Deciphering the Intersystem Crossing in Near-infrared BODIPY Photosensitizers for Highly Efficient Photodynamic Therapy

Overview

Journal Chem Sci

Publisher Royal Society of Chemistry

Specialty Chemistry

Date 2019 Apr 19

PMID 30996892

Citations 21

Authors

Xiaofei Miao

Wenbo Hu

Tingchao He

Haojie Tao

Qi Wang

Runfeng Chen

Lu Jin

Hui Zhao

Xiaomei Lu

Quli Fan

Wei Huang

Affiliations

Soon will be listed here.

Abstract

Deciphering singlet-to-triplet intersystem crossing (ISC) in organic near-infrared photosensitizers (PSs) is of fundamental importance in the designing of high-performance PSs to boost the clinical usage of photodynamic therapy (PDT). However, in-depth investigations of the ISC dynamics in near-infrared PSs have not been performed to date. Here, systematical investigations of the ISC dynamics in organic near-infrared BODIPY derivatives are presented, in which a multi-channel yet remarkably efficient ISC process is revealed by ultrafast femtosecond transient absorption (fs-TA) spectroscopy and theoretical calculation. The fs-TA verifies an exceptionally enhanced ISC efficiency ( = 91%) in iodine-substituted BODIPY () which is further supported by the calculation results. This endows with an ultrahigh singlet oxygen quantum yield ( = 88%), thus enabling a proof-of-concept application of highly efficient PDT under ultralow near-infrared light power density (10 mW cm). The in-depth understanding of ISC dynamics in organic near-infrared materials may provide valuable guidance in the designing of novel organic theranostic materials for clinical cancer treatment.

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References

Dolmans D, Fukumura D, Jain R . Photodynamic therapy for cancer. Nat Rev Cancer. 2003; 3(5):380-7. DOI: 10.1038/nrc1071. View

Schweitzer C, Schmidt R . Physical mechanisms of generation and deactivation of singlet oxygen. Chem Rev. 2003; 103(5):1685-757. DOI: 10.1021/cr010371d. View

Yogo T, Urano Y, Ishitsuka Y, Maniwa F, Nagano T . Highly efficient and photostable photosensitizer based on BODIPY chromophore. J Am Chem Soc. 2005; 127(35):12162-3. DOI: 10.1021/ja0528533. View

Descalzo A, Xu H, Shen Z, Rurack K . Red/near-infrared boron-dipyrromethene dyes as strongly emitting fluorophores. Ann N Y Acad Sci. 2008; 1130:164-71. DOI: 10.1196/annals.1430.016. View

Celli J, Spring B, Rizvi I, Evans C, Samkoe K, Verma S . Imaging and photodynamic therapy: mechanisms, monitoring, and optimization. Chem Rev. 2010; 110(5):2795-838. PMC: 2896821. DOI: 10.1021/cr900300p. View

Adarsh N, Avirah R, Ramaiah D . Tuning photosensitized singlet oxygen generation efficiency of novel aza-BODIPY dyes. Org Lett. 2010; 12(24):5720-3. DOI: 10.1021/ol102562k. View

Agostinis P, Berg K, Cengel K, Foster T, Girotti A, Gollnick S . Photodynamic therapy of cancer: an update. CA Cancer J Clin. 2011; 61(4):250-81. PMC: 3209659. DOI: 10.3322/caac.20114. View

Ma L, Zhang K, Kloc C, Sun H, Michel-Beyerle M, Gurzadyan G . Singlet fission in rubrene single crystal: direct observation by femtosecond pump-probe spectroscopy. Phys Chem Chem Phys. 2012; 14(23):8307-12. DOI: 10.1039/c2cp40449d. View

Adarsh N, Shanmugasundaram M, Avirah R, Ramaiah D . Aza-BODIPY derivatives: enhanced quantum yields of triplet excited states and the generation of singlet oxygen and their role as facile sustainable photooxygenation catalysts. Chemistry. 2012; 18(40):12655-62. DOI: 10.1002/chem.201202438. View

10.

Zhao J, Wu W, Sun J, Guo S . Triplet photosensitizers: from molecular design to applications. Chem Soc Rev. 2013; 42(12):5323-51. DOI: 10.1039/c3cs35531d. View

11.

Lu H, Mack J, Yang Y, Shen Z . Structural modification strategies for the rational design of red/NIR region BODIPYs. Chem Soc Rev. 2014; 43(13):4778-823. DOI: 10.1039/c4cs00030g. View

12.

Xiong X, Song F, Wang J, Zhang Y, Xue Y, Sun L . Thermally activated delayed fluorescence of fluorescein derivative for time-resolved and confocal fluorescence imaging. J Am Chem Soc. 2014; 136(27):9590-7. DOI: 10.1021/ja502292p. View

13.

Tao Y, Yuan K, Chen T, Xu P, Li H, Chen R . Thermally activated delayed fluorescence materials towards the breakthrough of organoelectronics. Adv Mater. 2014; 26(47):7931-58. DOI: 10.1002/adma.201402532. View

14.

Yuan Y, Zhang C, Gao M, Zhang R, Tang B, Liu B . Specific light-up bioprobe with aggregation-induced emission and activatable photoactivity for the targeted and image-guided photodynamic ablation of cancer cells. Angew Chem Int Ed Engl. 2014; 54(6):1780-6. DOI: 10.1002/anie.201408476. View

15.

Lucky S, Soo K, Zhang Y . Nanoparticles in photodynamic therapy. Chem Rev. 2015; 115(4):1990-2042. DOI: 10.1021/cr5004198. View

16.

An Z, Zheng C, Tao Y, Chen R, Shi H, Chen T . Stabilizing triplet excited states for ultralong organic phosphorescence. Nat Mater. 2015; 14(7):685-90. DOI: 10.1038/nmat4259. View

17.

Hu W, Ma H, Hou B, Zhao H, Ji Y, Jiang R . Engineering Lysosome-Targeting BODIPY Nanoparticles for Photoacoustic Imaging and Photodynamic Therapy under Near-Infrared Light. ACS Appl Mater Interfaces. 2016; 8(19):12039-47. DOI: 10.1021/acsami.6b02721. View

18.

Wang H, Jiang S, Chen S, Li D, Zhang X, Shao W . Enhanced Singlet Oxygen Generation in Oxidized Graphitic Carbon Nitride for Organic Synthesis. Adv Mater. 2016; 28(32):6940-5. DOI: 10.1002/adma.201601413. View

19.

Romero N, Nicewicz D . Organic Photoredox Catalysis. Chem Rev. 2016; 116(17):10075-166. DOI: 10.1021/acs.chemrev.6b00057. View

20.

Zhou Z, Song J, Nie L, Chen X . Reactive oxygen species generating systems meeting challenges of photodynamic cancer therapy. Chem Soc Rev. 2016; 45(23):6597-6626. PMC: 5118097. DOI: 10.1039/c6cs00271d. View