Influence of high energy γ-irradiation on some binuclear transition metal complexes of pentadentate ligand: Spectral, thermal, modelling, X-ray diffraction, morphological and solid electrical conductivity.

New binuclear Co(II) (1), Ni(II) (2) and Cu(II) (3) complexes of N,N'-(2,2'-azanediylbis(ethane-2,1-diyl))bis(2-aminobenzamide) have been synthesized and fully characterized by various chemical and spectral techniques. The synthesized complexes were irradiated by 60Co gamma rays to dose value of 100 kGy (hereafter referred to as 1a,2a,3a). Molar conductance, spectral, thermal, magnetic moment measurements, powder X-ray diffraction and solid electrical conductivity measurements were investigated before and after exposure to irradiation. The results showed that the current complexes slightly affected by the applied irradiation dose and that, the thermal decomposition profiles of non-irradiated and irradiated samples were changed upon irradiation. From powder X-ray diffraction the crystallite size as well as dislocation density were slightly changed. Surface morpholgical changes were observed for [Cu2LCl2(OH)2(H2O)]·2H2O (3) upon irradiation. Irradiation resulted in change in d.c solid electrical conductivity this change was, however, more pronounced for samples 2a,3a.

Influences of γ-ray irradiation on physico-chemical, structural, X-ray diffraction, thermal and antimicrobial activity of some γ-irradiated N',N'''-((Z)-ethane-1,2-diylidine)bis(2-aminobenzohydrazide) metal complexes.

A series of Co(II), Ni(II), Cu(II), Th(IV) and UO2(II) complexes have been synthesized from reaction of nitrogen based ligand (L) i.e. N',N'''-((Z)-ethane-1,2-diylidine)bis(2-aminobenzohydrazide)(L) with their salts. Investigation of synthesized metal complexes was achieved by using elemental analyses, magnetic moment, molar conductance, FT-IR, UV/Vis. spectroscopy, thermal techniques and 3D molecular modeling. An octahedral geometry has been suggested for all complexes except for Ni(II) complex (2) which adopted tetrahedral geometry. To through a light on the probability of structure changes with γ-irradiation, the effect of gamma irradiation on powder samples of the complexes [Co(L)Cl2].4H2O (1); [Ni2(L)(OAc)4].5H2O (2) and [Cu(L)Br2].5H2O (3) was investigated after being exposed to high energetic γ-rays at 100 kGy dose (hereafter referred to as (1A,2A,3A, respectively). Spectral, thermal, magnetic susceptibility, molar conductance and powder X-ray diffraction patterns (XRD) were performed before and after irradiation. In addition, the in vitro antimicrobial activity of the complexes against Staphylococcus aureus as Gram-positive strain, Escherichia coli as Gram-negative strain and antifungal Candida albicans was performed for both unirradiated and irradiated samples. The obtained results showed that the irradiated complexes were affected, but not greatly by the applied γ-irradiation dose.

Controlled morphology and dimensionality evolution of NiPd bimetallic nanostructures.

Controlling the morphology of noble metal-based nanostructures is a powerful strategy for optimizing their catalytic performance. Here, we report a one-pot aqueous synthesis of versatile NiPd nanostructures at room temperature without employing organic solvents or surfactants. The synthesis can be tuned to form zero-dimensional (0D) architectures, such as core-shell and hollow nanoparticles (NPs), as well as nanostructures with higher dimensionality, such as extended nanowire networks and three-dimensional (3D) nanodendrites. The diverse morphologies were successfully obtained through modification of the HCl concentration in the Pd precursor solution, and the reaction aging time. An in-depth understanding of the formation mechanism and morphology evolution are described in detail. A key factor in the structural evolution of the nanostructures was the ability to tune the reduction rate and to protonate the citrate stabiliser by adding HCl. Spherical core-shell NPs were formed by the galvanic replacement-free deposition of Pd on Ni NPs which can be transformed to hollow NPs via a corrosion process. High concentrations of HCl led to the transition of isotropic spherical NPs into anisotropic wormlike nanowire networks, created through an oriented attachment process. Aging of these nanowire networks resulted in the formation of 3D porous nanodendrites via a corrosion process. The diverse structures of NiPd NPs were anchored onto acid treated-activated carbon (AC) and exhibited improved catalytic efficiency towards the hydrogenation of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP).

New 15-membered tetraaza (N4) macrocyclic ligand and its transition metal complexes: spectral, magnetic, thermal and anticancer activity.

Novel tetraamidemacrocyclic 15-membered ligand [L] i.e. naphthyl-dibenzo[1,5,9,12]tetraazacyclopentadecine-6,10,11,15-tetraoneand its transition metal complexes with Fe(II), Co(II), Ni(II), Cu(II), Ru(III) and Pd(II) have been synthesized and characterized by elemental analysis, spectral, thermal as well as magnetic and molar conductivity measurements. On the basis of analytical, spectral (IR, MS, UV-Vis, (1)H NMR and EPR) and thermal studies distorted octahedral or square planar geometry has been proposed for the complexes. The antitumor activity of the synthesized ligand and some complexes against human breast cancer cell lines (MCF-7) and human hepatocarcinoma cell lines (HepG2) has been studied. The complexes (IC50=2.27-2.7, 8.33-31.1µg/mL, respectively) showed potent antitumor activity, towards the former cell lines comparable with their ligand (IC50=13, 26µg/mL, respectively). The results show that the activity of the ligand towards breast cancer cell line becomes more pronounced and significant when coordinated to the metal ion.

Transition metal complexes of a new 15-membered [N5] penta-azamacrocyclic ligand with their spectral and anticancer studies.

Novel penta-azamacrocyclic 15-membered [N5] ligand [L] i.e. 1,5,8,12-tetetraaza-3,4: 9,10-dibenzo-6-ethyl-7-methyl-1,12-(2,6-pyrido)cyclopentadecan-5,7 diene-2,11-dione and its transition metal complexes with Co(II), Ni(II), Cu(II), Ru(III) and Pd(II) have been synthesized and structurally characterized by elemental analysis, spectral, thermal as well as magnetic and molar conductivity measurements. On basis of IR, MS, UV-Vis 1H NMR and EPR spectral studies an octahedral geometry has been proposed for all complexes except Co(II), Cu(II) nitrate complexes and Pd(II) chloride complex that adopt tetrahedral, square pyramidal and square planar geometries, respectively. The antitumor activity of the synthesized ligand and some complexes against human breast cancer cell lines (MCF-7) and human hepatocarcinoma cell lines (HepG2) has been studied. The complexes (IC50=2.04-9.7, 2.5-3.7 µg/mL) showed potent antitumor activity comparable with their ligand (IC50=11.7, 3.45 µg/mL) against the above mentioned cell lines, respectively. The results evidently show that the activity of the ligand becomes more pronounced and significant when coordinated to the metal ion.

Coordination behavior of tetraaza [N4] ligand towards Co(II), Ni(II), Cu(II), Cu(I) and Pd(II) complexes: synthesis, spectroscopic characterization and anticancer activity.

Novel eight Co(II), Ni(II), Cu(II), Cu(I) and Pd(II) complexes with [N(4)] ligand (L) i.e. 2-amino-N-{2-[(2-aminobenzoyl)amino]ethyl}benzamide have been synthesized and structurally characterized by elemental analysis, spectral, thermal (TG/DTG), magnetic, and molar conductivity measurements. On the basis of IR, mass, electronic and EPR spectral studies an octahedral geometry has been proposed for Co(II), Ni(II) complexes and Cu(II) chloride complex, square-pyramidal for Cu(I) bromide complex. For Cu(II) nitrate complex (6), Pd(II) complex (8) square planar geometry was proposed. The EPR data of Cu(II) complexes in powdered form indicate d(x2-y2) ground state of Cu(II) ion. The antitumor activity of the synthesized ligand and some selected metal complexes has been studied. The palladium(II) complex (8) was found to display cytotoxicity (IC(50)=25.6 and 41 µM) against human breast cancer cell line MCF-7 and human hepatocarcinoma HEPG2 cell line.

Structural studies and anticancer activity of a novel (N6O4) macrocyclic ligand and its Cu(II) complexes.

A novel (N6O4) macrocyclic ligand (L) and its Cu(II) complexes have been prepared and characterized by elemental analysis, spectral, thermal (TG/DTG), magnetic, and conductivity measurements. Quantum chemical calculations have also been carried out at B3LYP/6-31+G(d,p) to study the structure of the ligand and one of its complexes. The results show a novel macrocyclic ligand with potential amide oxygen atom, amide and amine nitrogen atoms available for coordination. Distorted square pyramidal ([Cu(L)Cl]Cl·2.5H2O (1), [Cu(L)NO3]NO(3)·3.5H2O (2), and [Cu(L)Br]Br·3H2O (4) and octahedral ([Cu(L)(OAc)2]·5H2O (3)) geometries were proposed. The EPR data of 1, 2, and 4 indicate d1x2(-y)2 ground state of Cu(II) ion with a considerable exchange interaction. The measured cytotoxicity for L and its complexes (1, 2) against three tumor cell lines showed that coordination improves the antitumor activity of the ligand; IC50 for breast cancer cells are ≈8.5, 3, and 4 µg/mL for L and complexes (1) and (2), respectively.