Spectroscopic, SOD, anticancer, antimicrobial, molecular docking and DNA binding properties of bioactive VO(IV), Cu(II), Zn(II), Co(II), Mn(II) and Ni(II) complexes obtained from 3-(2-hydroxy-3-methoxybenzylidene)pentane-2,4-dione.

Novel macrocyclic Schiff base complexes [[ML]X; where M = Cu(II), Co(II), Ni(II), Zn(II), Mn(II) and VO(IV); L = macrocyclic ligand; X = Cl2 and SO42-] have been synthesized and characterized by microanalytical, 1H, 13C NMR, IR, Mass, UV-Vis, EPR spectral studies, as well as conductivity data. All the complexes exhibit square-planar geometry except vanadium complex. Magnetic susceptibility measurements and high conductance data reveal the monomeric and electrolytic nature of the complexes. Electronic absorption, cyclic voltammetry, viscosity measurements have been carried out on the interaction of the complexes with DNA. The results suggest that the complexes bind to DNA by intercalation via the aromatic ring of the macrocycle into the base pairs of DNA. Using gel electrophoresis experiment in the presence and absence of oxidant (H2O2) the nuclease cleavage activity of the complexes has been performed on plasmid DNA. The results demonstrate that most of the complexes have promising superoxide dismutase (SOD)-mimetic activity. The in vitro cytotoxicity of ligand and its complexes has also been evaluated against human breast and colon carcinoma cells. Binding interactions and energies of ligand and its metal complexes [ML]2+ (M = VO(IV), Mn(II), Co(II), Ni(II), Cu(II), Zn(II)) against the receptors EGFR and HER2 are performed using the Auto dock module. Consequently, it is found that the ligand is strong inhibitor for EGFR and HER2 while [VOL]SO4 is good inhibitor for EGFR and [ZnL]Cl2 is moderate inhibitor for HER2. The antimicrobial activity of the ligand and its complexes against bacteria Salmonella typhi, Staphylococcus aureus, Escherichia coli and Bacillus subtilis and fungi Aspergillus niger, Aspergillus flavus, Candida Albicans and Rhizoctonia bataicola. The complexes have higher activities than the macrocyclic free Schiff base. Communicated by Ramaswamy H. Sarma.

Synthesis, characterization, biological evaluation and docking studies of macrocyclic binuclear manganese(II) complexes containing 3,5-dinitrobenzoyl pendant arms.

A series of bis(phenoxo) bridged binuclear manganese(II) complexes of the type [Mn2L(1-3)](ClO4)2 (1-3) containing 3,5-dinitrobenzoyl pendant-arms have been synthesized by cyclocondensation of 2,6-diformyl-4-R-phenols (where R=CH3, C(CH3)3 or Br) with 2,2'-3,5-dinitrobenzoyliminodi(ethylamine) trihydrochloride in the presence of manganese(II) perchlorate. The IR spectra of complexes indicate the presence of uncoordinated perchlorate anions. The UV-Vis spectra of complexes suggest the distorted octahedral geometry around manganese(II) nuclei. The EPR spectra of Mn(II) complexes show a broad signal with g value 2.03-2.04, which is characteristic for octahedral high spin Mn(2+) complex. The observed room temperature magnetic moment values of the Mn(II) complexes (5.60-5.62B.M.) are less than the normal value (5.92B.M.), indicating weak antiferromagnetic coupling interaction between the two metal ions. Electrochemical studies of the complexes show two distinct quasi-reversible one electron transfer processes in the cathodic (E(1)pc=-0.73 to -0.76V, E(2)pc=-1.30 to -1.36V), and anodic (E(1)pa=1.02-1.11V, E(2)pa=1.32-1.79V) potential regions. Antibacterial efficacy of complexes have been screened against four Gram (-ve) and two Gram (+ve) bacterial strains. The DNA interaction studies suggest that these complexes bind with CT-DNA by intercalation, giving the binding affinity in the order 1>2>3. All the complexes display significant cleavage activity against circular plasmid pBR322 DNA. Docking simulation was performed to insert complexes into the crystal structure of EGFR tyrosine kinase and B-DNA at active site to determine the probable binding mode.

Novel metal-based pharmacologically dynamic agents of transition metal(II) complexes: designing, synthesis, structural elucidation, DNA binding and photo-induced DNA cleavage activity.

Novel Schiff base Cu(II), Ni(II), Co(II) and Zn(II) complexes have been designed and synthesized using the macrocyclic ligand derived from the condensation of diethylphthalate with Schiff base, obtained from benzene-1,2-diamine and 3-benzylidene-pentane-2,4-dione. The ligand and its complexes have been characterized by analytical and spectral techniques. DNA binding properties of these complexes have been investigated by UV-vis, viscosity measurements, cyclic voltammetric and differential pulse voltammogram studies. The intrinsic binding constants for Co(II), Ni(II), Cu(II) and Zn(II) complexes are 1.6x10(6), 1.8x10(6), 2.0x10(6) and 1.5x10(6) M(-1) respectively which are obtained from electronic absorption experiment. Control DNA cleavage experiments using pUC19 supercoiled (SC) DNA and minor groove binder (distamycin) suggest the major groove binding tendency for the synthesized complexes. In the presence of a reducing agent like 3-mercaptopropionic acid (MPA), the synthesized complexes show chemical nuclease activity under dark reaction condition. The complexes also show efficient photo-induced DNA cleavage activity on irradiation with a monochromatic UV light of 360 nm in the presence of inhibitors. Control experiments show inhibition of cleavage in the presence of singlet oxygen quencher like sodium azide and enhancement of cleavage in D(2)O, suggesting the formation of singlet oxygen as a reactive species in a type-II process.