TY - JOUR
T1 - Elucidation of the Intersystem Crossing Mechanism in a Helical BODIPY for Low-Dose Photodynamic Therapy
AU - Wang, Zhijia
AU - Huang, Ling
AU - Yan, Yuxin
AU - El-Zohry, Ahmed
AU - Toffoletti, Antonio
AU - Zhao, Jianzhang
AU - Barbon, Antonio
AU - Dick, Bernhard
AU - Mohammed, Omar F.
AU - Han, Gang
N1 - KAUST Repository Item: Exported on 2020-10-01
Acknowledgements: J.Z. thanks the NSFC (21673031, 21761142005, 21911530095 and 21421005), the State Key Laboratory of Fine Chemicals (ZYTS201901), the Fundamental Research Funds for the Central Universities (DUT19TD28), Dipartimento di Scienze Chimiche, Università degli Studi di Padova (Visiting Scientist) for support. B.D. thanks Dalian University of Technology for the Haitian Professorship support. L.H. and G.H. are supported by the startup funding of University of Massachusetts. Open access funding enabled and organized by Projekt DEAL.
PY - 2020/5/25
Y1 - 2020/5/25
N2 - Intersystem crossing (ISC) of triplet photosensitizers is a vital process for fundamental photochemistry and photodynamic therapy (PDT). Herein, we report the co-existence of efficient ISC and long triplet excited lifetime in a heavy atom-free bodipy helicene molecule. Via theoretical computation and time-resolved EPR spectroscopy, we confirmed that the ISC of the bodipy results from its twisted molecular structure and reduced symmetry. The twisted bodipy shows intense long wavelength absorption (ϵ=1.76×105 m−1 cm−1 at 630 nm), satisfactory triplet quantum yield (ΦT=52 %), and long-lived triplet state (τT=492 μs), leading to unprecedented performance as a triplet photosensitizer for PDT. Moreover, nanoparticles constructed with such helical bodipy show efficient PDT-mediated antitumor immunity amplification with an ultra-low dose (0.25 μg kg−1), which is several hundred times lower than that of the existing PDT reagents.
AB - Intersystem crossing (ISC) of triplet photosensitizers is a vital process for fundamental photochemistry and photodynamic therapy (PDT). Herein, we report the co-existence of efficient ISC and long triplet excited lifetime in a heavy atom-free bodipy helicene molecule. Via theoretical computation and time-resolved EPR spectroscopy, we confirmed that the ISC of the bodipy results from its twisted molecular structure and reduced symmetry. The twisted bodipy shows intense long wavelength absorption (ϵ=1.76×105 m−1 cm−1 at 630 nm), satisfactory triplet quantum yield (ΦT=52 %), and long-lived triplet state (τT=492 μs), leading to unprecedented performance as a triplet photosensitizer for PDT. Moreover, nanoparticles constructed with such helical bodipy show efficient PDT-mediated antitumor immunity amplification with an ultra-low dose (0.25 μg kg−1), which is several hundred times lower than that of the existing PDT reagents.
UR - http://hdl.handle.net/10754/665092
UR - https://onlinelibrary.wiley.com/doi/abs/10.1002/ange.202005269
UR - http://www.scopus.com/inward/record.url?scp=85090291124&partnerID=8YFLogxK
U2 - 10.1002/ange.202005269
DO - 10.1002/ange.202005269
M3 - Article
SN - 0044-8249
VL - 132
SP - 16248
EP - 16255
JO - Angewandte Chemie
JF - Angewandte Chemie
IS - 37
ER -