Wu, Cheng-HamCheng-HamWuKisel, Kristina SKristina SKiselThangavel, Muthu KumarMuthu KumarThangavelChen, Yi-TingYi-TingChenChang, Kai-HsinKai-HsinChangTsai, Ming-RungMing-RungTsaiCHIA-YU CHUShen, Yu-FangYu-FangShenWu, Pei-ChunPei-ChunWuZhang, ZhimingZhimingZhangLiu, Tzu-MingTzu-MingLiuJänis, JanneJanneJänisGrachova, Elena VElena VGrachovaShakirova, Julia RJulia RShakirovaTunik, Sergey PSergey PTunikKoshevoy, Igor OIgor OKoshevoyPI-TAI CHOU2021-09-072021-09-072021-08-192198-3844https://scholars.lib.ntu.edu.tw/handle/123456789/582412The encapsulation and/or surface modification can stabilize and protect the phosphorescence bio-probes but impede their intravenous delivery across biological barriers. Here, a new class of biocompatible rhenium (ReI ) diimine carbonyl complexes is developed, which can efficaciously permeate normal vessel walls and then functionalize the extravascular collagen matrixes as in situ oxygen sensor. Without protective agents, ReI -diimine complex already exhibits excellent emission yield (34%, λem   = 583 nm) and large two-photon absorption cross-sections (σ2   = 300 GM @ 800 nm) in water (pH 7.4). After extravasation, remarkably, the collagen-bound probes further enhanced their excitation efficiency by increasing the deoxygenated lifetime from 4.0 to 7.5 µs, paving a way to visualize tumor hypoxia and tissue ischemia in vivo. The post-extravasation functionalization of extracellular matrixes demonstrates a new methodology for biomaterial-empowered phosphorescence sensing and imaging.enReI diimine carbonyl complexes; phosphorescence lifetime imaging microscopy; phosphorescent oxygen sensors; tissue ischemia; tumor hypoxia; two-photon phosphorescencejournal article10.1002/advs.202102788344146962-s2.0-85113135189https://api.elsevier.com/content/abstract/scopus_id/85113135189