title: Isolation, Characterization and Synthesis of a Phenyl-substituted Pyrrole Isolated from the Flavonoid Fraction of Mānuka Honey

authors: Chan, Ching Wan

subjects: Mānuka Honey

abstract: Compound 1, which occurs in the flavonoid fraction of mānuka honey and showed a statistical correlation with the non-peroxide antibacterial activity of the honeys, was extracted from fifteen kilograms of mānuka honey using Amberlite XAD-2 resin and liquid-liquid extraction, and isolated by a combination of Sephadex-LH20 column chromatography and HPLC. Characterization of 1 was achieved by one and 2D- 1H and 13C NMR spectroscopy and GC-MS and 1 was identified as 2-formyl-5-(2-methoxyphenyl)-pyrrole. In addition to 1, two other non-flavonoids were isolated from the flavonoid fraction and their identities confirmed as caffeic acid and p-coumaric acid. Synthesis of 9 (3-hydroxy-1-(2-methoxyphenyl)-3-(oxazol-4-yl) propan-1-one), an intermediate in the route to 1, gave a yield of 67.5% as a pale yellow crystals after crystallization from CH2Cl2/hexane. Synthesis of 1 from 9 only resulted in barely traceable amount of 1. The dominant product after recrystallization from CH2Cl2/hexane was 10 ((E)-1-(2-methoxyphenyl)-3-(oxazol-4-yl)prop-2-en-1-one) which was the dehydrated analogue of 9. The synthesis of 1 was repeated. The product mixture was fractionated on a silica gel column, followed by two cycles of preparative layer chromatography applied to the fractions which contained 1 and yield 0.36 mg of 1 (0.00179 mmol, 0.2%).

text: Isolation, Characterization and Synthesis of a Phenyl-substituted Pyrrole Isolated from the Flavonoid Fraction of Mānuka Honey Compound 1, which occurs in the flavonoid fraction of mānuka honey and showed a statistical correlation with the non-peroxide antibacterial activity of the honeys, was extracted from fifteen kilograms of mānuka honey using Amberlite XAD-2 resin and liquid-liquid extraction, and isolated by a combination of Sephadex-LH20 column chromatography and HPLC. Characterization of 1 was achieved by one and 2D- 1H and 13C NMR spectroscopy and GC-MS and 1 was identified as 2-formyl-5-(2-methoxyphenyl)-pyrrole. In addition to 1, two other non-flavonoids were isolated from the flavonoid fraction and their identities confirmed as caffeic acid and p-coumaric acid. Synthesis of 9 (3-hydroxy-1-(2-methoxyphenyl)-3-(oxazol-4-yl) propan-1-one), an intermediate in the route to 1, gave a yield of 67.5% as a pale yellow crystals after crystallization from CH2Cl2/hexane. Synthesis of 1 from 9 only resulted in barely traceable amount of 1. The dominant product after recrystallization from CH2Cl2/hexane was 10 ((E)-1-(2-methoxyphenyl)-3-(oxazol-4-yl)prop-2-en-1-one) which was the dehydrated analogue of 9. The synthesis of 1 was repeated. The product mixture was fractionated on a silica gel column, followed by two cycles of preparative layer chromatography applied to the fractions which contained 1 and yield 0.36 mg of 1 (0.00179 mmol, 0.2%).

year: 2011

title: Late Miocene turnover of molluscan faunas, New Zealand: Taxonomic and ecological reassessment of diversity changes at multiple spatial and temporal scales

authors: Hendy, Austin J.W.

subjects: diversity

abstract: Previous estimates of molluscan biodiversity during the Neogene in New Zealand have revealed a pattern of significant diversity decline during the latest Miocene. This study uses an occurrence-based dataset (derived from published literature) to examine this pattern in further detail with both traditional synoptic measures and subsequent sampling standardization. Synoptic analyses of regional-scale data reveal diversity trajectories similar to those previously established, and rarefaction techniques demonstrate that the inferred pattern of Late Miocene diversity decline and Early Pliocene rebound is only somewhat biased by variations in sampling intensity. The pattern is also affected by temporal variations in the preservation of shelf paleoenvironments, with representation of highly diverse shallow-water facies varying considerably between biostratigraphic stages. The sampling and corresponding synoptic genus richness of biogeographic areas within the New Zealand region is also uneven. Within a single sedimentary basin sampled at high temporal resolution (Wanganui Basin), new data suggest that Late Miocene faunas were as diverse as those of the Early Pliocene, contrasting with the pattern of diversity decrease and subsequent increase observed at the regional spatial scale in prior studies. However, an ecological analysis of the new data demonstrates that turnover and restructuring of benthic communities did take place at the end of the Late Miocene. These findings suggest that spatial scale and temporal resolution are important considerations in determining the magnitude of diversity and ecological change observed in paleontologic studies. Contemporaneous biodiversity may not be similarly expressed at varying spatial or temporal scales in the fossil record. Rather, regional patterns of diversity change are governed by a complex interplay of not only large-scale environmental factors (e.g. temperature control), but also independent basin-scale processes (e.g. basin subsidence) and local sampling intensity.

text: Late Miocene turnover of molluscan faunas, New Zealand: Taxonomic and ecological reassessment of diversity changes at multiple spatial and temporal scales Previous estimates of molluscan biodiversity during the Neogene in New Zealand have revealed a pattern of significant diversity decline during the latest Miocene. This study uses an occurrence-based dataset (derived from published literature) to examine this pattern in further detail with both traditional synoptic measures and subsequent sampling standardization. Synoptic analyses of regional-scale data reveal diversity trajectories similar to those previously established, and rarefaction techniques demonstrate that the inferred pattern of Late Miocene diversity decline and Early Pliocene rebound is only somewhat biased by variations in sampling intensity. The pattern is also affected by temporal variations in the preservation of shelf paleoenvironments, with representation of highly diverse shallow-water facies varying considerably between biostratigraphic stages. The sampling and corresponding synoptic genus richness of biogeographic areas within the New Zealand region is also uneven. Within a single sedimentary basin sampled at high temporal resolution (Wanganui Basin), new data suggest that Late Miocene faunas were as diverse as those of the Early Pliocene, contrasting with the pattern of diversity decrease and subsequent increase observed at the regional spatial scale in prior studies. However, an ecological analysis of the new data demonstrates that turnover and restructuring of benthic communities did take place at the end of the Late Miocene. These findings suggest that spatial scale and temporal resolution are important considerations in determining the magnitude of diversity and ecological change observed in paleontologic studies. Contemporaneous biodiversity may not be similarly expressed at varying spatial or temporal scales in the fossil record. Rather, regional patterns of diversity change are governed by a complex interplay of not only large-scale environmental factors (e.g. temperature control), but also independent basin-scale processes (e.g. basin subsidence) and local sampling intensity.

year: 2009

title: Visitors' satisfaction with heritage sites in New Zealand: Causes and complexities, clusters and causes

authors: Trinh, Thi Thu

subjects: Heritage Tourism

abstract: The thesis presents findings from a survey of over 1,000 visitors at three New Zealand heritage sites. These sites were Te Puia, the Rotorua Bathhouse Museum and the Rangiriri Battlefield Interpretation Centre. All three represent a key period in New Zealand’s history from the period of approximately 1840 to 1900, but in the case of Te Puia there is also a continuing contemporary cultural importance. This last site, located in Rotorua, was founded as the Maori Arts and Crafts Institute and was established to perpetuate Maori tradition skills in areas such as carving and weaving. Its location was in part determined by the volcanic nature of the valley, long inhabited by members of Te Arawa tribal people. The site has a strong connection with tourism as Te Arawa have entertained tourists from the mid-nineteenth century in the volcanic area. The site therefore represents a tourism site from the perspective of history, culture and natural heritage. The Bathhouse Museum represents a period of late colonial architecture while the third site, the Rangiriri Battlefield is based on the remnants of the Pa (Maori fortifications) that was the site of a battle between the colonial government forces and the Maori Kingi movement on November 23rd 1840.

The motive for the research was to provide a profile of visitors for the respective sites and their management, and then to assess to what degree socio-demographics might be explanatory variables in determining future visitation. The core theories being employed revolved around concepts of levels of interest in heritage and historic sites, the intellectual search for knowledge, and the degree to which people became involved in the activity of heritage site visitation. The work was driven by the finding that only about 11 per cent of visits to cultural tourism sites were ‘purposeful’ tourists as defined by McKercher and Du Cros (2002). Being purposeful implies having specific degrees of interest, of becoming involved and possibly seeking meanings that implied senses of identity. That is, self-awareness accrued from having a better understanding of the past as a means of knowing about the present. This conceptualisation implies use of the theories of involvement, benefits and self-awareness, and the managerial aspects of interpretation.  Normally such an approach has been seen by many researchers as a determinant of satisfaction, but in this thesis satisfaction is not seen as simply an end to a process. Rather, this thesis argues that to be satisfied entails not only cognitive and affective components, but also the conative. That conative component can include making recommendations to others, making visits to other heritage sites, or joining organisations associated with heritage sites such as the New Zealand Historic Place Trust. These form key themes in the literature review.

Unfortunately, while these premises emerged from the literature review and informed the hypotheses that are later described in the thesis, they were not wholly supported by the data. It is suggested that one reason for this, from a statistical perspective, was that measures used were subject to multi-collinearity and auto-correlation – put simply, many of the variables are not independent from each other. For example, it is suggested that satisfaction is actually enhanced by subsequently being able to make recommendations to friends and others; that the act of making a recommendation enhances one’s own self in both the eyes of that friend or through an enhanced self- perception of being helpful, and thus auto-correlation may exist between these variables.

This realisation thus leads, in the conclusions of Chapter Eight, to new suggestions for potential future researchers concerning ways of looking at the nature of involvement that draw on distinctions between situational and enduring involvement. Finally, it also needs to be noted that tourists are not lay historians, but are the makers of their holidays, and hence the debate is contextualised within the act of being on holiday, which itself is a period of escape and relaxation for many. Hence the relationships being examined in this thesis are complex, interactive and yet rewarding to untangle.

text: Visitors' satisfaction with heritage sites in New Zealand: Causes and complexities, clusters and causes The thesis presents findings from a survey of over 1,000 visitors at three New Zealand heritage sites. These sites were Te Puia, the Rotorua Bathhouse Museum and the Rangiriri Battlefield Interpretation Centre. All three represent a key period in New Zealand’s history from the period of approximately 1840 to 1900, but in the case of Te Puia there is also a continuing contemporary cultural importance. This last site, located in Rotorua, was founded as the Maori Arts and Crafts Institute and was established to perpetuate Maori tradition skills in areas such as carving and weaving. Its location was in part determined by the volcanic nature of the valley, long inhabited by members of Te Arawa tribal people. The site has a strong connection with tourism as Te Arawa have entertained tourists from the mid-nineteenth century in the volcanic area. The site therefore represents a tourism site from the perspective of history, culture and natural heritage. The Bathhouse Museum represents a period of late colonial architecture while the third site, the Rangiriri Battlefield is based on the remnants of the Pa (Maori fortifications) that was the site of a battle between the colonial government forces and the Maori Kingi movement on November 23rd 1840.

The motive for the research was to provide a profile of visitors for the respective sites and their management, and then to assess to what degree socio-demographics might be explanatory variables in determining future visitation. The core theories being employed revolved around concepts of levels of interest in heritage and historic sites, the intellectual search for knowledge, and the degree to which people became involved in the activity of heritage site visitation. The work was driven by the finding that only about 11 per cent of visits to cultural tourism sites were ‘purposeful’ tourists as defined by McKercher and Du Cros (2002). Being purposeful implies having specific degrees of interest, of becoming involved and possibly seeking meanings that implied senses of identity. That is, self-awareness accrued from having a better understanding of the past as a means of knowing about the present. This conceptualisation implies use of the theories of involvement, benefits and self-awareness, and the managerial aspects of interpretation.  Normally such an approach has been seen by many researchers as a determinant of satisfaction, but in this thesis satisfaction is not seen as simply an end to a process. Rather, this thesis argues that to be satisfied entails not only cognitive and affective components, but also the conative. That conative component can include making recommendations to others, making visits to other heritage sites, or joining organisations associated with heritage sites such as the New Zealand Historic Place Trust. These form key themes in the literature review.

Unfortunately, while these premises emerged from the literature review and informed the hypotheses that are later described in the thesis, they were not wholly supported by the data. It is suggested that one reason for this, from a statistical perspective, was that measures used were subject to multi-collinearity and auto-correlation – put simply, many of the variables are not independent from each other. For example, it is suggested that satisfaction is actually enhanced by subsequently being able to make recommendations to friends and others; that the act of making a recommendation enhances one’s own self in both the eyes of that friend or through an enhanced self- perception of being helpful, and thus auto-correlation may exist between these variables.

This realisation thus leads, in the conclusions of Chapter Eight, to new suggestions for potential future researchers concerning ways of looking at the nature of involvement that draw on distinctions between situational and enduring involvement. Finally, it also needs to be noted that tourists are not lay historians, but are the makers of their holidays, and hence the debate is contextualised within the act of being on holiday, which itself is a period of escape and relaxation for many. Hence the relationships being examined in this thesis are complex, interactive and yet rewarding to untangle.

year: 2013