Mixed micelle formation among anionic gemini surfactant (212) and its monomer (SDMA) with conventional surfactants (C12E5 and C12E8) in brine solution at pH 11

The micellization of anionic gemini surfactant, N,N'-ethylene(bis(sodium N-dodecanoyl-beta-alaninate)) (212), and its monomer, N-dodecanoyl-N-methyl alaninate (SDMA), and polyethoxylated nonionic surfactants, C(12)E(5) and C(12)E(8), has been studied tensiometrically in pure and mixed states in an aqueous solution of 0.1 M NaCl at pH 11 to determine physicochemical properties such as critical micellar concentration (cmc), surface tension at the cmc (gamma(cmc)), maximum surface excess (Gamma(max)) and minimum area per surfactant molecule at the air/water interface (A(min)). The theories of Rosen, Rubingh, Motomura, Maeda, and Nagarajan have been applied to investigate the interaction between those surfactants at the interface and in the micellar solution, the composition of the aggregates formed, the theoretical cmc in pure and mixed states, and the structural parameters as proposed by Tanford and Israelachvili. Various thermodynamic parameters (free energy of micellization and interfacial adsorption) have been calculated with the help of regular solution theory and the pseudophase model for micellization.     

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.     

Influence of ionic and nonionic hydrotropes on micellar behavior of a cationic gemini surfactant butanediyl-1,4-bis(dimethylcetylammonium bromide)

Micellization of binary systems of a cationic gemini surfactant butanediyl-1,4-bis(dimethylcetylammonium bromide) (16-4-16) and cationic/nonionic hydrotropes (aniline-hydrochloride, 2-methylanilinehydrochloride, 4-methylanilinehydrochloride, hydroxybenzene, 1,3-benzenediol, benzene-1,2,3-triol) have been studied using a conductometric technique. The critical micelle concentrations (cmc) for different mixing mole fractions at different temperatures have been calculated. To explain and compare the results, theoretical models of Clint, Rubingh and Motomura have been used to obtain the ideal cmc, mixed micelle composition, interaction parameters (β(m)), free energies of micellization, and activity coefficients. The mixtures show nonideal behavior and the interactions between the surfactants and the hydrotropes are synergistic in nature which is confirmed by high negative β(m) values and low values of the activity coefficients. Thermodynamic parameters were also obtained from the temperature dependence of the cmc values.     

Mixed micellization of anionic–nonionic surfactants in aqueous media: a physicochemical study with theoretical consideration

Mixed micellization of binary and ternary mixtures of anionic and nonionic surfactants, such as lithium dodecyl sulfate, polyoxyethylene(23)laurylether, and polyoxyethylene-tert-octylphenylether, is studied in aqueous solution using tensiometric, conductometric, and spectrophotometric methods. Although tensiometry and conductometry complement each other closely, the spectroscopic critical micellar concentration (cmc) is far from agreement with tensiometric study. Several parameters, e.g., cmc, degree of counterion binding, free energies of micellization, and interfacial adsorption, have been evaluated. Established theories of Clint, Rosen, Rubingh, Motomura, Georgiev, Maeda, and Blankschtein were applied to evaluate the mole fraction of different components in the self-aggregated phase, the interaction parameter, free energy contributions, and expected cmc.     

Properties of polyethylene glycol (23) lauryl ether with cetyltrimethylammonium bromide in mixed aqueous solutions studied by self-diffusion coefficient NMR

NMR self-diffusion coefficient measurements have been used to study the properties of polyethylene glycol (23) lauryl ether (Brij-35) with cetyltrimethylammonium bromide (CTAB) in the mixed aqueous solutions with different mole fractions of CTAB. By fitting the self-diffusion coefficients to the two-state exchange model, the critical micelle concentrations of the two solutes in the mixed solutions (cmc*1 and cmc*2) were obtained. The critical mixed micelle concentrations (cmc*) were then evaluated by the sum of cmc*1 and cmc*2, which are in good agreement with the results measured by the surface tension method. The cmc* values are lower than those of the ideal case of mixing, which indicates that the behavior of the CTAB/Brij-35 system is nonideal. Moderate interactions between CTAB and Brij-35 in their mixtures can be deduced from the interaction parameters (betaM) based on the cmc* obtained by the NMR self-diffusion method. The compositions (x1) of the mixed micelles at different total surfactant concentrations were also evaluated. By using these results, a possible mechanism of mixed micellar formation and a picture of the formation of nonsimultaneous CTAB/Brij-35 binary mixed micelle were proposed. In contrast to the case of CTAB/TX-100 system, Brij-35 molecules have a tendency to form micelles first at any mole fraction of CTAB. The mixed micellar self-diffusion coefficients (Dm) increase slightly at lower CTAB molar ratios, and then speed up with increasing CTAB mole fraction.     

Studies on binary and ternary amphiphile combinations of tetradecyltrimethylammonium bromide (C14TAB), tetradecyltriphenylphosphonium bromide (C14TPB), and tetradecylpyridinium bromide (C14PB). A critical analysis of their interfacial and bulk behaviors

Mixed surfactants play a promising role in surface chemical applications. In this study, interfacial and bulk behaviors of binary and ternary combinations of tetradecyltrimethylammonium bromide (C(14)TAB), tetradecyltriphenylphosphonium bromide (C(14)TPB), and tetradecylpyridinium bromide (C(14)PB) have been examined in detail using the methods of tensiometry, conductometry, fluorimetry, and microcalorimetry. The state of micellar aggregation, amphiphile composition in the micelle, extent of counterion binding by the micelle, and interaction among the surfactant monomers in the binary and ternary combinations have been quantitatively assessed in the light of the regular solution theories of Rubingh and that of Rubingh and Holland. The monomer packing in the micelles and their expected shapes have also been estimated from topological considerations. Conceptual rationalization of results has been presented together with associated energetics of the interfacial adsorption and self-aggregation in the bulk.     

Mixed micellization of an anionic gemini surfactant (GA) with conventional polyethoxylated nonionic surfactants in brine solution at pH 5 and 298 K

The micellization behavior of an anionic gemini surfactant, GA with nonionic surfactants C₁₂E₈ and C₁₂E₅ in presence of 0.1 M NaCl at 298 K temperature, has been studied tensiometrically in pure and mixed states, and the related physicochemical parameters (cmc, γ _cmc, pC ₂₀, Γ _max, and A _min) have been evaluated. Tensiometric profile (γ vs log [surfactant]), for conventional surfactants, generally consists of a single point of intersection; a gradually decreasing line (normally linear, or with slight curvature) ultimately saturates in γ at a particular [surfactant], corresponding to complete monolayer saturation. The gemini, in this report, led to two unequivocal breaks in the tensiometric isotherm. An attempt to the interpretation of the two breaks from molecular point of view is provided, depending solely on the chemical structure of the surfactant. The gemini, even in mixed state with the conventional nonionic surfactants C₁₂E₅ and C₁₂E₈, manifested the dual breaks; of course, the dominance of the feature decreases with increasing mole fraction of the nonionics in the mixture. Theories of Clint, Rosen, Rubingh, Motomura, Georgiev, Maeda, and Nagarajan have been used to determine the interaction between surfactants at the interface and micellar state of aggregation, the composition of the aggregates, the theoretical cmc in pure and mixed states, and the structural parameters according to Tanford and Israelachvili. Several thermodynamic parameters have also been predicted from those theories.     

Micellization and interfacial behavior of binary and ternary mixtures of model cationic and nonionic surfactants in aqueous NaCl medium

Mixed micelle formation and interfacial properties of aqueous binary and ternary combinations of hexadecyltrimethylammonium bromide (C(16)Br), hexadecylbenzyldimethylammonium chloride (C(16)BzCl) and polyoxyethylene (20) cetyl ether (Brij58) at 25 degrees C in 30 mM aqueous NaCl have been studied in detail employing tensiometric and fluorimetric techniques. The micellar and adsorption characteristics like composition, activity coefficients, mutual interaction parameters and free energy of micellization have been estimated using the theoretical approaches of Clint, Rosen, Rubingh, Blankschtein et al., Rubingh-Holland and Maeda. A comprehensive account of the comparative performance of these models on the selected cationic-cationic-nonionic surfactant mixtures at constant ionic strength has been presented. The Blankschtein model predicted lower synergism than from Rubingh's method because it neglects the contribution due to steric interaction between surfactant head groups of different sizes and charges. Free energy of micellization calculated using Maeda's approach, which employs interaction parameter and micellar mole fraction from Rubingh's model as inputs, shows good correlation with that calculated from commonly used phase separation model. The present study also reveals that the modified Rubingh-Holland method along with the Rosen's model can be applied to analyze the interfacial characteristics of ternary surfactant mixtures with a fair degree of success thereby widening the domain of applicability of this model.     

Self-aggregation of binary mixtures of alkyltriphenylphosphonium bromides: a critical assessment in favor of more than one kind of micelle formation

The micellization behavior of binary combinations of alkyltriphenylphosphonium bromides (ATPBs) with alkyl chain carbons 10, 12, 14, and 16 has been studied by conductometry and calorimetry. The combinations C(10)-C(12), C(10)-C(14), C(10)-C(16), C(12)-C(14), C(12)-C(16), and C(14)-C(16) were found to form two cmc's by both the methods, with good agreement, except C(14)-C(16)TPB, which has evidenced only a single cmc by calorimetry for all combinations. The combinations C(10)-C(12) (for both cmc(1) and cmc(2)) and C(10)-C(14)TPB (for cmc(2)) formed ideal mixtures, whereas the rest were nonideal. In the nonideal binary mixtures, the ATPB components showed antagonistic interaction with each other. The cmc, interaction parameter (beta), mixed micellar composition, extent of counterion binding, and thermodynamic parameters for the micellization process have been reported and discussed. The enthalpy of mixed micelle formation has been found to have a fair correlation with a Clint-type relation applicable to ideal binary mixtures of surfactants.     

Physicochemistry of mixed micellization: Binary and ternary mixtures of cationic surfactants in aqueous medium

The importance of studying mixed micellization lies in tuning the performance of an amphiphile to bend through variation of stoichiometry of the blend. In this study, the binary and ternary mixed systems of cetylpyridinium chloride (CPC), tetradecyltrimethylammonium bromide, and dodecylpyridinium chloride (DPC) have been studied at 30°C using tensiometry and conductometry. In most cases, the cmc observed from either method is in close proximity whereas in CPC/DPC mixtures, tensometric cmc precedes conductometric cmc which may arise from a lowering in degree of counterion binding on micellar interface in the mixed system with lower stoichiometric mole fraction of CPC. Various existing theories have been used and the results were compared with the experimental observations.     

Mixed micelles containing sodium oleate: the effect of the chain length and the polar head group

We have investigated the mixing behavior of binary mixtures of the alkylglucosides (CnG) octyl beta-D-glucoside and decyl D-glucoside in combination with sodium oleate (NaOl), and the amine oxide surfactants (AO) N,N-dimethyldodecylamine oxide, N,N-bis (2-hydroxyethyl)dodecylamine oxide, and 3-lauramidopropyl-N,N-dimethylamine oxide in combination with NaOl. From the equilibrium surface tension measurements, the critical micelle concentration (cmc) data were obtained as functions of the composition. Values of the cmc were analyzed according to both the regular solution model developed by Rubingh for mixed micelles and Maeda's formulation for ionic/nonionic mixed micelles. Two interaction parameters, beta and B1, were estimated from the regular solution model and Maeda's formulation, respectively. For NaOl/CnG mixed systems, a decrease in the hydrocarbon chain length of CnG resulted in a stronger interaction with NaOl from both beta and B1 values. For NaOl/AO mixed systems, the bulkiness of a polar head group of AO surfactants influenced the interaction between NaOl and AO. The dynamic surface tension measurements show that all surface tension values of surfactant solutions examined decreased with the time. We found that the time dependence of surface tension values for NaOl mixed systems was greatly influenced by the presence of NaOl rather than the other component.     

Characterization of Binary Surfactant Mixtures (Cetylpyridinium Chloride and Tween 60) in an Aqueous Medium

Abstract

Micellar properties of the binary surfactant mixtures of cetylpyridinium chloride (CPC) and polyoxyethylene (20) sorbitan monostearate (Tween‐60) have been investigated in detail using tensiometric, conductometric, spectrophotometric, and fluorimetric techniques. The critical micelle concentration (CMC), counterion binding, interfacial adsorption, energetics of micellization, and micellar dielectric constant have been evaluated. The theories of Clint, Motomura, Rubingh, and Sarmoria, Puvvada and Blankschtein have been followed to understand the CMC, composition, activity coefficients, and synergism of the binary surfactant systems.     

Aggregation behavior and interaction of an amphiphilic drug imipramine hydrochloride with cationic surfactant cetyltrimethylammonium bromide: light scattering studies

The aggregation behavior and interaction of an amphiphilic antidepressant drug imipramine (IMP) hydrochloride with the cationic surfactant cetyltrimethylammonium bromide (CTAB) have been studied using light scattering (both static and dynamic) techniques. Due to rigid tricyclic hydrophobic moiety present in the molecule, the drug shows interesting association behavior. The static light scattering measurements show that the self-association of IMP commenced above a well-defined critical micellar concentration (CMC), which decreases with increasing the mole fraction of the CTAB surfactant. Both the excess Gibbs energy (ΔG(ex)) and the Gibbs energy of micellization (ΔG(M)°) are negative, and decrease with increasing mole fraction of the surfactant. The hydrodynamic diameters (d(h)) of the micellar aggregates were also evaluated using the dynamic light scattering measurements. The data indicate formation of larger aggregates by IMP and CTAB due to mixed micellization and subsequent micellar growth. The results have been analyzed using different models (viz., Clint, Motomura, Rosen, Rubingh, etc.) for mixed micelle formation.     

Physicochemical studies on the micellization behavior of cetylpyridinium chloride and triton X-100 binary mixtures in aqueous medium

Physicochemistry of micellization of binary mixtures of cetylpyridinium chloride (CPC) and Triton X-100 (TX-100) have been investigated and the data collected have been analyzed and correlated. Tensiometric, conductometric, spectrophotometric, calorimetric and polarographic methods have been employed in the study. Parameters like critical micellar concentration (CMC), counter-ion binding, energetics of micellization, interfacial surfactant adsorption and minimum area of amphiphile head groups at CMC have been determined. The diffusion coefficients of pure and mixed micelles in solution have been determined by the polarographic method. The regular solution theory of Rubingh has been considered to get information on the micellar composition and their mutual interaction (synergistic for the studied system) in solution. The packing of the monomer in micelle has been estimated to witness spherical geometry for CPC and its mixtures with TX-100, whereas the later has been found to be spheroidal. Polarographic measurements have evidenced comparable diffusion coefficients of CPC and TX-100 micelles whereas their mixed micelles have shown lower values with a minimum, at equimolar composition.     

HEXADECYLTRIMETHYLAMMONIUM BROMIDE + TETRADECYLTRIMETHYL-AMMONIUM BROMIDE MIXED MICELLES IN AQUEOUS GLYCOL OLIGOMERS

The conductances of hexadecyltrimethylammonium bromide (HTAB) + tetradecyltrimethylammonium bromide (TTAB) mixtures over the entire mole fraction range of HTAB (α_HTAB) were measured in pure water as well as in the presence of various aqueous ethylene glycol oligomers containing 5, 10 and 20 wt% of each additive in their respective binary mixtures at 30°C. From the conductivity data, the critical micellar concentration (cmc), degree of counter ion association (χ) and the standard free energy of transfer of the surfactant hydrocarbon chain from the medium to the micelle (ΔG^O _HP ) for HTAB and TTAB were computed. From the conductivity data of mixed surfactants systems, apart from cmc and χ, the regular solution theory parameters were also computed in order to explore the non-ideality in the mixed micelle formation in the presence of additives. The micellar parameters of both kind of surfactants and their mixtures show a significant dependence on the amount as well as on the number of repeating units of glycol oligomers. However, the non-ideality of mixed micelle formation remains unaffected in the presence of additives. These results have been explained on the basis of the medium effects of aqueous additive and it has been concluded that there are no significant interactions of glycol oligomers with the micelles of single and mixed surfactants.     

Abnormal micellar growth in sugar-based and ethoxylated nonionic surfactants and their mixtures in dilute regimes using analytical ultracentrifugation

To develop structure-property relationships for surfactants that control their adsorption, solubilization, and micellization behavior in mixed systems and to develop predictive models based on such relationships, it is necessary to acquire quantitative information on various species present in these complex systems. The analytical ultracentrifugation technique is selected for the first time to characterize the species present in mixed micellar solutions due to its powerful ability to separate particles on the basis of their size and shape. Two nonionic surfactants, n-dodecyl-beta-D-maltoside (DM) and nonyl phenol ethoxylated decyl ether (NP-10), and their 1:1 molar ratio mixture were investigated in this study. Micelles of the nonionic surfactants and their mixture are asymmetrical in shape at the critical micelle concentration (cmc). Interestingly, unlike ionic surfactants, the micellar growths of the nonionic surfactants were found to occur at concentrations immediately above the cmc. The results from both sedimentation velocity and sedimentation equilibrium experiments suggest coexistence of two types of micelles in nonyl phenol ethoxylated decyl ether solutions and in its mixture with n-dodecyl-beta-D-maltoside, while only one micellar species is present in n-dodecyl-beta-D-maltoside solutions. Type 1 micelles were primary micelles at the cmc, while type 2 micelles were elongated micelles. The differences in the micellar shapes of n-dodecyl-beta-D-maltoside and nonyl phenol ethoxylated decyl ether are attributed to packing parameters detected by their molecular structures.     

Mixed micellization and interfacial properties of dodecyltrimethylammonium bromide and tetraethyleneglycol mono-n-dodecyl ether in absence and presence of sodium propionate

Mixed micelle formation and interfacial properties of aqueous binary surfactant combinations of dodecyltrimethylammonium bromide (C12TAB) and tetraethyleneglycol mono-n-dodecyl ether (C12E4) at 30 degrees C in absence and presence of sodium propionate (NaPr) have been investigated. The critical micelle concentration, aggregation number, micropolarity and interfacial adsorption have been quantitatively estimated by surface tension and steady-state fluorescence measurements. The micellar and adsorption characteristics like composition, activity coefficients and mutual interaction parameters have been estimated following different theoretical treatments like that of Clint, Rubingh, Rodenas, Maeda, Blankschtein and Rosen. The analysis reveals very small mole fraction of cationic surfactant in both the mixed micelles and mixed monolayer inspite of synergism. Blankschtein's model predicts a continuous decrease in synergism due to the salt effect of NaPr; Rubingh's approach, on the contrary, indicates an increase in it above 30 mM of NaPr concentration. Aggregation number variation with NaPr indicates the same. Mixed monolayer shows better synergism compared to that in mixed micelles which increases with the addition of sodium propionate above 30 mM concentration.     

Study of micellar and phase separation behavior of mixed systems of triblock polymers

Cyclic voltammetric (CV) techniques have been employed to study the mixed micellar behavior of binary mixtures of triblock polymers (TBP) such as F127+P85, F127+P85, F88+P85, and F88+P123 using 2,2,6,6-tetramethyl-1-piperidinyloxy (Tempo) as an electroactive probe. Critical micellar concentration (cmc) has been obtained for pure triblock polymers and their mixed systems from the plots of peak current (i_p) variation versus the total concentration. Diffusion coefficients of the electroactive species have been determined from the Randles–Sevcik equation. The interaction parameter (β) for the mixed micelles was obtained from the regular solution theory. The values of β suggest that the synergism does exist especially with the F88+P123 system. Cloud point measurements have also been made on the binary mixtures of triblock polymers following similar mixing criteria. An effort has been made to correlate the micellar behavior and phase separation (cloud point) phenomenon. From the correlation, it can be concluded that in the systems studied, an increase in cmc increases the cloud point of mixed systems of triblock polymers.     

Mixed micelles of series of monomeric and dimeric cationic, zwitterionic, and unequal twin-tail cationic surfactants with sugar surfactants: a fluorescence study

Steady state fluorescence measurements have been carried out for binary mixtures of a series of monomeric cationic (MC), zwitterionic (ZI), dimeric cationic (DC), and twin-tail cationic (TC) surfactants with sugar (beta-C8G and beta-C12G) over the whole mole fraction range using pyrene as fluorescence probe. The cmc values thus determined for all the binary mixtures have been further evaluated using the regular solution theory. The various micellar parameters, such as micelle mole fraction (X1), regular solution interaction parameter (beta), micropolarity, and mean micelle aggregation number (Nagg), have been determined for all these series of mixtures. Variation in all these micellar parameters demonstrates that mixed micelles of these surfactants with beta-C8G are mostly synergistic in nature and the synergism increases with the increase in hydrophobicity of the cosurfactant in each case. The mixtures of beta-C12G with various cosurfactants do not show this behavior and instead of it, they show an increase in antagonism with the increase in hydrophobicity of cosurfactants. This discrepancy has been attributed to a large difference in hydrophobicity between beta-C8G and beta-C12G, and the chain folding of the latter is considered to be the reason for the antagonism.     

Cyclic voltammetry and viscosity measurements of aggregated assemblies of anionic surfactants with nonionic surfactants and triblock copolymers

Cyclic voltammetry (CV) and viscosity measurements have been employed to study the aggregation behavior of mixed micellar systems of anionic surfactant (dioctyl sulfosuccinate sodium salt, AOT) with conventional nonionic surfactants such as Brij 35/TritonX-100/Tween 20/Tween 80/Myrj 45 and two triblock copolymers (L64 and F68). Critical micelle concentration (cmc) values have been determined for various micellar systems from CV measurements using 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) as an electroactive probe at 25 °C. Diffusion coefficient (D) has been evaluated from Randles–Sevcik equation which showed an overall decrease for most of the binary systems. The negative values of interaction parameters (β) obtained from regular solution theory suggest the synergistic behavior in all the binary systems except AOT + Tween 80 mixtures. The mixed systems of AOT with triblock copolymers showed stronger synergistic interactions than that of mixed systems of AOT with nonionic surfactants. A comparative evaluation of mixed systems of anionic surfactants AOT and sodium dodecyl sulfate with Myrj 45 and AOT + L64 and F68 has been made on the basis of different micellar parameters and structural properties of surfactants. Viscosity measurements also show similar type of interactions in the mixed micelles.