Interaction of the Amphiphilic Drug Amitriptyline Hydrochloride with Gemini and Conventional Surfactants: A Physicochemical Approach

Pyrene fluorescence measurements were carried out on various binary mixtures of the antidepressant amphiphilic drug amitriptyline hydrochloride (AMT) with conventional (TTAB and CTAB) and gemini surfactants (14-4-14 and 16-4-16). In all cases mixed micellar aggregates were formed and the mixed critical micelle concentration (cmc) of various mixtures was computed from the I ₁/I ₃ versus total surfactant concentration plots. In the region where mixed micelles are formed, the interaction of the amphiphlic drug and four surfactants showed synergistic behavior. The results were analyzed using an interaction parameter, β, which characterize the interaction in the mixed micelle and is introduced by a regular solution theory. The β values are negative in all binary mixtures, and their magnitudes increase with increasing hydrophobicity of the amphiphile. The micellar mole fraction of AMT in the mixed micelle (x ₁) and in the ideal sate (x _ideal) were evaluated and their values (x ₁ > x _ideal) suggest that the contribution of the AMT component is greater in binary mixtures as compared to that in the ideal state. Activity coefficients (f ₁ and f ₂) and excess Gibbs energy (G _ex) were also calculated. The values of micelle aggregation numbers (N _agg) and various other parameters like the Stern–Volmer constant (K _sv), micropolarity and dielectric constant of mixed systems have also been evaluated from the ratios of respective peak intensities (I ₁/I ₃ or I ₀/I ₁).     

Markov chain model for the critical micelle concentration of surfactant mixtures

An extension of the Markov chain model (MC) for micellization is proposed, which allows the distribution of the surfactants between the monomer solution and the micelles in a mixed surfactant system to be predicted. The dependence of the critical micelle concentration (cmc) on the composition of the solution is investigated. The equilibrium thermodynamic relation between cmc and micelle composition is discussed. The case of ternary mixtures is analyzed, and theoretical triangular diagram is constructed according to MC. Available experimental data for binary and ternary mixtures agree well with the new MC theory. The dependence of MC parameters on the structure of the surfactants is discussed. Comparison of MC with the simple mixture (“regular solution”) model is presented. The parameters of the MC theory are related to the interaction parameter β _SM of the simple mixture model.     

Mixed micelle behavior of poly(ethylene glycol) alkyl ethers with series of monomeric cationic, phosphonium cationic, and zwitterionic surfactant

The steady state fluorescence measurements have been carried out for the binary mixtures of poly(ethylene glycol) alkyl ethers (C _i E _j ) with series of monomeric cationic (MC), zwitterionic (ZI), and phosphonium cationic (PC) surfactants over the whole mole fraction range by using pyrene as fluorescence probe. The cmc values for all the binary mixtures, thus, determined have been further evaluated by using the regular solution theory. The various micellar parameters such as regular solution interaction parameter (β), micropolarity (I ₁/I ₃), and mean micelle aggregation number (N _agg) have been determined. A strong influence of hydrophobicity of both nonionic as well as cosurfactant (CS) components has been observed on the nature of mixed micelles. The presence of bulky head groups of PC surfactants significantly contributes towards the unfavorable mixing.     

Interaction and Stability of Mixed Micelle and Monolayer of Nonionic and Cationic Surfactant Mixtures

Interaction and stability of binary mixtures of cationic surfactants hexadecyltrimethylammonium bromide (HTAB) or hexadecylpyridinium bromide (HPyBr) with nonionic surfactant decanoyl-N-methyl-glucamide (Mega-10) have been studied at different mole fraction of cationic surfactants by using interfacial tension measurements and fluorescence probe techniques. From interfacial tension measurements, the critical micellar concentration and various interfacial thermodynamic parameters have been evaluated. The experimental cmc's were analyzed with the pseudophase separation model, the regular solution theory, and the Maeda's approach. These approaches allowed us to determine the interaction parameter and composition in the mixed state. By using the static quenching method, the mean micellar aggregation numbers of pure and mixed micelles of HTAB + Mega-10 were obtained. It has been observed that the aggregation number of mixed micelles deviates negatively from the ideal behavior. The micropolarity of the micelle was monitored with pyrene fluorescence intensity ratio and found to be increase with the increase of ionic content. The polarization of fluorescence probe Rhodamine B was monitored at different mole fraction of cationic surfactants.     

Interfacial and Thermodynamic Properties of Anionic‐Nonionic Mixed Surfactant System: Influence of Hydrophobic Chain Length of the Nonionic Surfactant

The influence of hydrophobic chain length in nonionic surfactants on interfacial and thermodynamics properties of a binary anionic‐nonionic mixed surfactant was investigated. In this study, nonionic surfactants lauric‐monoethanolamide (C₁₂ MEA) and myrisitic‐monoethanolamide (C₁₄ MEA) were mixed with an anionic surfactant, α‐olefin sulfonate (AOS). The critical micelle concentration (cmc), maximum surface excess (Γ_max), and minimum area per molecule (A_min) were obtained from surface tension isotherms at various temperatures. The thermodynamic parameters of micellization and adsorption were also computed. Micellar aggregation number (N_agg), micropolarity, and binding constant (K_sv) of pure and mixed surfactant system was calculated by fluorescence measurements. Rubingh's method was applied to calculate interaction parameters for the mixed surfactant systems.     

Steady-state fluorescence investigations of aqueous binary mixtures of myristyl alcohol based bis-sulfosuccinate anionic gemini surfactant and effect of different conventional surfactants therein

The present research work is associated with the fluorescence investigations of binary aqueous mixed surfactants solutions of anionic bis-sulfosuccinate gemini surfactant (BSGSMA_1,8) and three different conventional surfactants—anionic viz. sodium dodecyl sulfate (SDS), cationic viz. cetyl trimethyl ammonium bromide (CTAB), and nonionic surfactant viz. Triton X 100. Steady-state fluorescence spectroscopy technique has been utilized to examine the micellization behavior of aqueous solution of pure myristyl alcohol-based BSGSMA_1,8 having flexible methylene chain [(CH₂)₈] as spacer group. Critical micelle concentration (CMC), aggregation number (N), and micropolarity of pure and mixed surfactants systems were explored during the investigations. The results revealed the best synergism behavior of prepared gemini BSGSMA_1,8 with SDS as compared to CTAB and Triton X 100. The maximum reduction in the value of pyrene intensity ratio (I₁/I₃) was observed for gemini and SDS mixed surfactant solution. On the other hand, the increased I₁/I₃ value of mixed gemini with Triton X 100 exhibited that mixed surfactant system of anionic gemini BSGSMA_1,8 with non-ionic Triton X 100 is not as compact as other mixed surfactant systems. Aggregation number increased and micropolarity decreased with increased concentration of gemini surfactants.     

Volumetric studies on binary mixtures of surfactants N,N′-bis(dimethyldodecyl)-1,2-ethanediammonium dibromide and 1-dodecyl-3-methylimidazolium bromide in aqueous solutions

The micellization of the binary mixed surfactants comprising of the Gemini surfactant N,N′-bis(dimethyldodecyl)-1,2-ethanediammonium dibromide and 1-dodecyl-3-methylimidazolium bromide has been studied by measurements of density. The apparent molar volumes were calculated for various surfactant concentrations and used to determine the critical micelle concentrations of the mixed surfactants at various compositions. An attractive effect was suggested by negative deviations of the experimental CMC values from the ideal ones. The Margules equation was applied to evaluate the micelle compositions, the activity coefficients of both components, and the excess molar Gibbs free energies of the mixed micelles. The stability of mixed micelles was shown to be enhanced as compared to those formed by single surfactants from the negative values of the excess Gibbs free energy. The comparison of the results obtained from the volumetric and ITC measurements indicated a reasonable good accordance with each other and confirmed the reliability of both methods for investigation on the properties of the mixed micelles.     

Enthalpies of transfer of pentanol from water to sodium dodecylsulfate-dodecyl-dimethylamine oxide-water mixtures

At a given surfactant-surfactant ratio, the enthalpies of transfer ΔH (W→W+S) of pentanol 0.03m from water to sodium dodecylsulfate (NaDS)-dodecyldimethylamine oxide-water mixtures as functions of the surfactants mixture concentration (m _t) were determined. ForX _NaDS=0.9, ΔH (W→W+S) increases monotonically withm _t such as observed for pure surfactants. ForX _NaDS=0.12 and 0.3, ΔH (W→W+S) increases withm _t up to 0.12m beyond which it decreases withm _t. AtX _NaDS=0.6, two monotonic curves can be distinguished in the ΔH (W→W+S)vs. m _t trend. Experimental data were fitted through an equation previously reported for additives in pure surfactants derived by assuming the pseudo-phase transition model for the micellization and a mass action model for the distribution of the additive between the aqueous and the micellar phases. This method did permit to simultaneously obtain the distribution constant of the alcohol between the aqueous and the micellar phase (and, then, the standard free energy of transfer) and its enthalpy of transfer from the aqueous to the micellar phases. By combining these properties the standard entropies of transfer were calculated. From these results, the excess properties of pentanol in the mixed micelles were calculated as a function of the mixture composition. The excess enthalpies and entropies are positive and compensate with each other leading to null values for the excess free energies in the whole range of the mixed micelles composition.     

Mixed micelles of homologous perfluoropolyether anionic surfactants in water

The mixtures of sodium and ammonium salts of three homologous perfluoropolyether carboxylic acids having Cl-terminated perfluoroalkyl group (Cl-PFPE) and differing in the average molecular weight (MW) were examined. The surfactants, namely n2, n3 and n4, have two, three and four PFPE units, respectively. Each surfactant was studied alone and in mixture with the other surfactants with the same counterion. NMR chemical shifts were measured for each surfactant and for the mixtures in different concentrations. For a given mixture the micelle composition, X_i, can be determined from the observation of the chemical shifts of the micellar components. It was found that Cl-PFPE surfactant mixtures form in water mixed micelles which contain the surfactants in equilibrium with monomeric species. The analysis of NMR chemical shift variations allowed evaluating the partition of the various surfactants in the mixed aggregates as a function of the total concentration. Composition of mixed micelles resembles ideal mixing predictions particularly at high surfactant concentrations.     

Volumetric Studies on Aqueous Solutions of Dodecyltrimethylammonium Bromide and 1-Dodecyl-3-methylimidazolium Bromide

The densities of aqueous solutions of mixed surfactants of dodecyltrimethylammonium bromide and 1-dodecyl-3-methylimidazolium bromide (DTAB/C₁₂mimBr) were measured at various compositions. The concentration dependent apparent molar volumes of these mixed surfactants were calculated and used to deduce the critical micelle concentrations (cmc) and the apparent molar volumes in the micelles and the continuous phase. The one-parameter Margules equation was applied to correlate the composition dependent cmc values and to obtain the activity coefficients and mole fractions of these surfactants in the mixed micelles, which were further used to calculate the excess Gibbs energies and the excess volumes. It was found that the excess Gibbs energies and the excess volumes of the mixed micelles are all negative, indicating that these mixed micelles are more stable and packed more tightly than their corresponding pure micelles.     

Surface and Solution Properties of Cationic Gemini Surfactants with Primary Linear Alkanols

Using surface tension and fluorescence methods, the surface and solution properties of two cationic gemini surfactants {pentanediyl-1,5-bis(dimethylcetylammonium bromide) and hexanediyl-1,6-bis(dimethylcetylammonium bromide)} (referred to as 16-5-16 and 16-6-16) have been studied in the presence and absence of primary linear alkanols. Parameters studied include the critical micelle concentration (CMC), C ₂₀ (the surfactant concentration required to reduce the surface tension of the solvent by 20 mN·m^?1), Г _max (maximum surface excess), and A _min (minimum surface area per molecule). These parameters indicate mixed micelle formation and, therefore, surfactant-additive interaction parameters in mixed micelles and mixed monolayers, as well as activity coefficients, were calculated. A synergistic effect was observed in all instances and was found to be correlated with the chain length of the alkanols. The CMC values of 16-s-16 (s = 5, 6) decrease with increasing alkanol concentration and the extent of this effect follows the sequence: 1-octanol (C₈OH) > 1-heptanol (C₇OH) > hexan-1-ol (C₆OH) > 1-pentanol (C₅OH) > butanol (C₄OH). The micelle aggregation number (N _agg) of mixed micelles has been obtained using the steady state fluorescence quenching method. The micropolarity of gemini/alkanol systems has been evaluated from the ratio of intensity of peaks (I ₁/I ₃) of the pyrene fluorescence emission spectra. Results are interpreted on the basis of the structure of mixed micelles and monolayers.     

Factors determining the catalytic activity of the mixed micellar system cetyltrimethylammonium bromide-Brij-35 in the hydrolysis of a phosphonic acid ester

The micellization and surface properties, Stern layer micropolarity, and catalytic action of the cetyltrimethylammonium bromide-Brij-35 system in the alkaline hydrolysis of O-ethyl O-p-nitrophenyl chloromethylphosphonate have been investigated at different proportions of the constituent surfactants. This system has unique, invertible catalytic properties ranging from acceleration of the hydrolysis reaction by more than one order of magnitude to strong inhibition of this reaction and even termination of the reaction at certain proportions of the surfactants. The factors in the changes of the catalytic effect under variation of the surfactant ratio are micropolarity in the reaction zone and surface potential. A likely cause of the termination of the process is the shift of the reaction zone from the surface layer to the micelle core, where the environment is less polar.     

Micellization properties and the catalytic effect of the aqueous cetyltrimethylammonium bromide-Triton X-100 binary system in nucleophilic substitution in esters of phosphorus acids

The aggregation properties and catalytic effect of the cetyltrimethylammonium bromide-Triton X-100 binary system in nucleophilic substitution in esters of phosphorus acids are studied in the region of normal micelles and oil/water microemulsions. In the presence of phenol, the dissociation of O-alkyl-O-para-nitrophenyl chloromethyl phosphonates is up to 200 times more rapid than the same reaction in water. The efficiency of catalysis depends on the molar ratio of the surfactants and is determined by several factors: concentration, changes in the microenvironment of the reactants, and the shift of the pK _a of phenol.     

Study of mixed micellar aqueous solutions of sodium dodecyl sulfate and amino acids

Thermodynamic properties of sodium dodecyl sulfate (SDS) in micellar aqueous solutions of L-serine and L-threonine were determined by fluorescence spectroscopy and dynamic light scattering techniques. The values of Gibbs free energy, enthalpy and entropy of the process of micelle formation were calculated using the critical micelle concentration and degree of dissociation. Changes in critical micelle concentration of SDS with the addition of amino acids were examined by both conductivity and pyrene I ₁/I ₃ ratio methods at different temperatures. The pyrene fluorescence spectra were used to study the change of micropolarity produced by the interaction of SDS with amino acids. The aggregation behavior of SDS was explained in terms of structural changes in mixed solutions. The data on dynamic light scattering suggest that size of SDS micelles was influenced by the presence of amino acids.     

THE EFFECT OF MIXED MICELLES OF SURFACTANTS ON THE ALKALINE HYDROLYSIS OF ESTERS

The alkaline hydrolysis of aromatic and normal aliphatic acid esters have been studied at 25°C In mixed micellar solution of surfactants (Brij35—SDS, Brij35 — DTAB, Brij35—TTAB.Brij35-CTAB. Triton X—100 —CTAB, Triton X— 100 —SDS) with UV spectrophotometry and the method of thermokinetics The critical mice liar concentrations of the corresponding systems have also been measured with UV spectrophotometry in this paper. K_jnln micellar pseudo-phase has been calculated- The ratios of ki.to ki.for all mixed micellar systems Investigated are less than 1. The results indicate that these reactions are inhibited by the mixed micelles and the mixed micelles exhibit a greater effect of Inhibition on the reactions than those do In corresponding single ones. The reason for this is that the micropolarity of the compact Stern layer of mixed micelle is lower, and the micro viscidity Is higher. The Inhibition effect! also depend on the hydrophobic chain length of the surfactants and the hydrophobicity of the substrate.     

Mixed micellization of gemini surfactant with nonionic surfactant in aqueous media: a fluorometric study

Herein we report on the study of the interactions between alkanediyl-α,ω-type cationic dimeric (gemini) surfactant and the nonionic Triton X-100 in aqueous medium. The critical micelle concentrations of binary mixtures were determined by fluorometric study. Using the regular solution theory for the analysis of the experimental data, the attractive nature of interactions and synergistic behavior of gemini surfactant and Triton X-100 mixture were demonstrated. The micelle aggregation number was measured using steady state fluorescence quenching method. The micropolarity, binding constant and dielectric constant of mixed systems were determined from the ratio of peak’s intensity (I ₁/I ₃) in the pyrene fluorescence emission spectrum.     

Interaction between biosurfactant surfactin and cationic surfactant cetyl trimethyl ammonium bromide in mixed micelle

An anionic/cationic mixed surfactant aqueous system of surfactin and cetyl trimethyl ammonium bromide (CTAB) at different molar ratios was studied by surface tension and fluorescence methods (pH 8.0). Various parameters that included critical micelle concentration (cmc), micellar composition (X ₁), and interaction parameter (β ^m) as well as thermodynamic properties of mixed micelles were determined. The β ^m was found to be negative and the mixed system was found to have much lower cmc than pure surfactant systems. There exits synergism between anionic surfactin and cationic CTAB surfactants. The degree of participation of surfactin in the formation of mixed micelle changes with mixing ratio of the two surfactants. The results of aggregation number, fluorescence anisotropy, and viscosity indicate that more packed and larger aggregates were formed from mixed surfactants than unmixed, and the mixed system may be able to form vesicle spontaneously at high molar fraction of surfactin.     

Study of the Interaction Between Promazine Hydrochloride and Surfactant (Conventional/Gemini) Mixtures at Different Temperatures

In the present paper, the micellization of an amphiphilic drug, promazine hydrochloride, and gemini surfactants (16-s-16) with s = 4–6 and the monomeric hexadecyltrimethylammonium bromide (CTAB) counterparts has been examined conductometrically in the pure and mixed states in aqueous solutions at different compositions and temperatures (298.15–308.15 K). Dicationic gemini surfactants provide much better environment for the micellization behavior than the corresponding monocationic counterpart CTAB. The critical micelle concentration (cmc) values are lower than the cmc for ideal mixing, cmc ^id, suggesting attractive interactions between the two components in mixed micelles. The micellar mole fractions of surfactants, evaluated by different models, show greater contributions of surfactants in mixed micelles and increase with increasing concentrations of these surfactants. The negative values of β suggest synergism in the mixtures, which is highly beneficial as it reduces the total amount of surfactants required in a particular application, leading to reductions of cost and environmental impact. Activity coefficients (f ₁ and f ₂) are always less than unity showing nonideality in the systems. The data have been also used for evaluation of thermodynamic parameters.     

Properties of mixed micelles of cationic gemini surfactants and nonionic surfactant triton X-100: effects of the surfactant composition and the spacer length

The mixed micelles of cationic gemini surfactants C12C(S)C12Br2 (S=3, 6, and 12) with the nonionic surfactant Triton X-100 (TX100) have been studied by steady-state fluorescence, time-resolved fluorescence quenching, electrophoretic light scattering, and electron spin resonance. Both the surfactant composition and the spacer length are found to influence the properties of mixed micelles markedly. The total aggregation number of alkyl chains per micelle (N(T)) goes through a minimum at X(TX100)=0.8. Meanwhile, the micropolarity of the mixed micelles decreases with increasing X(TX100), while the microviscosity increases. The presence of minimum in N(T) is explained in terms of the competition of the reduction of electrostatic repulsion between headgroups of cationic gemini surfactant with the enhancement of steric repulsion between hydrophilic headgroups of TX100 caused by the addition of TX100. The variations of micropolarity and microviscosity indicate that the incorporation of TX100 to the gemini surfactants leads to a more compact and hydrophobic micellar structure. Moreover, for the C12C3C12Br2/TX100 mixed micelle containing C12C3C12Br2 with a shorter spacer, the more pronounced decrease of N(T) at X(TX100) lower than 0.8 may be attributed to the larger steric repulsion between headgroups of TX100. Meanwhile, the increase of microviscosity and the decrease of micropolarity are more marked for the C12C12C12Br2/TX100 mixed micelle, owing to the looped conformation of the longer spacer of C12C12C12Br2.     

Protolytic properties of some bis(dimethylaminomethyl)phenols in the presence of surfactants

Aggregation and protolytic properties of bis(dimethylaminomethyl)phenols containing methyl (HA) and nonyl (HL) substituents at the benzene ring are studied in aqueous solutions of isopropanol and various surfactants with potentiometric titration, tensiometry, and mathematical modeling of equilibria. Monomers, dimers, and tetramers of HA and HL are found. It is shown that the degree of compound aggregation depends on the solution concentration and pH. Sodium dodecyl sulfate and HA form associates, whereas SDS and HL form mixed micelles at the CMC-1 and CMC-2 critical micellization concentrations. In micellar solutions of Triton X-100 and cetyltrimethylammonium bromide, the mixed micelles are not found via tensiometry. Protonated species of tetramer, dimer, and monomer of investigated compounds are revealed, depending on the acidity of the medium. Phenolate forms of HA and HL do not exist under experimental conditions. Apparent protonation constants are determined and it is shown that, for the HA compound that does not form micelles, the protonation constants of the same-type species increase in the presence of the three surfactants used as compared to the water-isopropanol solution. Decreasing constants of analogous HL forms in the solutions of CTAB, nonionic surfactant (C _Tx = 10 mM), and SDS (pH > 7) are attributed to the formation of associates or mixed micelles of this compound and surfactants under experimental conditions.