title: Photocytotoxic oxovanadium(IV) complexes of ferrocenyl-terpyridine and acetylacetonate derivatives.
abstract: Oxovanadium(IV) complexes [VO(Fc-tpy)(acac)](ClO4) (1), [VO(Fc-tpy)(nap-acac)](ClO4) (2), [VO(Fc-tpy)(py-acac)](ClO4) (3) and [VO(Ph-tpy)(py-acac)](ClO4) (4) of 4'-ferrocenyl-2,2':6',2"-terpyridine (Fc-tpy) and 4'-phenyl-2,2':6',2"-terpyridine (Ph-tpy) having monoanionic acetylacetonate (acac), naphthylacetylacetonate (nap-acac) or pyrenylacetylacetonate (py-acac) ligand were prepared, characterized and their photocytotoxicity in visible light studied. The ferrocenyl complexes 1-3 showed an intense charge transfer band near 585 nm in DMF and displayed Fc(+)/Fc and V(IV)/V(III) redox couples near 0.66 V and -0.95 V vs. SCE in DMF-0.1 M TBAP. The complexes as avid binders to calf thymus DNA showed significant photocleavage of plasmid DNA in green light (568 nm) forming OH radicals. The complexes that are photocytotoxic in HeLa and MCF-7 cancer cells in visible light (400-700 nm) with low dark toxicity remain nontoxic in normal fibroblast 3T3 cells. ICP-MS and fluorescence microscopic studies show significant cellular uptake of the complexes. Photo-irradiation of the complexes causes apoptotic cell death by ROS as evidenced from the DCFDA assay.
authors.affiliation: Department of Inorganic and Physical Chemistry, Indian Institute of Science, Sir C.V. Raman Avenue, Bangalore 560 012, India.
authors.forename: Babu
authors.initials: B
authors.lastname: Balaji
authors.affiliation: Department of Biochemistry, Indian Institute of Science, Sir C.V. Raman Avenue, Bangalore 560 012, India.
authors.forename: Babita
authors.initials: B
authors.lastname: Balakrishnan
authors.affiliation: Department of Inorganic and Physical Chemistry, Indian Institute of Science, Sir C.V. Raman Avenue, Bangalore 560 012, India.
authors.forename: Sravanakumar
authors.initials: S
authors.lastname: Perumalla
authors.affiliation: Department of Biochemistry, Indian Institute of Science, Sir C.V. Raman Avenue, Bangalore 560 012, India. Electronic address: anjali@biochem.iisc.ernet.in.
authors.forename: Anjali A
authors.initials: AA
authors.lastname: Karande
authors.affiliation: Department of Inorganic and Physical Chemistry, Indian Institute of Science, Sir C.V. Raman Avenue, Bangalore 560 012, India. Electronic address: arc@ipc.iisc.ernet.in.
authors.forename: Akhil R
authors.initials: AR
authors.lastname: Chakravarty
mesh_terms: D016475:3T3 Cells; D000818:Animals; D016923:Cell Death / Q000187:drug effects; D004305:Dose-Response Relationship, Drug; D005296:Ferrous Compounds / Q000737:chemistry*; D006367:HeLa Cells; D006801:Humans; D006885:Hydroxybutyrates / Q000737:chemistry*; D008027:Light; D061986:MCF-7 Cells; D000075163:Metallocenes; D051379:Mice; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry / Q000494:pharmacology*; D010422:Pentanones / Q000737:chemistry*; D017319:Photosensitizing Agents / Q000138:chemical synthesis / Q000737:chemistry / Q000494:pharmacology*; D011725:Pyridines / Q000737:chemistry*; D017382:Reactive Oxygen Species / Q000378:metabolism; D013329:Structure-Activity Relationship; D014638:Vanadates / Q000138:chemical synthesis / Q000737:chemistry / Q000494:pharmacology*
chemical_list: D005296:Ferrous Compounds; D006885:Hydroxybutyrates; D000075163:Metallocenes; D009942:Organometallic Compounds; D010422:Pentanones; D017319:Photosensitizing Agents; D011725:Pyridines; D017382:Reactive Oxygen Species; C049529:acetyl acetonate; C075743:oxovanadium IV; D014638:Vanadates; C004998:ferrocene
keywords: Apoptosis; Cellular imaging; Ferrocene; Medicinal chemistry; Photocytotoxicity; Vanadium