Deciphering the Intersystem Crossing in a Helical BODIPY for Recorded Low Dose Photodynamic Therapy.
Mohammed, Omar F.
KAUST DepartmentChemical Science Program
KAUST Solar Center (KSC)
Physical Science and Engineering (PSE) Division
Ultrafast Laser Spectroscopy and Four-dimensional Electron Imaging Research Group
Online Publication Date2020-06-30
Print Publication Date2020-09-07
Embargo End Date2021-05-26
Permanent link to this recordhttp://hdl.handle.net/10754/662954
MetadataShow full item record
AbstractIntersystem crossing (ISC) of triplet photosensitizers is a vital process for fundamental photochemistry and photodynamic therapy (PDT). However, the currently effective long wavelength operating photosensitizers have to rely on heavy atoms to enhance ISC. Unfortunately, the heavy atoms, besides their toxicity, can also cause significant reduction in the triplet lifetime of the photosensitizers, which is fundamentally detrimental to their applications. To overcome this challenge, herein we report the co-existence of efficient ISC and long triplet excited lifetime in a heavy atom-free Bodipy helicene molecule. Via advanced theoretical computation and time-resolved electron paramagnetic resonance spectroscopy, we confirmed the ISC of the Bodipy is resulted from its twisted molecular structure and reduced symmetry. The twisted Bodipy shows exceptionally intense long wavelength absorption (ε = 1.76 × 10 5 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 surprisingly efficient PDT mediated antitumor immunity amplification with ultra-low dose (0.25 μg/kg body weight), which is several hundred times lower than that of the existing PDT reagents. Our study paves the way to design the next generation of triplet photosensitizers.
CitationWang, Z., Huang, L., Yan, Y., El-Zohry, A. M., Toffoletti, A., Zhao, J., … Han, G. (2020). Deciphering the Intersystem Crossing in a Helical BODIPY for Recorded Low Dose Photodynamic Therapy. Angewandte Chemie International Edition. doi:10.1002/anie.202005269
SponsorsJ. Zhao thank 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. Dick thanks Dalian University of Technology for the Haitian Professorship support. L. Huang and G. Han are supported by the startup funding of University of Massachusetts.
- Spin-Orbit Charge-Transfer Intersystem Crossing (ISC) in Compact Electron Donor-Acceptor Dyads: ISC Mechanism and Application as Novel and Potent Photodynamic Therapy Reagents.
- Authors: Wang Z, Ivanov M, Gao Y, Bussotti L, Foggi P, Zhang H, Russo N, Dick B, Zhao J, Di Donato M, Mazzone G, Luo L, Fedin M
- Issue date: 2020 Jan 22
- Molecular Design of Highly Efficient Heavy-Atom-Free Triplet BODIPY Derivatives for Photodynamic Therapy and Bioimaging.
- Authors: Nguyen VN, Yim Y, Kim S, Ryu B, Swamy KMK, Kim G, Kwon N, Kim CY, Park S, Yoon J
- Issue date: 2020 Jun 2
- Efficient Radical-Enhanced Intersystem Crossing in an NDI-TEMPO Dyad: Photophysics, Electron Spin Polarization, and Application in Photodynamic Therapy.
- Authors: Wang Z, Gao Y, Hussain M, Kundu S, Rane V, Hayvali M, Yildiz EA, Zhao J, Yaglioglu HG, Das R, Luo L, Li J
- Issue date: 2018 Dec 12
- A Local CC2 and TDA-DFT Double Hybrid Study on BODIPY/aza-BODIPY Dimers as Heavy Atom Free Triplet Photosensitizers for Photodynamic Therapy Applications.
- Authors: Momeni MR, Brown A
- Issue date: 2016 Apr 28
- Visible light-absorbing rhenium(I) tricarbonyl complexes as triplet photosensitizers in photooxidation and triplet-triplet annihilation upconversion.
- Authors: Yi X, Zhao J, Sun J, Guo S, Zhang H
- Issue date: 2013 Feb 14