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Lanthanide(III) complexes [Ln(R-tpy)(cur)(NO3)2] (Ln = La(III) in 1, 2; Gd(III) in 5, 6) and [Ln(R-tpy)(scur)(NO3)2] (Ln = La(III) in 3, 4; Gd(III) in 7, 8), where R-tpy is 4′-phenyl-2,2′:6′,2′′-terpyridine (ph-tpy in 1, 3, 5, 7), 4′-(1-pyrenyl)-2,2′:6′,2′′-terpyridine (py-tpy in 2, 4, 6, 8), Hcur is curcumin (in 1, 2, 5, 6) and Hscur is diglucosylcurcumin (in 3, 4, 7, 8), were prepared and their DNA photocleavage activity and photocytotoxicity studied. Complexes [La(ph-tpy)(cur)(NO3)2] (1) and [Gd(ph-tpy)(cur)(NO3)2] (5) were structurally characterized. The complexes in aqueous-DMF showed an absorption band near 430 nm and an emission band near 515 nm when excited at 420 nm. The complexes are moderate binders to calf-thymus DNA. They cleave plasmid supercoiled DNA to its nicked circular form in UV-A (365 nm) and visible light (454 nm) via1O2 and ˙OH pathways. The complexes are remarkably photocytotoxic in HeLa cells in visible light (λ = 400–700 nm) and are non-toxic in the dark. FACScan analysis of the HeLa cells treated with 2 and 4 showed cell death via an apoptotic pathway. Nuclear localization of 1–4 is evidenced from confocal imaging on HeLa cells. The hydrolytic instability of curcumin gets significantly reduced upon binding to the lanthanide ions while retaining its photocytotoxic potential.
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