title: Synthesis, crystal structure, spectroscopic properties and potential biological activities of salicylate‒neocuproine ternary copper(II) complexes.
abstract: Mixed ligand copper(II) complexes containing derivatives of salicylic acid and heterocyclic ligands with nitrogen donor atoms have been the subject of various studies and reviews. In this paper, synthesis and characterization of the ternary copper(II) complexes of neocuproine (2,9-dimethyl-1,10-phenanthroline, Neo) and salicylate ligands (Sal) are reported. In addition, the crystal structures of ([Cu(H2O)(5-Cl-Sal)(Neo)] (1), [Cu(μ-Sal)(Neo)]2 (2), Cu2(μ-5-Cl-Sal)(5-Cl-HSal)2(Neo)2]·EtOH (3)) were determined. In order to compare structural and biological properties of the prepared complexes, spectroscopic and biological studies were performed. Results of X-ray diffraction show that prepared complexes form three types of crystal structures in a given system: monomeric, dimeric and dinuclear complex. The preliminary study on the DNA cleavage activity has shown that the complexes under study behave as the chemical nucleases in the presence of added hydrogen peroxide with slight differences in the activity (1 > 2 > 3). The complexes 1 and 2 exhibited nuclease activity itself indicating the interaction of complexes with the DNA. It has been proposed that the enhanced destructive effect of the complexes 1 and 2 on the DNA is a result of two possible mechanisms of action: (i) the conversion of closed circular DNA (form I) to the nicked DNA (form II) caused by the copper complex itself and (ii) damage of DNA by Reactive Oxygen Species (ROS)-products of the interaction of copper with hydrogen peroxide by means of Fenton reaction (hydroxyl radicals). Thus the biological activity of the prepared Cu(II) complexes containing derivatives of salicylic acid and phenanthroline molecules is substantiated by two independent mechanisms. While derivatives of salicylic acids in the coordination sphere of copper complexes are responsible for radical-scavenging activity (predominantly towards superoxide radical anion), the presence of chelating ligand 2,9-dimethyl-1,10-phenanthroline significantly enhances capability of Cu(II) complexes binding to DNA via intercalation.
authors: Department of Physical Chemistry, Faculty of Chemical and Food Technology, Slovak University of Technology, Radlinského 9, Bratislava SK-812 37, Slovak Republic. lenka.kuckova@stuba.sk.
authors: Lenka
authors: L
authors: Kucková
authors: Department of Chemistry, Faculty of Natural Sciences, Constantine the Philosopher University, Trieda A. Hlinku 1, Nitra SK-949 74, Slovak Republic. kjomova@ukf.sk.
authors: Klaudia
authors: K
authors: Jomová
authors: Department of Chemistry, Faculty of Natural Sciences, Constantine the Philosopher University, Trieda A. Hlinku 1, Nitra SK-949 74, Slovak Republic. andrea.svorcova14@gmail.com.
authors: Andrea
authors: A
authors: Švorcová
authors: Department of Physical Chemistry, Faculty of Chemical and Food Technology, Slovak University of Technology, Radlinského 9, Bratislava SK-812 37, Slovak Republic. marian.valko@stuba.sk.
authors: Marián
authors: M
authors: Valko
authors: Department of Inorganic Chemistry, Faculty of Chemical and Food Technology, Slovak University of Technology, Radlinského 9, Bratislava SK-812 37, Slovak Republic. peter.segla@stuba.sk.
authors: Peter
authors: P
authors: Segľa
authors: Department of Inorganic Chemistry, Faculty of Chemical and Food Technology, Slovak University of Technology, Radlinského 9, Bratislava SK-812 37, Slovak Republic. jan.moncol@stuba.sk.
authors: Ján
authors: J
authors: Moncoľ
authors: Department of Physical Chemistry, Faculty of Chemical and Food Technology, Slovak University of Technology, Radlinského 9, Bratislava SK-812 37, Slovak Republic. jozef.kozisek@stuba.sk.
authors: Jozef
authors: J
authors: Kožíšek
mesh_terms: D056831:Coordination Complexes / Q000737:chemistry*; D003300:Copper / Q000737:chemistry; D018360:Crystallography, X-Ray; D053837:DNA Cleavage; D006860:Hydrogen Bonding; D006861:Hydrogen Peroxide / Q000737:chemistry; D007364:Intercalating Agents / Q000737:chemistry; D008968:Molecular Conformation; D010084:Oxidation-Reduction; D010618:Phenanthrolines / Q000737:chemistry*; D010957:Plasmids / Q000737:chemistry; D012459:Salicylates / Q000737:chemistry*
chemical_list: D056831:Coordination Complexes; D007364:Intercalating Agents; D010618:Phenanthrolines; D012459:Salicylates; D003300:Copper; D006861:Hydrogen Peroxide
references: Antioxid Redox Signal. 2011 Aug 15;15(4):1085-127
references: 21275772
references: Biochimie. 2009 Oct;91(10):1286-93
references: 19563861
references: Nucleic Acids Res. 2005 Sep 26;33(16):5371-9
references: 16186134
references: J Med Chem. 2012 Mar 8;55(5):1957-68
references: 22313179
references: J Inorg Biochem. 2004 Nov;98(11):1734-49
references: 15522401
references: J Am Chem Soc. 2006 Jan 25;128(3):710-1
references: 16417347
references: J Inorg Biochem. 2002 Apr 28;89(3-4):163-73
references: 12062119
references: Acta Crystallogr Sect E Struct Rep Online. 2009 Apr 08;65(Pt 5):m485
references: 21583737
references: Eur J Med Chem. 2008 Oct;43(10):2082-91
references: 17988765
references: Arch Biochem Biophys. 1974 Dec;165(2):691-708
references: 4374138
references: Acta Crystallogr Sect E Struct Rep Online. 2010 Mar 10;66(Pt 4):m387-8
references: 21580494
references: Arch Med Res. 2005 Nov-Dec;36(6):697-705
references: 16216651
references: Acta Crystallogr C Struct Chem. 2015 Jan;71(Pt 1):3-8
references: 25567568
references: Herz. 2008 Jun;33(4):270-8
references: 18581076
references: J Inorg Biochem. 1996 Sep;63(4):291-300
references: 8757142
references: Acta Crystallogr C. 2012 Apr;68(Pt 4):m85-9
references: 22476141
references: Clin Infect Dis. 2000 Oct;31 Suppl 5:S154-6
references: 11113017
references: Arch Biochem Biophys. 1993 Jul;304(1):102-9
references: 8323275
references: Anticancer Agents Med Chem. 2009 Feb;9(2):185-211
references: 19199864
references: J Biol Chem. 1979 Dec 25;254(24):12269-72
references: 387784
references: Chem Rev. 2009 Oct;109(10):4921-60
references: 19715312
references: Acta Crystallogr Sect E Struct Rep Online. 2008 Nov 13;64(Pt 12):m1526-7
references: 21581143
references: Dalton Trans. 2013 Mar 7;42(9):3196-209
references: 23233164
references: J Biol Inorg Chem. 2012 Mar;17(3):409-23
references: 22189939
references: Curr Med Chem. 2009;16(11):1325-48
references: 19355889
references: Appl Biochem Biotechnol. 2013 Feb;169(4):1329-45
references: 23306896
references: Acta Crystallogr A. 2008 Jan;64(Pt 1):112-22
references: 18156677
references: Acta Crystallogr Sect E Struct Rep Online. 2008 Jul 26;64(Pt 8):m1062
references: 21203045
references: Acta Crystallogr Sect E Struct Rep Online. 2008 Jan 04;64(Pt 2):m294
references: 21201271