Synthesis and Properties of UCST-Type Thermo- and Light-Responsive Homopolypeptides with Azobenzene Spacers and Imidazolium Pendants

Homopolypeptide bearing azobenzene and triethylene glycol spacers, and 1-butylimidazolium pendants, namely P(Azo-OEG 3 -ImX) (X = Cl, I, BF 4 ) are prepared by 1,3-dipolar cycloaddition and subsequent ion-exchange reaction. Both 1 H NMR and FTIR confirm the polymer structures and reveal a high grafting efficiency (97%). P(Azo-OEG 3 -ImI) shows reversible upper critical solution temperature (UCST)-type thermoresponsive property in ethanol while P(Azo-OEG 3 -ImI/BF 4 ) shows a UCST in ethanol/water solvent mixtures. P(Azo-OEG 3 -ImI) shows UCST-type phase transitions in ethanol or ethanol/water solvent mixtures. After UV irradiation, the UCST-type cloud point temperature ( T cp ) remains constant in ethanol. However, it decreases after UV irradiation and increases after visible light irradiation in ethanol/water solvent mixtures due to the trans – cis isomerization of azobenzene moieties. P(Azo-OEG 3 -ImCl/I) shows NaI-induced UCST in water. The T cp of the P(Azo-OEG 3 -ImCl/I) aqueous solution is highly related to the polymer/salt concentration and nature of counteranions. P(Azo-OEG 3 -ImCl) also shows reversible light-responsive properties in NaI aqueous solutions. Higher NaI concentration is needed to induce a UCST for P(Azo-OEG 3 -ImCl) after UV irradiation. Moreover, ciprofloxacin-loaded hydrogel containing P(Azo-OEG 3 -ImCl) shows more efficient drug release while the UV irradiation leads to slightly low drug release.