Synthesis, characterisation and biological activity of 2-(methylthiomethyl)anilines, 2-(methylthio)anilines, their Schiff-base derivatives and metal(II) (Co, Ni, Cu) complexes
- Olalekan, Temitope Elizabeth
- 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.
- Full Text:
- Date Issued: 2013
- 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.
- Full Text:
- Date Issued: 2013
A commercial process development for plant food formulation using polyprotic acids from natural extracts as chelating agents
- Authors: Ndibewu, Peter Papoh
- Date: 2005
- Subjects: Chelates , Lemon juice , Liquid fertilizers
- Language: English
- Type: Thesis , Doctoral , DTech (Chemistry)
- Identifier: vital:10368 , http://hdl.handle.net/10948/153 , Chelates , Lemon juice , Liquid fertilizers
- Description: The citrus industry is one of South Africa's largest agricultural sectors in terms of export earnings with lemon fruits and juice as a trendsetter due to their high grade quality. According to growers, the Eastern Cape Province of South Africa alone produces an excess of about 10-14,000 tons of lemon juice which is presently of no economic value due to the sour taste and “bitterness”. As a result of this excess and in order to make use of the polyprotic acids naturally occurring in the lemon juice, four fertilizer nutrient mixtures are formulated, using lemon juice as base. From a conceptual scientific approach, characterization (physico-chemical and functional properties determinations) of Eureka Lemon fruit juices were undertaken, followed by smaller scale batch formulation experiments. On the basis that these lemon juice-based fertilizer mixtures are prepared following standard liquid fertilizer formulation guidelines, a field test was conducted to evaluate their potential effectiveness to influence plant growth. A growth chamber testing on tomato plants revealed high growth response (> 99.9 % certainty) potential in two of the semi-organic mixtures formulated while the organic mixture showed a relatively good growth rate as compared to the control (pure tap water). According to statistical analysis (ANOVA) comparison, two of the semi-organic mixtures performed considerably better than the two commercial samples evaluated. Potential benefits profoundly associated with these nutrient mixtures as compared to similar liquid fertilizer products on the market is that most nutrients are chelated and dissolved in solution. Also, the mixtures contain all necessary nutrients including plant growth substances required for healthier plant growth. The most important socioeconomic impact is the value addition to the technology chain in the citrus industry. The use of fluid fertilizers in significant quantities is less than twenty years old. Nevertheless, growth has been so rapid that in South Africa demand for mixed liquid fertilizer has greatly increased from 90 000 tons NPK & blended micronutrients in 1955 to more than 600 000 per annum tons today (Report 41/2003, Department of Minerals and Energy). The liquid fertilizers market is sparsely specialized with major competitors like Omnia, Kynoch and Foskor supplying more than 50 % of the market demand. Amongst the nutrient mixtures formulated, mixture one is an NPK (1-1-2) based nutrient mixture containing both secondary nutrients (0.5 % Mg & 1.0 % Ca) and seven micronutrients (0.1 % Fe, 0.05 % Cu, 0.05 % Zn, 0.05 % Mn, 0.02 % B, 0.0005 % Mo and 0.0005 % Co). The composition of this mixture offers the formula a potential to be used as a general purpose (all stages of plant growth) fertilization mixture in view of its balanced composition (containing all essential plant nutrients). Mixture two contains essentially the micronutrients and in higher concentrations (0.3 % Fe, 0.3 % Cu, 0.1 % Zn, 0.2 % Mn, 0.02 % B, 0.0005 % Mo and 0.0005 % Co) as compared to mixture one except for boron, molybdenum and cobalt. The concentration of the micronutrients contained in this mixture is adequately high which offers a potential for it to be used in supplementing nutrition in plants with critical micronutrient-deficient symptoms. Mixture three is very similar to mixture two (1.0 % Fe, 0.05 % Cu, 0.05 % Zn, 0.05 Mn, 0.05 % B, 0.0005 % Mo and 0.0005 % Co) except that the concentrations of all seven micronutrients are considerably less than those of contained in mixture two. However, the concentration of iron in this mixture is as high as 1.0 %. The mixture has a potential to be used in high iron-deficient situations. Mixture four is an organic formula with relatively low nutrient concentrations (NPK-0.02-0.02-1, 0.27 % Mg, 0.02 % Ca, 0.008 % Fe, 0.26 % Cu, 0.012 % Zn, 0.009 % Mn). Nevertheless, this mixture is appealing for organically grown crops where the use of chemicals is prohibited by standards. These lemon juice-based nutrient mixtures were further characterized and tested for stability and storability over a period of eight weeks. This study revealed no major change in the physical quality (colour, pH and “salt out” effect). The basic formulation methodology is a two-step procedure that involves filtration of the lemon juice to remove membranous materials, mixing at ambient temperature and stabilization of the nutrient mixtures. However, for the organic nutrient formula mix, filtration follows after extraction of nutrients from plant materials using the lemon juice.
- Full Text:
- Date Issued: 2005
- Authors: Ndibewu, Peter Papoh
- Date: 2005
- Subjects: Chelates , Lemon juice , Liquid fertilizers
- Language: English
- Type: Thesis , Doctoral , DTech (Chemistry)
- Identifier: vital:10368 , http://hdl.handle.net/10948/153 , Chelates , Lemon juice , Liquid fertilizers
- Description: The citrus industry is one of South Africa's largest agricultural sectors in terms of export earnings with lemon fruits and juice as a trendsetter due to their high grade quality. According to growers, the Eastern Cape Province of South Africa alone produces an excess of about 10-14,000 tons of lemon juice which is presently of no economic value due to the sour taste and “bitterness”. As a result of this excess and in order to make use of the polyprotic acids naturally occurring in the lemon juice, four fertilizer nutrient mixtures are formulated, using lemon juice as base. From a conceptual scientific approach, characterization (physico-chemical and functional properties determinations) of Eureka Lemon fruit juices were undertaken, followed by smaller scale batch formulation experiments. On the basis that these lemon juice-based fertilizer mixtures are prepared following standard liquid fertilizer formulation guidelines, a field test was conducted to evaluate their potential effectiveness to influence plant growth. A growth chamber testing on tomato plants revealed high growth response (> 99.9 % certainty) potential in two of the semi-organic mixtures formulated while the organic mixture showed a relatively good growth rate as compared to the control (pure tap water). According to statistical analysis (ANOVA) comparison, two of the semi-organic mixtures performed considerably better than the two commercial samples evaluated. Potential benefits profoundly associated with these nutrient mixtures as compared to similar liquid fertilizer products on the market is that most nutrients are chelated and dissolved in solution. Also, the mixtures contain all necessary nutrients including plant growth substances required for healthier plant growth. The most important socioeconomic impact is the value addition to the technology chain in the citrus industry. The use of fluid fertilizers in significant quantities is less than twenty years old. Nevertheless, growth has been so rapid that in South Africa demand for mixed liquid fertilizer has greatly increased from 90 000 tons NPK & blended micronutrients in 1955 to more than 600 000 per annum tons today (Report 41/2003, Department of Minerals and Energy). The liquid fertilizers market is sparsely specialized with major competitors like Omnia, Kynoch and Foskor supplying more than 50 % of the market demand. Amongst the nutrient mixtures formulated, mixture one is an NPK (1-1-2) based nutrient mixture containing both secondary nutrients (0.5 % Mg & 1.0 % Ca) and seven micronutrients (0.1 % Fe, 0.05 % Cu, 0.05 % Zn, 0.05 % Mn, 0.02 % B, 0.0005 % Mo and 0.0005 % Co). The composition of this mixture offers the formula a potential to be used as a general purpose (all stages of plant growth) fertilization mixture in view of its balanced composition (containing all essential plant nutrients). Mixture two contains essentially the micronutrients and in higher concentrations (0.3 % Fe, 0.3 % Cu, 0.1 % Zn, 0.2 % Mn, 0.02 % B, 0.0005 % Mo and 0.0005 % Co) as compared to mixture one except for boron, molybdenum and cobalt. The concentration of the micronutrients contained in this mixture is adequately high which offers a potential for it to be used in supplementing nutrition in plants with critical micronutrient-deficient symptoms. Mixture three is very similar to mixture two (1.0 % Fe, 0.05 % Cu, 0.05 % Zn, 0.05 Mn, 0.05 % B, 0.0005 % Mo and 0.0005 % Co) except that the concentrations of all seven micronutrients are considerably less than those of contained in mixture two. However, the concentration of iron in this mixture is as high as 1.0 %. The mixture has a potential to be used in high iron-deficient situations. Mixture four is an organic formula with relatively low nutrient concentrations (NPK-0.02-0.02-1, 0.27 % Mg, 0.02 % Ca, 0.008 % Fe, 0.26 % Cu, 0.012 % Zn, 0.009 % Mn). Nevertheless, this mixture is appealing for organically grown crops where the use of chemicals is prohibited by standards. These lemon juice-based nutrient mixtures were further characterized and tested for stability and storability over a period of eight weeks. This study revealed no major change in the physical quality (colour, pH and “salt out” effect). The basic formulation methodology is a two-step procedure that involves filtration of the lemon juice to remove membranous materials, mixing at ambient temperature and stabilization of the nutrient mixtures. However, for the organic nutrient formula mix, filtration follows after extraction of nutrients from plant materials using the lemon juice.
- Full Text:
- Date Issued: 2005
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