Mixed-ligand copper(ii)-diimine complexes of 3-formylchromone- -phenyl thiosemicarbazone: 5,6-dmp co-ligand confers enhanced cytotoxicity.

The promising biological applications of thiosemicarbazone derivatives have inspired the design, synthesis, and study of their Cu(ii) complexes for anticancer therapeutic applications. Herein, we have evaluated the DNA/protein binding, DNA cleaving, and cytotoxic properties of four mixed-ligand Cu(ii) complexes of the type [Cu(L)(diimine)](NO) 1-4, where HL is 4-oxo-4-chromene-3-carbaldehyde-4()-phenylthiosemicarbazone and diimine is 2,2'-bipyridine (bpy, 1) 1,10-phenanthroline (phen, 2), 5,6-dimethyl-1,10-phenanthroline (5,6-dmp, 3), or dipyrido-[3,2-:2',3'-]-quinoxaline (dpq, 4). Interestingly, complex 3 with higher lipophilicity shows stronger DNA binding and oxidative DNA cleavage, higher ROS production, and more reversible redox behaviour, resulting in its remarkable cytotoxicity (IC, 1.

Mixed ligand copper(II)-diimine complexes of 2-formylpyridine--phenylthiosemicarbazone: diimine co-ligands tune the nanomolar cytotoxicity.

Recently, mixed-ligand copper(II) complexes have received much attention in searching for alternative metallodrugs to cisplatin. A series of mixed ligand Cu(II) complexes of the type [Cu(L)(diimine)](ClO) 1-6, where the HL is 2-formylpyridine--phenylthiosemicarbazone and the diimine is 2,2'-bipyridine (1), 4,4'-dimethyl-2,2'-bipyridine (2), 1,10-phenanthroline (3), 5,6-dimethyl-1,10-phenanathroline (4), 3,4,7,8-tetramethyl-1,10-phenanthroline (5) and dipyrido-[3,2-:2',3'-]quinoxaline (6), has been synthesized and their cytotoxicity in HeLa cervical cancer cells examined. In the molecular structures of 2 and 4, as determined by single-crystal X-ray studies, Cu(II) assumes a trigonal bipyramidal distorted square-based pyramidal (TBDSBP) coordination geometry.

Crystal structure of [2-({[2-(dimethylamino-κ)ethyl]imino-κ}methyl)phenolato-κ](1,10-phen-anthroline-κ ,')copper(II) perchlorate.

The title compound, [Cu(CHNO)(CHN)]ClO or [Cu()(phen)](ClO) {where refers to the deprotonated form of 2-[(2-di-methyl-amino-ethyl-imino)-meth-yl]phenol} and phen is 1,10-phenanthroline) is a mononuclear mixed ligand copper(II) complex. The Cu atom is coordinated by two N and one O atoms of the tridentate Schiff base ligand (H) and two N atoms of the 1,10-phenanthroline ligand, resulting in a five-coordinate complex. The asymmetric unit of the title complex contains two crystallographically independent complex cations ( and ) with a slightly different geometry around the Cu ion.

Induction of Redox-Mediated Cell Death in ER-Positive and ER-Negative Breast Cancer Cells by a Copper(II)-Phenolate Complex: An In Vitro and In Silico Study.

This research was aimed at finding the cytotoxic potential of the mixed ligand copper(II) complex [Cu(tdp)(phen)](ClO)-where H(tdp) is the tetradentate ligand 2-[(2-(2-hydroxyethylamino)-ethylimino)methyl]phenol, and phen is 1,10-phenanthroline-to two genotypically different breast cancer cells, MCF-7 (p53 and ER) and MDA-MB-231 (p53 and ER). The complex has been already shown to be cytotoxic to ME180 cervical carcinoma cells. The special focus in this study was the induction of cell death by apoptosis and necrosis, and its link with ROS.

Metalloporphyrin Nanoparticles: Coordinating Diverse Theranostic Functions.

Metalloporphyrins serve key roles in natural biological processes and also have demonstrated utility for biomedical applications. They can be encapsulated or grafted in conventional nanoparticles or can self-assemble themselves at the nanoscale. A wide range of metals can be stably chelated either before or after porphyrin nanoparticle formation, without the necessity of any additional chelator chemistry.

Assessing Photosensitizer Targeting Using Meso-Tetra(Carboxyphenyl) Porphyrin.

Mesotetra(4-carboxyphenyl)porphyrin (mTCPP) is a commercially available small molecule fluorophore and photosensitizer with four free carboxylic acid groups. mTCPP can readily be conjugated with amines for facile attachment of functional groups. In this work, we synthesized and assessed tetravalent, lysine-conjugated mTCPP, for its potential applications in targeted imaging and photodynamic therapy.

New [Ru(5,6-dmp/3,4,7,8-tmp)₂(diimine)]²⁺ complexes: non-covalent DNA and protein binding, anticancer activity and fluorescent probes for nuclear and protein components.

A series of Ru(II) complexes of the type [Ru(5,6-dmp)(2)(diimine)](2+)1-3 and [Ru(tmp)(2)(diimine)](2+)4-6, where 5,6-dmp is 5,6-dimethyl-1,10-phenanthroline, tmp is 3,4,7,8-tetramethyl-1,10-phenanthroline and diimine is dipyrido-[3,2-d:2',3'-f]-quinoxaline (dpq), dipyrido[3,2-a:2',3'-c]phenazine (dppz) and 11,12-dimethyl-dipyrido[3,2-a:2',3'-c]phenazine (11,12-dmdppz), has been isolated and the DNA binding mode of the complexes studied by using emission and circular dichroic (CD) spectral techniques. All the complexes exhibit induced circular dichroism upon binding to calf thymus (CT) DNA and show preferential binding to AT and mixed (d(CGCGATCGCG)(2)) sequences rather than to GC sequences. The complex [Ru(tmp)(2)(dpq)](2+)4 exhibits enhancement in luminescence higher than [Ru(5,6-dmp)(2)(dpq)](2+)1 upon binding to DNA.

[Ru(phen)2(dppz)]2+ as an efficient optical probe for staining nuclear components.

The 'molecular light switch' complexes [Ru(bpy)(2)(dppz)](2+) (1) and [Ru(phen)(2)(dppz)](2+) (2), where bpy=2,2'-bipyridine, phen=1,10-phenanthroline and dppz=dipyrido[3,2-a:2',3'-c]phenazine, have been explored as probes for diagnosing and staining nuclear components. The phen complex acts as a better staining agent for nonviable cells than for viable cells and exhibits a staining efficiency in tail region of comet more specific and stronger than the already known dye Hoechst 33258.

Induction of cell death by ternary copper(II) complexes of L-tyrosine and diimines: role of coligands on DNA binding and cleavage and anticancer activity.

The mononuclear mixed ligand copper(II) complexes of the type [Cu(L-tyr)(diimine)](ClO(4)), where tyr is L-tyrosine and diimine is 2,2'-bipyridine (bpy) (1), 1,10-phenanthroline (phen) (2), 5,6-dimethyl-1,10-phenanthroline (5,6-dmp) (3), and dipyrido[3,2-d:2',3'-f]quinoxaline (dpq) (4), have been isolated and characterized by analytical and spectral methods. In the X-ray crystal structure 3 Cu(II) possesses a distorted square pyramidal coordination geometry with the two nitrogen atoms of 5,6-dmp ligand and the amine nitrogen and carboxylate oxygen atoms of L-tyrosine located at the equatorial sites and the coordinated water molecule present in the apical position. The electronic absorption and electron paramagnetic resonance (EPR) spectral parameters reveal that the complexes retain their square-based geometries even in solution.

Mixed ligand ruthenium(II) complexes of bis(pyrid-2-yl)-/bis(benzimidazol-2-yl)-dithioether and diimines: study of non-covalent DNA binding and cytotoxicity.

A series of mixed ligand ruthenium(II) complexes [Ru(pdto)(diimine)](ClO4)2/(PF6)2 1-3 and [Ru(bbdo)(diimine)](ClO4), 4-6, where pdto is 1,8-bis(pyrid-2-yl)-3,6-dithiooctane, bbdo is 1,8-bis(benzimidazol-2-yl)-3,6-dithiooctane and diimine is 1,10-phenanthroline (phen), dipyrido-[3,2-d:2',3'-f]-quinoxaline (dpq) and dipyrido[3,2-a:2',3'-c]phenazine (dppz), have been isolated and characterised by analytical and spectral methods. The complexes [Ru(pdto)(phen)](PF6)2 la, [Ru(pdto)(dpq)(Cl](PF6) 2a, [Ru(bbdo)(phen)](PF6)2 4a and [Ru(bbdo)(dpq)](ClO4)2 5 have been structurally characterized and their coordination geometries around ruthenium(II) are described as distorted octahedral. In la, 4a and 5 the two thioether sulfur and two py/bzim nitrogen atoms of the tetradentate pdto/bbdo ligand are folded around Ru(II) to give predominantly a "cis-alpha" configuration.

Non-covalent DNA binding and cytotoxicity of certain mixed-ligand ruthenium(II) complexes of 2,2'-dipyridylamine and diimines.

A series of mixed ligand ruthenium(II) complexes [Ru(Hdpa)2(diimine)](ClO4)2, 1-5 where Hdpa is 2,2'-dipyridylamine and diimine is 1,10-phenanthroline (phen) and a modified/extended 1,10-phenanthroline such as, 5,6-dimethyl-1,10-phenanthroline (5,6-dmp), dipyrido[3,2-d:2',3'-f]quinoxaline (dpq), 5-methyldipyrido[3,2-d:2',3'-f]quinoxaline (mdpq) and dipyrido[3,2-a:2',3'-c]phenazine (dppz) have been isolated and characterized by analytical and spectral methods. The complex [Ru(Hdpa)2(phen)](PF6)2 1 has been structurally characterized and the coordination geometry around Ru(II) in it is described as distorted octahedral. 1H NMR spectral data reveal that 1-5 should have a C2 symmetry lying on the diimine plane due to the rapid flapping of the coordinated Hdpa ligands.

Cleavage of proteins by a mixed-ligand copper(II) phenolate complex: hydrophobicity of the diimine co-ligand promotes cleavage.

The mixed-ligand copper(II) complex [Cu(tdp)(tmp)](ClO4), where H(tdp) is 2-[(2-(2-hydroxyethylamino)ethylimino)methyl]phenol and tmp is 3,4,7,8-tetramethyl-1,10-phenanthroline, exhibits cleavage of the proteins bovine serum albumin and lysozyme, producing approximately 5 and 4 kDa protein fragments respectively within a few minutes at micromolar concentrations. The hydrophobic tmp ligand recognizes the hydrophobic site and enhances protein binding and cleavage even at physiological pH and temperature.

Mixed-ligand copper(II)-phenolate complexes: effect of coligand on enhanced DNA and protein binding, DNA cleavage, and anticancer activity.

The copper(II) complex [Cu(tdp)(ClO4)].0.5H2O (1), where H(tdp) is the tetradentate ligand 2-[(2-(2-hydroxyethylamino)ethylimino)methyl]phenol, and the mixed ligand complexes [Cu(tdp)(diimine)]+ (2-5), where diimine is 2,2'-bipyridine (bpy) (2), 1,10-phenanthroline (phen) (3), 3,4,7,8-tetramethyl-1,10-phenanthroline (tmp) (4), and dipyrido-[3,2-d:2',3'-f]-quinoxaline (dpq) (5), have been isolated and characterized by analytical and spectral methods.

Structures, spectra, and DNA-binding properties of mixed ligand copper(II) complexes of iminodiacetic acid: the novel role of diimine co-ligands on DNA conformation and hydrolytic and oxidative double strand DNA cleavage.

The coordination geometry around copper(II) in [Cu(imda)(phen)(H2O)] (1) (H2imda = iminodiacetic acid, phen = 1,10-phenanthroline) is described as distorted octahedral while those in [Cu(imda)(5,6-dmp)] (2) (5,6-dmp = 5,6-dimethyl-1,10-phenanthroline) and [Cu(imda)(dpq)] (3) (dpq = dipyrido-[3,2-d:2',3'-f]-quinoxaline) as trigonal bipyramidal distorted square-based pyramidal with the imda anion facially coordinated to copper(II). Absorption spectral (Kb: 1, 0.60+/-0.

Interaction of rac-[Ru(5,6-dmp)3]2+ with DNA: enantiospecific DNA binding and ligand-promoted exciton coupling.

The X-ray crystal structure of the complex rac-[Ru(5,6-dmp)(3)]Cl(2) (5,6-dmp = 5,6-dimethyl-1,10-phenanthroline) reveals a distorted octahedral coordination geometry with the Ru-N bond distances shorter than in its phen analogue. Absorption spectral titrations with CT DNA reveal that rac-[Ru(5,6-dmp)(3)](2+) interacts (K(b), (8.0 +/- 0.

Synthesis, characterization and DNA-binding properties of rac-[Ru(5,6-dmp)2(dppz)]2+--enantiopreferential DNA binding and co-ligand promoted exciton coupling.

The new mixed ligand complex [Ru(5,6-dmp)2(dppz)]Cl2 [5,6-dmp = 5,6-dimethyl-1,10-phenanthroline, dppz = dipyrido[3,2-a:2',3'-c]phenazine] has been isolated and its DNA-binding properties studied by employing UV-visible (UV-Vis), steady-state and time-resolved emission and circular dichroism spectral methods, viscometry, thermal denaturation and cyclic/differential pulse voltammetric techniques. The complex acts as a 'molecular light-switch' on binding to DNA, but the enhancement in emission intensity is only 75% of that of the parent complex [Ru(phen)2(dppz)]2+ (phen = 1,10-phenanthroline). The emission decay curves and quenching studies suggest two different DNA-binding modes both involving intercalation of the dppz ligand of [Ru(5,6-dmp)2(dppz)]Cl2.

Copper(II) complexes of tridentate pyridylmethylethylenediamines: role of ligand steric hindrance on DNA binding and cleavage.

Copper(II) complexes of three linear unsymmetrical tridentate ligands viz. N-methyl-N'-(pyrid-2-ylmethyl)ethylenediamine (L1), N,N-dimethyl-N'-(pyrid-2-ylmethyl)ethylenediamine (L2) and N,N-dimethyl-N'-((6-methyl)pyrid-2-ylmethyl)ethylenediamine (L3) have been isolated and characterized by elemental analysis, electronic absorption and EPR spectroscopy and cyclic and differential pulse voltammetry. Of these complexes [Cu(L2)Cl2] and [Cu(L3)Cl2] have been structurally characterized by X-ray crystallography.