Bhaskar Biswas

Synthesis, structural characterization and biological activity of a trinuclear zinc(II) complex: DNA interaction study and antimicrobial activity

AbstractA trinuclear zinc(II) complex [Zn3L2(μ-O2CCH3)2(H2O)2]·H2O·2CH3OH (1) was synthesized from an in situ reaction between zinc acetate and a Schiff base ligand (H2L = 2-((2-hydroxyphenylimino)methyl)-6-methoxyphenol). The ligand was prepared by (1:1) condensation of ortho-vanillin and ortho-aminophenol. The ligand and zinc(II) complex were characterized by elemental analysis, Fourier Transform Infrared (FTIR), 1H-Nuclear Magnetic Resonance (NMR), UV-Vis spectroscopy, Powder X-ray Diffraction (PXRD) and thermogravimetric analysis. 1 crystallizes in P-1 space group with a = 11.9241(3) Å, b = 12.19746 Å, c = 20.47784 Å with unit cell volume is 2674.440 (Å)3. Binding property of the complex with calf thymus DNA (CT-DNA) has been investigated using absorption and emission studies. Thermal melting and viscosity experiments were further performed to determine the mode of binding of 1 with CT-DNA. Spectroscopic and viscosity investigations revealed an intercalative binding mode of 1 with CT-DNA. The ligand and its zinc complex were screened for their biological activity against bacterial species and fungi. Activity data show that the metal complex has more antibacterial and antifungal activity than the parent Schiff base ligand and against those bacterial or fungi species. Graphical AbstractA trinuclear Zinc(II) complex, [Zn3L2(μ-O2CCH3)2(H2O)2]·H2O·2CH3OH (1) of a (N,O)-donor Schiff base ligand has been synthesized and structurally characterized. The Zn(II) complex interacts significantly with CT-DNA and spectroscopic and viscosity investigations revealed an intercalative binding mode of 1 with DNA. The biological activity of the zinc(II) complex against different bacterial and fungal organisms is very promising.

Synthesis and bio-catalytic activity of isostructural cobalt(III)-phenanthroline complexes

AbstractWe have synthesized two isostructural mononuclear cobalt(III) complexes [1]NO3⋅3H2O and [1]NO3⋅CH3CO2H⋅H2O {[1]+ = [Co(1,10-phenanthroline)2Cl2]+} and characterized by single crystal X-ray structural analyses. Mass spectral studies of the complexes indicate both the compounds to produce identical cationic species viz., [Co(phen)2Cl2]+ in methanol solution. [1]+ has been evaluated as model system for the catechol oxidase enzyme by using 3,5-di-tert-butylcatechol (3,5-DTBC) as the substrate in methanol medium, which revealed that the cationic complex efficiently inhibits catalytic activity with kcat value 9.65 ×102 h−1. [1]+ cleaved pBR 322 DNA without addition of an activating agent. Further, the anti-cancer activity of [1]+ on human hepatocarcinoma cell line (HepG2) has been examined. The induction of apoptosis induced in the cell line was assessed base on the changes in cell morphology, which showed the efficacy of [1]+ to induce apoptosis in 53% of cells during 24 h treatment. Interestingly, the observed IC50 values reveal that [1]+ brings about conformational change on DNA strongly and exhibits remarkable cytotoxicity. The cationic cobalt(III) complex exhibits good catalytic activity in saturated oxygen environment towards 3,5-ditertbutylcatechol with kcat value 9.65×102 h-1. It also exhibits important cytotoxicity against human hepatocarcinoma cell line (HepG2).

Structural systematics of some metal complexes with 4,5-diazafluoren-9-one

AbstractSynthesis and X-ray structural characterization of three complexes of type cis-[M(dafone)2(NCS)2] (M = Co(II), 1; Ni(II), 2; Zn(II), 3; dafone = 4,5-diazafluoren-9-one) and a polymer cis-[Cd(dafone)(NCS)2]n (4) have been reported. Each of the four complexes is crystallized in orthorhombic crystal system. Structural study reveals that each metal(II) centre in the four complexes adopts distorted octahedral geometry with MN6 chromophore in 1-3 and MN4S2 chromophore in 4. The room temperature steady-state fluorescent intensity of dafone in dimethyl formamide at 402 nm is found to be quenched in these reported dafone complexes (1-4). Graphical AbstractSynthesis and X-ray structural characterization of three complexes of type cis-[M(dafone)2(NCS)2] (M = Co(II), 1; Ni(II), 2; Zn(II), 3; dafone = 4,5-diazafluoren-9-one) and a polymer cis-[Cd(dafone)(NCS)2]n (4) have been reported. The fluorescent intensity of dafone in DMF is found to be quenched in these reported dafone complexes (1-4).

Synthesis, structural characterization, and solution properties of a 1-D Pb(II)-bipyridine coordination polymer

A new one-dimensional (1-D) Pb(II) coordination polymer, [Pb(2,2′-bpy)(NO3)2(H2O)]n (1) (2,2′-bpy = 2,2′-bipyridine), has been synthesized and characterized by different spectroscopic techniques and X-ray single-crystal analysis. From the X-ray crystal structure of 1, the Pb2+ can be best described as a highly distorted pentagonal bipyramid with O4 (water) and O6 (nitrate) at apical positions (O4–Pb–O6 of 143.7(1)°). Variability in bond distances reveals that Pb2+ is unsymmetrically surrounded by two nitrates, one 2,2′-bpy and one water. Nitrates bridge between monomers. The molecule crystallizes in the monoclinic P21/n (14) space group. This is the first example of a 1-D Pb(II) polymer in which nitrates show three different coordination motifs (terminal, chelating, and bridging). Solid state as well as solution phase UV–vis spectral analysis and mass spectrometric studies clearly reveal instability with breakdown of Pb(II) polymer in aqueous solution. The arrangement of the 2,2′-bpy, water, and nitrates leaves a coordination gap at the Pb(II) occupied probably by a stereo-active lone pair of electrons.

Synthesis, spectroscopic, and crystallographic characterizations of an antiferromagnetically coupled, oxobridged trinuclear manganese(IV) cluster [Mn3O4(H2O)2(phen)4](NO3)4 · 3H2O [phen = 1,10-phenanthroline]

Design and synthesis of a triangular manganese compound, [Mn3O4(H2O)2(phen)4](NO3)4 · 3H2O (1) with mono-µ-oxo and di-µ-oxo, is described. The complex has been characterized by elemental analysis, spectroscopy, single crystal and powder diffraction measurements, thermogravimetric analysis, etc. Bond Valence Sum calculations and X-ray photoelectron spectroscopy reveal that each manganese at each vertex of the triangle is +IV oxidation state. Variable temperature magnetic measurements show strong antiferromagnetic coupling between metal ions with the following set of parameters: g = 1.99, J 1 = −50.0 cm−1, and J 2 = −90.2 cm−1 (where J 1 describes the interaction across the two mono-µ-oxo bridges and J 2 is the exchange coupling across the di-µ-oxo bridge). The compound breaks down in three steps when heated from room temperature to 900°C. The final ash of the compound is confirmed by infrared spectrum with standard MnO2.

A thiocyanate-based hybrid molecular salt as a new fluorescent chemosensor for fluoride

An organic–inorganic hybrid solid [(dpaH)+(NCS)−] (1) (dpa = 2,2′-dipyridylamine) based on an anionic template NCS− has been synthesized. Single crystal X-ray structural analysis reveals that NCS− templates assemble dpaH+ units into a 3-D layer structure along the b axis through strong hydrogen bonding. Molecular salt 1 works as an anion-binder efficiently and selectively for recognition and sensing purposes in aprotic solvents. This receptor shows changes both in its UV-Vis absorption and fluorescence emission spectra upon the addition of F−, resulting in high selectivity for fluoride detection in CH3CN. It is promising to use these systems in various sensing applications.

Unprecedented hetero-geometric discrete copper(II) complexes: Crystal structure and bio-mimicking of Catecholase activity

AbstractAn unprecedented solid of coper(II) complexes, [Cu(dpa)2NCS]2[Cu(dpa)2(NCS)2](ClO4)2 (1) [dpa = 2,2′-dipyridylamine; SCN = thiocyanate], has been synthesized and crystallographically characterized with the aim to study the catecholase activity. The Cu(II) complex mimics the full catalytic cycle of the active site of catechol oxidase enzyme in acetonitrile medium with a turnover number of 4.788×103 h −1 along with the production of semiquinone radical and hydrogen peroxide. In situ generation of Cu(I) species in the catalytic pathway of catechol oxidation was established by electrochemical study and further confirmed by electron paramagnetic resonance (EPR) spectroscopy. Graphical AbstractThis paper reports an X-ray crystallographically characterized Cu(II) complexes which mimics the full catalytic cycle of functional model of catechol oxidase enzyme with significant turnover number (4.788×103 h-1) along with the production of semiquinone radical and hydrogen peroxide.

Recognition of self-assembled water-nitrate cluster in a Co(III)-2,2′-bipyridine host: Synthesis, X-ray structure, DNA cleavage, molecular docking and anticancer activity

AbstractA mononuclear cobalt(III) complex [Co(bpy)2Cl2]NO3⋅2H2O (1) (bpy = 2,2′-bipyridine) has been synthesized and crystallographically characterized. Self-assembly of the lattice water molecules from rectangular tetrameric water cluster interacts with nitrate anion along the c-axis forming a six membered hexagonal water-nitrate cluster. It presents a new mode of association of water molecules with nitrate molecules which is not predicted theoretically or found experimentally. The molecule effectively cleaves bacterial genomic DNA and shows important cytotoxicity against human hepatocarcinoma cell (HepG2). Graphical AbstractThis paper reports an X-ray crystallographic characterization of a Co(III)-bpy complex which also presents a new mode of association of water molecules with nitrate molecules which was not predicted theoretically or found experimentally or reported in literature. The molecule effectively cleaves bacterial genomic DNA and shows important cytotoxicity against human hepatocarcinoma cell (HepG2).

Desert actinobacteria as a source of bioactive compounds production with a special emphases on Pyridine-2,5-diacetamide a new pyridine alkaloid produced by Streptomyces sp. DA3-7

In the present study, 134 morphologically distinct actinobacteria isolates were obtained from soil samples from 10 different localities in the Saudi Arabian desert. The preliminary screening revealed that 16 of these isolates possessed antimicrobial activity. One isolate, which was identified as Streptomyces sp. DA3-7, possessed broad-spectrum antimicrobial activity against both gram-positive and gram-negative bacteria, as well as against fungi, and modified nutrient glucose medium was suitable for Streptomyces sp. DA3-7 to produce extracellular metabolites. The ethyl acetate extract of Streptomyces sp. DA3-7 exhibited antimicrobial activity against Enterococcus faecalis and Salmonella typhimurium, with minimum inhibitory concentrations of 78 and 156μg/mL, respectively, as well as strong cytotoxicity (24h IC50 85μg/mL) against MCF-7 human breast adenocarcinoma cells. The active compound was separated, purified, and identified as Pyridine-2,5-diacetamide (C9H11N3O2+H+, 194.21), which possessed a lowest minimum inhibitory concentration (31.25μg/mL) against both Escherichia coli and Cryptococcus neoformans. The antimicrobial activities of this novel compound are reported here for the first time.

Catalytic aspects of a copper(II) complex: biological oxidase to oxygenase activity

A coper(II) complex,