Semiconducting Open‐Shell Radicals for Precise Tumor Activatable Phototheranostics
Abstract Semiconducting open‐shell radicals (SORs) have promising potential for the development of phototheranostic agents, enabling tumor bioimaging and boosting tumorous reactive oxygen species (ROS). Herein, a new class of semiconducting perylene diimide (PDI), designated as PDI(Br)n with various...
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| Format: | Article |
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Wiley
2025-05-01
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| Series: | Advanced Science |
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| Online Access: | https://doi.org/10.1002/advs.202500293 |
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| author | Jie Zhang Haifen Luo Wen Ma Jingqi Lv Bo Wang Fengwei Sun Weijie Chi Zhuting Fang Zhen Yang |
| author_facet | Jie Zhang Haifen Luo Wen Ma Jingqi Lv Bo Wang Fengwei Sun Weijie Chi Zhuting Fang Zhen Yang |
| author_sort | Jie Zhang |
| collection | DOAJ |
| description | Abstract Semiconducting open‐shell radicals (SORs) have promising potential for the development of phototheranostic agents, enabling tumor bioimaging and boosting tumorous reactive oxygen species (ROS). Herein, a new class of semiconducting perylene diimide (PDI), designated as PDI(Br)n with various numbers of bromine (Br) atoms modified on PDI's bay/ortho positions is reported. PDI(Br)n is demonstrated to transform into a radical anion, [PDI(Br)n]•−, in a reducing solution, with a typical g‐value of 2.0022. Specifically, [PDI(Br)4/6]•− is generated in the weakly reductive tumor‐mimicking solution and exhibits high stability in air. Quantum chemical kinetic simulation and ultrafast femtosecond transient absorption spectroscopy indicate that [PDI(Br)6]•− has a low π–π stacking energy (0.35 eV), a fast electron transfer rate (192.4 ps) and energy gap of PDI(Br)6 (ΔES1, T1 = 1.307 eV, ΔES1, T2 = 0.324 eV) respectively, which together result in excited‐state charge transfer characters. The PDI(Br)6 nanoparticle radicals, [PDI(Br)6] NPs•−, specifically enable chemodynamic and type‐I photodynamic ROS generation in tumors, including superoxide and hydroxyl radicals, which elicit immunogenic cell death effect. Also, [PDI(Br)6] NPs•− facilitate activatable bioimaging‐guided therapy due to their photoacoustic signal at 808 nm and NIR‐II emission at 1115 nm. The work paves the way for the design of SORs for precise cancer theranostics. |
| format | Article |
| id | doaj-art-6013171b79ba4d0c8d00b94ec8e74b9a |
| institution | Kabale University |
| issn | 2198-3844 |
| language | English |
| publishDate | 2025-05-01 |
| publisher | Wiley |
| record_format | Article |
| series | Advanced Science |
| spelling | doaj-art-6013171b79ba4d0c8d00b94ec8e74b9a2025-08-20T03:48:47ZengWileyAdvanced Science2198-38442025-05-011217n/an/a10.1002/advs.202500293Semiconducting Open‐Shell Radicals for Precise Tumor Activatable PhototheranosticsJie Zhang0Haifen Luo1Wen Ma2Jingqi Lv3Bo Wang4Fengwei Sun5Weijie Chi6Zhuting Fang7Zhen Yang8Strait Laboratory of Flexible Electronics (SLoFE) Fujian Key Laboratory of Flexible Electronics Strait Institute of Flexible Electronics (Future Technologies) Fujian Normal University Fuzhou 350117 ChinaStrait Laboratory of Flexible Electronics (SLoFE) Fujian Key Laboratory of Flexible Electronics Strait Institute of Flexible Electronics (Future Technologies) Fujian Normal University Fuzhou 350117 ChinaStrait Laboratory of Flexible Electronics (SLoFE) Fujian Key Laboratory of Flexible Electronics Strait Institute of Flexible Electronics (Future Technologies) Fujian Normal University Fuzhou 350117 ChinaStrait Laboratory of Flexible Electronics (SLoFE) Fujian Key Laboratory of Flexible Electronics Strait Institute of Flexible Electronics (Future Technologies) Fujian Normal University Fuzhou 350117 ChinaStrait Laboratory of Flexible Electronics (SLoFE) Fujian Key Laboratory of Flexible Electronics Strait Institute of Flexible Electronics (Future Technologies) Fujian Normal University Fuzhou 350117 ChinaStrait Laboratory of Flexible Electronics (SLoFE) Fujian Key Laboratory of Flexible Electronics Strait Institute of Flexible Electronics (Future Technologies) Fujian Normal University Fuzhou 350117 ChinaSchool of Chemistry and Chemical Engineering Hainan University Haikou 570228 ChinaDepartment of Oncology and Vascuar Interventonal Therapy Clinical Oncology School of Fujian Medical University Fujian Cancer Hospital Fuzhou 350014 ChinaStrait Laboratory of Flexible Electronics (SLoFE) Fujian Key Laboratory of Flexible Electronics Strait Institute of Flexible Electronics (Future Technologies) Fujian Normal University Fuzhou 350117 ChinaAbstract Semiconducting open‐shell radicals (SORs) have promising potential for the development of phototheranostic agents, enabling tumor bioimaging and boosting tumorous reactive oxygen species (ROS). Herein, a new class of semiconducting perylene diimide (PDI), designated as PDI(Br)n with various numbers of bromine (Br) atoms modified on PDI's bay/ortho positions is reported. PDI(Br)n is demonstrated to transform into a radical anion, [PDI(Br)n]•−, in a reducing solution, with a typical g‐value of 2.0022. Specifically, [PDI(Br)4/6]•− is generated in the weakly reductive tumor‐mimicking solution and exhibits high stability in air. Quantum chemical kinetic simulation and ultrafast femtosecond transient absorption spectroscopy indicate that [PDI(Br)6]•− has a low π–π stacking energy (0.35 eV), a fast electron transfer rate (192.4 ps) and energy gap of PDI(Br)6 (ΔES1, T1 = 1.307 eV, ΔES1, T2 = 0.324 eV) respectively, which together result in excited‐state charge transfer characters. The PDI(Br)6 nanoparticle radicals, [PDI(Br)6] NPs•−, specifically enable chemodynamic and type‐I photodynamic ROS generation in tumors, including superoxide and hydroxyl radicals, which elicit immunogenic cell death effect. Also, [PDI(Br)6] NPs•− facilitate activatable bioimaging‐guided therapy due to their photoacoustic signal at 808 nm and NIR‐II emission at 1115 nm. The work paves the way for the design of SORs for precise cancer theranostics.https://doi.org/10.1002/advs.202500293CDTimmunotherapyNIR‐II FLIsemiconducting open‐shell radicalstumor activatable phototheranosticstype‐I PDT |
| spellingShingle | Jie Zhang Haifen Luo Wen Ma Jingqi Lv Bo Wang Fengwei Sun Weijie Chi Zhuting Fang Zhen Yang Semiconducting Open‐Shell Radicals for Precise Tumor Activatable Phototheranostics Advanced Science CDT immunotherapy NIR‐II FLI semiconducting open‐shell radicals tumor activatable phototheranostics type‐I PDT |
| title | Semiconducting Open‐Shell Radicals for Precise Tumor Activatable Phototheranostics |
| title_full | Semiconducting Open‐Shell Radicals for Precise Tumor Activatable Phototheranostics |
| title_fullStr | Semiconducting Open‐Shell Radicals for Precise Tumor Activatable Phototheranostics |
| title_full_unstemmed | Semiconducting Open‐Shell Radicals for Precise Tumor Activatable Phototheranostics |
| title_short | Semiconducting Open‐Shell Radicals for Precise Tumor Activatable Phototheranostics |
| title_sort | semiconducting open shell radicals for precise tumor activatable phototheranostics |
| topic | CDT immunotherapy NIR‐II FLI semiconducting open‐shell radicals tumor activatable phototheranostics type‐I PDT |
| url | https://doi.org/10.1002/advs.202500293 |
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