Self-aggregation of synthesized novel bolaforms and their mixtures with sodium dodecyl sulfate (SDS) and cetyltrimethylammonium bromide (CTAB) in aqueous medium.

Bolaforms B(1), B(2), and B(3) of the formulas, Br(-)Me(3)N(+)(CH(2))(10)N(+)Me(3)Br(-), Br(-)Me(3)N(+)(CH(2))(10)OH, and Br(-)Me(3)N(+)(CH(2))(10)COO(-)Na(+), respectively, were synthesized, and their properties in the bulk as well as at the air/aqueous NaBr (10 mM) solution interface have been studied. Their interactions with sodium dodecyl sulfate (SDS) and cetyltrimethylammonium bromide (CTAB) also have been investigated. Tensiometry, conductometry, spectrophotometry, and microcalorimetry techniques were used for characterization and estimation. Both pure bolaforms and their mixtures with SDS and CTAB have been found to self-aggregate, forming micelles in solution. The mixed systems of bolaform and SDS have been observed to form both micelles and vesicles. Their mutual interactions were synergistic, which at the interface was more spontaneous than in the bulk. The interfacial and bulk compositions of the mixed binary systems (bolaform and SDS or CTAB) with their associated interaction parameters have been estimated from the Rosen interaction model and the regular solution theory of Rubingh, respectively. The formed vesicles have been found to entrap the water-soluble dye, bromophenol blue, and the dye solubilized vesicles of B(1)-SDS and B(2)-SDS completely eluted out of the sephadex column proving their formation. A rough estimation of the size and polydispersity index of the formed micelles and vesicles has been made from DLS measurements.

Amphiphile self-aggregation: an attempt to reconcile the agreement-disagreement between the enthalpies of micellization determined by the van't Hoff and Calorimetry methods.

In this article, discrepancies between the enthalpies of micellization of amphiphiles in aqueous solution determined by the methods of van't Hoff (VH) and calorimetry have been addressed. The contributions of the hydrophobic interaction, electrostatic interaction and the micellar size effect have been considered to assess the total picture of the amphiphile self-association process and related energetic parameters, especially the enthalpy and the specific heat capacity. Literature results on 23 amphiphile systems (six nonionics, five anionics, and twelve cationics) have been analyzed, and the assessed enthalpies by VH method and direct calorimetry have been presented and compared. VH results considering participation of 5% of total amphiphile monomer to form micelle at cmc have been also compared. In addition to this, the changes in the standard specific heat of micellization for all the amphiphile aggregation processes evaluated by the VH and calorimetry procedures have been presented. The differences between the standard enthalpy of micellization DeltaH(m)(o) by the methods of VH and calorimetry are minor for nonionic surfactants but major for ionics, whereas the standard specific heat capacities of micellization (DeltaC(Pm)(o)) by both the procedures fairly agree for all types of surfactants. Like DeltaH(m)(o)-DeltaS(m)(o) compensation observed in kinetic and equilibrium processes, a linear correlation between Lt(T-->0)DeltaH(m)(o) and DeltaC(Pm)(o) has been observed with no distinction between the VH and calorimetry derived results for all the surfactant systems herein dealt with.

A LB film morphological study with reference to biopolymer-surfactant interaction taking gelatin-CTAB system as a model.

The interaction of gelatin with cetyltrimethylammonium bromide (CTAB) studied at pH 9 and an ionic strength of 0.005, produces an interfacial surface active gelatin-CTAB (monomer) complex (GS(n)(I)), a surface inactive gelatin-CTAB (micelle) complex in bulk (GS(m)(B)), followed by coacervation, and its solubilization in micellar solution of CTAB. We have herein attempted to probe the interfacial morphological changes of gelatin and its CTAB complexes, and not the bulk properties like coacervation and/or micellar solubilization. The morphologies of pure gelatin and CTAB films and that of gelatin-CTAB interacted complex at the interface have been investigated using LB, SEM, AFM and ellipsometric techniques. The stability of the gelatin monolayer at varied concentrations with and without CTAB has been examined. The SEM images of stabilized films of gelatin and gelatin-CTAB complex have witnessed compact smooth as well as rough surfaces with formation of distinct domains. Drastic morphological change in the film before the critical aggregational concentration of CTAB (T(2)) has been in line with an initial abrupt decrease in surface tension. This has been corroborated by AFM measurements, which along with morphology demonstration has provided information on the diameter of the ensembles formed and roughness of the LB films constituted of pure components and their complexes. Thickness of the film was at its maximum in the domain region, as corroborated by ellipsometric technique. Such an elaborate interfacial monolayer and film morphology study of biopolymer-amphiphile system has been rarely documented in literature.

Physicochemical studies on the interaction of gelatin with cationic surfactants alkyltrimethylammonium Bromides (ATABs) with special focus on the behavior of the hexadecyl homologue.

The interaction of a denatured interfacially active protein, gelatin (G) (at pH 9, above its isoelectric pH 4.84, and ionic strength mu=0.005), with a cationic amphiphile, hexadecyl (or cetyl) trimethylammonium bromide, CTAB, has been elaborately studied using a variety of techniques. Two types of protein-surfactant complexes at a concentration below the normal critical micellar concentration (cmc) were formed in solution. The first, G-CTAB (monomer) combined complex (GS(n)(I)) adsorbed at the air/solution interface, followed by its gradual transformation to the poor interfacially active second G-CTAB (aggregate) complex (GS(m)(B)) at a critical aggregation concentration (cac) of the interacting oppositely charged surfactant. In the higher concentration range, upon completion of GS(m)(B) formation, coacervation (association of GS(m)(B)) led to add turbidity. With increasing addition of CTAB, the coacervates became disintegrated and ultimately remained dissolved in the free micellar solution of CTAB. The above features were studied using the techniques of tensiometry, conductometry, turbidimetry, fluorimetry, and microcalorimetry. The interaction features were prominent at [G] >or= 0.05 g %, and several of these were either marginal or absent at [G]<0.05 g %. The denatured protein was found to form viscous as well as gel-forming consistencies at higher [G] and at lower temperature. A temperature variation study on the interaction of G with CTAB has revealed that enhanced interaction takes place at higher temperature. The effect of [G] on its interaction with cationic surfactants of varying chain length in the alkyltrimethylammonium bromide (ATAB) series has been also studied; a similar interactional profile as that of CTAB has been exhibited by octadecyltrimethylammonium bromide; however, the lower homologues (dodecyl- and tetradecyl-) of ATAB have offered different profiles. It has been found that the ATABs with higher alkyl chain lengths were more interactive with negatively charged G than their lower homologues. Quantification of the results in terms of different transition points, counterion binding of the protein-bound surfactant aggregates and free micelles, the enthalpy of binding interactions and energetics of ATAB micellization, and so forth have been studied. The results have been rationalized in terms of an interaction model.

Interfacial and solution properties of tetraalkylammonium bromides and their sodium dodecyl sulfate interacted products: a detailed physicochemical study.

The adsorption and solution behaviors of symmetrical tetramethyl-, tetraethyl-, tetrapropyl-, and tetrabutylammonium bromides (TMAB, TEAB, TPAB, and TBAB, respectively) were studied at the air/water interface and in the bulk aqueous environments. Their salts were prepared by reacting tetraalkylammonium bromide (TAAB) with sodium dodecyl sulfate (SDS) in a solution from which the products of the higher two homologues (tetrapropylammonium dodecyl sulfate (TPADS) and tetrabutylammonium dodecyl sulfate (TBADS)) could only be isolated as solids and for which detailed characterization has been performed. The interfacial behaviors of 1:1 molar mixtures of TAAB and SDS and the prepared TPADS and TBADS were examined. Micellization of the 1:1 mixtures along with the isolated species were studied in the presence and absence of NaBr salt. The energetics of the micellization process and the counterion binding of the micelles were evaluated. The interaction of the TAABs with SDS micelles was examined, and the results were evaluated in terms of single- and two-site binding interaction models. Of the formed tetraalkylammonium dodecyl sulfates (TAADSs), only TBADS evidenced clouding, which was investigated in detail along with 1:1 molar mixtures of TBAB and SDS in aqueous solution in the presence of additives such as NaBr, SDS, and TBAB. The solution behaviors of the TAADS and the clouding of TBADS have been rationalized in terms of a mixed micellar model.

Physicochemical studies on cetylammonium bromide and its modified (mono-, di-, and trihydroxyethylated) head group analogues. Their micellization characteristics in water and thermodynamic and structural aspects of water-in-oil microemulsions formed with them along with n-hexanol and isooctane.

The micellization behavior of cetylammonium bromide and its mono-, di-, and trihydroxyethylated head group analogues and water/oil (w/o) microemulsion formation with them have been studied with detailed thermodynamic and structural considerations. The critical micellar concentration, micellar aggregation number, and behavior of the surfactants at the air/solution interface have been studied in detail. The results have been analyzed and discussed. The formation of the w/o microemulsion stabilized by the aforesaid surfactants in conjunction with the cosurfactant n-hexanol in isooctane has been investigated by the dilution method. The energetics of the transfer of cosurfactant from oil to the interface has been estimated. The structural parameters, namely, droplet dimension, droplet number, and population of surfactant and cosurfactant on the droplet surface, have also been estimated. The efficacy of the surfactants in respect to water dispersion in oil and cosurfactant concentration level at the oil/water interface has been worked out. Such microemulsions are prospective compartmentalized systems to assist enzyme activities. In this respect, the trihydroxyethylated head group analogue in the above series has been found to be a better performer for the preparation and stabilization of microemulsions that has correlated well with its performance than the others in the hydrolysis of p-nitrophenyl-n-hexanoate by the enzyme Chromobacterium viscosum lipase.