Enhancing near-infrared AIE of photosensitizer with twisted intramolecular charge transfer characteristics via rotor effect for AIE imaging-guided photodynamic ablation of cancer cells

Near-infrared (NIR) aggregation-induced emission (AIE) of previous organic photosensitizers is usually weak because of the competition between twisted intramolecular charge transfer (TICT) effect and AIE. Herein, we report a rational molecular design strategy to boost NIR AIE of photosensitizers and still to keep strong O-1(2) production capacity via rotor effect. To this end, one new triphenylamine (TPA)-based AIE photosensitizer, TPAM-1, is designed to give strong ability to generate O-1(2) but weak NIR fluorescence in the aggregate state due to the strong TICT effect. Another new TPA-based AIE photosensitizer, TPAM-2, is designed by introducing three p-methoxyphenyl units as rotors into the structure of TPAM-1 to modulate the competition between AIE and TICT. TPAM-1 and TPAM-2 exhibit stronger ability to generate O-1(2) in the aggregate state than the commercial photosensitizer, Ce6. Furthermore, TPAM-2 gives much brighter NIR luminescence (25-times higher quantum yield) than TPAM-1 in the aggregate state due to the rotor effect. TPAM-2 with strong NIR AIE and O-1(2) production capability was encapsulated by DSPE-PEG(2000) to give good biocompatibility. The DSPE-PEG(2000-)encapsulated TPAM-2 nanoparticles show good cell imaging performance and remarkable photosensitive activity for killing HeLa cells. This work provides a new way for designing ideal photosensitizers for AIE imaging-guided photodynamic therapy.

Automated summary

This study presents a novel molecular design strategy to enhance the near-infrared aggregation-induced emission (AIE) of photosensitizers while maintaining strong singlet oxygen (O-1(2)) production capacity. The newly designed materials show stronger ability to generate O-1(2) in the aggregate state compared to commercial photosensitizers, and exhibit brighter near-infrared luminescence in the aggregate state. The encapsulated nanoparticles also demonstrate good biocompatibility and efficient photosensitive activity for killing cancer cells.