Counterion Binding Research Articles

Aggregation and pH Responsive Behavior of Thioester Surfactants and Formation of Disulfide Linkages in Aqueous Solutions.

pH responsive surfactants, [C12H25N(CH3)2(CH2)nSCOCH3]Br (C12nSAc, n = 4, 11, 12), were prepared, and their properties in aqueous solution were examined. The critical micelle concentration (cmc) and critical vesicle concentration (cvc) were determined based on changes in conductivity, as well as by fluorescence measurements, and light scattering methods. A significant increase in the light scattering intensities of the C12nSAc (n=11, 12) systems suggested that the growth of aggregates was accompanied by considerable counterion binding with increasing surfactant concentration. The diameter of C1211SAc, recorded by the dynamic light scattering measurements, was about 9.6 ±1.0 nm, which was slightly smaller than that for didodecyldimethylammonium bromide (DDAB) vesicles. The thioester group was easily hydrolyzed upon the addition of NaOH, while it was hardly hydrolyzed with the addition of HCl. The time course of alkaline hydrolysis was examined by the conductivity measurements and high-performance liquid chromatography analysis. [C12H25N(CH3)2(CH2)11SS(CH2)11N(CH3)2C12H25]2Br (2C1211SS) was generated in the C1211SAc alkaline solution because of air oxidation. The C1211SAc alkaline solution gradually became an opaque blue color with increasing light scattering at 346 nm, indicating the remarkable growth of vesicles. The chemical structure of 2C1211SS was consistent with that of a disulfide linked double tailed surfactant, similar to DDAB. The disulfide linkage between the double tailed surfactants will contribute to the stabilization and growth of vesicles.

Distribution of zwitter-ionic tryptophan between the micelles of 1-dodecyl-3-methyl imidazolium and aqueous medium from molecular dynamic simulation.

Ionic liquids that form micelles have great potential as drug carriers and separating agents for bioactive substances. For such applications, a key issue is the distribution of the target substance between the micelle and its environment. We perform MD simulations to study solubilization of zwitter-ionic tryptophan in micelles of 1-dodecyl-3-methylimidazolium bromide. We found that the distribution of tryptophan depends strongly on the degree of counterion binding. A decrease in binding of bromide counterions leads to a substantial increase of the distribution coefficient. A dense layer of counterions at the micellar surface impedes the solubilization of the zwitter-ionic tryptophan but at the same time the presence of such a dense layer obstructs the washout of the solubilized tryptophan molecules from the micelle. Based on our simulation data, we conclude that an increase of the distribution coefficient of tryptophan between the micelle and water may be achieved by several means: by introducing counterions that bind weakly to the micelle (bulky ions whose charge is not strongly localized) and/or by employing micelle-forming ionic liquids with shorter alkyl chains to diminish the degree of counterion binding.

A new surfactant-copper(ii) complex based on 1,4-diazabicyclo[2.2.2]octane amphiphile. Crystal structure determination, self-assembly and functional activity.

A new surfactant-copper(ii) complex [Cu(L)Br3] (where LBr is 1-cetyl-4-aza-1-azoniabicyclo[2.2.2]octane bromide) containing a transition metal in the head group has been synthesized and characterized. Physicochemical properties, thermal stability and 3D structure were determined using X-ray diffractometry, UV-vis spectroscopy, simultaneous thermogravimetry and differential scanning calorimetry combined with mass-spectrometry of evolved vapors. The study of the self-assembly and morphological features of associated structures was performed by potentiometry using a bromide ion selective electrode and fluorescence of pyrene and 1,6-diphenyl-1,3,5-hexatriene. The influence of the metal ion embedded into the surfactant structure on critical micelle concentration, degree of counterion binding, aggregation numbers and morphology of the associates was elucidated. High solubilizing capacity and complexation ability of the metal containing micelles with respect to Orange-OT hydrophobic dye and oligonucleotide were determined. Importantly, the functional properties of this metallosurfactant complex are much better compared to those of classical cationic surfactants bearing cyclic and acyclic head groups, LBr and the LBr-CuBr2 mixture. The new cationic metallosurfactant could be recommended for investigation in gene therapy.

Enhanced Physical Stability of Mixed Ion Pair Amphiphile/Double-chained Cationic Surfactant Vesicles in the Presence of Cholesterol

In this study, a pseudodouble-chained ion pair amphiphile (IPA), hexadecyltrimethylammoniumdodecylsulfate (HTMA-DS), and dialkyldimethylammonium bromide (DXDAB) with different chain lengths were used as the main materials to fabricate positively charged catanionic vesicles with various mole fractions of cholesterol. The effects of cholesterol and DXDAB alkyl chain length on physical stability of the catanionic vesicles were then investigated by size, zeta potential, and Fourier transform infrared analyses. With the presence of cholesterol in the mixed HTMA-DS/DXDAB vesicles or with increasing the DXDAB content in the presence of a proper amount of cholesterol, the physical stability of the catanionic vesicles could be enhanced. The spacing effect of cholesterol would reduce the counterion binding tendency at the charged vesicle surfaces, resulting in a more pronounced charge character of the catanionic vesicles. Furthermore, cholesterol-induced disordered structure contributed to the flexibility of the vesicular bilayers. Thus the physical stability of the vesicles was improved by adding cholesterol. With increasing the hydrocarbon chain length of DXDAB, cholesterol located toward the middle of the bilayers, enhancing the effects of cholesterol on charge and molecular packing characteristics of the vesicles. This led to a more pronounced stability enhancement effect on the vesicles with a longer alkyl chain length of DXDAB. The results suggested that the presence of cholesterol in the HTMA-DS/DXDAB catanionic vesicles could enhance vesicle stability through adjusting intra-vesicle and/or inter-vesicle interactions. In addition, the stability enhancement effect was more pronounced in the systems with a long DXDAB alkyl chain. The findings will be useful for developing new formulas of catanionic vesicles as drug delivery carriers.

Counterion binding alters surfactant self-assembly in deep eutectic solvents.

Micellisation of surfactants in deep eutectic solvents has been recently demonstrated to provide a controllable way to modify micelle morphology. Ion-pair interactions between the solvent and the surfactant headgroup were identified as affecting the micellisation by modifying the charge density of the micelle. Here we explore the micellisation of dodecylsulfate surfactants with different counterions (Li+, Cs+, Mg2+, Bmim+, Emim+, cholinium+) dissolved in two deep eutectic solvents: choline chloride:urea and choline chloride:glycerol. Surface tension results show a solvent and counterion dependence of the CMC of the surfactants. Small-angle neutron scattering was subsequently used to investigate the morphology of the micelles formed. The results show that the elongation of the micelles is strongly dependent on the solvent, showing more elongated aggregates in choline chloride:urea than in choline chloride:glycerol. The morphology of micelles in DES was also found to depend on the counterion, where the affinity of binding showed similarities to that in water.

Heparin-dependent aggregation of hen egg white lysozyme reveals two distinct mechanisms of amyloid fibrillation

Heparin, a biopolymer possessing high negative charge density, is known to accelerate amyloid fibrillation by various proteins. Using hen egg white lysozyme, we studied the effects of heparin on protein aggregation at low pH, raised temperature, and applied ultrasonic irradiation, conditions under which amyloid fibrillation was promoted. Heparin exhibited complex bimodal concentration-dependent effects, either accelerating or inhibiting fibrillation at pH 2.0 and 60 °C. At concentrations lower than 20 μg/ml, heparin accelerated fibrillation through transient formation of hetero-oligomeric aggregates. Between 0.1 and 10 mg/ml, heparin rapidly induced amorphous heteroaggregation with little to no accompanying fibril formation. Above 10 mg/ml, heparin again induced fibrillation after a long lag time preceded by oligomeric aggregate formation. Compared with studies performed using monovalent and divalent anions, the results suggest two distinct mechanisms of heparin-induced fibrillation. At low heparin concentrations, initial hen egg white lysozyme cluster formation and subsequent fibrillation is promoted by counter ion binding and screening of repulsive charges. At high heparin concentrations, fibrillation is caused by a combination of salting out and macromolecular crowding effects probably independent of protein net charge. Both fibrillation mechanisms compete against amorphous aggregation, producing a complex heparin concentration-dependent phase diagram. Moreover, the results suggest an active role for amorphous oligomeric aggregates in triggering fibrillation, whereby breakdown of supersaturation takes place through heterogeneous nucleation of amyloid on amorphous aggregates.

Conductometric investigations of surfactant behavior in aqueous polar aprotic organic additives

Micellar properties of sodiumdodecyl sulfate (SDS) and cetyltrimethylammonium bromide (CTAB) in aqueous polar aprotic additives viz., dimethylsulfoxide (DMSO), dimethylformamide (DMF), acetonitrile (AN) and 1,4-dioxane were determined between 25 and 45°C. The critical micelle concentration (CMC) determined using electrical conductivity measurements have been used to evaluate thermodynamic properties of micellization. By detailed experiments, it was observed that the DMSO and DMF have an inhibitory effect on micellization of the targeted surfactants, i.e. SDS and CTAB in aqueous solutions over the entire solvent composition range from 0.67–5.94mol% by weight. The addition of dioxane and AN initially increase CMC of CTAB and then it decreases gradually with further increase in the concentration of dioxane and AN. A contrary trend is observed in the micellar behavior of SDS in the presence of dioxane and AN. The changes in standard enthalpy and entropy of micellization values are found to be consistent with the observed behavior of the two surfactants in the presence of these additives. Near constant counter-ion binding values are indicative of the fact that no structural transition of the micelles of the two surfactants takes place in the range of the composition studied.

Structural Insight into the Unbound State of the DNA Analogue of the PreQ1 Riboswitch: A Thermodynamic Approach.

The preQ1 riboswitch aptamer domain is very dynamic in its unbound state with the ability to form multiple structures: a hairpin, kissing hairpins, and pseudoknot-like structure. The aim of this study is to determine whether the DNA analogue (PreQ1) is able to form structures similar to that of the reported RNA aptamer. Using a thermodynamic approach, we report on structural determination using differential scanning calorimetry under different salt conditions. Further analysis of the primary sequence allowed us to design modified molecules to determine what potential structures are forming in this single-stranded DNA analogue. We found, in a 16 mM Na+ solution, PreQ1 has three transitions with TM values of 14.8, 19.4, and 26.2 °C and a total ΔH of -44.7 kcal/mol. With the increase in salt concentration to 116 mM, there are TM values of 22.3, 28.7, and 38.9 °C and a ΔH of -69.1 kcal/mol, while at 216 mM, the three transitions have TM values of 24.4, 31.6, and 42.9 °C with a total ΔH of -71.5 kcal/mol. Therefore, the increase in enthalpy is due to the formation of additional base-pair stacks. The modified molecules, which would inhibit pseudoknot formation, kissing hairpins, and internal loop interactions, were fully characterized and compared to the native DNA analogue. The analysis of the enthalpy and differential binding of counterions allows us to conclude this single-stranded DNA analogue under physiological conditions is not forming a pseudoknot-like structure. Instead, two potential structures, Compact-Hairpin and Kissing-Complex, are more likely and could be in equilibrium.

On the Problem of Determining Aggregation Numbers from Surface Tension Measurements.

In view of the recent discovery of variable aggregation numbers in the vicinity of the critical micelle concentration (CMC), the mass-action-law theory of the surface tension isotherm of a micellar solution with variable aggregation numbers is formulated both for nonionic and ionic surfactants. It is shown that the shape of the surface tension isotherm should be concave in the logarithmic scale above the CMC. Considering a change in the isotherm slope at the CMC apparent break point, the problems of determining the aggregation number for nonionic micelles and the degree of counterion binding for ionic micelles are discussed. In case of the aggregation number variability near the CMC, finding the aggregation number above the CMC apparent break point is considered and a computational scheme is elaborated, requiring a higher precision for experiment. Some experimental data from the literature are analyzed, and the method of estimating the degree of counterion binding is improved.

Association, Distribution, Liberation, and Rheological Balances of Alkyldimethylbenzylammonium Chlorides (C12-C16).

It is known that cationic surfactants have an antimicrobial effect and act as enhancers. This paper studies three cationic surfactants from the group of alkyldimethylbenzylammonium chlorides (dodecyl-, tetradecyl-, and hexadecyl). Interest is focused on the association of the surfactants with respect to temperature, partition balances and their influence on drug release, rheological properties, and the pH of hydrogels. The critical micelle concentrations (CMC) of the surfactants were estimated from dependencies of conductivity, density, spectrofluorimetry, and UV–VIS spectrophotometry on molarity in the temperature range of 25–50 °C. It was found that the temperature dependence of a CMC is U-shaped, with its minimum at 30 °C, and the CMC value decreases as the length of the chain increases. The pseudo-phase separation model was used for the calculation of various thermodynamic parameters, such as the Gibbs free energies (spontaneous process), enthalpies (exothermic process), and entropies of the micelles’ formation, CMCs, and the degree of counterion binding. All thermodynamic parameters, as functions of the temperature, were estimated. It was found that partition coefficients increase as the length of the alkyl chain and the pH = (5.0–7.0) increase. The influences of surfactants, below and above the CMC, on drug (chlorhexidine dihydrochloride) release from hydrogels, rheological properties, and pH at 30 °C were studied. Also, the amounts of the released drug increase as the alkyl chains of the surfactants prolongate. The amounts of the released drug with the surfactant below the CMC are greater than that above the CMC. All hydrogels (regardless of the length of the alkyl chain) exhibit a non-Newtonian pseudo-plastic flow. The results obtained will be used in the formulation of the drug and surfactants into dosage forms.

The Davies equation of state of ionic surfactant adsorbed monolayer and related problems

The Davies equation and relative expressions belong to the most popular tools for describing the equilibrium state of ionic surfactants on the water–air or water–hydrocarbon interface. During over half a century, this equation was repeatedly discussed and modified and various attempts of its derivation/reconsideration were proposed for both insoluble and soluble monolayers. In this paper, the corresponding publications are regarded. Basing on the previously derived modification of the fundamental Gibbs equation [Surface Eng. 50 (2014) 173–182; https://doi.org/10.3103/S1068375514020100.], another expression for the monolayer of the adsorbed ionic surfactant (2D layer) is proposed, which implies dividing the total effect into the electrostatic and non-electrostatic contributions. The dependence of the surface pressure, П, on the area per adsorbed amphiphilic ion in the interface, A, excluded area, A0, and the electrical potential Ψ of the compact monolayer against the bulk aqueous phase is obtained taking into account the degree of counter ion binding, β, and cohesion. In the following equation, the second term of the right-hand side is caused by the electrostatic energy of transfer of the charged amphiphile from the bulk to the monolayer, whereas the third one represents the electrostatic contribution to the surface pressure:Π + Πc= − kT∫∞A(1 + β)(A − A0)−2dA + ∫0Ψ(1 + β) z2eA−1dΨ + ∫0Ψ(1 − β)z2eA−1dΨ, where k, T, and e have their usual meaning. In particular, in its limited form, for β=0 and neglecting the cohesion term, Πc, the equation of state is as follows:Π=kT(A−A0)−1+2∫0ΨeA−1dΨ.This relation differs from the common Davis equation by the coefficient "2" in the last rhs term. Some limiting cases are considered, and an attempt to adapt the equation to experimental data is made.

Hydration and Counterion Binding of [C12MIM] Micelles.

Surface-active ionic liquids based on imidazolium cations are promising targets for micellar catalysis in aqueous solution, yielding enhanced rate constants compared to surfactants based on n-alkyltrimethylammonium cations and exhibiting a pronounced counterion dependence ( Bica Chem. Commun. 2012 , 48 , 5013 - 5015 ; Cognigni Phys. Chem. Chem. Phys. 2016 , 18 , 13375 - 13384 ). Probably most relevant to these effects is the interplay between headgroup hydration and counterion binding. To obtain more detailed information on these effects, aqueous solutions of 1-dodecyl-3-methylimidazolium ([C12MIM]) bromide, iodide, and triflate (TfO-) were investigated at 45 °C using broadband dielectric spectroscopy, viscosity measurements, and small-angle X-ray scattering experiments. Effective hydration numbers were determined, and information on the locations and mobilities of the condensed counterions, X-, was derived. It was found that [C12MIM] halide micelles were less hydrated than the corresponding n-dodecyltrimethylammonium ([C12TA]X) aggregates. Together with their somewhat weaker counterion condensation, this difference probably explains their higher catalytic activity. Whereas [C12MIM]Br micelles remained roughly spherical in the studied concentration range, rodlike aggregates were formed at high concentrations of the iodide and, in particular, the triflate surfactants. It appears that the much lower mobility of condensed TfO- counterions is the reason for the very low catalytic activity of [C12MIM]TfO micelles.

Non-uniform self-assembly: On the anisotropic architecture of \u03b1-synuclein supra-fibrillar aggregates

Although the function of biopolymer hydrogels in nature depends on structural anisotropy at mesoscopic length scales, the self-assembly of such anisotropic structures in vitro is challenging. Here we show that fibrils of the protein α-synuclein spontaneously self-assemble into structurally anisotropic hydrogel particles. While the fibrils in the interior of these supra-fibrillar aggregates (SFAs) are randomly oriented, the fibrils in the periphery prefer to cross neighboring fibrils at high angles. This difference in organization coincides with a significant difference in polarity of the environment in the central and peripheral parts of the SFA. We rationalize the structural anisotropy of SFAs in the light of the observation that αS fibrils bind a substantial amount of counterions. We propose that, with the progress of protein polymerization into fibrils, this binding of counterions changes the ionic environment which triggers a change in fibril organization resulting in anisotropy in the architecture of hydrogel particles.

Effect of electrostatic correlations on micelle formation

Micellization phenomena are fundamental to countless biological and chemical processes. Salts can dramatically change the micellization, depending on the kind of electrolyte and its concentration. Traditional approaches to model and describe these phenomena do not take into account electrostatic correlation interactions. Those interactions are essential when modeling surfactant solutions containing multivalent and/or highly concentrated electrolytes. Therefore, the development of a theory that is able to correctly predict the behavior of surfactant solutions with salts is a key to improve the application of surfactants in industrial processes. Here, we propose a simple methodology that uses a mean field approach to include electrostatic correlation effects and we coupled it with the well-established molecular thermodynamics approach to describe the micellization phenomena. From the proposed model, we can obtain the critical micelle concentration (CMC) of ionic and zwitterionic surfactant solutions and information about the size and shape of the micelles. We also propose an approach to take into account the binding of cations and anions on the surface of zwitterionic surfactants. To validate the model we compared our results with experimental data of CMC and counterion binding for different surfactants. We obtained very good agreement with the experimental data with a completely predictive model.

Thermal, aggregation, counterion binding, light scattering, and adsorption behavior of cis-chlorobis(ethylenediamine)dodecylaminecobalt(III) perchlorate metallosurfactant in aqueous sodium perchlorate medium

Studying the fundamental aspects of aggregation and adsorption of metallosurfactants is necessary by looking at the potential applications of these novel surfactants. cis-Chlorobis(ethylenediamine)dodecylaminecobalt(III) perchlorate (CDCP) metallosurfactant was synthesized and its thermal gravimetric analysis showed that it is stable up to 217 °C. Critical micelle concentration (cmc) of CDCP in aqueous sodium perchlorate medium was determined by using surface tension, conductivity, and spectrophotometric methods. It is shown that the cmcs of metallosurfactants do not follow the trend according to the positions of the counterions in the Hofmeister series, which is contrary to the trend observed in the case of conventional ionic surfactants. The counterion binding constant of CDCP is equal to 0.81. The variation of surface excess of CDCP with sodium perchlorate concentration exhibits a minimum. Dynamic light scattering measurements showed the presence of large size aggregates of CDCP in solution, and these aggregates grow further as the counterion concentration increased.

Effect of Electrolyte (NaCl) and Temperature on the Mechanism of Cetyl Trimethylammonium Bromide Micelles

In the last few decades, surfactants and electrolyte interaction has gained considerable attention of researchers due to their industrial and domestic applications. In this work, the effects of electrolyte (NaCl) on the critical micelle concentration (CMC) of the cationic surfactant cetyltrymethyl ammonium bromide (CTAB) at different temperatures were investigated through different techniques such as conductometry, surface tensiometer and viscosimeter. The results showed that the values of CMC of CTAB decreased with the increase in temperature as well as with the addition of NaCl. The value of CMC for pure CTAB was calculated 0.98M at 303K, which was observed to decrease as temperature increased and got value of 0.95M at 318K. Moreover the addition of electrolyte NaCl into the surfactant lead to lowering of the CMC and obtained value of 0.90M at 3M of NaCl, indicating significant electrostatic interactions between surfactant and electrolyte. Moreover the degree of ionization(α) calculated for pure cationic surfactant CTAB was 0.219, which tends to increase with the addition of electrolyte, while that of counter ion binding values (β) was observed to decrease from 0.780 to 0.201. Furthermore, the conductivity of charged micelle of surfactant and free ions of electrolyte contributed to electric conductivity of aqueous micellar solution of surfactant. The results can be helpful to develop better understanding about interaction between electrolyte and surfactant.

Effect of biological buffers on the colloidal behavior of sodium dodecyl sulfate (SDS)

This study investigates the influence of three commonly used buffers (TRIS, TES and TAPS) on the conductivities and the colloidal behavior of the aqueous solutions containing a surfactant, sodium dodecyl sulfate (SDS). To find the effect of these buffers on the aggregation behavior of the aqueous SDS solutions, we experimentally determined the conductivities of the solutions containing different concentrations of SDS (0.002M–0.025M) in water and in 0.2M, 0.5M, and 1.0M TRIS, TES, and TAPS buffers, respectively, at 298.2K under atmospheric pressure. To get insight into the effect of the buffers on the aggregation behavior of the aqueous SDS solutions, the critical micelle concentration (CMC) values of the aqueous solutions are estimated from the experimental results of conductivity measurements. Interestingly, in comparison with the CMC of SDS in water, the presence of TRIS is found to increase the CMC, whereas the addition of TES or TAPS is found to decrease the CMC, especially at higher concentration (1.0M). The influence of the buffers on the CMC or aggregation of the SDS is further characterized by calculating various aggregation parameters such as the degree of ionization of the micelle (αm), the degree of counter ion binding in micelle (fm), and the standard Gibbs free energy of micellization (ΔG°m) for all the studied systems. Moreover, the outcomes from the conductivities measurement are reconfirmed by using the fluorescence probe analysis.

Spectroscopic and conductometric studies on the interactions of thionine with anionic and nonionic surfactants

In this study, the interaction of thionine, a cationic dye, with anionic [sodium dodecyl sulphate (SDS), lithium dodecyl sulphate (LiDS), and sodium dodecylbenzene sulphonate (SDBS)], nonionic (Tween 20 and Triton X‐100), and binary mixtures of anionic and nonionic surfactants was studied by conductometric and spectrophotometric measurements. The degree of ionisation, the counterion binding parameters, and the equilibrium constants in the premicellar region were obtained from conductivity data. Binding constants of thionine to anionic, nonionic, and mixtures of anionic and nonionic micelles were determined by spectrophotometric measurements. The binding tendency of thionine to anionic micelles followed the order SDBS > SDS > LiDS. The presence of nonionic surfactants increased significantly the binding affinity of thionine to anionic micelles, and the highest binding constant was calculated in the presence of Tween 20. The results obtained from conductometric studies correlated with those obtained from spectroscopic studies. Data concerning dye–surfactant interaction are important for a fundamental understanding of the performance of single and mixed surfactants and for their industrial application.

Head-group effect of surfactants of cationic type in interaction with propoxylated sodium salt of polyacrylic acid in aqueous solution

Polyacrylic acid (PAA) partially (50mol.%) neutralized by sodium hydroxide was propoxylated by propylene oxide (PO) obtaining terpolymer (PNPAA). The conductivity and tensiometry measurements were used to study an interaction of PNPAA with ionic-liquid surfactants of cationic type–nonylethylolammonium bromides in aqueous solutions of different concentrations at 25°C. From the results of these measurements, critical aggregation concentrations, critical micelle concentrations and the effective degree of counterion binding were determined. Depending on the nature of head-group of the cationic surfactant, the polyelectrolyte-surfactant interaction was studied and its impact on colloidal-chemical parameters of the polyelectrolyte/surfactant complexes was clarified. Petroleum-collecting properties of the obtained polyelectrolyte/surfactant complexes have been studied in various waters of a different mineralization degree.

Microscopic Evidence for the Correlation of Micellar Structures and Counterion Binding Constant for Flexible Nanoparticle Catalyzed Piperidinolysis of PS− in Colloidal System

Abstract The interest to determine the ionization degree of counterion initiates the need to study the relationship between counterion binding constant (RX Br) and the growth of self-assembly micellar structure. This paper discussed the microscopic evidence for the correlation of counterion binding constant values and micellar structure of cationic surfactants in the presence of phenolates and 2-ethyl phenolates ions in flexible nanoparticle (FN)-system of ionized phenyl salicylate-catalyzed piperidinolysis. The sizes of micelles were determined by particle size analysis. Transmission electron microscopy (TEM) results showed a spherical micellar structure for phenolates and 2-ethyl phenolates ions at counterion binding constant values 6.3 ± 1.0 and 24.0 ± 1.1 respectively. A study using a semi-emperical kinetic technique in published article proved that the suggested micellar structures at respective counterion binding constant values corresponded with the present microscopic evidence.