title: Oxovanadium(IV) based hypocrellin B complexes with enhanced photodynamic activity.
abstract: Hypocrellin B (HB), a naturally occurring photosensitizer, has been extensively and intensively studied as a promising photodynamic therapy (PDT) agent. In this work, three new oxovanadium(IV) complexes were designed and synthesized with HB as a bridging ligand and phen (1,10-phenanthroline, complex 1), tmp (3,4,7,8-tetramethyl-1,10-phenanthroline, complex 2) and dpq (dipyrido[3,2-f:2'3'-h]quinoxaline, complex 3) as terminal ligands. The use of a diimine terminal ligand avoids the formation of polymeric complexes and ensures the three VO(2+)-HB complexes possess a definite molecular formula and molecular weight to meet the single component requirement for an ideal PDT agent. Compared to HB, the VO(2+)-HB complexes exhibit improved water solubility, enhanced absorptivity in the phototherapeutic window, increased binding affinity toward dsDNA, and similar singlet oxygen quantum yield, therefore advanced DNA photocleavage activity. Both the DNA binding constants and photo nuclease activities of the complexes follow the order 2 (tmp) > 3 (dpq) > 1 (phen), demonstrating the importance of the binding affinity to biomolecules, which improves the bioavailability of reactive oxygen species. Our work opens a new avenue for the development of HB-based PDT agents.
authors: Key Laboratory of Photochemical Conversion and Optoelectronic Materials, Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing, 100190, PR China.
authors: Yi
authors: Y
authors: Sun
authors: Yue
authors: Y
authors: Zheng
authors: Wan-Hua
authors: WH
authors: Lei
authors: Qian-Xiong
authors: QX
authors: Zhou
authors: Yuan-Jun
authors: YJ
authors: Hou
authors: Bao-Wen
authors: BW
authors: Zhang
authors: Xue-Song
authors: XS
authors: Wang
mesh_terms: D004247:DNA / Q000737:chemistry; D053837:DNA Cleavage / Q000187:drug effects; D004563:Electrochemistry; D008968:Molecular Conformation; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D010569:Perylene / Q000031:analogs & derivatives* / Q000138:chemical synthesis / Q000737:chemistry; D010777:Photochemistry; D010778:Photochemotherapy; D017319:Photosensitizing Agents / Q000138:chemical synthesis* / Q000737:chemistry; D011809:Quinones / Q000138:chemical synthesis* / Q000737:chemistry; D012995:Solubility; D021241:Spectrometry, Mass, Electrospray Ionization; D014638:Vanadates / Q000737:chemistry*
chemical_list: D009942:Organometallic Compounds; D017319:Photosensitizing Agents; D011809:Quinones; C075743:oxovanadium IV; D014638:Vanadates; D010569:Perylene; D004247:DNA; C064522:hypocrellin B