Preparation and properties of hydrogel photonic crystals assembled by biodegradable nanogels.

ABSTRACT

Thermally induced physical hydrogels formed through the sol-gel transition of nanogels usually lose structural color above phase transition temperature (Tp). Herein, temperature/pH/redox-responsive nanogels that undergo sol-gel transition still keep structural colors above the Tp have been synthesized and studied. N-isopropylacrylamide (NIPAm) was copolymerized with N-tert-butylacrylamide (TBA) and N-acrylamido-l-phenylalanine (Aphe) to form P(NIPAm/TBA/Aphe) nanogel crosslinked with N,N'-bis(acryloyl)cystine (BISS) (referred to as PNTA-BISS). PNTA-BISS nanogel with a broad range of biodegradable crosslinker BISS content can achieve a reversible sol-gel transition above the Tp, surprisingly, while PNTA nanogels with a comparable content of biodegradable N,N'-Bis(acryloyl)cystam (BAC) crosslinker (referred to as PNTA-BAC) didn't form sol-gel transition. Although BISS and BAC possess same disulfide bonds with redox properties, BISS, unlike BAC, is water-soluble and features two carboxyl groups. The mechanism by which PNTA-BISS nanogels form hydrogel photonic crystals has been deeply explored with temperature-variable NMR. The results showed the introduction of Aphe with both steric hindrance and carboxyl groups greatly slowed down the shrinkage of PNTA-BISS nanogels. Therefore, PNTA-BISS nanogels can form sol-gel transition and further structural color of hydrogel photonic crystals due to carboxyl groups above the Tp. Furthermore, the properties of biodegradable hydrogel photonic crystals above the Tp were investigated for the first time, attributed to the presence of the strong reducing agent 1,4-dithiothreitol (DTT). When loaded with doxorubicin (DOX), PNTA-BISS exhibited favorable degradation properties under the influence of DTT. In summary, the PNTA-BISS nanogel, in addition to its in-situ gelation capabilities, demonstrated degradability, potentially providing a novel nanoplatform for applications in drug delivery, biotechnology, and related fields.