In this paper, results of physicochemical studies on the interaction of bovine serum albumin (BSA) with alkyltrimethylammonium bromide (ATAB), pentaethylene glycol mono-n-dodecyl ether (C12E5), and sodium dodecyl sulfate (SDS) under the experimental conditions of phosphate buffer at pH 7 in the presence of 10 mM sodium bromide (NaBr), maintaining the ionic strength of the overall solution at micro = 0.015 M, have been presented and discussed. Here, BSA-ATAB corresponds to a polyion-surfactant system bearing opposite charges. BSA precipitated out of the solution on addition of ATAB solution over a certain range of ATAB concentration, the concentration range being dependent on the particular member of the ATAB family. In our earlier reports on the precipitation of oppositely charged polymer-surfactant, the tensiometric profile for surfactant addition in polymer solution differed significantly from that expected from addition of surfactant in the dispersion medium. In the present study, the precipitation process could hardly affect the smoothness of the tensiometric profile. This indicates the interaction process is operative in bulk solution. Microcalorimetric profiles also evidenced an extra hump in the interaction profile at lower surfactant concentrations, without much affecting the dilution enthalpograms beyond micellization. This interaction appeared unimodal and the extent of interaction increased with increasing tail length of ATAB, evidencing the hydrophobic effect to be an important factor. Addition of salt (NaBr) also affected the nature of interaction: at lower concentration of NaBr, the interaction was mildly assisted, whereas 50 mM NaBr fairly assisted the interaction. The nonionic surfactant C12E5 modestly interacted with BSA. The anionic amphiphile SDS, on the other hand, interacted with BSA in two distinctly different stages, as evidenced from the tensiometric profile. The complexity of the BSA-SDS tensiometric isotherm compared to that of BSA-ATAB arose from the presence of cationic binding sites adjacent to hydrophobic patches of BSA in its native state, so that electrostatic and hydrophobic interactions can cooperatively operate side by side. The interfacial saturation occurred at a lower concentration in the presence of BSA compared to the normal cmc of SDS under identical solution conditions in the absence of BSA, which was slightly delayed for nonionic C12E5. The multitechnique approach evidenced that different experimental techniques probe different physicochemical phenomena and an attempt to show the concurrence of the break points in different techniques is only diluting the essence of this area.

Interaction between polymer and surfactant bearing opposite charges is much more complex from a physicochemical point of view as compared to interaction between ionic surfactant and nonionic polymer. Electrostatic and hydrophobic interactions interplay in the former, whereas the hydrophobic effect is the prevailing factor in the latter. We have studied the interaction between a water-soluble polyanion, sodium salt of carboxymethylcellulose (NaCMC), with a cationic amphiphile, CTAB, in aqueous medium. There were manifold discrepancies with the reported works in NaCMC-alkyltrimethylammonium bromide, which is assumed to be an effect of difference in degree of substitution, which in turn affects the charge density of the polymer chain. We have noticed that the bulk complexation and interfacial interaction driven by electrostatic forces operate side by side. Thereafter, there is a wrapping process by the polyanion to the polymer-induced smaller surfactant aggregates driven by increase in entropy of the solution as a result of expulsion of the counterions from the ionic atmosphere around the surfactant aggregate. Because of the electrostatic interaction, hydrophobicity of the polymer-surfactant complex increases, leading to coacervation, and again solubilization in the hydrophobic core of the self-aggregated structure provided by the added excess CTAB. The tensiometric, conductometric, microcalorimetric, and turbidimetric techniques have been applied to address these problems.

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The interaction between pepsin and CTAB has been elaborately studied with a number of techniques. The enzyme-induced interaction produced complexes, aggregates, and micelles of CTAB with distinct physicochemical features. It was found that at very low surfactant concentration (much below the critical micellar concentration (cmc) of pure CTAB), the surfactant got adsorbed both in monomeric and lower aggregated forms to the high-energy sites of the native biopolymer, leading to enhanced hydrophobicity of the combine, and hence, lowering of the interfacial (air/solution) tension. This was followed by the formation of a faintly turbid solution of the polymer-surfactant coacervate. The CTAB interacted unfolded pepsin along with the surfactant monomer remained adsorbed at the interface to decrease the interfacial tension (gamma) to a low level to produce a break in the gamma vs log [CTAB] plot prior to the normally observed extended cmc (cmce) in presence of polymers. The cac-like aggregation (as observed in tensiometry and viscometry) was not found in conductometry and microcalorimetry, whereas microcalorimetry evidenced the formation of the cmce of CTAB in the presence of the biopolymer. The CTAB influenced structural features of the pepsin were assessed from spectral, viscometric, and circular dichroism measurements.

The detailed interfacial adsorption and micellization behavior of pure and mixed alkyltrimethylammonium bromides (ATABs: C10-, C12-, C14-, and C16TAB) were studied using tensiometric, conductometric, fluorimetric, viscometric, and calorimetric methods. The critical micellar concentration (CMC), thermodynamics of adsorption and micellization, counterion binding, aggregation number, and micellar polarity were determined. It was observed that the studied 1:1 molar mixtures of C10-C12TAB, C10-C14TAB, and C10-C16TAB, and the mixtures C12-C14TAB and C12-C16TAB at different mole ratios produced two CMCs that were supported by the conductometric, calorimetric and viscometric methods. Compared to the first micelle, the second micelle condensed more counterions and produced a higher aggregation number, but their interior polarity states were the same. The surface excess, area minimum of the ATABs at the CMC and Gibbs free energy of adsorption were evaluated and compared. The ideality/nonideality states of the mixed micelles formed in solution were tested in the light of Clint and Rubingh's formalisms; the mixed systems were found to undergo moderate to weak synergistic interaction. The contributions of the terminal methyl group, the intermediate methylene groups, and the hydrophilic tetramethylammonium group toward the standard Gibbs free energy, enthalpy, and entropy of the micellization processes were deciphered and discussed.

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.

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The micellization behavior of MEGA 10 has been studied at nine different temperatures by isothermal titration calorimetry (ITC), and thermodynamics of the process have been evaluated and examined in detail. The aggregation number of the nonionic surfactant has been estimated from the ITC results by a simulation procedure based on the mass action principle of micellization of the surfactant. The cmc of MEGA 10 has shown a minimum in temperature dependence as observed for ionic surfactants. For a comparison, the cmc and related thermodynamic parameters of an ionic surfactant, tetradecyltriphenylphosphonium bromide (C(14)TPB) studied at several temperatures in aqueous medium has been considered. The contributions of the headgroups of both the surfactants to the free energies of their respective micellization have been deciphered and presented.