Synthesis, X-ray structure and in vitro cytotoxicity studies of Cu(I/II) complexes of thiosemicarbazone: special emphasis on their interactions with DNA

4-(p-X-phenyl)thiosemicarbazone of napthaldehyde {where X = Cl (HL1) and X = Br (HL2)}, thiosemicarbazone of quinoline-2-carbaldehyde (HL3) and 4-(p-fluorophenyl) thiosemicarbazone of salicylaldehyde (H2L4) and their copper(I) {Cu(HL1)(PPh3)(2)Br]center dot CH3CN (1) and Cu(HL2)(PPh3)(2)Cl]center dot DMSO (2)} and copper(II) {((Cu2L2Cl)-Cl-3)(2)(mu-Cl)(2)]center dot 2H(2)O (3) and Cu(L-4)(Py)] (4)} complexes are reported herein. The synthesized ligands and their copper complexes were successfully characterized by elemental analysis, cyclic voltammetry, NMR, ESI-MS, IR and UV-Vis spectroscopy. Molecular structures of all the Cu(I) and Cu(II) complexes have been determined by X-ray crystallography. All the complexes (1-4) were tested for their ability to exhibit DNA-binding and - cleavage activity. The complexes effectively interact with CT-DNA possibly by groove binding mode, with binding constants ranging from 10(4) to 10(5) M-1. Among the complexes, 3 shows the highest chemical (60%) as well as photo-induced (80%) DNA cleavage activity against pUC19 DNA. Finally, the in vitro antiproliferative activity of all the complexes was assayed against the HeLa cell line. Some of the complexes have proved to be as active as the clinical referred drugs, and the greater potency of 3 may be correlated with its aqueous solubility and the presence of the quinonoidal group in the thiosemicarbazone ligand coordinated to the metal.

The Corogal: one of the big dredges in Culebra Cut, Panama Canal (ca. 1914)

Leonard Carpenter Panama Canal Collection. Photographs: Dredging, Soldiers, and Ships. [Box 1] from the Special Collections & Area Studies Department, George A. Smathers Libraries, University of Florida.

First U.S. battleships through Panama Canal: Missouri, Ohio, Wisconsin (postcard ca 1914)

Leonard Carpenter Panama Canal Collection. Photographs: Dredging, Soldiers, and Ships. [Box 1] from the Special Collections & Area Studies Department, George A. Smathers Libraries, University of Florida.

Tow boat fleet at Paraiso, Panama Canal (ca. 1914)

Leonard Carpenter Panama Canal Collection. Photographs: Dredging, Soldiers, and Ships. [Box 1] from the Special Collections & Area Studies Department, George A. Smathers Libraries, University of Florida.