Aggregation-Caused Quenching-Type Naphthalimide Fluorophores Grafted and Ionized in a 3D Polymeric Hydrogel Network for Highly Fluorescent and Locally Tunable Emission.

Polymer hydrogels with intense yet tunable fluorescence are of great research interest due to their wide potential use in biological imaging, sensing, information storage, etc. However, the conventional fluorophores such as naphthalimide and its derivatives are usually not recommended to prepare highly fluorescent hydrogels because of their aggregation-caused quenching (ACQ) nature and spontaneous tendency to undergo fluorescence self-quenching in quasi-solid-state hydrogel systems. Additionally, local regulation over fluorescent behavior of hydrogels, despite being important, still remains underdeveloped. Herein, we report highly fluorescent polymeric hydrogels based on conventional ACQ-type naphthalimide fluorophores, followed by spatial and temporal control of their fluorescent behavior. The hydrogels were prepared by one-pot radical copolymerization of naphthalimide-containing monomer and acrylamide in chitosan-acetic acid solution. Their intense emission comes from synergetic anchoring and diluting effect of the protonated naphthalimide moieties grafted on polymer chains, which result in the electrostatic repulsion among ACQ luminogens and reduced PET (photoinduced electron transfer) effect from adjacent dimethylamine groups to naphthalimide fluorophores. After being deprotonated in alkaline conditions, both PET and the ACQ effect work again to greatly quench fluorescence, endowing the hydrogels with pH-sensitive emission behavior. These properties encourage us to develop a diffusion-reaction (D-R) method to spatially and temporally control their fluorescent behavior. Based on these results, the ion-transfer-printing-assisted D-R method was further developed to fabricate many high-precision and meaningful fluorescent patterns on hydrogels. These fluorescent patterns are invisible under daylight but become vivid under specific UV light illumination, suggesting their wide potential applications in information security and transmission.