Submitted in complete fulfillment for the Degree of Master of Technology: Biotechnology, Durban University of Technology, 2013. / The biosynthesis of NPs has many advantages over the tedious, expensive and toxic physical and chemical methods of synthesis. Plants are stocked with valuable metabolites that are capable of reducing metal salts to form NPs. In this study, aqueous leaf extracts of A. dubius, G. perpensa, C. roseus and C. triloba were reacted with AgNO3 and HAuCl4 to determine the plants reducing abilities and hence synthesis of Ag and Au NPs capabilities. The synthesis reactions were carried out at different temperatures and extract concentrations for optimization. The goal was to form NPs within the specific wavelength range. Polar solvents: methanol and ethyl acetate extractions were carried out at the optimized conditions to evaluate the best solvent for the extraction of phytochemicals from the plants. The plant leaf extracts that were successful (A. dubius, G. perpensa and C. triloba) in synthesizing NPs were then micropropagated to form callus cultures. The reducing abilities of these callus cultures extracts were determined by varying temperature and concentration parameters. Characterization of the NPs formed by the different extracts was performed using UV-vis, TEM and FTIR. UV-vis spectrophotometry was used as a confirmatory as well as characterizing tool. TEM analysis was able to provide a description on the size and shape of the NPs whereas FTIR provided information on the biomolecules responsible for synthesis and capping of NPs. The stability of the NPs was determined by UV-vis scans over a period of 30 days which allowed observation of the alteration in peak shape and absorbance and hence condition of particles. Phytochemical tests were performed on the leaf extracts of the four plants to elucidate possible phytochemicals responsible for the reduction of metal salts. Antibacterial activity of the NPs was evaluated by using the disk diffusion assay and MICs were determined by the broth dilution method against pathogenic bacteria. A. dubius, G. perpensa and C. triloba were capable of synthesizing Ag NPs and Au NPs which were indicated by yellowish orange and reddish purple colour changes respectively. G. perpensa was able to spontaneously form Ag and Au NPs without any addition of heat whereas A. dubius and C. triloba required heat to form Au NPs. As the temperature of the reactions increased, the absorbance and possibly the number of NPs produced, increased. When the concentration of the extract was doubled, the absorbance was seen to decrease. C. roseus did not produce any Ag or Au NPs with any of the leaf extracts. Only A. dubius and C. triloba callus extracts were investigated for NP synthesis and it was found that A. dubius callus extracts were unsuccessful in synthesizing NPs and C. triloba callus extracts were able to form unstable Ag and Au NPs. The spherical Ag NPs that were formed from aqueous extracts of A. dubius were slightly larger than the methanolic Ag NPs. The Ag NPs produced by G. perpensa were in the same size range for aqueous and methanolic extracts. C. triloba Ag NPs formed from the methanolic extract were closer in size to A. dubius aqueous Ag NPs but the C. triloba aqueous extract produced much larger Ag NPs than the other extracts. The Ag NPs produced from A. dubius aqueous and methanolic extracts as well as C. triloba methanolic extracts exhibited the longest stability of 30 days. Ag NPs from G. perpensa aqueous extracts had the least stability. G. perpensa did not form any hexagonal Au NPs and the spherical and triangular Au NPs were smaller unlike in A. dubius and C. triloba Au NPs. The Au NPs formed by the aqueous extracts of A. dubius and C. triloba were larger in comparison to their methanolic counterparts. The Au NPs produced from G. perpensa aqueous and methanolic extracts as well as A. dubius and C. triloba methanolic extracts exhibited the longest stability of 30 days. Au NPs were stable for longer in comparison to Ag NPs. FTIR provided evidence that Ag and Au NPs have a chemical bond with the amide group in amino acids. However the intensities of biomolecules for Au NPs are more pronounced compared to the Ag NPs. It was also found that the Ag NPs synthesized by methanolic leaf extracts have slightly higher intensities than Ag NPs synthesized from aqueous leaf extracts. Phytochemical screening showed the absence of tannins in the C. roseus leaf, A. dubius and C. triloba callus extracts and presence in the other three plants. C. triloba methanolic extract Ag NPs showed the highest activity against Gram-positive S. aureus. Aqueous and methanolic Ag NPs from G. perpensa and C. triloba as well as A. dubius methanolic Ag NPs had activity against all fourteen bacteria. A. dubius aqueous Ag NPs had no activity against Enterobacter spp. and a strain of Klebsiella pneumoniae. G. perpensa Ag NPs had better antibacterial activity and lower MICs against Gram-positive and Gram-negative pathogenic bacteria compared to A. dubius and C. triloba. There was no antibacterial activity seen with Au NPs. The size and shape of NPs are the keys to their biomedical properties. Green synthesis of NPs is a feasible way for the future. This study showed that NPs can be synthesized very easily and economically. A key finding of this study is that different plants produce varying sizes and aggregation of NPs. / National Research Foundation

published_or_final_version / Chemistry / Doctoral / Doctor of Philosophy

M.Sc. / The main objective of this project was to synthesize carbohydrates that contain a thiol functional group, commonly known as thiocarbohydrates and subsequently employ them as stabilizing agents in the synthesis of gold nanoparticles and as ligands in the synthesis of phosphine thiocarbohydrate gold(I) complexes. In achieving our objective, thiocarbohydrate compounds 62, 64, 69 and 71 were successfully synthesized from acetylated 60 or benzylated glucal 66 using a Ferrier rearrangement reaction. NaHSO4-SiO2 was used as a catalyst for Ferrier rearrangement reaction in the presence of dithiol type nucleophiles (i.e. 1,2-dithiol ethane or 1,5-dithiol pentane) to afford the desired thiocarbohydrate compounds. The S-acetate derivatives 63, 65, 70 and 72 of the corresponding thiocarbohydrates were prepared as a confirmatory test for the presence of the terminal thiol (SH) in the thiocarbohydrate compounds. C-2 modified thiocarbohydrate compounds 78 and 80 were synthesized from C-2 iodomethyl glycoside 77 following a literature reported procedure in the presence of 1,2-dithiol ethane or 1,5-dithiol pentane as nucleophiles. S-acetate derivatives 79 and 81 of the corresponding thiocarbohydrate compounds were synthesized again to confirm the presence of the terminal thiol (SH). All the thiocarbohydrate compounds and their corresponding S-acetate derivatives were characterized with NMR spectroscopy and HRMS. Ethyl thiocarbohydrate compounds 62, 69 and 78 were successfully employed as stabilizing agents in the preparation of gold nanoparticles GNP1-GNP9 following a Brust-Schiffrin procedure. UV-Vis spectroscopy and transmission electron microscopy (TEM) were used to characterize these gold nanoparticles. Phosphine thiocarbohydrate gold(I) complexes 84-94 were synthesized from selected thiocarbohydrate compounds. NMR spectroscopy and HRMS were used to characterize these gold(I) complexes. Having synthesized the target thiocarbohydrate compounds, gold nanoparticles and gold(I) complexes, our aim was to investigate their biological activity against cancer and HIV. However, the biological testing process took considerably longer and as a result this dissertation was submitted without the biological tests results.

Recently, there has been growing interest in using transition metals (TM) for catalytic and electromagnetic applications, due to the ability of TMs to form stable compounds in multiple oxidation states. In this research, the focus has been on the synthesis and characterization of carbon-supported TM nanoparticles (NPs), specifically palladium (Pd) and gold (Au) NPs, for catalytic applications, and transition metal oxides (TMO) NPs, specifically Fe3O4 NPs for electromagnetic applications. Carbon supports have several advantages, such as enabling even distribution of particles, offering large specific surface area with excellent electron conductivity, and relative chemical inertness. In this dissertation, for catalytic applications, emphasis was on removal of trichloroethylene (TCE) from groundwater. For this application, carbon-supported Pd/Au NP catalysts were developed. Pd was chosen because it is more active, stable and selective for desired end-products, and Au has shown to be a good promotor of Pd's catalytic activity. Often, commercially available Pd-based catalysts are made using harsh chemicals, which can be harmful to the environment. Here, an environmentally friendly process with aspects of green chemistry was developed to produce carbon-supported Pd/Au NP catalysts. This process uses a combination of sonochemistry and solvothermal syntheses. The carefully designed carbon-supported Pd/Au NP catalyst material was systematically characterized, tested against TCE, and optimized for increased rate of removal of TCE. Electron microscopy and spectroscopy techniques were used to study the material including structure, configuration and oxidative state. The Pd/Au NPs were found mainly to form clusters with an aggregate-PdShellAuCore structure. Using state-of-the-art direct detection with electron energy loss spectroscopy, the Pd NPs were found to have an oxidative state of zero (0). The formation of the catalyst material was studied in detail by varying several synthesis parameters including type of solvent, sonication time, synthesis temperature etc. The most optimized catalyst was found remove TCE at double the rate of corresponding commercial Pd-based catalysts in a hydrogen headspace. This material was found to catalyze the removal of TCE via traditional hydrodehalogenation and shows promise for the removal of other contaminants such as trichloropropane (TCP), carbon tetrachloride (CT). This green approach to make and optimize TM materials for specific applications was extended to TMOs, specifically magnetite (Fe3O4) and further developed for the application of electromagnetism. As catalysts, Fe3O4 is used for removal of p-nitrophenol from water. However, since the carbon-supported Pd/Au material system was developed and optimized for catalysis, here, carbon-supported Fe3O4 NPs were developed for electromagnetic applications. There has been growing interest in tuning the magnetic properties of materials at room temperature with the use of external electric fields, for long-term applications in data storage and spintronic devices. While a complete reversible change of material properties has not yet been achieved, some success in partial switching has been achieved using multiferroic spinel structures such as Fe3O4. These materials experience a change in magnetic moment at room temperature when exposed to the electric fields generated by electrochemical cells such as lithium ion batteries (LIBs) and supercapacitors (SC). In the past, a 1% reversible change was observed in Fe3O4 using LIBs. Here, building on the developments from previous material system, Fe3O4 NPs were directly hybridized onto the graphene support in order to increase the observable change in magnetic moment. The material was systematically designed and tested for this application, including a study of the material formation. A simple, environmentally friendly synthesis using the solvothermal process was implemented to make the graphene-supported Fe3O4 NPs. This new material was found to produce a reversible change of up to 18% in a LIB. In order to overcome some of the difficulties of testing with a LIB, a corresponding hybrid SC was designed, built and calibrated. The graphene-supported Fe3O4 NPs were found to produce a net 2% reversibility in the SC, which has not been reported before. The results from both the LIB and SC were analyzed to better understand the mechanism of switching in a spinel ferrite such as Fe3O4, which can help optimize the material for future applications. The focus of this dissertation was on the development of a methodology for carbon-supported TM and TMO NPs for specific applications. It is envisioned that this approach and strategy will contribute towards the future optimization of similar material systems for a multitude of applications.

Surfactant bound stable colloids of Au, Ag, and Pd were prepared by the solvated Metal Atom Dispersion (SMAD) method, a method involving co-condensation of metal and solvent vapors on the walls of a reactor at 77 k. The as=prepared dodecanethiol-capped Au and Ag colloids consisting of polydisperse nanoparticles were transformed into colloids consisting of highly monodisperse nanoparticles by the digestive ripening process. In the case of Pd colloids, digestive ripening led to the formation of thiolate complexes. The [Pd(SC12H25)2]6 complex formed from the dodecanethiol-capped Pd nanoparticles was found to be a versatile precursor for the synthesis of a variety of Pd nanophases such as Pd(0), PdS, and Pd@PdO by soventless thermolysis. Co-digestive ripening of as-prepared dodecanethiol-capped Au or Ag colloids with Pd colloid resulted in Au@Pd and Ag@Pd core-shell nanoparticles, respectively; attempts to transform the core-shell structures into alloy phases even at high temperatures were unsuccessful. Phosphine-capped Au nanoparticles were also prepared by the SMAD method and refluxing of this colloid resulted in an Ostwald ripening process rather than the expected digestive ripening due to the labile nature of bound PPh3. The labile nature of the bound phosphine was studied using 31P NMR spectroscopy and utilized in the adsorption of CO. Palladium nanoparticles obtained from the SMAD Pd-butanone colloids and Pd@PdO nanoparticles prepared by the solventless thermolysis of Pd-dodecanethiolate complex were found to be good catalysts for the generation of H2 from AB via either hydrolysis and methanolysis. The active hydrogen atoms produced during the hydrolysis and methanolysis diffuse into the Pd lattice. It was also noticed that hydrogen atoms that were buried deep inside the Pd lattice cannot be removed completely by heating the sample even at 600°C. Wet chemical reduction method was employed for the synthesis of PVP capped, nearly monodisperse, spherical Ir nanoparticles which undergo a polymer driven self-assembly at 80°C to afford rectangular structures and interlinked particles.