Light-Controlled Reversible Manipulation of Microgel Particle Size Using Azobenzene-Containing Surfactant

The light‐induced reversible switching of the swelling of microgel particles triggered by photo‐isomerization and binding/unbinding of a photosensitive azobenzene‐containing surfactant is reported. The interactions between the microgel (N‐isopropylacrylamide, co‐monomer: allyl acetic acid, crosslinker: N,N′‐methylenebisacrylamide) and the surfactant are studied by UV‐Vis spectroscopy, dynamic and electrophoretic light scattering measurements. Addition of the surfactant above a critical concentration leads to contraction/collapse of the microgel. UV light irradiation results in trans‐cis isomerization of the azobenzene unit incorporated into the surfactant tail and causes an unbinding of the more hydrophilic cis isomer from the microgel and its reversible swelling. The reversible contraction can be realized by blue light irradiation that transfers the surfactant back to the more hydrophobic trans conformation, in which it binds to the microgel. The phase diagram of the surfactant‐microgel interaction and transitions (aggregation, contraction, and precipitation) is constructed and allows prediction of changes in the system when the concentration of one or both components is varied. Remote and reversible switching between different states can be realized by either UV or visible light irradiation. Remote reversible control of swelling/contraction transition of a microgel is realized using azobenzene‐containing surfactant. The azobenzene unit is switched between more hydrophilic cis (UV light) and more hydrophobic trans (blue light) state, which alters the surfactant's affinity to the microgel. The trans‐surfactant binds to the gel, triggering its contraction, and the cis‐surfactant unbinds, leading to microgel swelling.