title: Ru(II)-Complex-Based DNA Photocleaver Having Intense Absorption in the Phototherapeutic Window.
abstract: Ru(II)-complex-based DNA photocleavers have been extensively studied for their potential application in photodynamic therapy (PDT) and photodynamic antimicrobial chemotherapy (PACT). However, their MLCT absorption maxima are generally shorter than 600 nm, limiting PDT/PACT application severely. In this work, by incorporating a 5-chloro-8-oxyquinolate-based noninnocent ligand into a merocyanine scaffold Cl-7-IVQ, we obtained a new Ru complex of this ligand, [Ru(bpy)2(Cl-7-IVQ)]2+, which has intense absorption in the window 600-700 nm and enables an efficient•OH-mediated DNA photocleavage. This long-wavelength absorption band has a character of MLLCT transition from the hybrid Ru(dπ)-Cl-7-IVQ(π) orbital to the π*(Cl-7-IVQ) orbital and thus a contribution from the ππ* transition of the merocyanine framework, which endows the complex with a molar extinction coefficient as high as 1.73 × 104M-1cm-1at 649 nm and allows for an efficient DNA photocleavage under an irradiation of low intensity. [Ru(bpy)2(Cl-7-IVQ)]2+represents the first Ru(II)-complex-based DNA photocleaver that has an MLCT absorption maximum above 600 nm and can selectively inactivate E. coli bacterial cells over HeLa cells upon red light irradiation.
authors.affiliation: Key Laboratory of Photochemical Conversion and Optoelectronic Materials, Technical Institute of Physics and Chemistry Chinese Academy of Sciences Beijing 100190, P.R. China.|Graduate School of Chinese Academy of Sciences , Beijing 100049, P. R. China.
authors.forename: Yangyang
authors.initials: Y
authors.lastname: Zhang
authors.affiliation: Key Laboratory of Photochemical Conversion and Optoelectronic Materials, Technical Institute of Physics and Chemistry Chinese Academy of Sciences Beijing 100190, P.R. China.
authors.forename: Qianxiong
authors.initials: Q
authors.lastname: Zhou
authors.affiliation: Key Laboratory of Photochemical Conversion and Optoelectronic Materials, Technical Institute of Physics and Chemistry Chinese Academy of Sciences Beijing 100190, P.R. China.|Graduate School of Chinese Academy of Sciences , Beijing 100049, P. R. China.
authors.forename: Na
authors.initials: N
authors.lastname: Tian
authors.affiliation: Key Laboratory of Photochemical Conversion and Optoelectronic Materials, Technical Institute of Physics and Chemistry Chinese Academy of Sciences Beijing 100190, P.R. China.
authors.forename: Chao
authors.initials: C
authors.lastname: Li
authors.affiliation: Key Laboratory of Photochemical Conversion and Optoelectronic Materials, Technical Institute of Physics and Chemistry Chinese Academy of Sciences Beijing 100190, P.R. China.
authors.forename: Xuesong
authors.identifier: http://orcid.org/0000-0002-4552-5762
authors.initials: X
authors.lastname: Wang
mesh_terms: D065567:Absorption, Physiological; D002470:Cell Survival / Q000187:drug effects; D056831:Coordination Complexes / Q000138:chemical synthesis / Q000737:chemistry / Q000494:pharmacology*; D004247:DNA / Q000737:chemistry / Q000187:drug effects*; D004305:Dose-Response Relationship, Drug; D004926:Escherichia coli / Q000166:cytology / Q000187:drug effects* / Q000378:metabolism; D006367:HeLa Cells; D006801:Humans; D008027:Light; D015394:Molecular Structure; D055668:Photochemical Processes; D010778:Photochemotherapy; D011789:Quantum Theory; D017382:Reactive Oxygen Species / Q000378:metabolism; D012428:Ruthenium / Q000737:chemistry / Q000494:pharmacology*; D013329:Structure-Activity Relationship; D014407:Tumor Cells, Cultured
chemical_list: D056831:Coordination Complexes; D017382:Reactive Oxygen Species; D012428:Ruthenium; D004247:DNA