Ligand Regulation Strategy to Modulate ROS Nature in a Rhodamine-Iridium(III) Hybrid System for Phototherapy

Wei, Fangfang1,2,3; Chen, Feng2; Wu, Siye1; Zha, Menglei2; Liu, Jiqiang1; Wong, Ka-Leung3; Li, Kai2; Wong, Keith Man-Chung1

2024-03-18

10.1021/acs.inorgchem.3c04350

INORGANIC CHEMISTRY   影响因子和分区

0020-1669

1520-510X

The efficacy of photodynamic therapy (PDT) is highly dependent on the photosensitizer features. The reactive oxygen species (ROS) generated by photosensitizers is proven to be associated with immunotherapy by triggering immunogenic cell death (ICD) as well. In this work, we establish a rhodamine-iridium(III) hybrid model functioning as a photosensitizer to comprehensively understand its performance and potential applications in photodynamic immunotherapy. Especially, the correlation between the ROS generation efficiency and the energy level of the Ir(III)-based excited state (T-1'), modulated by the cyclometalating ((CN)-N-Lambda) ligand, is systematically investigated and correlated. We prove that in addition to the direct population of the rhodamine triplet state (T-1) formed through the intersystem crossing process with the assistance of a heavy Ir(III) metal center, the fine-tuned T-1' state could act as a relay to provide an additional pathway for promoting the cascade energy transfer process that leads to enhanced ROS generation ability. Moreover, type I ROS can be effectively produced by introducing sulfur-containing thiophene units in (CN)-N-Lambda ligands, providing a stronger M1 macrophage-activation efficiency under hypoxia to evoke in vivo antitumor immunity. Overall, our work provides a fundamental guideline for the molecular design and exploration of advanced transition-metal-based photosensitizers for biomedical applications.

SCI ; EI

英语

第一 ; 通讯

National Natural Science Foundation of China[2020YFA0908900] ; Ministry of Science and Technology of China["22171126","U21A2097"] ; National Natural Science Foundation of China["JCY20210324104609025","JSGG20200225151916021","JCY20190809165411528"] ; Science, Technology and Innovation Commission of Shenzhen Municipality[2022B1212010003] ; Guangdong Provincial Key Laboratory of Advanced Biomaterials[2019ZT08Y191]

Chemistry

Chemistry, Inorganic & Nuclear

WOS:001187263400001

AMER CHEMICAL SOC

CHEMISTRY

Web of Science

1.Southern Univ Sci & Technol, Dept Chem, Shenzhen 518055, Peoples R China
2.Southern Univ Sci & Technol, Dept Biomed Engn, Guangdong Prov Key Lab Adv Biomat, Shenzhen 518055, Peoples R China
3.Hong Kong Baptist Univ, Dept Chem, Hong Kong, Peoples R China

Wei, Fangfang,Chen, Feng,Wu, Siye,et al. Ligand Regulation Strategy to Modulate ROS Nature in a Rhodamine-Iridium(III) Hybrid System for Phototherapy[J]. INORGANIC CHEMISTRY,2024,63(13).

Wei, Fangfang.,Chen, Feng.,Wu, Siye.,Zha, Menglei.,Liu, Jiqiang.,...&Wong, Keith Man-Chung.(2024).Ligand Regulation Strategy to Modulate ROS Nature in a Rhodamine-Iridium(III) Hybrid System for Phototherapy.INORGANIC CHEMISTRY,63(13).

Wei, Fangfang,et al."Ligand Regulation Strategy to Modulate ROS Nature in a Rhodamine-Iridium(III) Hybrid System for Phototherapy".INORGANIC CHEMISTRY 63.13(2024).