees of counterion binding to micelles. DeltaG degrees for solubilization decreased linearly with carbon number of aromatic solubilizate for each micellar solution. Copyright 2000 Academic Press.     

Interaction between zwitterionic and anionic surfactants: spontaneous formation of zwitanionic vesicles

The physicochemical properties, such as critical micelle concentration (cmc), surface tension at cmc (γ(cmc)), and surface activity parameters of the mixtures of a new amino acid-based zwitterionic surfactant, N-(n-dodecyl-2-aminoethanoyl)-glycine (C(12)Gly) and an anionic surfactant, sodium dodecyl sulfate (SDS) at different molar fractions, X(1) (= [C(12)Gly]/([C(12)Gly] + [SDS])) of C(12)Gly were studied. A synergistic interaction was observed between the surfactants in mixtures of different X(1). The self-organization of the mixtures at different molar fractions, concentrations, and pH was investigated. Fluorescence depolarization studies in combination with dynamic light scattering, and transmission electron microscopic and confocal fluorescence microscopic images suggested the formation of bilayer vesicles in dilute solutions of SDS rich mixtures with X(1) ≤ 0.17 in the pH range 7.0 to 9.0. However, the electronic micrographs showed structures with fingerprint-like texture in moderately dilute to concentrated C(12)Gly/SDS mixture at X(1) = 0.50. The vesicles were observed to transform into small micelles upon lowering the solution pH and upon increase of total surfactant concentration in mixtures with X(1) ≤ 0.17. However, decrease of SDS content transformed vesicles into wormlike micelles. The structural transitions were correlated with bulk viscosity of the binary mixtures.     

Effects of SDS on the thermo- and pH-sensitive structural changes of the poly(acrylic acid)-based copolymer containing both poly(N-isopropylacrylamide) and monomethoxy poly(ethylene glycol) grafts in water

The effects of SDS on the structural changes of the thermally induced polymeric micelles from a graft copolymer comprising poly(acrylic acid) (PAAc) as the backbone and poly(N-isopropylacrylamide) (PNIPAAm) and monomethoxy poly(ethylene glycol) (mPEG) as the grafts in aqueous solution are studied. At low temperature, SDS micelles form via the hydrophobic association of SDS molecules with the PNIPAAm grafts at a critical aggregation concentration of SDS (cac(SDS)) much lower than its critical micelle concentration. Consequently, the critical aggregation temperature of the graft copolymer is elevated. The corresponding structure of the thermally induced polymeric micelles is characterized by an abrupt reduction in the particle size and an increased tendency toward formation of the monocore structure with a more compact and hydrophobic PNIPAAm microdomain being developed. On the other hand, upon the polymeric micelle formation at high temperature, the copolymer-bound SDS micelle structure is disrupted and the dissociated SDS molecules migrate to the core-shell interface with their alkyl chains residing in the liquidlike region of the hydrophobic PNIPAAm microdomain. The correlation between the polymeric particles and copolymer-bound micelles is further substantiated by showing the change of the colloidal particle size in response to changes in cac(SDS) via adjusting the pH of the aqueous copolymer/SDS solutions.     

The solubilization of n-pentane gas in sodium dodecyl sulfate-polyethylene glycol solutions with and without electrolyte

The solubility of n-pentane gas in aqueous solution of sodium dodecyl sulfate (SDS), SDS-0.1 wt% polyethylene oxide (PEG), SDS-0.1 wt% PEG+NaCl (0.1 mol/l), and SDS-0.1 wt% PEG+NaOH (0.1 mol/l) has been determined at 318.15 K. The concentration of SDS (m(SDS)) is up to 50 mmol/kg. The solubility increases linearly with the concentration of SDS above its critical micelle concentration (CMC) or critical aggregation concentration (CAC), indicating that micelles in the solutions solubilize the gas molecules and the solubility of n-pentane gas in the micelles is independent of the SDS concentration. It was found that the solubilization ability of micelles bound to PEG and free micelles to n-pentane gas is almost the same. The solubility of n-pentane gas in micelle phase is three magnitudes higher than that in the bulk solution. The solubilization property of SDS is changed by the addition of PEG, although the solubilizing effect of the polymer alone is not considerable. NaCl and NaOH affect the solubilization noticeably and increase the interaction strength between SDS and PEG. The standard Gibbs energies for the transfer of n-pentane gas from bulk phase to micelle phase are large negative values, indicating that the hydrocarbon gas prefers to exist in the hydrophobic interior of the micelles.     

Electrokinetic chromatographic characterization of novel catanionic surfactants vesicle as pseudostationary phase

A novel catanionic surfactants vesicle system composed of octyltriethylammonium bromide/ sodium dodecyl benzene sulfonate (C₈NE₃Br/SDBS) has been developed as pseudostationary phase (PSP) in EKC. The C₈NE₃Br/SDBS system possesses a large vesicle phase region and none of agglomeration phenomena appeared while mixing cationic and anionic surfactants at any molar ratio. Electrophoretic and chromatographic parameters including elution window, hydrophobic selectivity, polar group selectivity, and shape selectivity were characterized using the vesicle at molar ratio of C₈NE₃Br to SDBS of 3:7 as PSP. Compared with SDS micelles, the vesicle PSP possessed a wider elution window and a better selectivity. The retention behavior and selectivity differences between the novel vesicle and SDS micelles were evaluated through linear solvation energy relationship (LSER) analysis. Though the cohesiveness and the hydrogen bond acidity have greatest influences on the solutes retention and selectivity in both the vesicle and SDS micelle, the vesicle PSP demonstrated a higher hydrophobicity and a lower hydrogen bonding donating capability owing to compact bilayer structure of vesicle. Additionally, the vesicle system had a stronger hydrogen bond accepting capability than SDS micelle. Consequently, according to LSER analysis, the bigger coefficients for v, b, and a revealed the vesicle PSP had a better separation selectivity than conventional SDS micelle.     

Kinetics and mechanism of intramolecular general base-catalyzed alkanolysis of phenyl salicylate in the presence of anionic micelles

The alkanolysis of ionized phenyl salicylate, PS^?, has been studied in the presence and absence of micelles of sodium dodecyl sulphate, SDS, at 0.05 M NaOH, 30 or 32°C and within the alkanol, ROH, (ROH = HOCH₂CH₂OH and CH₃OH) contents of 15–74 or 92%, v/v. The alkanolysis of PS^? involves intramolecular general base catalysis. At a constant concentration of SDS, [SDS]_T, the observed pseudo first-order rate constants, k_obs, for the reactions of ROH with PS^? obtained at different concentration of ROH, [ROH]_T, obey the relationship: k_obs = k[ROH]_T/(1 + K_A[ROH]_T) where k is the apparent second-order rate constant and K_A is the association constant for dimerization of ROH molecules. Both k and K_A decrease with increase in [SDS]_T. At a constant [ROH]_T, the rate constants, k_obs, show a decrease of nearly 2-fold with increase in [SDS]_T from 0.0–0.3M. These results are explained in terms of pseudo-phase model of micelle. The rate constants for alkanolysis of PS^? in micellar pseudophase are insignificant compared with the corresponding rate constants in aqueous-alkanol pseudophase. This is attributed largely to considerably low value of [ROH] in the specific micellar environment where micellar bound PS^? molecules exist. The increase in [ROH]_T decrease the value of the binding constant of PS^? with SDS micelle. The effects of anionic micelles on the rates of alkanolysis of PS^? are explained in terms of the porous cluster micellar structure.     

Structure-ionization relationship of tyrosine-containing peptides

The arid-base chemistry of tyrosine-containing peptides such as enkephalin, tyrosylglycylglycine, tyrosylglycine and analogous peptides is described. For each peptide and tyrosine derivative, microscopic and macroscopic acid dissociation constants and the thermodynamic parameters for proton dissociations were determined from pH-titrations and ultraviolet absorption spectra. The relative concentrations of various ionic forms for the peptides were calculated from the microscopic constants. The concentration ratio, represented by the tautomeric equilibrium constant (K(t)), showed a definite relationship to structure.     

Hydrogen ion titration of alkyldimethylamine oxides by 13C and 1H NMR and conventional methods

In the hydrogen ion titration of micelles, the degree of ionization of the micelle at a given pH has to be evaluated to obtain a pKa value of micelles (Ka being the proton dissociation constant) at the pH. We compared the degree of ionization obtained from 13C and 1H NMR spectra with that obtained from the stoichiometric method. We used dodecyldimethylamine oxide (C12DMAO) and hexyldimethylamine oxide (C6DMAO) to examine the titration behavior of micelles and monomers, respectively. We determined pKa values of amine oxides both in H2O and D2O. As to the monomer (C6DMAO), the degree of ionization from NMR, alpha(NMR), coincided with that from the conventional stoichiometric method alpha. The difference of pK1 of amine oxide monomer between D2O and H2O was about 0.5: pK1(D) approximately pK1(H) + 0.5. The difference was about the same as that for carboxylic acids. As to the C12DMAO micelle, alphaNMR did not coincide with alpha over a considerable range of alpha. The NMR chemical shift might be influenced by micellar structure changes induced by the ionization, such as the sphere-to-rod transition. The intrinsic logarithmic dissociation constants of the micelle were 5.9+/-0.1 for H2O, and 6.5+/-0.1 for D2O.