Interfacial complexation of a neutral amphiphilic 'tardigrade' co-polymer with a cationic surfactant: Transition from synergy to competition

Abstract

Hypothesis: Neutral amphiphilic PEG-g-PVAc co-polymer (a "tardigrade" polymer consisting of a hydrophilic polyethylene glycol, PEG, backbone with hydrophobic polyvinyl acetate, PVAc, grafts) can form complexes at the air-water interface with cationic dodecyltrimethylammonium bromide (DTAB) via self-assembly. Compared to anionic SDS, cationic DTAB headgroups are expected to interact strongly with the negatively charged OH^- groups from the partial dissociation of the PVAc grafts. We anticipate a transition from synergistic to competitive behaviour, which is expected to be dependent on the surfactant structural characteristics and concentration.

Experiments: DTAB/PEG-g-PVAc mixtures were investigated using a combination of dynamic and equilibrium surface tension measurements, neutron reflectivity (NR) at the air-water interface, and foaming tests. We varied the concentrations of both the DTAB (0.05 to 5 critical micelle concentration, cmc) and that of PEG-g-PVAc (0.2 and 2 critical aggregation concentration, cac).

Findings: Our results show that the interfacial interactions between DTAB and PEG-g-PVAc were both synergistic and antagonistic, depending sensitively on the surfactant concentration. At DTAB concentrations below its cmc, a pronounced cooperative adsorption behaviour was likely driven by the hydrophobic interactions between the DTAB tail and the PVAc grafts and the attraction between the DTAB headgroups and the partially dissociated -O^- groups in the partially hydrolysed PVAc grafts, forming a mixed layer. This synergistic adsorption behaviour transitioned to a competitive adsorption behaviour at DTAB concentrations above its cmc, leading to polymer-surfactant partition, forming a "hanging" polymer layer underlying a surfactant monolayer at the interface. We postulate that DTAB/PEG-g-PVAc complexation in the bulk contributed to partial depletion of the mixture from the interface. We therefore consider this polymer/surfactant system to be a moderately interacting system at the air-water interface. No discernible differences in the foaming behaviour were observed between the DTAB/PEG-g-PVAc systems and the pure surfactant. Our results suggest that surfactant headgroup characteristics (particularly charges) were crucial in determining the structure and composition of polymer-surfactant complexes at the air-water interface, as well as the foamability and foam stability, whilst the coexistence of the synergistic and competitive adsorption behaviour is attributed to the unique architecture of the tardigrade polymer with amphiphilicity and partial charge, facilitating different surfactant-polymer interactions at different DTAB concentrations.