Photoresponsive Behavior of Amphiphilic Copolymers of Azobenzene and N,N-Dimethylacrylamide in Aqueous Solutions

Copolymers of 4-methactyloyloxyazobenzene and N,N-dimethylacrylamide (MOAB-DMA) can aggregate strongly in aqueous solution (they are soluble in water up to a MOAB molar fraction of 0.2) to give concentration-dependent aggregate size distributions and well-defined boundaries between the dilute and semidilute regimes, as determined by dynamic fight scattering, surface tension, and probe solubilization experiments. The copolymers are strongly surface active, an uncommon observation for random copolymers, and exhibit pronounced photoviscosity effects at higher concentrations. The concentration dependence of the kinetic parameters for the reversible polymer rearrangement upon photoisomerization, as determined by electronic absorption spectroscopy, is attributed to steric hindrances. Trans-to-cis isomerization under UV light leads to partial dissociation of the azobenzene aggregates that cross-link the polymers, thereby significantly affecting the polymer solution rheology, with a consequent loss of viscoelasticity upon UV irradiation, especially in concentrated polymer solutions.