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Photocytotoxic ternary copper(II) complexes of histamine Schiff base and pyridyl ligands

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Abstract

Ternary copper(II) complexes of salicylaldehyde-histamine Schiff base (HL) and pyridyl ligands, viz. [Cu(bpy)(L)](ClO4) (1) and [Cu(dppz)(L)](ClO4) (2), where bpy is 2,2\(^{\prime }\)-bipyridine (in 1) and dppz is dipyrido[3,2-a:2\(^{\prime }\),3\(^{\prime }\)-c]phenazine (in 2), were synthesized, characterized and their DNA binding, photo-activated DNA cleavage activity and photocytotoxicity studied. The 1:1 electrolytic one-electron paramagnetic complexes showed a d-d band near 670 nm in aqueous DMF (1:1 v/v). The crystal structure of complex 1 showed the metal in CuN4O distorted square-pyramidal geometry. Complex 2 intercalatively binds to calf-thymus (ct) DNA with a binding constant (K b) of ∼10 5 M−1. It exhibited moderate chemical nuclease activity but excellent DNA photocleavage activity in red light of 647 nm forming •OH radicals. It showed remarkable photocytotoxicity in human cervical cancer cells (HeLa) giving IC50 of 1.6 μM in visible light (400-700 nm) with low dark toxicity. The photo-induced cell death is via generation of oxidative stress by reactive oxygen species.

Schiff base copper(II) complex of dipyridophenazine shows remarkable photocytotoxic effect in HeLa cells in visible light (400-700 nm) with reduced dark toxicity via apoptotic pathway. The complex intercalatively binds to ct-DNA, exhibits moderate chemical nuclease activity but excellent DNA photocleavage activity in red light of 705 nm forming •OH radicals.

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Acknowledgements

We thank the Department of Science and Technology (DST), Government of India, for financial support (SR/S5/MBD-02/2007). ARC thanks the DST for J.C. Bose national fellowship and the Alexander von Humboldt Foundation, Germany, for donation of an electrochemical system. S.B. thanks Indian Institute of Science (IISc) for a postdoctoral fellowship. A.D. thanks the University Grants Commission (UGC), New Delhi, for research fellowship. K.S.M. thanks Indian Academy of Sciences for a summer teacher fellowship. The use of the FACS facility of the Department of Biotechnology, Government of India, is gratefully acknowledged.

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Authors and Affiliations

  1. Department of Inorganic and Physical Chemistry, Indian Institute of Science, Bangalore, 560 012, India

    SAMYA BANERJEE, K SESHA MAHESWARAMMA, BASUDEV MAITY, SANJOY MUKHERJEE, ARUN KUMAR & AKHIL R CHAKRAVARTY

  2. Department of Biochemistry, Indian Institute of Science, Bangalore, 560 012, India

    AKANKSHA DIXIT & ANJALI A KARANDE

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  1. SAMYA BANERJEE
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  2. AKANKSHA DIXIT
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  3. K SESHA MAHESWARAMMA
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Correspondence to ANJALI A KARANDE or AKHIL R CHAKRAVARTY.

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Supplementary Information (SI)

All additional information pertaining to the characterization of the complexes using ESI-MS technique (Figures S1, S2), IR spectra (Figures S3, S4), cyclic voltammograms (Figure S5), unit cell packing diagram of complex 1 (Figure S6), energy optimised structure of 1 along with FMO (Figure S7), EB displacement assay plot for complex 1 (Figure S8), Gel diagram (Figure S9), MTT assay of complex 1 (Figure S10) and coordinates for the energy minimized structures (Tables S1, S2) are given as supporting information, available at www.ias.ac.in/chemsci.

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BANERJEE, S., DIXIT, A., MAHESWARAMMA, K.S. et al. Photocytotoxic ternary copper(II) complexes of histamine Schiff base and pyridyl ligands. J Chem Sci 128, 165–175 (2016). https://doi.org/10.1007/s12039-015-1017-5

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