UV-Responsive Behavior of Multistate and Multiscale Self-Assemblies Constructed by Gemini Surfactant 12-3-12·2Br- and trans- o-Methoxy-cinnamate.

Abstract

Photoresponsive systems with adjustable self-assembly morphologies and tunable rheological properties have aroused widespread concern of researchers in recent years because of their prospect applications in controlled release, microfluidics, sensors, and so forth. In this paper, we combine a cationic Gemini surfactant 12-3-12·2Br- and trans-2-methoxy-cinnamate ( trans-OMCA) together to create a representative UV-responsive self-assembly system. The system displays abundant self-assembly behaviors, and the self-assemblies with different states and different scales including wormlike micelles, vesicles, and lyotropic liquid crystals (LCs) as well as an aqueous two-phase system (ATPS) are observed even at lower surfactant concentration. The UV-responsive behavior of the formed self-assemblies is investigated systematically. The results have shown that the photoisomerization of OMCA from trans form to cis form under UV light irradiation alters the hydrophobicity and steric hindrance effect of OMCA and thus affects the molecular packing at the micellar interface and further leads to the transformation of assembly morphologies. The long wormlike micelles can gradually transform into much shorter rodlike micelles under UV irradiation and companied by the decrease of solution viscosity by 2 orders of magnitude. In addition, the vesicles can evolve into multistate self-assembly structures including the ATPS, wormlike micelles, rod-like micelles, and small spherical micelles depending on the UV irradiation time. The ATPS and its adjacent anisotropic LC phase can respectively combine into a single phase and separate into ATPS under UV irradiation. The morphologies of assemblies in the 12-3-12·2Br-/ trans-OMCA mixed system can be tailored by adjusting the system composition and duration of UV light irradiation on purpose. The photoresponsive system with abundant self-assembly behaviors and tunable rheological properties has wide application prospect in numerous fields such as drug delivery, materials science, smart fluids, and so forth, and the macroscopic phase separation and combination provide novel strategies for effective separation and purification of certain substances.