Semiconductor nanocrystal-based photovoltaics are an interesting new technology with the potential to achieve high efficiencies at low cost. CuInSe2 nanocrystals have been synthesized in solution using arrested precipitation and dispersed in solvent to form a “solar ink”. The inks have been deposited under ambient conditions to fabricate photovoltaic devices with efficiency up to 3%. Despite the low cost spray coating deposition technique, device efficiencies remain too low for commercialization. Higher efficiencies up to 7% have been achieved using a high temperature selenization process, but this process is too expensive. New nanocrystal film treatment processes are necessary which can improve the device efficiency at low cost. To this end, CuInSe2 nanocrystals were synthesized using a diphenyl phosphine:Se precursor which allows for precise control over the nanocrystal size. The size is controlled by changing the temperature of the reaction. The smallest size nanocrystals demonstrated extremely high device open circuit voltage. Ligand exchange procedures were used to replace the insulating oleylamine capping ligand used during synthesis with more conductive halide ions or inorganic chalcogenidometallate cluster (ChaM) ligands. These ligands led to improved charge transport in the nanocrystal films. A high-intensity pulsed light processing technique known as photonic curing was used which allows for high temperature sintering of nanocrystal films on temperature-sensitive substrates. High energy pulses cause the nanocrystals to sinter into large grains, primarily through melting and resolidification. The choice of metal back contact has a dramatic effect on the final film morphology, with Au and MoSe2 back contacts providing much better adhesion with the CuInSe2 than Mo back contacts. Nanocrystal sintering without melting can be achieved by replacing the oleylamine ligands with ChaM ligands prior to photonic curing. Low energy photonic curing pulses vaporize the oleylamine ligands without inducing sintering or grain growth. This greatly improved nanocrystal coupling and interparticle charge transport. Multiexcitons were successfully extracted from these nanocrystal films and external quantum efficiencies over 100% were observed. Transient absorption spectroscopy was used to study the multiexciton generation process in CuInSe2 nanocrystal films and colloidal suspensions. The multiexciton generation efficiency, threshold, and Auger lifetimes for CuInSe2 compare well with other nanocrystal materials. / text

Marama bean (Tylosema esculentum (Burch) A. Schreib) is an underutilised, drought-tolerant legume native to the drier parts of Botswana, Namibia and South Africa. The bean is comparable to soya beans in protein content and quality whereas its oil content is comparable to that of peanuts. By adding value to the marama bean through processing into protein-rich flours, its utilisation may be increased. Therefore, one of the objectives of this study was to adopt suitable low-cost processing technologies used for soya processing to produce protein-rich marama bean flours. The effect of dry heating of whole marama beans on lipoxygenase enzymes of its defatted flour was determined since oxidative rancidity catalysed mainly by lipoxygenase enzymes can reduce the shelf-life of the flour. The presence of trypsin inhibitors can affect the protein digestibility of the marama bean flour adversely. The effect of dry heating of whole marama beans on in-vitro protein digestibility and amino acid content of its defatted flour was determined. Lastly, the effect of dry heating of whole marama beans on the protein-related functional properties of the resultant defatted flour was determined. The presence of lipoxygenase iso-enzymes (L-1 and L-2) activity in marama beans was determined by a visual and spectrophotometeric method using unheated soya beans as reference. Lipoxygenase iso-enzymes (L-1 and L-2) activity was not detected in marama beans. This may possibly suggest that these lipoxygenase iso-enzymes are absent or possibly inhibited in marama beans. In an attempt to optimise dry heating to inactivate trypsin inhibitors in marama beans, whole marama beans were dry heated at 100°C, 120°C and 150°C, respectively for 20 min. Defatted flours prepared from the heated marama beans (HMF’s) were analysed for their trypsin inhibitor activity using defatted flours from unheated marama beans (UMF) and soya beans (USF) as control and reference samples, respectively. Trypsin inhibitor activity in UMF was almost four and half times higher than in USF. Dry heating of whole marama beans at 150°C/20 min significantly reduced the trypsin inhibitor activity in its defatted flour to almost zero probably due to inactivation of the trypsin inhibitor. The effect of dry heating of whole marama beans at 150°C/20 min on the physico-chemical, nutritional and protein-related functional properties of defatted marama bean flour was determined. UMF was used as a control while USF and HSF were used as reference samples. HMF had higher protein content but lower fat content than UMF. It is suggested that dry heating disrupted the lipid bodies of the marama beans allowing more oil to be expelled during coarse milling of the flour. Heating significantly reduced the L* values of marama and soya bean flours possibly due to Maillard browning reactions. Heating significantly increased in-vitro protein digestibility of marama and soya bean flours probably due to protein denaturation and inactivation of trypsin inhibitors. Heating generally decreased the amino acid contents of marama and soya bean flours possibly due to chemical modification of the amino acids. UMF and HMF can potentially be used to improve protein quality in marama-cereal composite flours, porridges and breads. Heating significantly decreased the nitrogen solubility index (NSI) and emulsifying capacity (EC) of marama and soya bean flours possibly due to protein denaturation and/or cross-linking. This may make HMF and HSF not suitable for applications in emulsion type meat products such as sausages because emulsion formation is critical during processing of sausages. Heating significantly decreased the foaming capacity of soya flour but did not have an effect on that of marama bean flour probably due to their high residual fat content which may have disrupted protein films during foam formation. UMF has a potential to be used in comminuted meat products because of its relatively high NSI, EC and OAC. The laboratory process used in this study can be modified and adopted by SME’s to produce defatted marama bean flours with potential applications in bakery and meat products and as a protein supplement in composite marama-cereal products. / Dissertation (MSc)--University of Pretoria, 2011. / Food Science / unrestricted