Kinetics of Photocontrollable Micelles: Light-Induced Self-Assembly and Disassembly of Azobenzene-Based Surfactants Revealed by TR-SAXS.

The kinetics of micelles involving photosensitive surfactants is still not well understood. In this work, we unravel the mechanistic pathways involved in the micelle formation and dissolution of photocontrollable micelles. We focus on the fast self-assembly processes of photosensitive cationic azobenzene-containing surfactants (AzoTMA) that display a change in hydrophobicity induced by a reversible cis-trans conformational transition upon exposure to light. By combining both in situ time-resolved small-angle X-ray scattering (SAXS) and light scattering, we characterized the detailed structure and phase behavior of AzoTMA in mixtures of water and dimethylformamide (DMF). Time-resolved synchrotron SAXS with monochromatic light as a trigger enabled us to observe the nonequilibrium formation and dissolution process of micelles (demicellization) directly on the nanoscale with a time resolution starting from milliseconds. The structural results show that in pure water UV-light illumination leads to a 12% reduction of the aggregation number of the micelles and more than a 50% increase in the critical micelle concentration (CMC). Close to the CMC, adjusted by the addition of DMF, UV light illumination leads to a complete dissolution of the micelles, while shining blue light reverses the process and leads to the reformation of micelles. The UV-triggered dissolution follows a two-step mechanism; the first and rapid (second time scale) release of unimers is followed by a slower decomposition of the micelles (over tens of seconds) as a result of an increase in temperature due to optical absorption. Similarly, the reverse process, i.e., micelle formation, occurs rapidly upon photoconversion to trans conformers under blue light, and micelles are disrupted at long exposure time due to the optical absorption and corresponding increase in temperature. Interestingly, the coexistence of unimers with regular micelles is found at all times, and no other transient assemblies could be detected by SAXS.