文献类型：期刊文献

英文题名：Oxygen-Driven [2+2] Photocycloaddition for In Vivo Chemiluminescence

作者：Zhang, Yutao[1];Li, Juan[1];Pu, Ruihua[2];Chi, Weijie[3];Pan, Yufei[4];Dong, Liwei[4];Lu, Yao[1];Zhao, Xiuyan[1];Yang, Jing[1];Yan, Chenxu[1];Liu, Weimin[2];Guo, Zhiqian[1];Zhu, Wei-Hong[1]

机构：[1]East China Univ Sci & Technol, Inst Fine Chem,State Key Lab Green Chem Engn & Ind, Feringa Nobel Prize Scientist Joint Res Ctr,State, Frontiers Sci Ctr Materiobiol & Dynam Chem,Sch Che, Shanghai 200237, Peoples R China;[2]ShanghaiTech Univ, Sch Phys Sci & Technol, Shanghai 201210, Peoples R China;[3]Hainan Univ, Sch Chem & Chem Engn, Haikou 570228, Peoples R China;[4]Naval Med Univ, Natl Ctr Liver Canc, Shanghai 201805, Peoples R China

年份：2026

外文期刊名：JOURNAL OF THE AMERICAN CHEMICAL SOCIETY

收录：;WOS:【SCI-EXPANDED(收录号:WOS:001825568700001)】；

基金：This work was supported by the National Key Research and Development Program (2023YFA1802000), NSFC/China (22225805, T2488302, 32394001, 22378126, 32121005, and 22308101), Shanghai Science and Technology Innovation Action Plan (23J21901600), Science and Technology Commission of Shanghai Municipality (24DX1400200). Thanks to Minghua Wang and Professor Dingkun Ji of Renji Hospital, Shanghai Jiao Tong University School of Medicine, for their help in two-photon microscopy of mouse brain vessels.

语种：英文

摘要：Chemiluminescence, the direct conversion of chemical energy into light, offers an exceptionally sensitive platform for molecular imaging. However, its in vivo application is practically hindered by the lack of a biocompatible strategy for generating highly strained cyclic peroxides-the energetic cores of light emission. Herein, we present an in vivo [2 + 2] intermolecular photocycloaddition that harnesses molecular oxygen as a direct reactant to in situ generate high-energy 1,2-dioxetanes within living systems. Rationally designed electron donor-substituted olefins provide oxygen-specific addition sites and exhibit prolonged intermediate lifetimes (25-fold) via bioconfined catalysis, as demonstrated by femtosecond transient absorption spectroscopy. Our de novo designed chemiluminophores, termed as Rubines, emit bright red in vivo luminescence, greatly surpassing conventional luminescent substrates. Rubines enable direct visualization in Biomphalaria snails and living mice, and particularly function as nonradioactive "chemiluminescent nuclides" probes to monitor progressive degradation and self-repair of the blood-brain barrier (BBB) integrity in real time. This work establishes a next-generation, high-brightness in vivo chemiluminescence platform suited for ultrasensitive, noninvasive molecular imaging and diagnostics.