Elucidation of the Intersystem Crossing Mechanism in a Helical BODIPY for Low-Dose Photodynamic Therapy

Zhijia Wang; Ling Huang; Yuxin Yan; Ahmed M. El-Zohry; Antonio Toffoletti; Jianzhang Zhao; Antonio Barbon; Bernhard Dick; Omar F. Mohammed; Gang Han

doi:10.1002/anie.202005269

Elucidation of the Intersystem Crossing Mechanism in a Helical BODIPY for Low-Dose Photodynamic Therapy

Zhijia Wang
, Ling Huang
, Yuxin Yan
, Ahmed M. El-Zohry
, Antonio Toffoletti
, Jianzhang Zhao^*
, Antonio Barbon^*
, Bernhard Dick^*
, Omar F. Mohammed^*
, Gang Han^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

221 Scopus citations

Abstract

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 (Φ_T=52 %), and long-lived triplet state (τ_T=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.

Original language	English
Pages (from-to)	16114-16121
Number of pages	8
Journal	Angewandte Chemie - International Edition
Volume	59
Issue number	37
DOIs	https://doi.org/10.1002/anie.202005269
State	Published - 7 Sep 2020
Externally published	Yes

Bibliographical note

Publisher Copyright:
© 2020 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Keywords

bodipy
intersystem crossing
photodynamic therapy
photosensitizers
twisted π-systems

ASJC Scopus subject areas

Catalysis
General Chemistry

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10.1002/anie.202005269

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@article{82ff0d4fa171416bb55ef4ebe6ce05b5,

title = "Elucidation of the Intersystem Crossing Mechanism in a Helical BODIPY for Low-Dose Photodynamic Therapy",

abstract = "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.",

keywords = "bodipy, intersystem crossing, photodynamic therapy, photosensitizers, twisted π-systems",

author = "Zhijia Wang and Ling Huang and Yuxin Yan and El-Zohry, \{Ahmed M.\} and Antonio Toffoletti and Jianzhang Zhao and Antonio Barbon and Bernhard Dick and Mohammed, \{Omar F.\} and Gang Han",

note = "Publisher Copyright: {\textcopyright} 2020 The Authors. Published by Wiley-VCH Verlag GmbH \& Co. KGaA, Weinheim",

year = "2020",

month = sep,

day = "7",

doi = "10.1002/anie.202005269",

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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 M.

AU - Toffoletti, Antonio

AU - Zhao, Jianzhang

AU - Barbon, Antonio

AU - Dick, Bernhard

AU - Mohammed, Omar F.

AU - Han, Gang

PY - 2020/9/7

Y1 - 2020/9/7

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.

KW - bodipy

KW - intersystem crossing

KW - photodynamic therapy

KW - photosensitizers

KW - twisted π-systems

UR - https://www.scopus.com/pages/publications/85087177641

U2 - 10.1002/anie.202005269

DO - 10.1002/anie.202005269

M3 - Article

C2 - 32449273

AN - SCOPUS:85087177641

SN - 1433-7851

VL - 59

SP - 16114

EP - 16121

JO - Angewandte Chemie - International Edition

JF - Angewandte Chemie - International Edition

IS - 37

ER -

Elucidation of the Intersystem Crossing Mechanism in a Helical BODIPY for Low-Dose Photodynamic Therapy

Abstract

Bibliographical note

Keywords

ASJC Scopus subject areas

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