Aromaticity Tuning of Heavy-Atom-Free Photosensitizers for Singlet Fission-Enhanced Immunogenic Photodynamic Oncotherapy.

Nano Lett

Key Laboratory of Flexible Electronics (KLOFE) and School of Flexible Electronics (Future Technologies), Nanjing Tech University, Nanjing 211816, China.

Published: June 2024

AI Article Synopsis

  • The study explores the significance of quantum yield of reactive oxygen species in optimizing organic photosensitizers for photodynamic therapy (PDT), addressing the issues posed by incorporating heavy atoms.
  • A novel heavy-atom-free (HAF) photosensitizer design uses "single-atom surgery" to modify pyrazino[2,3-]quinoxaline structures, allowing for generation of two triplet excitons via the singlet fission (SF) mechanism.
  • The HAF photosensitizers PhPQ and TriPhPQ show remarkable triplet-state quantum yields and improved PDT efficacy, making them promising candidates for cancer treatment in combination with immune checkpoint therapy.

Article Abstract

The quantum yield of reactive oxygen species is of central importance for the development of organic photosensitizers and photodynamic therapy (PDT). A common molecular design approach for optimizing organic photosensitizers involves the incorporation of heavy atoms into their backbones. However, this raises concerns regarding heightened dark cytotoxicity and a shortened triplet-state lifetime. Herein, we demonstrate a heavy-atom-free (HAF) photosensitizer design strategy founded on the singlet fission (SF) mechanism for cancer PDT. Through the "single-atom surgery" approach to deleting oxygen atoms in pyrazino[2,3-]quinoxaline skeleton photosensitizers, photosensitizers PhPQ and TriPhPQ are produced with Huckel's aromaticity and Baird's aromaticity in the ground state and triplet state, respectively, enabling the generation of two triplet excitons through SF. The SF process endows photosensitizer PhPQ with an ultrahigh triplet-state quantum yield (186%) and an outstanding O quantum yield (177%). Notably, HAF photosensitizers PhPQ and TriPhPQ enhanced PDT efficacy and potentiated αPD-L1 immune check blockade therapy , which show their promise for translational oncology treatment.

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Source
http://dx.doi.org/10.1021/acs.nanolett.4c01862DOI Listing

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