Head-group-influenced mixed micellization of sodium deoxycholate with conventional hydrocarbon surfactants of identical hydrocarbon tails

Conductivity, viscosity, turbidity, and NMR measurements were performed over most of the mole fraction range for sodium deoxycholate (SDC) with hexadecyltrimethylammonium bromide (HTAB), hexadecylpyridinium bromide (HPyBr), and hexadecylpyridinium chloride (HPyCl). All studies demonstrate that the mixed-micelle formation is more favorable in SDC plus HTAB rather than SDC plus HPyBr or SDC plus HPyCl mixtures. The results showed that the bulky pyridinium head groups of HPyBr or HPyCl create steric incompatibility with rigid SDC monomers in the mixed state.     

Estimation of degree of counterion binding and thermodynamic parameters of ionic surfactants from cloud point measurements by using triblock polymer as probe

Cloud point (C(P)) was measured for ternary mixtures of different ionic surfactants such as sodium dodecyl sulfate (SDS), dodecyltrimethylammonium bromide (DTAB), and dimethylene bis(dodecyldimethylammonium bromide) (12-2-12) plus triblock polymer (TBP) ((PEO)(2)(PPO)(15.5)(PEO)(2)) plus water, keeping the concentration of TBP constant and varying the surfactant concentration from pre- to postmicellar regions. These experiments were also performed in the presence of different fixed amounts of NaBr to evaluate the salt effect on the clouding behavior of these ternary mixtures. The C(P) value of TBP exhibits a drastic change at the cmc of each surfactant. The cmc values thus obtained both in the absence and in the presence of NaBr were used to evaluate counterion binding (beta) with the Corrin-Harkins method. beta values were also used to evaluate the thermodynamic parameters of these ionic surfactants. The results suggest that the beta values evaluated using this method, especially at low [TBP], are in good agreement with those reported in the literature.     

Volumetric study on the inclusion complex formation of α- and β-cyclodextrin with 1-alkanols at different temperatures

The partial molar volumes (V_a) of 1-alkanols (carbon number, m=5, 6, 7) in - and -cyclodextrin (CD) solutions at 5.00 mmol kg^–1 have been determined as a function of alkanol concentration (C_a) between 293.2 and 308.2 K by using a dilatometer. It has been observed that with an increase in C_a, V_a increased in -CD solution but decreased in -CD solution, asymptotically to a value of V_a in CD-free water. The dependence of V_a on C_a provided the binding constant (K) of 1:1 complex, the volume change in complex formation, and the partial molar volume of complex itself. The complex formation mechanism has been discussed on the basis of these values and their carbon number dependences in the respect of geometric behavior, hydrophobic interaction, and van der Waals interaction. It is concluded that the CD cavity in water is not rigid but flexible for fitting in nicely with guest molecule.     

Surfactant polymer interactions between strongly interacting cationic surfactants and anionic polyelectrolytes from conductivity and turbidity measurements

The interactions between oppositely charged surfactant/polymer mixtures have been studied using conductivity and turbidity measurements. The dependence of aggregation phenomenon on the chain length and head group modifications of conventional cationic surfactants, i.e., hexadecyl- (HTAB), tetradecyl- (TTAB), and dodecyltrimethylammonium bromides (DTAB) and dimeric cationic surfactants, i.e., decyl- (DeDGB) and dodecyldimethylgemini bromides (DDGB), is investigated. It was observed that cationic surfactants induce cooperative binding with anionic polyelectrolytes at critical aggregation concentration (cac). The cac values are considerably lower than the critical micelle concentration (cmc) values for the same surfactant. After the complete complexation, free micelles are formed at the apparent critical micelle concentration (acmc), which is slightly higher in aqueous polyelectrolyte than in pure water. Among the conventional and dimeric cationic surfactants, DTAB and DeDGB, respectively, have been found to have least interactions with oppositely charged polyelectrolytes.     

Mixed micelle behavior of Pluronic L64 and Triton X-100 with conventional and dimeric cationic surfactants

The mixed micellar properties of a triblock copolymer, Pluronic L64, (EO)13(PO)30(EO)13, and a nonionic surfactant, Triton X-100, in aqueous solution with conventional alkyl ammonium bromides and their dimeric homologues were investigated with the help of fluorescence and cloud point measurements. The composition of mixed micelles and the interaction parameter, beta, evaluated from the critical micelle concentration (cmc) data for different mixtures using Rubingh's and Motomura's theories are discussed. It has been observed that the mixed micelle formation between monomeric/dimeric alkyl ammonium bromides and L64 was due to synergistic interactions which increase with the increase in hydrophobicity of the cationic component. On the other hand, synergistic mixing was observed in the mixed micelles of Triton X-100 and monomeric cationic surfactants, the magnitude of which decreases slightly with the increase in hydrophobicity of the cationic component. Antagonistic interactions were observed in the case of Triton X-100 and dimeric cationic surfactants.     

Interfacial and micellar properties of binary mixtures of surfactant and phospholipid in an aqueous medium

Mixed micelles formed by zwitterionic surfactant dimethyldodecylammniopropane sulfonate and short-chain phospholipid 1,2-diheptanoyl-sn-glycero-3-phosphocholine in different proportions in an aqueous medium have been studied physicochemically at an air/water interface and in the bulk by using interfacial tension and pyrene fluorescence intensity measurements, respectively. The critical micellar concentration and free energies of micellization and of interfacial adsorption have been determined. The interfacial study reveals that a mixed monolayer is formed at the air/water interface by the adsorption of surfactant and phospholipid monomers. This has been confirmed by evaluating the interfacial parameters; the maximum surface excess, the minimum area per molecule of a surface-active compound, and the Gibbs surface excess related to surface pressure. The nonideality of mixing, expressed in the terms of the regular solution interaction parameter, #, has negative values over the whole mole fraction range. The negative # values indicate the mutual synergism between the surfactant and phospholipid monomers. The equilibrium distribution of components between micelle and monomer phases was evaluated using a theoretical treatment based on excess thermodynamics quantities evaluated by Motomura's formulation.     

Favorable interactions of amine- and ester-terminated PAMAM with cationic surfactants: photophysical and transport studies

Conductivity (kappa), turbidity (tau), and fluorescence (I1/I3) studies of hexadecyltrimethylammonium bromide (HTAB), hexadecylpyridinium bromide (HPyBr), and hexadecylpyridinium chloride (HPyCl) in aqueous poly(amido amine) (PAMAM) dendrimers of generations 0 to 2.5 G have been carried out. The complexation of surfactant monomers with the PAMAM surface groups is demonstrated by the critical aggregation concentration (cac), which is two to three orders of magnitude less than the micellization of cationic surfactants in aqueous PAMAM and denoted by critical micelle concentration (cmc*). In the presence of aqueous amine-terminated PAMAM, the cmc* value for each surfactant was much lower than the cmc in pure water, while they remain close to each other in the presence of aqueous ester-terminated PAMAM for each surfactant. The fluorescence studies demonstrated that both amine- and ester-terminated PAMAM interact with the cationic surfactants, though the mode of interaction varied due to the different nature of surface groups.     

Depression in the cloud point of Tween in the presence of glycol additives and triblock polymers

Cloud point (C_P) measurements of Tween 20 and Tween 80 were carried out in the presence of various glycol oligomers and triblock polymers (TBP). The cloud points of both Tween 20 and 80 decrease in the presence of both types of additives. Among the glycol oligomeric additives, ethylene glycol monobutyl ether was found to reduce the C_P maximum. An increase in the repeating units of polymeric glycol additives leads to a decrease in C_P. Reduction in the C_P in the presence of TBP depends upon the increase in hydrophobic/hydrophilic ratio among the polypropylene to polyethylene units.     

MICELLE FORMATION BY ANIONIC AND CATIONIC SURFACTANTS IN AQUEOUS 18-CROWN-6 ETHER,P-CYCLODEXTRIN,AND 1,10-PHENANTHROLINE SOLUTIONS AT DIFFERENT TEMPERATURES

The conductances of sodium perfluorooctanoate (SPFO), sodium dodecylsulphate (SDS), dodecyltrimethylammonium bromide (DTAB), and tetradecyltrimethylammonium bromide (TTAB) in 18-crown-6 ether + water (CR+W), p-cyclodextrin + water (CY+W), and 1,10-phenanthroIine + water (Phen+W) mixtures with fixed 4 mM of each additive were determined over the temperature range of 5-55 °C. The conductivity plots for all the surfactants showed single break from which the critical micellization concentration (cmc) and degree of micelle ionization (x) were computed. From the pre and the post micellar slopes of the conductivity curves, the equivalent conductivities of the monomeric (Aass) and the micellar states (Amjc), respectively, were calculated and discussed with respect to the surfactant-additive complexation. It was observed that the micelle formation of all the ionic surfactants irrespective of the nature of their head groups were delayed in CYC+W in comparison to that in CR+W and Phen+W systems over the temperature range studied. The micelle formation of SPFO and SDS in CR+W and Phen+W systems showed stabilization of the respective micelles due to the adsorption of Na⁺-CR and Na+-Phen complexes at the micelle solution interface in comparison to that of DTAB and TTAB.