Theses And Dissertations

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Synthesis, characterisation and evaluation of functionalized Lignocelluloses-clay nanocomposites for organic pollutant removal from water
(University of Fort Hare, 2015) Mafukidze, Donovan M; Tichagwa, L; Lutz, M; Katwire, D M
PMPSgLig-NaMMT nanocomposites were prepared from methacryloxypropyltrimethoxysilane (MPS), lignocellulose and montmorillonite clay. The potential enhancement of organic pollutant adsorption capabilities of PMPSgLig-NaMMT nanocomposite from water through functionalization was investigated. PMPSgLig-NaMMT was functionalized by esterification and etherification using different methods so as to increase the surface hydrophobicity of the material and hence improve its compatibility with the target pollutants. Specific chemical routes specially tailored for PMPSgLig-NaMMT were established for functionalization mostly based on the common esterification (Fischer esterification) and etherification (Williamson‟s etherification) reactions. In the functionalization methods, factors such as pH environment, nanocomposite composition, nature of functionalization moiety, and use of or absence of solvents and their variations were studied. FT-IR, XRD, SEM and TGA were used to characterize the synthesized and functionalized nanoadsorbents. The techniques showed successful functionalization via esterification and etherification methods albeit to different extents, with clear retention of the material‟s original structure though there were signs of degradation with some methods. Characterization was supported by adsorption studies to validate implications and draw conclusions. The use of 1,10-phenathroline as a model organic pollutant in water in the adsorption studies showed that adsorbents conformed to monolayer adsorption following pseudo-second order kinetics for adsorption of organic pollutants accurately represented. Most importantly the studies revealed the significant impact of the nanocomposite composition on the overall absorbent performance. Adsorption studies also showed that functionalization via esterification methods gave rise to better adsorbents.
Isolation, characterisation of terpenoids and biosynthesis of silver nanoparticles of acacia mearnsii de wild and acacia Karroo Hayne and their Bioassays
(University of Fort Hare, 2015) Avoseh, Opeyemi Nudewhenu; Oyedeji, O O; Oyedeji, O A
Great wealth of traditional knowledge about the use of plants had been transferred from generation to generations leading to the present day drug discovery and invention of new scientific methods of isolation, purification and identification. With the discovery of new diseases and drug-resistant organisms, there is no other source or deposit of lead compounds or drugs than the plant kingdom. As a result of this, about 25% of the current drug administered owe their origin to plant sources with the view to reduce the carcinogenic effect of synthetic drugs. Volatile terpenoids among other broad spectrum of natural product had been implicated to show high therapeutic properly. In the present study, selected locally-used medicinal plants were exploited for the presence of potent bioactive compounds and ability to form nanoparticles with distinctive property for use as chemoprotective agent against inflammation, tumors, cancer and other chronic diseases. Acacia mearnsii De Wild and Acacia karroo Hayne studied in this report are known to be invasive species with no proper regulation to conserve and preserve them. However, ethnopharmacology report of these plant species in the Southern Africa region reveals that they are good antiseptic, anti-diarrhea, anti-inflammation and a forage for livestock. These plants were subjected to volatile extraction protocol of some parts of the plants (stem and leaves) followed by examination of the anti-inflammation capacity of the extracts using an animal model. In addition, the bye-product (hydrosol) from the stem bark of each species possess a high reducing and stabilizing property leading to synthesis of silver nanoparticles, followed by investigation of the anti-inflammation potential of the synthesized silver nanoparticles using animal model. The volatile oils of the leaves and stem bark of Acacia mearnsii De Wild obtained by hydro-distillation were analyzed by Gas Chromatography-Mass Spectrometry (GC-MS). Twenty, Thirty-Eight, Twenty-nine and Thirty-Eight components accounting for 93.8%, 92.1%, 78.5% and 90.9% of the total oils of the fresh, dry leaves and fresh, dry stem bark respectively. The major components of the oil were octadecyl alcohol (25.5%) and phytol (10.5%); cis-verbenol (29.5%); phytol (10.1%) and phytol (23.4%) for the fresh leaves, dried leaves, and fresh stem, dry stem bark respectively. Oral administration of essential oils at the dose of 2% showed significant (p<0.05) anti-inflammatory properties in the albumin induced test model in rats. Oils from the fresh leaves and dry stems inhibited inflammation beyond 4 h post treatment. Furthermore, the chemical composition of the essential oils obtained by hydro-distillation from the leaves and stem bark (dry and fresh) of Acacia karroo Hayne, analysed by GC-MS, shows that hexanal (10.67%) and ß-ionone (9.74%) were dominant in the dried leaves, β-pinene (14.30%), and (Z)-2-Hexen-1-ol (10.21%) in the fresh leaves while Octacosane (10.59%) and phytol (23.38%) were dominant in the dry and fresh stem respectively. The anti-inflammation ability of these oils after an albumin-induced inflammation on wistar rats, shows a significant effect at the 1st h of treatment with a significance of P< 0.01 for all part plants, while the fresh leaves shows further inhibitory activities at the 2nd h of analysis. Silver nanoparticles (AgNPs) were successfully synthesized from AgNO3 through a green route using the aqueous extract (hydrosols) of Acacia mearnsii De Wild and Acacia karroo Hayne as reducing agent and as well as capping agent. The Acacia-mediated AgNPs were characterized with the use of UV-vis absorption spectroscopy, Fourier Transform Spectroscopy (FT-IR), Transmission electron microscope (TEM), Scanning Electron Microscope (SEM), Energy Dispersive Spectroscopy (EDX), and X-ray Diffractometry (XRD). A spherical, 10-40 nm diameter silver nanoparticles were synthesized with very low level of stability for the AMDS and the AKDS-AgNPs. In addition, nociceptive activity with a mice rat reveals higher inhibition at the neurogenic phase for the AKDS-AgNPs, while AMDS-AgNPs exhibited a high inhibition at the inflammatory phase. The potent anti-inflammatory activity of essential oils of A. mearnsii De Wild and A. karroo Hayne hereby confirmed its traditional use in treating various inflammatory diseases, while the inflammatory studies on the synthesized AgNPs reveals a very active compound which can be used as a potent opioid or non-steroidal anti-inflammatory drug (NSAID).
Chemical constituents and biological studies of Tagetes minuta L. and Rauvolfia caffra Sond
(University of Fort Hare, 2015) Mlala, Sithenkosi; Oyedeji, O O; Nkeh-Chungag, B N
Consequently, specific parts or the whole plant can be used for various treatments. The aim of this study was to extract, isolate and characterize the biologically active volatile and non-volatile compounds from Tagetes minuta and Rauvolfia caffra respectively. Tagetes minuta plant was considered for extraction of essential oils using hydrodistillation method. Cis-β-ocimene (38.03%), caryophyllene oxide (18.04%), alloocimene (25.35 %), isopropyl tetradecanoate (17.02 %), cis-ocimene (38.14%) and trans-β-ocimene (37.03%) were the major components of essential oil analyzed from fresh stem, dried stem, fresh leaf, dried leaf, fresh flower and dried flower respectively. The volatile compounds were identified by Gas Chromatography-Mass Spectrometry (GC-MS) and Gas Chromatography (GC). Essential oil of dried stem leaf and flower parts of T. minuta exhibit antioxidant activity as demonstrated by the DPPH and FRAP bioassays. Crude extracts were extracted from R. caffra stem bark using sequence of solvents namely n-hexane, dichloromethane, ethyl acetate, methanol and ethanol. A white powder, a β-sitosterol (non-volatile compound) was isolated by column chromatography from ethyl acetate fractions of R. caffra stem bark and identified on various spectroscopic techniques such as FTIR and (1D and 2D) NMR. Melting point was also determined to be a sharp 129-130 ºC. DCM, EA, MetOH and EtOH fractions as well as β-Sitosterol (compound SM/01), showed antioxidant activity when tested on DPPH, FRAP, total phenolic and flavonoid bioassays. This antioxidant activity might be due to the presence of hydroxyl groups in the compound and crude fractions. On the other hand, T. minuta’s essential oil showed high antioxidant activity when evaluated on the DPPH and FRAP bioassays, which can be attributed to the presence of oxygenated monoterpenes and sesquiterpenes known to act as free radical scavenging and reducing agents. The use of R. caffra stem bark extracts against hypertension and other diseases by traditional healers could be attributed to the presence of phytochemicals (polyphenols and flavonoids) with known health benefits. Thus, it is recommended that the plant should be exploited further using modern techniques involving separation and purification of compounds that can be used for drug formulation. This study supports the use of T. minuta and R. caffra as the potential natural antioxidant source to manage various diseases including hypertension.
Synthesis and structural studies of NiS and PdS nanoparticles/nanocomposites from dithiocarbamates single source precursors
(University of Fort Hare, 2016) Nqombolo, Azile; Ajibade, P A
The main aim of this research is to synthesize Ni(II) and Pd(II) dithiocarbamate complexes and use them as single source precursors for the synthesis of NiS and PdS nanoparticles and metal sulphides potato starch nanocomposites. Four dithiocarbamate ligands were synthesized and characterized using elemental analysis and spectroscopic techniques. The ligands were used to prepared homoleptic Ni(II) and Pd(II) complexes of the dithiocarbamate ligands. The metal complexes were characterized with elemental analysis, UV-Vis, FTIR and 1H-NMR spectroscopic techniques. Conductivity measurements indicate that all the complexes are non-electrolytes in solution and results from the electronic spectra studies confirmed the proposed 4-coordinate square planar geometry around the metal ions. The nickel complexes showed d-d transitions around 477 nm while in the palladium complexes, no d-d transitions were observed but the compounds showed strong metal to ligand charge transfer transitions. From the FTIR spectra studies, it can be confirmed that the complexes were successfully synthesised because all peaks of interest were observed at expected regions from the literature. The νC-N was observed around 1469-1495 cm-1, νC=S around 1101-1188 cm-1 and νC-S around 738-1060 cm-1 for both Ni(II) and Pd(II) complexes. νNi-S was observed around 375-543 cm-1 and νPd-S around 529-545 cm-1. The FTIR also confirmed that the dithiocarbamate ligands act as bidentate chelating ligands through the sulfur atoms. The complexes were used as single source precursors and thermolysed in hexadecylamine (HDA) at 220 °C to prepare four HDA-capped nickel sulfide nanoparticles and four palladium sulfide nanoparticles. The as-prepared nanoparticles were studied with optical absorption spectra, photoluminescence, powder X-ray diffraction (PXRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDS). The optical studies results showed that NiS have large band gaps that are greater than that of the bulk, therefore they are found to be blue shifted relative to the bulk, which shows that they have small particle size and thus confirming their quantum confinement effect. PL spectra reveal that the emission peaks are red shifted compared to the absorption band edges of the nanoparticles. The XRD patterns confirmed the formation of cubic and rhombohedral phase for NiS nanoparticles and cubic phase for PdS nanoparticles. SEM images of both NiS and PdS show uniform surface morphology at low and high magnification with different shapes. EDS analyses confirmed the presence of Ni, S, and Pd in each of the spectrum indicating that the nanoparticles were successfully synthesized. TEM images showed that the synthesised nanoparticles have uniform and narrow size distribution with no agglomeration. The sizes of the NiS nanoparticles were found to be in the range of 12-38 nm for NiS1, 8-11 nm for NiS2, 9-16 nm for NiS3 and 4-9 nm for NiS4. The TEM images for the as-prepared PdS nanoparticles showed that the average crystallite sizes are 6.94-9.62 nm for PdS1, 8-11 nm for PdS2, 9-16 nm for PdS3 and 4-9 nm for PdS4 respectively. The nanoparticles were used to prepare potato starch nanocomposites and SEM images indicate that the surface morphology of starch polymer nanocomposites compose of potato starch and few particles in between the pores of the matrix, this is due to the small ratio of nanoparticles used.
Remediation of metal ions in aqueous solution using activated carbon from Zea may stem
(University of Fort Hare, 2016) Matandabuzo, Mzukisi; Ajibade, P A
Zea mays stem and its activated carbon were prepared through chemical activation method using four different activating reagents (NaOH, H₃PO₄, H₂SO₄, KOH) and were used as adsorbents for the removal of Pb(II), Cu(II), Hg(II) and Cr(III) from aqueous solution. The results shows that activated carbon has high surface area and pore volume compared to the powdered raw Zea mays stem. Prepared activated carbon was characterized using physico-chemical properties such as carbon yield, iodine number, moisture content, percentage adsorption, and analytical instruments such as Fourier transform Infrared spectroscopy (FTIR), atomic absorption spectrometer (AAS), scanning electron microscopy (SEM), Energy Dispersive X-ray analysis (EDS), powder X-ray Diffraction (pXRD). The adsorption of Pb(II), Cu(II), and Cr(III) ions were pH, contact time, and concentration dependent. Based on the results obtained from the batch experiments, activated carbon prepared from Zea mays stem is not good enough for the removal of Hg(II) from aqueous solution. Adsorption ability was calculated and found to be 66.67% for activated carbon obtained from H₂SO₄, 21.21% for activated carbon obtained from KOH, and 20% for activated carbons obtained from NaOH and H₃PO₄. The pH 5-6 was chosen for all experiments, contact time was 2 hours, and adsorbent dosage was 2 g, initial concentration range from 200, 400, 600, 800, and 1000 ppm at room temperature. The metal ion removal trend was found in the order Pb(II)>Cu(II)>Cr(III)>>Hg(II). The Langmuir model fitted well in most of the cases with > 0.99. Consequently, the adsorption of Pb(II) and Cu(II) followed Langmuir isotherm model while that of Cr(III) best fitted the Freundlich isotherm model. The results indicated that the adsorption process followed two possible mechanisms. (I) Metal ion – adsorbent complex model and (II) Metal ion – ion-exchange adsorbent complex model.
Investigation into the characteristics and possible applications of biomass gasification by-products from a downdraft gasifier system
(University of Fort Hare, 2015) Melapi, Aviwe; Mamphweli, D; Katwire, D M
Biomass gasification has attracted the interest of researchers because it produces zero carbon to the atmosphere. This technology does not only produce syngas but also the byproducts which can be used for various application depending on quality.The study conducted at Melani village in Alice in the Eastern Cape of South Africa was aimed at investigating the possible applications of the gasification byproducts instead of being thrown away. Pine wood was employed as the parent feedstock material for the gasifier. Biomass gasification by-products were then collected for further analysis. The studied by-products included tar(condensate), char, soot and resin. These materials were also blended to produce strong materials.The essence of the blending was to generate ideal material that is strong but light at the same time.The elemental analysis of the samples performed by CHNS analyser revealed that carbon element is in large quantities in all samples. The FTIR spectra showed almost similar results for all the studied samples, since the samples are end products of lignocellulosegasification. SEM gave the sticky images of resin as well as porous char structures. Char showed a higher heating value of 35.37MJ/Kg when compared to other by-products samples.
Ni(II) and Pb(II) dithiocarbamate complexes as precursors for the synthesis of HDA-capped NiS and PbS nanoparticles
(University of Fort Hare, 2015) Chintso, Thobani; Ajibade, P A
Ni(II) and Pb(II) dithiocarbamate complexes were synthesized and characterized by elemental analysis, UV-Vis, FTIR and TGA and some of the Ni(II) complexes and one Pb(II) were further analyzed by 1H-NMR and 13C-NMR spectroscopy. Generally all the dithiocarbamate ligands are soluble in water while the complexes were soluble mostly in solvents such as chloroform, toluene, DMSO and DCM. Based on the elemental analysis, the dithiocarbamate complexes are formulated as four coordinate (tetrahedral or square planar) compounds. However, the FTIR showed that each of the dithiocarbamate ligands acted as bidentate ligand through two sulfur atoms. The TGA of the most complexes showed one major decomposition step to give respective metal sulfide above 200 oC. In this research project, dithiocarbamate complexes were used as single source precursor for the synthesis of metal sulfide nanoparticles. We studied the optical and structural properties of metal sulfide nanoparticles using UV-Vis, photoluminescence (PL), powder X-ray diffraction (XRD), energy dispersive X-ray (EDX), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The absorption spectra of the metal sulfide nanoparticles are blue shifted in respect to bulk material and they also showed broad emission. The XRD of the NiS nanoparticles were indexed to the cubic and rhombohedral phase, with crystallite sizes of 15 - 18 nm. The XRD of PbS nanoparticles were indexed to the face centered cubic and cubic rock salts, with the crystallite sizes 12 - 18 nm. The TEM images of the metal sulfide nanoparticles showed particles with spherical and rectangular shapes with crystallite sizes 4 - 35 nm.
Isolation, Characterisation, and biological activity evaluation of essential Oils of Cymbopogon validus (Stapf) Stapf ex Burtt Davy and Hyparrhenia hirta (L.) Stapf
(University of Fort Hare, 2014) Rungqu, Pamela; Oyedeji, O O; Oyedeji, A O
Cymbopogon validus and Hyparrhenia hirta belong to the Poaceae botanical family. Both plants are used as thatching material; H. hirta is also used for weaving mats and baskets. In this study, we investigated the anti-inflammatory effects of C. validus and H. hirta essential oils on fresh egg-albumin induced edema on Wistar rats. To fully understand the chemically induced anti-inflammatory properties of these plants, we first analyzed the chemical composition of the essential oils. The essential oils were analyzed using gas chromatography-mass spectrometry (GC-MS). In C. validus, 13 compounds accounted for 74.3% of fresh leaves oil, 14 compounds 71.8% of dried leaves oil and 12 compounds 73.3% of flower oil were identified from the GC-MS Chromatogram. The percentage yields were as follows fresh leaves oil 2.2%, dried leaves oil 2.0% and flower oil 2.4% v/w respectively. Linalool (3.2-29.6%) and northujane (4.4-16.9%) were the dominant compounds found in the 3 oils analyzed. While, α-terpineol 37.5% and verbenone 13.5% was only found in the fresh leaf oil, this was absent in the dried leaves oil and the flowers oil of C. validus. In H. hirta, 25 compounds accounted for 68.1% of fresh leaves oil, 40 compounds 71.9% of dried leaves oil, 23 compounds 77.6% of fresh flowers oil and 18 compounds 80.1% of dried flowers oil were identified from the GC-MS Chromatogram. The percentage yields obtained from the different parts were 3.4% for fresh leaves oil, 2.8% for dried leaves oil, 2.8% for fresh flowers oil and 0.7% for dried flowers oil v/w respectively. Northujane (8.5-30.0%), diisooctyl phthalate (4.4-26.5%), phytone (1.1-10.4%) were the dominant compounds found in the 4 oils analyzed. While, dibutyl phthalate 26.9% was only found in the fresh flowers and was absent in the dried flowers oil. Moreover, caryophyllene oxide (1.7-9.6%) was found in fresh leaves and dried flowers oil of H. hirta. In vivo analysis revealed that the two essential oils displayed significant edema inhibition effect overtime. They displayed strong anti-inflammatory properties when compared to control group. However, the H. hirta essential oil was more effective than that of C. validus. Linalool, α-terpineol, and northujane extracted from C. validus and H. hirta essential oils might have contributed to the anti-inflammatory effects observed in Wistar rats. This study, confirms the anti-inflammatory properties of C. validus and H. hirta suggesting that they may be used in diseases related to anti-inflammation.
Biological evaluation and semi-synthesis of Isolated compounds from (Syzygium aromaticum (L.) Merr. & Perry) Buds
(University of Fort Hare, 2014) Sibusiso, Rali; Oyedeji, O O; Nkeh-Chungag, B N
Natural products play a fundamental role in modern drug discovery as they continue providing diverse bioactive lead compounds for new drug formulation. However, isolation of these valued compounds is problematic. On the other hand, the morbidity and mortality rates caused by non-communicable diseases are increasing with improved longevity. Thus, the study herein focused on the isolation of plant-derived compounds from Syzygium aromaticum and evaluated their biological properties. Syzygium aromaticum is a well-known plant which belongs to family Myrtaceae. Dried flower buds of S. aromaticum were subjected to sequential solvent extraction. The ethyl acetate extract (15.535 g) was subjected to column chromatography using a silica gel (0.063-0.200 mm) for isolation. This has led to the isolation of three distinct compounds that were identified as eugenol, maslinic acid (MA) and oleanolic acid (OA). The structural elucidation of these valued compounds was done using NMR, GC-MS, LC-MS, FT-IR and Mp. Further semi-synthesis of the oleanolic acid afforded acetate and ester OA-derived compounds with better solubility properties. All these compounds were evaluated for analgesic and anti-inflammatory properties. All tested compounds were administered at a dose of 40 mg/kg to both Wistar rats and Swiss mice. Significant (p<0.01) analgesic and anti-inflammatory properties are obtained for all compounds. The effects of eugenol in all experiment were better except in the thermal-induced pain or tail flick test. In the case of modified compounds, the formalin induced pain test disclosed that oleanane derived compounds confessed analgesic and anti-inflammatory effects better than OA, whereas, in tale flick test oleanolic acid proved superior analgesic effects compared to all its derivatives with the exception of the acetyl-derivative. Acute anti-inflammatory test showed that acetyl-derivatives were more active than other compounds. In conclusion, chromatographic techniques and semi-synthesise of oleanolic acid have resulted to several plant-derived compounds with analgesic and anti-inflammatory properties. The semi-synthesized compounds may serve as alternative drug candidates for new analgesic and anti-inflammatory drug formulation
Synthesis and characterization of Ru(II) phenyl-3-indenylidene olefin metathesis type complexes
(University of Fort Hare, 2015) Yalezo, Ntsikelelo; Ajibade, P A
In this study, a series of Ru(II) phenyl-3-indenylidene complexes with general formula of [RuCl2(NHC)(Ind)(L)] (where L= triphenylphosphine, pyridine and NHC = five different types of N-heterocyclic carbene ligands), have been synthesized and characterized using FT-IR, UV-Vis, elementally analysis and melting/decomposition point. The N,N’-diarylimidazolinium chlorides have been used as N-heterocyclic carbene precursors and were synthesized from their corresponding N,N’-diarylformamidines and further characterized using 1H-NMR, 13C-NMR, FTIR and melting point determination. The infrared spectra of the N,N’-diarylimidazolinium chlorides show a quaternary nature (R2N=C+) with broad vibration band in region 3300-3400 cm-1. The disappearance of this vibration band in the infrared spectra of the ruthenium(II) complexes was used to confirm the coordination of the ligand to the ruthenium ions. The percentage analysis of carbon, hydrogen and nitrogen obtained corresponded with the calculated percentages of these atoms in the complexes with the slight difference of less than 1%. The electronic spectra of the complexes show three distinct absorption bands. The two bands are due to intraligand charge transfers transition assigned to π→π*, n→π* and third band is due to d-d transition, signifying the presence of the metal ion. The synthesized Ru(II) complexes did not show any of melting, however a change in colour was observed signifying the decomposition of the complexes.
Synthesis, characterization & application of visible light responsive nitrogen doped Tio2 and copolymer-grafted asymmetric membranes with ozonolysis for water treatment
(University of Fort Hare, 2015) Mungondori, Henry H; Tichagwa, L; Katwire, D M; Green, E
The use of titanium dioxide for the photo-catalytic removal of organic, inorganic, and microbial pollutants from natural water and wastewater has been considered a very promising technique. The aim of this study was to prepare nitrogen doped titanium dioxide, immobilize it on asymmetric polymeric membranes of poly (methacrylic acid) grafted onto poly (vinylidene difluoride) (PVDF) blended with poly (acrylonitrile) (PAN), and evaluate the photo-catalytic, antimicrobial, and antifouling properties of the membranes. Nitrogen doped titanium dioxide (N-TiO2) nano-particles were prepared by a low temperature sol gel synthesis technique. The modification of TiO2 with nitrogen allows photo-sensitization of the photo-catalyst towards visible light utilization. The N-TiO2 nano-particles were characterized by fourier transform infrared spectroscopy (FT-IR), scanning x-ray photoelectron spectroscopy (SXPS), X-ray diffraction analysis (XRD), diffuse reflectance spectroscopy (DRS), Brunauer Emmett Teller (BET) surface area analysis, and transmission electron microscopy (TEM). The characterizations revealed the presence of the expected functional groups and confirmed successful doping and that the product was visible light responsive. Novel poly (methacrylic acid) grafted onto poly (vinylidene difluoride)/ poly (acrylonitrile) (PMAA-g-PVDF/ PAN) asymmetric membranes were prepared by the dry-wet phase inversion technique. The poly (methacrylic acid) (PMAA) side chains where grafted onto an activated PVDF backbone by reversible addition fragmentation chain transfer (RAFT) polymerization. The photo-catalytic membranes were generated by blending N-TiO2 with the polymer solution before casting the membranes. The membranes were characterized by FT-IR, nuclear magnetic resonance spectroscopy (NMR), scanning electron microscopy (SEM), and thermo-gravimetric analysis (TGA). FT-IR and NMR analyses confirmed successful grafting of MAA chains onto PVDF while SEM confirmed the successful preparation of membranes with asymmetric structure. The efficacy of the photo-catalytic asymmetric membranes was evaluated on the removal of herbicides from synthetic water. Bentazon was easily degraded while atrazine and paraquat were recalcitrant and proved difficult to degrade. The best results were observed with 3 % N-TiO2-PMAA-g-PVDF/ PAN asymmetric membranes on the photo-degradation of bentazon, atrazine and paraquat in water. Significant enhancement in the photo-degradation of the three herbicides was observed when photo-catalytic degradation was coupled with ozonation. Liquid chromatography-mass spectrometry (LC-MS) analysis confirmed the presence of a degradation by-product during the photo-catalytic degradation of bentazon. The photo-catalytic membranes were also evaluated on the photo-catalytic reduction of heavy metals Pb2+ and Fe3+ in water, and the best results were obtained using 1 % N-TiO2-PMAA-g-PVDF/ PAN and 1 % N-TiO2-PAN asymmetric membranes. All prepared photo-catalytic membranes where capable of completely inactivating E. coli ATCC 8739 within 120 minutes of exposure and inactivation rate increased with increasing N-TiO2 photo-catalyst loading. However, there was an indication from the results obtained that N-TiO2 supported on PMAA-g-PVDF/ PAN showed a higher inactivation rate of E. coli ATCC 8739 compared to N-TiO2-PAN and N-TiO2-PVDF membranes. The 1 % N-TiO2-PMAA-g-PVDF/ PAN membranes gave the highest pure water flux (421.83 L/m2h). This increase (PVDF = 30.50 L/m2h, PAN = 73.85 L/m2h) in pure water flux is owedb to PMAA grafting as well as addition of N-TiO2. These modifications resulted in an increased membrane surface hydrophilicity, which promoted permeation of pure water through the membrane structure. A high bovine serum albumin (BSA) rejection (76.5 %) was noted and can be attributed to steric hindrance brought about by PMAA side chains which prevented the bulky BSA molecules from attaching to the membrane surface for PMAA-g-PVDF/ PAN membranes. However, the supporting porous sub-layer of an asymmetric membrane seemed to play a very important role in the overall permeability of a membrane. PVDF membranes are highly hydrophobic hence they gave a very low pure water flux.
Preparation and characterisation of nanocomposites of biomass and montmorillonite clay for use as biofuels
(University of Fort Hare, 2014) Nyamutswa, Lavern Tendayi; Tichagwa, L
The aim of the study was to prepare composites of clay and biomass which burn longer than unmodified biomass. Montmorillonite clay was converted to mono-ionic clay by ion exchange with sodium using sodium chloride solution. The mono-ionic clay was organically modified with an organic surfactant, methyl triphenyl phosphonium bromide. Nanocomposites were then prepared by combining the modified forms of the clay with sawdust. The three forms of clay used for the formation of composites were unmodified montmorillonite, mono-ionic montmorillonite and organically modified montmorillonite. The solution blending method was used to make the nanocomposites. FT-IR and XRD analysis showed that organic surfactant increases the interlayer space of the clay since it is bulkier than the inorganic cations that are naturally present in the interlayer space of montmorillonite. The combination of clay and sawdust resulted in the formation of exfoliated nanocomposites as shown by the absence of peaks in the low 2 theta angle in the x-ray diffraction data of the nanocomposite. The nanocomposite which was made from sawdust and 1% organically modified clay showed the best results in terms of burning time and thermal stability, as well as giving a calorific value closest to unmodified sawdust and the least amount of residue.
Gasification characteristics of sugarcane bagasse
(University of Fort Hare, 2013) Anukam, Anthony Ike; Meyer, E L; Mamphweli, S; Okoh, O
Sugarcane is a major crop in many countries. It is the most abundant lignocellulosic material in tropical countries such as South Africa. It is one of the plants with the highest bioconversion efficiency. The sugarcane crop is able to efficiently fix solar energy, yielding some 55 tons of dry matter per hectare of land annually. After harvest, the crop produces sugar juice and bagasse. Sugarcane bagasse is a residue that results from the crushing of sugarcane in the sugar industry. It is a renewable feedstock that can be used for power generation and manufacturing cellulosic ethanol. As biomass, sugarcane bagasse holds promise as a fuel source since it can produce more than enough electricity and heat energy to supply the needs of a common sugar factory. However, in the sugarcane industry the bagasse is currently burnt inefficiently in boilers that provide the heating for the industry. This project seeks to investigate the possibility of gasifying sugarcane bagasse as an efficient conversion technology. The investigation is necessary because fuel properties govern the gasifier design and ultimately, the gasification efficiency. Proximate and ultimate analysis of sugarcane bagasse was conducted after which the results were used to conduct a computer simulation of the mass and energy balance during gasification. The kinetic investigation undertaken through the TGA and DTG analyses revealed the activation energy and pre – exponential factor which were obtained by the model – free Kissinger method of kinetic analysis and were found to be 181.51 kJ/mol and 3.1 × 103/min respectively. The heating value of sugarcane bagasse was also measured and found to be 17.8 MJ/kg, which was used in the calculation of the conversion efficiency of the gasification process. Fuel properties, including moisture content and gasifier operating parameters were varied in order to determine optimum gasifier operating conditions that results in maximum conversion efficiency. The highest conversion efficiency was achieved at low moisture content after computer simulation of the gasification process. Moisture content also affected the volume of CO and H2 as the former decreases with increasing moisture content while the latter increases with increasing moisture content, accelerating the water – gas reaction. Scanning electron microscope fitted to an Energy dispersive X – ray spectroscopy was also used in order to view the shape and size distribution as well as determine the elemental composition of sugarcane bagasse. The results obtained established that the fuel properties and gasification conditions affect the conversion efficiency. During computer simulation, it was established that smaller particle size resulted in higher conversion efficiency. The smaller throat diameter also resulted in higher conversion efficiency. The throat angle of 25° also resulted in higher conversion efficiency. The temperature of input air was also found to be one of the major determining factors in terms of conversion efficiency. The dissertation presents the proximate and ultimate analysis results as well as the kinetic analysis results. The SEM/EDX analysis as well as the computer simulation results of the gasification process is also presented. The major contribution of this project was on the investigation of the gasification characteristics of sugarcane bagasse and the utilization of these in the design of a laboratory scale sugarcane bagasse gasifier with enhanced conversion efficiency through computer simulation.
Structural, optical and electrical characterization of nano-sized c-tio2 quamtum dots synthesized by spray pyrolysis
(University of Fort Hare, 2014) Taziwa, Raymond Tichaona; Meyer, E L; Ajibade, P A
In the 21st century, scientific communities face challenges and opportunities concerning future development, where innovations must be a key driver over the past, evolution of African societies were based on incomplete models, only taking into account economical growth and not paying attention to environmental deterioration as a consequence of anthropogenic activity and environmental pollution. We have to learn from our past mistakes in order not to repeat them. Education and research of today as the embryonic stages of the development models of tomorrow should be directed toward a sustainable mentality. In this sense, solar energy technologies have emerged as key instruments for minimizing environmental impact as well as reducing economic cost in the field of renewable energies. Titanium dioxide is a fascinating low cost material exhibiting unique properties of stability and photo catalytic activities, leading to clean technologies in water purification and energy conversion of sunlight. However, conventional techniques (high temperature, high vacuum, high pressures) of processing titanium dioxide are a technological limitation due to excessive energy consumption. This poses a handicap for practical applications in areas such as preparation of hybrid organic/Titanium dioxide materials or devices on thermo flexible substrates such as plastic material. It is for this reason that the investigation presented in this Ph.D thesis deals with the development of spray pyrolysis techniques for preparation of carbon doped titanium dioxide nano powders for solar cell applications. This thesis is therefore structured as follows: Chapter 1 gives a general overview of the work done in this thesis. This work relies greatly on the excellent structural optical and electrical properties of TiO2 thin films, as well as its chemical resistance and insulating properties. A summary of the physical, optical, electrical and chemical properties reported in the literature, with an emphasis on those relevant to solar cell fabrication, is presented in Chapter 2. Chapter 3 gives a concise literature review on models governing droplet formation in ultrasonic spray pyrolysis (USP) techniques, the limitations of these models have been exposed and a new relation model for estimating the final particle size given a set of initial reaction conditions has been proposed. The presently derived model is quite advantageous in that it does not require the investigator to look up values of surface tension and density for every precursor solution. Chapter 4 presents in detail the designed and constructed spray pyrolysis system capable of realizing desired nano structures for photovoltaic applications. The first system employed an ultrasonic atomization spray nozzle in order to create an aerosol of the TiO2 precursor. The reasons for choosing ultrasonic spray deposition (USP) and the TiO2 precursors, titanium iso propoxide and titanium tetra butoxide are discussed. Chapter 5 outlines experimental methodologies used in synthesis and characterization of the materials used in this study. Chapter 5 further provides experimental methodologies used in fabrication of a new type of photo electrochemical solar cells (PECs). Chapter 6 reveals the opto-electrical results of PECs solar cells fabricated. There are numerous properties that are affected by the size but emphasis will be placed on nano-size and confinement effects. Chapter 7 presents a confirmation of the phonon confinement effects in C-TiO2 QDs for the first time. In addition Chapter 7 also presents a new phonon confinement model. Chapter 8 reveals the optical, structural and electronic properties of C-TiO2 QDs synthesized by USP and PSP techniques. In addition the electrical properties of C-TiO2 QDs PEC solar cells devices are reported in Chapter 8. Concluding remarks, with potential future research projects are presented in Chapter 9. Through these 9 chapters, all research questions have been answered satisfactorily and all objectives met. Most of the work contained in this thesis has been subjected to external reviews through publication of these peer reviewed articles.
Ethanol production from lignocellulosic sugarcane leaves and tops
(University of Fort Hare, 2014) Dodo, Charlie Marembu; Manene, N; Tichagwa, L
Various methods for the production of bioethanol using different feedstocks have been researched on. In most work on bioethanol synthesis from sugar cane, tops and leaves have been regarded as waste and generally removed and thrown away. In this work, lignocellulosic sugarcane leaves and tops were not discarded but instead used as biomass to evaluate their hydrolyzate content. The leaves and tops were hydrolysed using different methods, namely concentrated acid, dilute acid pre-treatment with subsequent enzyme hydrolysis and compared with a combination of oxidative alkali pretreatment and enzyme hydrolysis. Subsequent fermentation of the hydrolyzates into bioethanol was done using the yeast saccharomyces cerevisae. Acid hydrolysis has the problem of producing inhibitors, which have to be removed and this was done using overliming with calcium hydroxide and compared to sodium hydroxide neutralization. Oxidative alkali pre-treatment with enzyme hydrolysis gave the highest yields of fermentable sugars of 38% (g/g) using 7% (v/v) peroxide pre-treated biomass than 36% (g/g) for 5% (v/v) with the least inhibitors. Concentrated and dilute acid hydrolysis each gave yields of25% (g/g) and 22% (g/g) yields respectively although for acid a neutralization step was necessary and resulted in dilution. Alkaline neutralization of acid hydrolyzates using sodium hydroxide resulted in less dilution and loss of fermentable sugars as compared to overliming. Higher yields of bioethanol, 13.7 (g/l) were obtained from enzyme hydrolyzates than 6.9 (g/l) bioethanol from dilute acid hydrolyzates. There was more bioethanol yield 13.7 (g/l) after 72h of fermentation with the yeast than 7.0 (g/l) bioethanol after 24h. However, the longer fermentation period diminishes the value of the increase in yield by lowering the efficiency of the process.
Synthesis and characterization of metal sulfide nanoparticles/polymer nanocomposites
(University of Fort Hare, 2013) Mbese, Johannes Zanoxolo; Ajibade, P A
The focus of this project was to synthesize and characterize metal sulfide nanoparticles /polymer nanocomposites. The work involved the synthesis of dithiocarbamato ligands and complexes derived from aniline. Zn(II), Cd(II) and Hg(II) dithiocarbamato complexes were used as single-molecule precursors for the synthesis of the ZnS, CdS and HgS nanoparticles and their optical and structural properties studied. The other focus of this work was to synthesize a combined functionality metal sulfide nanoparticles/polymer nanocomposites by dispersing as-synthesized ZnS, CdS and HgS nanoparticles in polymethyl methacrylate (PMMA) matrix. The characterization of the ligands, complexes, nanoparticles and nanocomposites were investigated using relevant instrumental tools like UV-Vis, photoluminescence (PL), Fourier transform infrared (FTIR), X-ray diffraction (XRD), energy dispersion X-ray (EDX), nuclear magnetic resonance (NMR), scanning electron microscopy (SEM) and transmission electron microscopy (TEM).
The characterization and electrochemistry of dye-sensitized solar cells
(University of Fort Hare, 2013) Caga, Noloyiso; Meter, E L; Mamphweli, S N; Ajibade, P A
In this study a presentation of the technology behind dye-sensitized solar cells, their design as well as the role of the different parts of the cell. The characterization of the cell is divided into four sections namely: the characterization of the paste required to make the TiO2 film and its optical properties using SEM-EDX and XRD analytical techniques; Analysis of the various absorptions of three Ru-based dyes using UV-Vis spectroscopy, Photoluminescence and Fourier Transform Infra-Red spectroscopy; the characterization and the analyses of the entire cell using Electrochemical Impedance Spectroscopy. The nine cells were prepared by examining RuL2(CN)2 , RuL2(NCS)2 or N3 dye and RuL2(NCS)2 TBA+ or N719 dye. [L = 2,2'-bipyridyl-4,4'-dicarboxylic acid ;TBA = tetra-butyl ammonium] were combined with three electrolytes namely: Z–150 , AN–50 and PN–50. The Iodolyte PN–50 is an iodide based low viscosity electrolyte with 50 mM of tri-iodide dissolved in a solvent called propionitrile (PN). The Iodolyte AN–50 is an iodide based low viscosity electrolyte with 50 mM of tri-iodide dissolved in a solvent called acetonitrile (AN). The Iodolyte Z–150 is an iodide based low viscosity electrolyte with 150 mM of tri-iodide dissolved in a solvent called 3-methoxypropionitrile (MPN) and with additives such an ionic liquid, malkylbenziimidazole and guanidine thiocyanate. A solar simulator was utilized with which the standard solar irradiation can be created in laboratory conditions. The fill factors as well as overall performance efficiencies of the these cells are quite low < 1.0%,.
Synthesis, characterization, and biological studies of pyrazolone Schiff bases and their transition metal complexes
(University of Fort Hare, 2014) Idemudia, Omoruyi Gold; Sadimenko, A P; Afolayan, A J
Some new acylpyrazolone Schiff bases have been synthesized from the condensation reaction of two acylpyrazolone diketone precursors with phenylhydrazine, 2,4-dinitrophenylhydrazine and sulfanilamide. They have been fully characterized by elemental analysis and spectroscopic techniques (IR,1H and 13C NMR, and mass-spectra). The single crystal structure of the benzoyl derivative acylpyrazolone Schiff bases have been obtained and analyzed by X-ray crystallography technique. Solid state X-ray diffraction revealed a keto tautomer Schiff base in solid state. Mn(II), Co(II), Ni(II) and Cu(II) complexes with the Schiff bases have been synthesized and characterized by elemental analysis, IR and UV-VIS spectroscopy, magnetic susceptibility measurements, and thermal studies (TGA and DTG). An octahedral geometry around the transition metal ion, consisting of two bidentate Schiff base ligands bonding through the azometine nitrogen and ketonic oxygen have been proposed based on careful interpretation of available analytical and spectroscopic characterization results. Two water molecules as ligands complete the octahedral geometry in all cases. Using the invitro disc diffusion method for screening synthesized compounds against selected gram positive and gram negative bacterial at 40 mg/mL, and the DPPH free radical scavenging methods at 0.50, 0.25 and 0.13 mg/mL, the synthesized Schiff base and metal complexes showed varying biological activities. 4-benzoyl-3-methyl-1-phenyl-2-pyrazolin-5-one sul29 fanilamide showed more activity generally, exhibiting a broad spectrum activity against all selected bacterial in some cases. Mn(II), Co(II) and Ni(II) complexes of sulfanilamide Schiff base with the acetylpyrazolone derivative 4-acetyl-3-methyl-1-phenyl-2-pyrazolin-5-one sulfanilamide, exhibited a stronger and very good DPPH radical scavenging activity as good as ascorbic acid on comparing, but not with Cu(II). As such they could be important antitumour candidates.
Photocatalytic activity and antibacterial properties of Ag/N-doped TiO2 nanoparticles on PVAE-CS nanofibre support
(University of Fort Hare, 2012) Ocwelwang, Atsile Rosy; Tichagwa, L
Lack of potable water is one of the major challenges that the world faces currently and the effects of this are mainly experienced by people in developing countries. This has therefore propelled research in advanced oxidation technologies AOTs to improve the current water treatment methods using cost effective, non toxic and efficient treatment methods. Hence, in this study the sol-gel synthesis method was used to prepare TiO2 nanoparticles that were photocatalytically active under UV and visible solar light as well as possessing antibacterial properties. Silver and nitrogen doping was carried out to extend the optical absorption of TiO2. For easy removal and reuse of the photocatalyst the nanoparticles were immobilized on chitosan and poly (vinyl-alcohol-co-ethylene) using the electrospining technique. The synthesized nanomaterials were characterized by FTIR, XRD, SEM/EDS, TEM, DRS, and TGA. FTIR and EDS analysis confirmed the formation and composition of TiO2 nanopowders for the doped and undoped nanoparticles. XRD analysis showed that the anatase phase was the dominant crystalline phase of the synthesized nanopowders. SEM and TEM respectively illustrated the distribution and size of the electrospun nanofibers and the nanoparticles of TiO2. DRS results showed that there was a significant shift in the absorption band edge and wavelength of Ag-TiO2 to 397 nm, followed by N-TiO2 at 396 nm compared to the commercial titania which was at 359 nm. The photocatalytic activities and antibacterial properties of these materials were tested on methylene blue dye and E.coli microorganism respectively. Ag-TiO2 immobilized on nanofibers of chitosan and PVAE had the highest photocatalytic activity compared to N-TiO2. Similar results were observed when the biocide properties of these materials were tested on E. coli.
Computational studies, synthesis and characterization of ruthenium (ii) anticancer complexes
(University of Fort Hare, 2014) Adeniyi, Adebayo Azeez; Ajibade, P A
This thesis is centred on the application of Ru-based complexes as a promising alternative to cis-platin in cancer chemotherapy. Cis-platin is known to be the most prescribed chemotherapy which has more than 70% application in cancer cases especially the testicular cancer. An insight is provided in Chapter One and Two into the literatures reports on the application of Ru(II)-based complexes in cancer chemotherapy. In order to address some of the pressing challenges in rational design of Ru-based anticancer complexes, section 3.3 and 3.4 deal with efforts to elucidate the complication of their chemistry and instability while in section 3.5 efforts are made to find solution to the lack of proper knowledge of their targets using different theoretical approaches as presented in Chapter Three. In addition to the theoretical study, this thesis also comprises of the synthesis of the bis-pyrazole derivatives type of ligands and the derivatives of their Ru(II)-based complexes as provided in Chapter Four and Five respectively. Also the computational methods were used to elucidate the structural and spectroscopic properties of the synthesised ligands and their Ru(II)-based complexes. The geometrical and electronic properties are studied in relation to the stability and the reported anticancer activities of Ru(II)-based complexes in section 3.3. In subsection 3.3.1, several quantum properties including the natural energy decomposition analysis (NEDA) and quantum theory of atoms in a molecule (QTAIM) are computed on three models of RAPTA-C complexes using DFT with hybrid functional and basis set with ECP and without ECP. The higher stability of Carbo-RAPTA-C and Oxalo-RAPTA-C over RAPTA-C comes from the lower exchange repulsion and higher polarization contributions to their stability which gives insight into experimental observation. A similar study was carried out in subsection 3.3.2 on half-sandwich Ru(II)-based anticancer complexes with 6-toluene and 6-trifluorotoluene.

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