Application of bidentate N,N'-donor extractants in the hydrometallurgical separation of base metals from an acidic sulfate medium
- Authors: Okewole, Adeleye Ishola
- Date: 2013
- Subjects: Hydrometallurgy Sulfates Nanofibers Electrospinning Sorbents Extraction (Chemistry) Solvent extraction Stereochemistry
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4281 , http://hdl.handle.net/10962/d1002610
- Description: Bidentate imidazole-based extractants, 1-octylimidazole-2-aldoxime (OIMOX) and 1-octyl-2-(2′-pyridyl)imidazole (OPIM), along with dinonylnaphthalene sulfonic acid (DNNSA) as a synergist, were investigated as potential selective extractants for Cu²⁺and Ni²⁺ respectively from base metals in a solvent extraction system. The study was extended to evaluate the sorption and separation of Ni²⁺ from other base metals in a solid-solution system using microspherical Merrifield resins and nanofibers functionalized with 2,2′-pyridylimidazole. Copper was effectively separated with OIMOX and DNNSA as extractants from nickel with ΔpH½ ≈1.05 and the extraction order of Cu²⁺ > Ni²⁺ > Zn²⁺ > Cd²⁺> Co²⁺ was achieved as a function of pH. At pH 1.65 the extracted copper, from a synthetic mixture of the base metals reached 90.13(±0.90)%, and through a two-step extraction process 98.22(±0.29)% copper was recovered with negligible nickel and cobalt impurities. Stripping of the copper from the loaded organic phase using TraceSelect sulphuric acid at pH 0.35 yielded 96.60(±0.44)% of the loaded quantity after the second stage of stripping. The separation of Ni²⁺ from the borderline and hard acids; Co²⁺, Cu²⁺, Zn²⁺, Fe2²⁺, Fe²⁺, Mn²⁺, Mg2²⁺ and Ca²⁺ at a pH range of 0.5-3.5 with OPIM and DNNSA was acvieved to the tune of a ΔpH½≈ 1.6 with respect to cobalt from a sulfate and sulfate/chloride media. A three-stage counter-current extraction of Ni²⁺, at the optimized pH of 1.89, from a synthetic mixture of Ni²⁺, Co²⁺ and Cu²⁺, yielded 99.01(±1.79)%. The total co-extracted Cu²⁺ was 48.72(±0.24)% of the original quantity in the mixture, and it was 19.85(±0.28%) for Co²⁺. The co-extracted Cu²⁺ was scrubbed off from the loaded organic phase at pH≈8.5 by using an ammonium buffer, while co-extracted Co²⁺ was selectively and quantitatively stripped with H₂SO₄ at pH 1.64. The total recovery of Ni²⁺ by stripping at pH 0.32 was 94.05(±1.70)%. In the solid-liquid system, Ni²⁺ was separated from Co²⁺, Cu²⁺, and Fe²⁺ with the microspherical resins funtionalised with 2,2′-pyridylimidazole by a separation factor (β) in the range 22-45. Electrospun nanofibers as sorbents yielded high sorption capacity in the range of 0.97 - 1.45 mmol.g⁻¹ for the same metals ions. Thus, 1-octylimidazole-2-aldoxime (OIMOX), and1-octyl-2-(2′-pyridyl)imidazole (OPIM) can be effectively utilized alongside DNNSA as a co-extractant in the separation of Cu²⁺ and Ni²⁺ respectively from base metals in acidic sulfate medium in a solvent extraction process, and the latter as a selective ligand in the solid-liquid separation of Ni²⁺ from Co²⁺, Cu²⁺, and Fe²⁺.
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- Date Issued: 2013
Characterisation of surfaces modified through self-assembled monolayers and click chemistry
- Authors: Coates, Megan Patricia
- Date: 2013
- Subjects: Monomolecular films Gold Adsorption Nanotubes Self-assembly (Chemistry) Self-assembly (Chemistry) Scanning electrochemical microscopy X-ray photoelectron spectroscopy
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4277 , http://hdl.handle.net/10962/d1001684
- Description: Different approaches to surface modification were investigated in this work on gold, glassy carbon, multi-walled carbon nanotube paper and on single-walled carbon nanotubes adsorbed on glassy carbon. These approaches include electrochemical grafting, electropolymerisation, click chemistry, axial ligation, adsorption and self-assembled monolayers. The modified surfaces were characterised using a variety of techniques; predominantly electrochemistry, scanning electrochemical microscopy and X-ray photoelectron spectroscopy. For the formation of self-assembled monolayers on gold, four new manganese(III) phthalocyanines (1a-d), octa-substituted at the peripheral position with pentylthio, decylthio, benzylthio, and phenylthio groups were synthesized and characterised. X-ray photoelectron spectroscopy was used to show the formation of a sulphur-gold bond. A number of approaches using 4-azidoaniline (2a) combined with azide-alkyne click chemistry and electrochemistry were also used to anchor ferrocene and pyridine moieties on to the carbon surfaces, including direct in situ diazotation and grafting, electropolymerisation, and the synthesis of the diazonium salt followed by grafting. Iron phthalocyanine was linked to the pyridine-clicked surfaces through axial ligation, where the strong axial bond formed by the interaction between the central metal and the lone pair of the nitrogen in the pyridine group resulted in stable modified electrodes. The potential of these surfaces for the detection of analytes such as thiocyanate, hydrazine and sulphite are briefly shown as well. This work also describes for the first time the possibility of performing local micro-electrochemical grafting of a gold substrate by 4-azidobenzenediazonium (2b) using scanning electrochemical microscopy in a single and simple one step approach, without complications from adsorption.
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- Date Issued: 2013
Critical studies in carbon electrode materials with applications in the electroanalysis of the mycotoxin citrinin
- Authors: Niland, Michael John
- Date: 2013
- Subjects: Electrodes, Carbon , Mycotoxins
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4555 , http://hdl.handle.net/10962/d1018256
- Description: Guided by increasing legislation, the analysis of food borne toxins, including mycotoxins, seeks to address market related demands for the development of analytical systems to monitor this threat to food security and human health. This Thesis is directed at the assessment of the application of electrochemistry for direct electroanalysis and characterisation of the mycotoxin citrinin (CIT) in aqueous media as well as fundamental investigations of the surface of polished and oxidised glassy carbon electrodes (GCE). This study provides the first known account of CIT detection through electrochemical methods. Although electrochemically active, CIT current responses (Ip) were highly irreproducible at polished GCE with a coefficient of variation (C.V.) of 20.16 %. As stability of Ip across multiple electrode preparations is a key requirement in electroanalysis, investigations were directed at attaining stability in CIT Ip. Achieving stability in CIT Ip was investigated via two approaches, including: accounting for Ip variability between electrode preparations as a result of variable GCE surface conditions as a post-data-acquisition analysis and secondly, removing Ip variability through modification of GCE. Accounting for variability in Ip was investigated through the application of double layer capacitance as an indicator of the activity of an electrode, and in so doing serving as a relative mediator of Ip responses between electrodes. Application of this procedure dropped CIT C.V. to a third of starting value across polished GCE (C.V. = 7.18 %), chemically oxidised GCE (Pi-GCE, C.V = 8.47 %) and functionalised multi-walled carbon nanotube modified GCE (fMWCNT, C.V. = 25.79 %) and was effective with analysis of structurally distinct molecules, 2,4-dimethylaniline (2,4-DMA) and 1,2,4-trihydroxybenzene (Triol). Furthermore, it afforded the ability to determine discreet solution overlapping data sets of Ip. Stabilising Ip through GCE surface modification was achieved by anodic electro-oxidation of GCE and allowed for direct electroanalysis of CIT and subsequent characterisation and analysis of CIT in complex media as it reduced C.V. of CIT Ip to 0.73 %. Fundamental investigations of the electrode surface condition are described such that the source of variability could be identified and the interactions of CIT with the electrode understood. Two surface oxidation techniques were applied in modification of GCE; anodic electro-oxidation (EOx GCE) and chemical oxidation using piranha solution (Pi-GCE), analysis of which has previously not been reported. Fundamental analyses to determine surface morphology and chemistry of Pi-GCE, EOx-GCE and polished GCE were conducted using high resolution scanning electron microscopy (HRSEM), scanning electrochemical microscopy (SECM), energy dispersive X-ray spectroscopy (EDX), X-ray photoelectron spectroscopy (XPS), fourier transform infrared spectroscopy (FTIR) and via electroanalytical methods. These studies showed that both oxidation procedures introduced a variety of oxide species at GCE surface, and further that the extent of those species was similar with total % O being 27.67 % and 33.47 % at Pi-GCE and EOx-GCE respectively. Although chemically similar, each surface was morphologically distinct. Electrochemical analyses at the surfaces revealed Pi-GCE to behave more similarly to polished GCE than EOx-GCE. As CIT responses were found to be stable at EOx-GCE (C.V. = 0.73 %) as opposed to Pi-GCE (C.V. = 22.87 %), stability of CIT Ip was likely to be as a result of a physical interaction with electrode morphology rather than interaction on a chemical basis. Morphological analyses revealed polished GCE and Pi-GCE to be highly morphologically irregular at the micro-scale. Although comparatively smooth, the surface morphology of EOx-GCE does not account for the stability of Ip. This study thus proposed a theory to describe the mechanism by which the limited conductivity and porosity of EOx-GCE allow for it to provide a relatively stable surface area within the oxide layer, adjacent to the electrode surface, and thus provided a stable platform for electroanalysis. Voltammetric characterization of CIT at EOx-GCE revealed that anodic oxidation in aqueous media involved an uneven number of electrons to protons via an ECE mechanism. This was illustrated to be nt = 2e- accompanied by the transfer of 1H⁺ per molecule oxidised. A proposed reaction scheme for the initial stages of CIT oxidation was suggested to involve both hydroxyl and carboxyl moieties of the CIT molecule. CIT oxidation was shown to arise as a result of a relatively complex mass transport regime which included both adsorptive and diffusive derived Ip₁. The LOD in buffered aqueous media was found to be 16 nM, a highly competitive result in relation to chromatographic techniques. Further application of EOx-GCE in complex media illustrated that CIT associates non-specifically with the components of food samples, primarily proteins. As a result of this, extraction of CIT from such media is mandatory. Liquid-liquid extraction illustrated a recovery in CIT Ip₁ and in so doing provided a means of accurately and sensitively detecting CIT from food samples with an LOD of 20 nM. These responses were corroborated by HPLC analyses on the same extractions and illustrate the applicability of electroanalysis as an analytical technique.
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- Date Issued: 2013
Electrocatalytic detection of pesticides with electrodes modified with nanoparticles of phthalocyanines and multiwalled carbon nanotubes
- Authors: Siswana, Msimelelo Patrick
- Date: 2013
- Subjects: Phthalocyanines Pesticides Electrocatalysis Electrochemistry Nanotubes Nanoparticles Transmission electron microscopy Scanning electron microscopy
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4282 , http://hdl.handle.net/10962/d1002613
- Description: Three types of electrodes: carbon paste electrodes modified with nanoparticles of metallophthalocyanines (MPcNP-CPEs, M = Mn, Fe, Ni, Co), basal plane pyrolytic graphite electrodes modified with iron or nickel phthalocyanine nanoparticles and multiwalled carbon nanotube composites (FePcNP/MWCNT-BPPGE or NiPcNP/MWCNT-BPPGE),and basal plane pyrolytic graphite electrodes modified with multiwalled carbon nanotubes and electropolymerized metal tetra-aminophthalocyanines (poly-MTAPc-MWCNT-BPPGE), where M is Mn, Fe, Ni or Co, were prepared. Electrochemical characterizations showed that faster electron transfer kinetics occurred at the NiPcNP/MWCNT-BPPGE than at the FePcNP/MWCNT-BPPGE surface. SEM and electrochemical characterizations of poly-MTAPc-MWCNT-BPPGE showed that MTAPc had been deposited on the MWCNTBPPGE surface, and that the poly-CoTAPc-MWCNT-BPPGE exhibited the fastest electron transfer kinetics of all the poly-MTAPc-MWCNT-BPPGEs. Using amitrole and asulam as test analytes, electrochemical experiments showed that, amongst the CPEs, the FePcNP-CPE and NiPcNP-CPE displayed the most electrocatalytic behavior towards amitrole and asulam oxidation, respectively, and further experiments were done to obtain the electrochemical parameters associated with these electrodes and the corresponding analytes. Although, the FePcNP/MWCNT- BPPGE displayed electrocatalytic behavior towards amitrole oxidation in comparison with the bare BPPGE, it was less electrocatalytic than the FePcNP-CPE in terms of detection potential. The NiPcNP/MWCNT-BPPGE displayed the same detection potential as the NiPcNP-CPE. The poly-FeTAPc-MWCNT-BPPGE exhibited the most electrocatalytic behavior towards amitrole, of all the electrodes investigated, and the poly-CoTAPc-MWCNT-BPPGE displayed the best electrocatalytic behavior towards asulam, amongst the poly-MTAPc-MWCNT-BPPGEs.
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- Date Issued: 2013
Low symmetry metallophthalocyanines and their nanoparticle conjugates for photodynamic antimicrobial chemotherapy
- Authors: Masilela, Nkosiphile
- Date: 2013
- Subjects: Nanoparticles Anti-infective agents Chemotherapy Photochemotherapy Quantum dots Gold Silver , Phthalocyanines
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4278 , http://hdl.handle.net/10962/d1001906
- Description: This thesis reports on the syntheses of novel low symmetrically substituted Zn, Sn, Ge and Ti MPc complexes containing a single carboxylic or cysteinyl group available for attachments to MNPs. The complexes were extensively characterized by various techniques to ensure their purity. Various metallic nanoparticles consisting of silver (AgNPs), gold (AuNPs) as well as quantum dots (QDs) were successfully prepared and conjugated to the low symmetry phthalocyanine complexes. The conjugates were successfully characterized using many techniques. The Q-band maxima of the MPcs were observed at completely different wavelength regions depending on the nature of the substituents and the central metal used. Blue shifting of the Q band in the absorption spectra was observed for the complexes in the presence of AuNPs, while aggregation was observed in the presence of quantum dots. The complexes were successfully electrospun into polymer fibers for the antimicrobial inhibition of bacteria. The photophysical and photochemical properties of these complexes were extensively investigated. Higher triplet and singlet oxygen quantum yields were achieved for the Ge Pc complexes, with all the complexes giving reasonable singlet oxygen quantum yields. An enhancement in triplet and singlet oxygen quantum yields was observed for all the complexes in the presence of metal nanoparticles. However, the singlet oxygen quantum yields decreased for all the complexes when incorporated into electrospun fibers. The antimicrobial behaviour of the complexes was investigated against Bacillus Subtilis and Staphylococcus Aureus in solution and in the fiber matrix. High antimicrobial inhibitions were observed for the Ge complexes followed by the ZnPc derivatives. All the low symmetry ZnPc derivatives were conjugated to AgNPs and their antimicrobial behaviour was compared to their symmetrical counterparts. The best antimicrobial inhibition behaviour was observed for the low symmetry Pcs when compared to their symmetrical counterparts. In the absence and in the presence of AgNPs, axially ligated SiPc also showed better antimicrobial activity when it was compared to the unsubstituted ZnPc complex.
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- Date Issued: 2013
Novel applications of Morita-Baylis-Hillman methodology in organic synthesis
- Authors: Mciteka, Lulama Patrick
- Date: 2013 , 2013-04-22
- Subjects: Organic compounds -- Synthesis -- Research Asymmetric synthesis Asymmetry (Chemistry) Chemical reactions -- Research Camphor -- Research AZT (Drug) -- Research Chemical inhibitors -- Research Chemistry -- Methodology
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4439 , http://hdl.handle.net/10962/d1007598
- Description: The overall approach in the present investigation has been to explore applications of the Morita-Baylis-Hillman (MBH) reaction in asymmetric synthesis and in the continuation of systems with medicinal potential. To this end, a series of varied camphor-derived acrylate esters was prepared to serve as chiral substrates in asymmetric Morita-Baylis- Hillman reactions. Reduction of N-substituted camphor-10-sulfonamides afforded the 3- exo-hydroxy derivatives as the major products. Acylation of the corresponding sodium alkoxides gave the desired 3-exo-acrylate esters, isolation of which was complicated by concomitant formation of hydrochlorinated and diastereomeric competition products. Bulky camphorsulfonamides containing alkyl, dialkyl, aromatic and adamantyl groups were selected as N-substituents with the view of achieving stereoselective outcome in subsequent MBH reactions. The synthesis of novel camphor-derived Morita-Baylis-Hillman adducts using various pyridine-carboxaldehydes proceeded with exceptionally high yields with diastereoselectivities ranging from 7-33 % d.e. Both 1D and 2D NMR and HRMS techniques were employed to confirm the structures and an extensive study of the electropositive fragmentation patterns of a number of camphor-derived chiral acrylate esters was conducted. Attention has also been given to the application of MBH methodology in the construction of heterocyclic ‘cinnamate-like’ AZT conjugates which were designed to serve as dualaction HIV-1 integrase-reverse transcriptase (IN-RT) inhibitors. A number of pyridine carboxaldehyde-derived MBH adducts were synthesized using methyl, ethyl and t-butyl acrylates in the presence of 3-hydroxyquinuclidine (3-HQ) as catalyst. The yields for these reactions were excellent. The resulting MBH adducts were acetylated and subjected to aza-Michael addition using propargylamine. The resulting alkylamino compounds were then used in ‘Click reactions’ to form the targeted AZT-conjugates in moderate to excellent yield. In silico docking of computer modelled AZT-conjugates into the HIV-1 integrase and reverse transcriptase enzyme-active sites and potential hydrogen-bonding interaction with active-site amino acid residues were identified. The electrospray MS fragmentations of the AZT and the novel AZT-conjugates were also investigated and common fragmentation pathways were identified.
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- Date Issued: 2013
Phototransformation of pollutants using lutetium and zinc phthalocyanines anchored on electrospun polymer fibers
- Authors: Zugle, Ruphino
- Date: 2013
- Subjects: Electrospinning Phthalocyanines Lutetium Zinc Polymers Dysprosium Pollutants Air Pollution Photochemistry
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4286 , http://hdl.handle.net/10962/d1002962
- Description: Novel lanthanide phthalocyanines containing dysprosium, erbium and lutetium as central metals were synthesized using phthalonitrile:metal salt ratio of 4:1 or lower phthalonitrile content as well as using unmetallated phthalocyanine. They were characterized using various spectroscopic and elemental analyses. Dysprosium bis-phthalocyanine was obtained while monomers were obtained for erbium and lutetium phthalocyanines. Theopen-shelldysprosiumbis-phthalocyanine and the monomeric complex of the open-shell erbium were neither fluorescent nor showed the ability to generate singlet oxygen. The triplet states of all the lutetium phthalocyanines were found to be populated with high triplet quantum yields and corresponding high singlet oxygen quantum yields. The fluorescence quantum yields of the lutetium phthalocyanines were however found to be very low. The lutetium phthalocyanines together with unsubstituted zinc phthalocyanine and its derivatives were successfully incorporated into electrospun polymer fibers either by covalent linkage or sorption forces. Spectral characteristics of the functionalized electrospun polymer fibers indicated that the phthalocyanines were bound and their integrity maintained within the fiber matrices. Most importantly the fluorescence and photoactivity of the phthalocyanines were equally maintained within the electrospun fibers. The functionalized electrospun polymer fibers especially those containing the zinc phthalocyanines could qualitatively detect nitrogen dioxide, a known environmental air pollutant. Also all the functionalized electrospun polystyrene and polysulfone fibers containing lutetium and zinc phthalocyanines could be applied for the photoconversion of 4-chlorophenol, 4-nitrophenol and methyl orange. Those of polystyrene could be re-used. Polyacrylic acid and polyurethane functionalized electrospun fibers were found not to be suitable for photocatalytic applications in aqueous medium. 4-Chlorophenol was found to be more susceptible to photodegradation while methyl orange very difficult to degrade.
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- Date Issued: 2013
Polymer based electrospun nanofibers as diagnostic probes for the detection of toxic metal ions in water
- Authors: Ondigo, Dezzline Adhiambo
- Date: 2013
- Subjects: Heavy metals , Nanofibers , Nanoparticles , Colorimetric analysis
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4557 , http://hdl.handle.net/10962/d1018261
- Description: The thesis presents the development of polymer based electrospun nanofibers as diagnostic probes for the selective detection of toxic metal ions in water. Through modification of the chemical characteristics of nanofibers by pre- and post-electrospinning treatments, three different diagnostic probes were successfully developed. These were the fluorescent pyridylazo-2-naphthol-poly(acrylic acid) nanofiber probe, the colorimetric probe based on glutathione-stabilized silver/copper alloy nanoparticles and the colorimetric probe based on 2-(2’-Pyridyl)-imidazole functionalized nanofibers. The probes were characterized by Fourier transform infrared spectroscopy (FTIR), Energy dispersive x-ray spectroscopy (EDX), Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM). The fluorescent nanofiber probe was developed towards the determination of Ni²⁺. Covalently functionalized pyridylazo-2-naphthol-poly(acrylic acid) polymeric nanofibers were employed. The solid state Ni²⁺ probe exhibited a good correlation between the fluorescence intensity and nickel concentration up to 1.0 mg/mL based on the Stern-Volmer mechanism. The detection limit of the nanofiber probe was found to be 0.07 ng/mL. The versatility of the fluorescent probe was demonstrated by affording a simple, rapid and selective detection of Ni²⁺ in the presence of other competing metal ions by direct analysis without employing any sample handling steps. For the second part of the study, a simple strategy based on the in-situ synthesis of the glutathione stabilized silver/copper alloy nanoparticles (Ag/Cu alloy NPs) in nylon 6 provided a fast procedure for fabricating a colorimetric probe for the detection of Ni²⁺ in water samples. The electrospun nanofiber composites responded to Ni²⁺ ions but did not suffer any interference from the other metal ions. The effect of Ni²⁺ concentration on the nanocomposite fibers was considered and the “eye-ball” limit of detection was found to be 5.8 μg/mL. Lastly, the third probe was developed by covalently linking an imidazole derivative; 2-(2′-Pyridyl)-imidazole (PIMH) to Poly(vinylbenzyl chloride) (PVBC) and nylon 6 nanofibers by post-electrospinning treatments using a wet chemical method and graft copolymerization technique, respectively. The post-electrospinning modifications of the nanofibers were achieved without altering their fibrous morphology. The color change to red-orange in the presence of Fe²⁺ for both the grafted nylon 6 (white) and the chemically modified PVBC (yellow) nanofibers was instantaneous. The developed diagnostic probes exhibited the desired selectivity towards the targeted metal ions.
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- Date Issued: 2013
Synthesis, characterisation and biological activity of 2-(methylthiomethyl)anilines, 2-(methylthio)anilines, their Schiff-base derivatives and metal(II) (Co, Ni, Cu) complexes
- Authors: Olalekan, Temitope Elizabeth
- Date: 2013
- Subjects: Aniline , Schiff bases , Ligands , Nuclear magnetic resonance spectroscopy , Chelates , X-ray crystallography , Antimalarials
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4562 , http://hdl.handle.net/10962/d1020868
- Description: A series of 31 sulfur-nitrogen donor ligands and 64 metal(II) complexes have been investigated. The thiomethylated aniline ligands 2–(methylthiomethyl)aniline 2MT and 2–(methylthio)aniline 2MA were synthesized with their substituted derivatives (-Me, -MeO, -Cl, -Br, -NO2) to serve as chelating agents. These ligands behave as bidentate ligands with SN donor group with Co(II), Ni(II) and Cu(II). The Co(II) and Ni(II) complexes have the ML2Cl2 molecular formula while the Cu(II) complexes formed with MLCl2 stoichiometry where L is the bidentate ligand. The ligands and their metal(II) complexes have been characterized by elemental analysis and with spectroscopic techniques. The trend observed in the NMR spectra and IR frequencies of the thiomethylated compounds shows there is a significant difference between the 2MT and 2MA series as a result of sulfur lone pairs extending the conjugation of the aromatic ring in the case of the latter. The effect of the position and electronic nature of ring substituent on the NMR shifts of the amine protons is discussed. The 6- and 5-membered chelate complexes formed by the 2MT and 2MA ligands respectively do not show significant diversity in their spectroscopic properties. From the elemental analysis for the Co(II) and Ni(II) complexes, their compositions reveal 1:2 M:L stoichiometry with 2 chlorine atoms from the respective metal salts. In addition, the spectroscopic data are largely indicative of tetragonally distorted structures for these solid complexes. The X-ray crystallography data reveal the Cu(II) complexes exist as square pyramidal dimers and with long Cu–Cl equitorial bonds fit into the tetragonally distorted octahedral structure. The electrolytic nature of Co(II) and Cu(II) complexes in DMF were found to be similar, they behave as non electrolytes in contrast to Ni(II) complexes which are 1:1 electrolytes. The electronic spectra of these metal(II) complexes were found to be different for both their solid forms and in solutions of DMF and DMSO and this has been discussed. The thiomethylated aniline ligands possess the amine and thioether groups which are present in many known biologically active compounds, hence the biological activity of the ligands and their metal complexes were tested against three strains of bacteria and one fungus. The methoxy-substituted derivatives were found to possess better inhibitory activity and this was similarly reflected in the metal(II) complexes. The activity of the complexes can be said to be in the order, Cu(II) > Co(II) > Ni(II). The Schiff-base derivatives were prepared from the ligands and para-methoxysalicylaldehyde and their Cu(II) complexes were synthesized in order to determine their biological activity. The Schiff-base ligands were found to be less active than their parent ligands. The Cu(II) complexes are not soluble in water, DMSO or DMF, as a result and could not be evaluated for their biological activity. Based on the good results from the antimicrobial evaluation, the antiplasmodial activity of some of the Co(II), Ni(II) and Cu(II) complexes of the thiomethylated ligands against Plasmodium falciparum (FCR-3) was determined. At 50 μM concentration level, the Cu(II) complexes show activity equal or better than the prophylactic chloroquine. The Cu(II) complexes with the methoxy-substituted demonstrated exceptional activity but their Co(II) and Ni(II) analogues did not show any activity. The cytotoxicity of the active Cu(II) complexes at 50 μM concentration was determined against the breast cancer cell line (MDA-MB-231). The compounds destroyed the cancer cell in the range of 28–40%, thus showing their preferred activity against the parasitic cell instead of the cancer cell. The selectivity demonstrated by these compounds have shown them to be potential antimalarial agents and this could be further investigated.
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- Date Issued: 2013