Light and Temperature as Dual Stimuli Lead to Self-Assembly of Hyperbranched Azobenzene-Terminated Poly(N-isopropylacrylamide).

Hyperbranched poly(-isopropylacrylamide)s (HBPNIPAMs) end-capped with different azobenzene chromophores (HBPNIPAM-Azo-OC₃H₇, HBPNIPAM-Azo-OCH₃, HBPNIPAM-Azo, and HBPNIPAM-Azo-COOH) were successfully synthesized by atom transfer radical polymerization (ATRP) of -isopropylacrylamide using different azobenzene-functional initiators. All HBPNIPAMs showed a similar highly branched structure, similar content of azobenzene chromophores, and similar absolute weight/average molecular weight. The different azobenzene structures at the end of the HBPNIPAMs exhibited reversible isomerization behavior under alternating UV and Vis irradiation, which lowered the critical solution temperature (LCST) due to different self-assembling behaviors. The spherical aggregates of HBPNIPAM-Azo-OC₃H₇ and HBPNIPAM-Azo-OCH₃ containing hydrophobic para substituents either changed to bigger nanorods or increased in number, leading to a change in LCST of -2.0 and -1.0 °C, respectively, after UV irradiation. However, the unimolecular aggregates of HBPNIPAM-Azo were unchanged, while the unstable multimolecular particles of HBPNIPAM-Azo-COOH end-capped with strongly polar carboxyl groups partly dissociated to form a greater number of unimolecular aggregates and led to an LCST increase of 1.0 °C.