title: The Composition of Arylstibonic Acids

authors: Wright, Cody Elvin

subjects: Antimony

abstract: This thesis describes a detailed ESI-MS investigation into the arylstibonic acids, organo-antimony-containing compounds that are currently of interest as anticancer reagents. Four arylstibonic acids, of nominal formula RC6H4SbO3H2 [R = p-chloro-, p-tolyl-, p-nitro- and α-naphthyl-] were synthesised, and a further eight archival samples from the National Cancer Institute Repository were obtained for use in the project. Results indicate clearly that the acids exist as polyoxometalate aggregates [H8(RSb)12O28], rather than monomeric species, in both the solid state and in acetonitrile solution, thus resolving a century-old debate concerning the nature of their molecular composition. Variations in solvent, time in solution and pH have also defined the stability of these aggregates under different conditions. Synthesis of arylstibonic acids by traditional methods (pre-1940) has been shown to lead to products contaminated with cations present during their preparation. An improved method of synthesis has been devised, and the crystal structure of an intermediate in the synthesis of these acids, [C6NH6][p-O2NC6H4SbCl5], is reported. Salts of arylstibonic acids with a range of cations were investigated by ESI-MS and shown to form a diverse family of polyoxostibonates with nuclearities including Sb12, Sb14 and Sb16. Crystal structures containing some of these aggregates, verified through parallel studies with collaborators, are described. Preliminary study of mixed polyoxometalates (Sb/As) showed a strong tendency to form As4Sb2 species but these could not be fully characterised.

text: The Composition of Arylstibonic Acids This thesis describes a detailed ESI-MS investigation into the arylstibonic acids, organo-antimony-containing compounds that are currently of interest as anticancer reagents. Four arylstibonic acids, of nominal formula RC6H4SbO3H2 [R = p-chloro-, p-tolyl-, p-nitro- and α-naphthyl-] were synthesised, and a further eight archival samples from the National Cancer Institute Repository were obtained for use in the project. Results indicate clearly that the acids exist as polyoxometalate aggregates [H8(RSb)12O28], rather than monomeric species, in both the solid state and in acetonitrile solution, thus resolving a century-old debate concerning the nature of their molecular composition. Variations in solvent, time in solution and pH have also defined the stability of these aggregates under different conditions. Synthesis of arylstibonic acids by traditional methods (pre-1940) has been shown to lead to products contaminated with cations present during their preparation. An improved method of synthesis has been devised, and the crystal structure of an intermediate in the synthesis of these acids, [C6NH6][p-O2NC6H4SbCl5], is reported. Salts of arylstibonic acids with a range of cations were investigated by ESI-MS and shown to form a diverse family of polyoxostibonates with nuclearities including Sb12, Sb14 and Sb16. Crystal structures containing some of these aggregates, verified through parallel studies with collaborators, are described. Preliminary study of mixed polyoxometalates (Sb/As) showed a strong tendency to form As4Sb2 species but these could not be fully characterised.

year: 2010

title: Modeling the Neolithic Transition in Europe. Archaeobotanical Aspect of the Expansion of Neolithic Population in Europe.

authors: Ahmad, Laeeq

subjects: Neolithic Expansion in Europe

abstract: Whether or not the spread of agriculture in Europe was accompanied by movements of people is a long-standing question in archaeology and anthropology, which has been frequently addressed with the help of population genetic data.

The development and spread of agriculture across Europe is one of the most important events in human history. Studies have addressed questions regarding this Neolithic expansion from three perspectives – the flow of people, the flow of genes, and the flow of culture. Conclusions from these disparate approaches can be contradictory.
The goal of this project is to investigate the movement of the Neolithic people across Europe with respect to Archaeobotany. 

Archaeological evidence, radiocarbon dates and genetic markers are consistent with the spread of farming from a source in the Near East.
Data has been collected comprising pollen counts at layers within cores of sediment. Spatial coordinates are associated with each core, and the layers are separated according to a chronology. Identification of a strong and enduring signal of cereal pollen should indicate the arrival of Neolithic migrants to the area, bringing with them the practice of agriculture. 
I will be using a diffusion model developed by Davison et al (2006). This model takes a set of parameters and simulates the spread of a population from an original starting point, taking account of factors such as topography and geography. This model might help in the evaluation of results of the observed cereal pollen data from this study, by suggesting whether those results are sensible with respect to the underlying theory of population movement inherent in the diffusion model.

text: Modeling the Neolithic Transition in Europe. Archaeobotanical Aspect of the Expansion of Neolithic Population in Europe. Whether or not the spread of agriculture in Europe was accompanied by movements of people is a long-standing question in archaeology and anthropology, which has been frequently addressed with the help of population genetic data.

The development and spread of agriculture across Europe is one of the most important events in human history. Studies have addressed questions regarding this Neolithic expansion from three perspectives – the flow of people, the flow of genes, and the flow of culture. Conclusions from these disparate approaches can be contradictory.
The goal of this project is to investigate the movement of the Neolithic people across Europe with respect to Archaeobotany. 

Archaeological evidence, radiocarbon dates and genetic markers are consistent with the spread of farming from a source in the Near East.
Data has been collected comprising pollen counts at layers within cores of sediment. Spatial coordinates are associated with each core, and the layers are separated according to a chronology. Identification of a strong and enduring signal of cereal pollen should indicate the arrival of Neolithic migrants to the area, bringing with them the practice of agriculture. 
I will be using a diffusion model developed by Davison et al (2006). This model takes a set of parameters and simulates the spread of a population from an original starting point, taking account of factors such as topography and geography. This model might help in the evaluation of results of the observed cereal pollen data from this study, by suggesting whether those results are sensible with respect to the underlying theory of population movement inherent in the diffusion model.

year: 2013

title: E Whakatipuranga o te Tāpoi Māori - Māori Indigenous Tourism Development: A Whānau based Māori Tourism development

authors: Puriri, Ashley Reed

subjects: Maori Tourism

abstract: This Doctoral thesis uses a Kaupapa Māori research methodology, which is culturally grounded to identify the indigenous Māori underpinnings and processes that a Whānau (Māori family) experience when developing their Māori tourism business. The thesis discusses the following four issues, which are addressed using a Kaupapa Māori research methodology:
1. The gap in the current literature for Māori tourism development and authenticity from a Māori perspective.
2. The cultural underpinnings and processes of a Whānau (Māori family) tourism business.
3. Identification of the Māori cultural values that inform Māori tourism development
4. Development of a cultural framework that positions Māori values on levels of significance from a Māori perspective.
A cultural tourism experience is investigated, involving a Whānau Māori tourism business developed from a conceptual stage in preparation for financial investment. Using a Kaupapa Māori research methodology this research contributes to a gap in the academic literature relating to Whānau (Māori family) tourism development. The research contributes new academic literature to support the notion that the Whānau unit is at the core of social and economic development for Māori tourism. This thesis captures and describes the various stages, developed over a year, of Whānau Hui (family meetings), of a Whānau tourism business. As a Māori researcher, I gained emancipated access to a Whānau using Kaupapa Māori methods, applying a cultural set of protocols and values to unlock access to a Māori worldview of how a Whānau navigates the processes of developing their Whānau tourism experience in New Zealand. The engagement of a Kaupapa Māori research methodology enabled me to apply my personal skills of a lifetime of knowledge of Te Ao Māori (a Māori worldview) and Te Reo Māori (Māori language) combined with over 20 years of global advancement of indigenous tourism in the cruise industry. As a Tohunga Whakairo (master carver) I applied seven distinctive steps of a master carver’s processes in carving a Pou Tokomanawa (the main centre post of a Tipuna Whare orancestralmeeting house), providing a unique cultural process that frames the chapters of this dissertation. The research data provided an enriched flow of cultural information, which was analysed using a cultural analytical process to validate the key themes that emerged from the research findings. The cultural analyses are completed in two stages; the processes of Whakapapa and Whanaungatanga (cultural relationships), which are culturally-grounded methods for analysing research data using a Māori worldview, and the validation of cultural significance by Kaumātua (elders) of the Whānau. The thesis is imbued with cultural paradigms that frame and identify the cultural underpinnings and processes of a Whānau tourism development. The study expands on two cultural models,‘Te Tāpoi Poutama’ and Te Matua Poutama (Māori tourism frameworks for identifying cultural levels of significance) and these cultural paradigms are applied to demonstrate cultural levels of significance that a Whānau place on their proposed Māori tourism business.

text: E Whakatipuranga o te Tāpoi Māori - Māori Indigenous Tourism Development: A Whānau based Māori Tourism development This Doctoral thesis uses a Kaupapa Māori research methodology, which is culturally grounded to identify the indigenous Māori underpinnings and processes that a Whānau (Māori family) experience when developing their Māori tourism business. The thesis discusses the following four issues, which are addressed using a Kaupapa Māori research methodology:
1. The gap in the current literature for Māori tourism development and authenticity from a Māori perspective.
2. The cultural underpinnings and processes of a Whānau (Māori family) tourism business.
3. Identification of the Māori cultural values that inform Māori tourism development
4. Development of a cultural framework that positions Māori values on levels of significance from a Māori perspective.
A cultural tourism experience is investigated, involving a Whānau Māori tourism business developed from a conceptual stage in preparation for financial investment. Using a Kaupapa Māori research methodology this research contributes to a gap in the academic literature relating to Whānau (Māori family) tourism development. The research contributes new academic literature to support the notion that the Whānau unit is at the core of social and economic development for Māori tourism. This thesis captures and describes the various stages, developed over a year, of Whānau Hui (family meetings), of a Whānau tourism business. As a Māori researcher, I gained emancipated access to a Whānau using Kaupapa Māori methods, applying a cultural set of protocols and values to unlock access to a Māori worldview of how a Whānau navigates the processes of developing their Whānau tourism experience in New Zealand. The engagement of a Kaupapa Māori research methodology enabled me to apply my personal skills of a lifetime of knowledge of Te Ao Māori (a Māori worldview) and Te Reo Māori (Māori language) combined with over 20 years of global advancement of indigenous tourism in the cruise industry. As a Tohunga Whakairo (master carver) I applied seven distinctive steps of a master carver’s processes in carving a Pou Tokomanawa (the main centre post of a Tipuna Whare orancestralmeeting house), providing a unique cultural process that frames the chapters of this dissertation. The research data provided an enriched flow of cultural information, which was analysed using a cultural analytical process to validate the key themes that emerged from the research findings. The cultural analyses are completed in two stages; the processes of Whakapapa and Whanaungatanga (cultural relationships), which are culturally-grounded methods for analysing research data using a Māori worldview, and the validation of cultural significance by Kaumātua (elders) of the Whānau. The thesis is imbued with cultural paradigms that frame and identify the cultural underpinnings and processes of a Whānau tourism development. The study expands on two cultural models,‘Te Tāpoi Poutama’ and Te Matua Poutama (Māori tourism frameworks for identifying cultural levels of significance) and these cultural paradigms are applied to demonstrate cultural levels of significance that a Whānau place on their proposed Māori tourism business.

year: 2017