Reversible Solubility Switching of a Polymer Triggered by Visible‐Light Responsive Azobenzene Photochromism with Negligible Thermal Relaxation

Abstract

AbstractThis study reports the reversible solubility switching of a polymer triggered by non‐phototoxic visible light. A photochromic polymerizable azobenzene monomer with four methoxy groups at the ortho‐position (mAzoA) was synthesized, exhibiting reversible photoisomerization between trans‐ and cis‐states using green (546 nm) and blue light (436 nm). Free radical copolymerization of hydrophilic dimethylacrylamide (DMAAm) with mAzoA produced a light‐responsive random copolymer (P(mAzoA‐r‐DMAAm)) that shows a reversible photochromic reaction to visible light. Optimizing mAzoA content resulted in P(mAzoA10.7‐r‐DMAAm)3.0 kDa exhibiting LCST‐type phase separation in PBS (pH 7.4) with trans‐ and cis‐states at 39.2 °C and 32.9 °C, respectively. The bistable temperature range of 6.3 °C covers 37 °C, suitable for mammalian cell culture. Reversible solubility changes were demonstrated under alternating green and blue light at 37 °C. 1H NMR indicated significant retardation of thermal relaxation from cis‐ to trans‐states, preventing undesired thermal mechanical degradation. Madin Darby Canine Kidney (MDCK) cells adhered to the P(mAzoA‐r‐DMAAm) hydrogel, confirming its non‐cytotoxicity and potential for biocompatible interfaces. This principle is useful for developing hydrogels that can reversibly stimulate cells mechanically or chemically in response to visible light.