Thesis--University of Helsinki, 1991. / Includes bibliographical references.

Thesis--University of Helsinki, 1991. / Includes bibliographical references.

Thesis (Ph. D.)--University of Canterbury, 2006. / Typescript (photocopy). Includes bibliographical references (p. 155-178). Also available via the World Wide Web.

Thesis (M. For. Sc.)--University of Canterbury, 2006. / Typescript (photocopy). "August 2006." Includes bibliographical references (leaves 101-114). Also available via the World Wide Web.

Memoria para optar al Título Profesional de Ingeniero Foresta

Memoria para optar al Título Profesional de Ingeniero Forestal

Memoria para optar al Título Profesional de Ingeniero de la Madera

South Africa lags behind the rest of the world with regard to the availability of allometric biomass information. There is a complete lack of site specific allometric data for Pinus radiata in the southern Cape region, impeding investment in the renewable energy sector. This shortcoming was addressed by developing up-scalable, single tree biomass models. These models quantify the aboveground biomass of rotation age P. radiata grown in the southern Cape across a range of site conditions. The models use diameter at breast height (DBH) to predict the aboveground component biomass. A nutrient loss risk potential was assigned to each biomass component. Nineteen trees were destructively harvested using a full fresh weight sampling approach. Basic density was determined using a water displacement method, while Newton’s volume equation was used for stemwood volume determination. Log linear models were simultaneously regressed through seemingly unrelated regression (SUR) using the “Systemfit” R statistical package to force component additivity. A categorical variable was applied to the models, grouping the data into two Site Index (SI) based categories, namely “Low” SI and “Medium to High” SI, to account for inter-site variability. The corrected Akaike Information Criteria (AICc) and coefficient of determination (R2) was used to determine the goodness of fit of the models. The McElroy R2 for the SUR system was 0.95. Biomass models were developed that are able to predict various tree component masses at high levels of certainty within site and stand attribute ranges similar to this study. The importance of accurate, site specific wood basic density was demonstrated by its substantial weighting on stem and hence total biomass. Results showed that the stemwood mean basic density range was between 503 kg m-3 and 517 kg m-3 for the “Low” SI sites and 458 kg m-3 for the “Medium to High” SI sites. Site quality can have a major impact on the models, particularly on poorer sites where stemwood production is proportionally less than other tree components. Total aboveground biomass was estimated to range between 58.61 odt ha-1 and 70.85 odt ha-1 for “Low” SI sites, and 185.31 odt ha-1 to 266.58 odt ha-1 for “Medium to High” SI sites. Stemwood biomass accounted for 65% of the total aboveground biomass for “Low” SI sites and 70% for “Medium to High” SI sites.

>Magister Scientiae - MSc / Due to the negative impact on the environment and the associated biological risks on human and animal life, the need for eco-friendly synthetic protocols is critical. With the rapid advancement in nanotechnology, this extends to the synthesis of nanomaterials. Eco-friendly nanoparticle synthesis protocols have led to the use of fungi, plants and other biological substances, due to their remarkable ability in reducing metal ions. This led to the formation of very efficient hybrid catalysts, which are partially organic/inorganic composites. Palladium nanoparticles have drawn much interest due to its potential in catalytic applications and in photovoltaic cell development. In this study, the brown marine algae, Ecklonia radiata, was employed as a putative palladium nanoparticle bioreactor. Aqueous extracts of the algae were used as a supporting matrix for the synthesis of palladium nanoparticle (AE-PdNPs) catalysts according to the principles of green chemistry. The catalysts were then assessed for their capability in various carbon-carbon coupling reactions such as Suzuki-Miyaura, Sonogashira, and Heck coupling reactions. Selectivity studies were also performed. The PdNPs were compared to “model” polyvinylpyrrolidone palladium nanoparticles (PVP-PdNPs), synthesized according to literature methods. A variety of spectroscopic techniques were used to characterize the nanoparticles and the organic reaction products, including HRTEM, EDX, NMR, FTIR, DLS, TGA, UV-Vis, ICP-AES, GC-MS and XRD spectroscopy. qNMR was used to determine the product % yields. The aqueous extracts were characterised using NMR and a variety of assays, including total antioxidant potential, total reducing power and radical scavenging ability) to assess its ability to reduce the Pd metal salt. 2D NMR revealed polysaccharides and polyphenols to be the major and minor components, respectively, present in the extract. HRTEM images revealed the average size of the AE-PdNPs and PVP-PdNPs to be 12 nm and 8 nm, respectively. The images also showed the shapes of the NPs to be cubic for the AE-PdNPs and cubic or triangular for the PVP-PdNPs. SAED and XRD spectroscopy revealed the face-centred cubic phase and polycrystalline nature of the AE-PdNPs. No reliable data, other than the HRTEM images was obtained for the PVP-PdNPs. Zeta potential and DLS measurements confirmed the negative charge present on the surface of the nanoparticles, while the hydrodynamic radii were found to be 65 nm and 99 nm for the AE- and PVP-PdNPs, respectively, substantiating the presence of the capping agents. ICP-AES analysis revealed the Pd content of the NPs to be 48.8 and 28.9 ppm for the AE- and PVP-PdNPs. Following characterization, the PdNPs were assessed as potential catalysts in the Suzuki-Miyaura, Heck and Sonogashira carbon-carbon coupling reactions. Bromo and iodo substrates were employed, together with sterically hindered substrates, with a nitro moiety in the ortho or para positions. For the Suzuki-Miyaura reactions, both sets of PdNPs revealed slightly higher yields for the products synthesized using the bromo substrate (>90%), while low yields (40 – 55% yields) were obtained for the ortho substituted substrate in comparison to the para substrate (>90% yields). The Heck coupling reactions with butyl acrylate and 4-iodoacetphenone were successful (~70% yields), while reactions with 4-bromoacetophenone failed. However, the Sonogashira couplings did not proceed at all. With the series of reactions NPs showed some selectivity, with the AE-PdNPs consistently producing higher yields for the products obtained. This may be due to overall nature of the NPs, or due to the higher platinum loading content for the AE-PdNPs.

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