Polymer−surfactant interactions in aqueous solutions of a hydrophobically modified polymer, poly(maleic acid/octyl vinyl ether) (PMAOVE), with sodium dodecyl sulfate (SDS) were studied using surface tension, viscosity, electron paramagnetic resonance spectroscopy, and fluorescence spectroscopic techniques. When the anionic surfactant SDS was added to the aqueous solutions of the similarly charged polymer PMAOVE, the surfactant was incorporated into the hydrophobic nanodomains of PMAOVE far below the critical micelle concentration of the surfactant. Two inflection points were observed corresponding to the critical complexation concentration (formation of mixed micelles composed of SDS and the octyl chains of PMAOVE) and the saturation concentration (saturation of the polymer with SDS molecules). Above the saturation concentration, coexistence of pure SDS micelles and mixed micelles of PMAOVE and SDS was observed. At a PMAOVE concentration of 0.1% (w/w), a critical complexation concentration of 2 mM SDS and a saturation concentration of approximately 12 mM SDS were found; both the critical complexation concentration and the saturation concentration increase with increasing PMAOVE concentration.

The interaction of a hydrophobically modified anionic polymer (PMAOVE) with a cationic surfactant (DTAB) was studied using a multi-technique approach: turbidity, surface tension, and viscosity measurements, as well as EPR (5-doxyl stearic acid) and fluorescence (pyrene) probe techniques were used. In the investigated pH range (4-10), the cationic surfactant headgroups interact with the anionic carboxylic groups of the polymer backbone. In addition, nonpolar interactions of the surfactant chains with the n-octyl chains of PMAOVE stabilize the PMAOVE-DTAB complexes. Charge neutralization of the anionic polymer by the cationic surfactant leads to precipitation of the PMAOVE-DTAB complex at a certain DTAB concentration range. Further addition of DTAB causes a charge reversal of the complex and, subsequently, resolubilization of the precipitate. At an acidic pH (pH = 4), a second precipitation was observed, which is probably caused by conformational changes in the PMAOVE-DTAB complex. This second precipitate can be resolubilized by further addition of surfactant. At a neutral and basic pH, this second precipitation is absent. EPR analysis indicates that the surfactants form an ordered structure at the extended polymer chain at a neutral and basic pH, whereas at an acidic pH, a less ordered surfactant layer is formed on the coiled polymer with more hydrophobic microdomains.

Interactions of surfactants with hydrophobically modified polyelectrolytes in aqueous solutions are important in several applications such as detergency, cosmetics, food, and paints. Complexes formed in these systems raise some fundamental questions about the polymer-surfactant interactions that control their behavior. In this work, the interactions of a nonionic surfactant, penta-ethyleneglycol mono n-dodecyl ether (C(12)EO(5)), with a hydrophobically modified anionic polymer, poly(maleic acid/octyl vinyl ether) (PMAOVE), in aqueous solutions were studied using surface tension, viscosity, electron paramagnetic resonance (EPR) spectroscopy, light scattering, and fluorescence spectroscopic techniques. When the nonionic surfactant C(12)EO(5) was added to aqueous solutions of the anionic polymer PMAOVE, it was incorporated into the hydrophobic nanodomains of PMAOVE far below the the critical micelle concentration (cmc) of the surfactant. Two inflection points were observed corresponding to the critical complexation concentration (formation of mixed micelles composed of C(12)EO(5) and the octyl chains of PMAOVE) and the saturation concentration (saturation of the polymer with C(12)EO(5) molecules). Above the saturation concentration, the coexistence of pure C(12)EO(5) micelles and mixed micelles of PMAOVE and C(12)EO(5) was observed. Such a coexistence of complexes has major implications in their performance in colloidal processes.

A ‘touch me not’ plant folding up rapidly upon being attacked or microbes depositing on teeth or ocean vessels even under hostile conditions are examples in nature that provide inspiration for developing new classes of personal care release or deposition systems. In this paper, development of such systems based on polymer/surfactant colloid chemistry is explored for achieving transport and release of cosmetic and pharmaceutical molecules at desired rates at desired sites. The successful development of products depends upon understanding and utilizing key interactions among surfactants, polymers and hybrid polymers that are relevant to personal care products. Thus, the absorbed layers or tethers on the particulates can be manipulated for desired dispersion of actives or depositions on substrate under any and all conditions. New hybrid polymers and nanogels have been synthesized for tuning up nanodomains that can extract and deliver at will cosmetics/drugs/toxins by perturbing pH, temperature or ionic strength of the system. Particularly, hydrophobically modified polymers have features of both polymers and surfactants and due to the associative nature of the hydrophobic groups, such polymers can form intramolecular nanodomains for performing carrier functions. Nanogels developed recently include that of polyacrylamide, poly(acrylic acid) and starch nanogels modified for extraction and subsequent slow release of fragrances and overdosed toxic drugs. Binding and release processes were investigated using surface plasmon resonance and fluorescence spectroscopies, powerful techniques for monitoring short term and long term changes.