Damian C. Onwudiwe

ZnS, CdS and HgS Nanoparticles via Alkyl-Phenyl Dithiocarbamate Complexes as Single Source Precursors

The synthesis of II-VI semiconductor nanoparticles obtained by the thermolysis of certain group 12 metal complexes as precursors is reported. Thermogravimetric analysis of the single source precursors showed sharp decomposition leading to their respective metal sulfides. The structural and optical properties of the prepared nanoparticles were characterized by means of X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM) UV-Vis and photoluminescence spectroscopy. The X-ray diffraction pattern showed that the prepared ZnS nanoparticles have a cubic sphalerite structure; the CdS indicates a hexagonal phase and the HgS show the presence of metacinnabar phase. The TEM image demonstrates that the ZnS nanoparticles are dot-shaped, the CdS and the HgS clearly showed a rice and spherical morphology respectively. The UV-Vis spectra exhibited a blue-shift with respect to that of the bulk samples which is attributed to the quantum size effect. The band gap of the samples have been calculated from absorption spectra and werefound to be about 4.33 eV (286 nm), 2.91 eV (426 nm) and 4.27 eV (290 nm) for the ZnS, CdS and HgS samples respectively.

Synthesis, Characterization and Thermal Studies of Zn(II), Cd(II) and Hg(II) Complexes of N-Methyl-N-Phenyldithiocarbamate: The Single Crystal Structure of [(C6H5)(CH3)NCS2]4Hg2

Zn(II), Cd(II) and Hg(II) complexes of N-methyl-N-phenyl dithiocarbamate have been synthesized and characterized by elemental analysis and spectral studies (IR, (1)H and (13)C-NMR). The single crystal X-ray structure of the mercury complex revealed that the complex contains a Hg centre with a distorted tetrahedral coordination sphere in which the dinuclear Hg complex resides on a crystallographic inversion centre and each Hg atom is coordinated to four S atoms from the dithiocarbamate moiety. One dithiocarbamate ligand acts as chelating ligand while the other acts as chelating bridging ligand between two Hg atoms, resulting in a dinuclear eight-member ring. The course of the thermal degradation of the complexes has been investigated using thermogravimetric and differential thermal analyses techniques. Thermogravimetric analysis of the complexes show a single weight loss to give MS (M = Zn, Cd, Hg) indicating that they might be useful as single source precursors for the synthesis of MS nanoparticles and thin films.

Thermal Studies of Zn(II), Cd(II) and Hg(II) Complexes of Some N-Alkyl-N-Phenyl-Dithiocarbamates

The thermal decomposition of Zn(II), Cd(II) and Hg(II) complexes of N-ethyl-N-phenyl and N-butyl-N-phenyl dithiocarbamates have been studied using thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The products of the decomposition, at two different temperatures, were further characterized by scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDX). The results show that while the zinc and cadmium complexes undergo decomposition to form metal sulphides, and further undergo oxidation forming metal oxides as final products, the mercury complexes gave unstable volatiles as the final product.

Phytosynthesis of silver nanoparticles using aqueous leaf extracts of Lippia citriodora: Antimicrobial, larvicidal and photocatalytic evaluations

Nanoscience and nanotechnology represent new and enabling platforms that promise to provide broad range of novel and improved technologies for environmental, biological and other scientific applications. This study reports the synthesis of silver nanoparticles mediated by aqueous leaf extract of Lippia citriodora at two different temperatures of 50°C and 90°C. The synthesis of colloidal silver nanoparticles (AgNPs) was monitored by the use of UV-visible spectroscopy at different temperatures and time intervals. The surface plasmon bands (SPBs) showed peaks between 417 and 421nm at 90°C and around 430nm at 50°C, indicating a red shift at lower temperature. Fourier transform infrared (FTIR) analysis of the nanoparticles showed the presence of similar peaks found in the spectra of the plant extract. The size of the AgNPs was confirmed by transmission electron microscopy (TEM) which indicated an average size of 23.8nm (90°C) and 25nm (50°C). The nanoparticles showed better antimicrobial activities when compared to the crude plant extract against several screened pathogens: Gram negative (Escherichia coli, and Salmonella typhi) and Gram positive (Bacillus subtilis and Staphylococcus aureus) strains and a fungi organism; Candida albicans. In addition, the AgNPs showed good larvicidal efficacy against early 4th instar of Culex quinquefasciatus (a vector of lymphatic filariasis). Finally, the nanoparticles exhibited photocatalytic properties on an industrial waste pollutant, methylene blue.

Spectral, thermal stability and antibacterial studies of copper, nickel and cobalt complexes of N-methyl-N-phenyl dithiocarbamate

Copper(II), cobalt(II) and nickel(II) bis(N-methyl-N-phenyl dithiocarbamate) complexes having the general formula [M{S2CN(MePh)}2] (where M = Cu, Co and Ni) have been prepared and characterized by spectral and thermal analysis. The IR spectra suggest that coordination of dithiocarbamate (DTC) occurred through the two sulfur atoms in a symmetrical bidentate fashion. The electronic spectra, conductance measurement and magnetic moment analysis support the proposed geometry for the electronically dilute complexes. The results of the thermal analysis showed that after dehydration, a one-step decomposition pattern leading to the formation of respective metal sulfide as the end-product occurred. The results are consistent with the proposed composition of the complexes. The in vitro antibacterial activity of the complexes was investigated against strains of gram-negative Escherichia coli, Klebsiella oxytoea and Pseudomonas aureginosa, and gram-positive Bacillus cereus, Staphylococcus aureus and Protues mirabilis. The antibacterial activity of the complexes compared favorably with that of streptomycin and augmentine against S. aureus and B. cereus. The cobalt complex had the best antibacterial activity against the test compounds with inhibitory zone range of 11–14.5 mm. GRAPHICAL ABSTRACT

Mixed Ligand Complexes of N-Methyl-N-phenyl Dithiocarbamate: Synthesis, Characterisation, Antifungal Activity, and Solvent Extraction Studies of the Ligand.

A series of mixed ligand dithiocarbamate complexes with a general formula [ML2(py)2], where M = Mn(II), Co(II), Ni(II), and Cu(II), py = pyridine, and L = N-methyl-N-phenyl dithiocarbamate have been prepared and characterised by elemental analysis, FTIR and Uv spectroscopy, magnetic moment, and thermogravimetric and conductance analysis. The infrared spectra showed that symmetrical bidentate coordination occurred with the dithiocarbamate moiety through the sulfur atoms, while neutral monodentate coordination occurred through the nitrogen atom for the pyridine molecule in the complexes. The electronic spectra, elemental analysis, and magnetic moment results proved that the complexes adopted octahedral geometry. The conductance measurement showed that the complexes are nonelectrolytes proving their nonionic nature. The compounds were screened for three human pathogenic fungi: Aspergillus flavus, Aspergillus niger, and Candida albicans. The cobalt complex showed the best antifungal activity among the test compounds. Liquid-liquid extractive abilities of the ligand towards copper and nickel ions in different solvent media were investigated. The ligand showed a strong binding affinity towards the metals ions with an extractive efficiency of about 99%.

Effect of some nitrogen donor ligands on the optical and structural properties of CdS nanoparticles

The cadmium complex of N-ethyl-N-phenyl dithiocarbamate, 1, and its 2,2′-bipyridine and 1,10-phenanthroline adducts, 2, and 3, respectively, have been used as single source precursors for the synthesis of CdS nanoparticles. The formation of CdS nanoparticles was achieved by thermal decomposition of the complexes (pyrolysis) and thermolysis in the presence of hexadecylamine – HDA (solvothermal). Scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX) and high resolution transmission electron microscopy (HRTEM) analyses were carried out to study the structural properties of the nanoparticles. Complex 1 afforded rod-shaped nanoparticles while star-shaped nanoparticles were obtained from complexes 2 and 3. The optical property of the CdS nanoparticles was studied by UV–visible and fluorescence spectroscopy. The spectral features for the nanoparticles prepared via the solvothermal route were significantly sharper and blue shifted to a greater extent relative to the corresponding bulk semiconductor, compared to the observed shift in the nanoparticles prepared via pyrolysis. All the as-synthesized material exhibited band edge luminescence.

Synthesis, Characterization, Antimicrobial Studies and Corrosion Inhibition Potential of 1,8-dimethyl-1,3,6,8,10,13-hexaazacyclotetradecane: Experimental and Quantum Chemical Studies

The macrocylic ligand, 1,8-dimethyl-1,3,6,8,10,13-hexaazacyclotetradecane (MHACD) was synthesized by the demetallation of its freshly synthesized Ni(II) complex (NiMHACD). Successful synthesis of NiMHACD and the free ligand (MHACD) was confirmed by various characterization techniques, including Fourier transform infra-red (FT-IR), proton nuclear magnetic resonance (1H-NMR), carbon-13 nuclear magnetic resonance (13C-NMR), ultraviolet-visible (UV-vis), and energy dispersive X-ray (EDX) spectroscopic techniques. The anti-bacteria activities of MHACD were investigated against Staphylococcus aureus and Enterococcus species and the results showed that MHACD possesses a spectrum of activity against the two bacteria. The electrochemical cyclic voltammetry study on MHACD revealed that it is a redox active compound with promising catalytic properties in electrochemical applications. The inhibition potential of MHACD for mild steel corrosion in 1 M HCl was investigated using potentiodynamic polarization method. The results showed that MHACD inhibits steel corrosion as a mixed-type inhibitor, and the inhibition efficiency increases with increasing concentration of MHACD. The adsorption of MHACD obeys the Langmuir adsorption isotherm; it is spontaneous and involves competitive physisorption and chemisorption mechanisms. Quantum chemical calculations revealed that the energy of the highest occupied molecular orbital (HOMO) of MHACD is high enough to favor forward donation of charges to the metal during adsorption and corrosion inhibition. Natural bond orbital (NBO) analysis revealed the presence of various orbitals in the MHACD that are capable of donating or accepting electrons under favorable conditions.

Bis diallyl dithiocarbamate Pt(II) complex: synthesis, characterization, thermal decomposition studies, and experimental and theoretical studies on its crystal structure

Platinum dithiocarbamate (DTC) complex has been synthesized from the ligand diallyl DTC, and its structure was established from elemental analysis, IR, NMR, and single-crystal X-ray analyses to be Pt[S2CN(C3H5)2]2. The thermal properties were studied using a simultaneous thermal analyzer, and showed two main steps of decomposition. The structural geometry analysis was determined using X-ray diffraction and Density Functional Theory (DFT) calculations. The single-crystal X-ray analysis showed that the complex has a square planar geometry. The diallyl groups of the DTC ligands are not symmetrical making the complex non-centrosymmetric, and the complexes are stacked with intermolecular ring–ring interactions. The DFT calculations were performed to obtain the theoretical information and compared with the experimental data obtained from the experimental crystal structure. GRAPHICAL ABSTRACT

Silver Nanoparticles Mediated by Costus afer Leaf Extract: Synthesis, Antibacterial, Antioxidant and Electrochemical Properties

Synthesis of metallic and semiconductor nanoparticles through physical and chemical routes has been extensively reported. However, green synthesized metal nanoparticles are currently in the limelight due to the simplicity, cost-effectiveness and eco-friendliness of their synthesis. This study explored the use of aqueous leaf extract of Costus afer in the synthesis of silver nanoparticles (CA-AgNPs). The optical and structural properties of the resulting silver nanoparticles were studied using UV-visible spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM) and Fourier transform infra–red spectrophotometer (FTIR). TEM images of the silver nanoparticles confirmed the existence of monodispersed spherical nanoparticles with a mean size of 20 nm. The FTIR spectra affirmed the presence of phytochemicals from the Costus afer leaf extract on the surface of the silver nanoparticles. The electrochemical characterization of a CA-AgNPs/multiwalled carbon nanotubes (MWCNT)-modified electrode was carried out to confirm the charge transfer properties of the nanocomposites. The comparative study showed that the CA-AgNPs/MWCNT-modified electrode demonstrated faster charge transport behaviour. The anodic current density of the electrodes in Fe(CN)6]4−/[Fe(CN)6]3− redox probe follows the order: GCE/CA-Ag/MWCNT (550 mA/cm2) > GCE/MWCNT (270 mA/cm2) > GCE (80 mA/cm2) > GCE/CA-Ag (7.93 mA/cm2). The silver nanoparticles were evaluated for their antibacterial properties against Gram negative (Escherichia coli, Klebsiella pneumonia, Pseudomonas aeruginosa) and Gram positive (Bacillus subtilis and Staphylococcus aureus) pathogens. The nanoparticles exhibited better inhibition of the bacterial strains compared to the precursors (leaf extract of Costus afer and silver nitrate). Furthermore, the ability of the nanoparticles to scavenge DPPH radicals at different concentrations was studied using the DPPH radical scavenging assay and compared to that of the leaf extract and ascorbic acid. The nanoparticles were better DPPH scavengers compared to the leaf extract and their antioxidant properties compared favorably the antioxidant results of ascorbic acid. The green approach to nanoparticles synthesis carried out in this research work is simple, non-polluting, inexpensive and non-hazardous.