title: The Flavonoid Profile of New Zealand Manuka Honey

authors: Deadman, Benjamin Jade

subjects: honey

abstract: Flavonoids are a class of natural products derived from plants which are incorporated into honeys through propolis, nectar and pollen. Research has shown that many honeys possess characteristic flavonoid profiles which can be used as markers for the geographical and floral origin of honey. The objective of this study has been to determine the flavonoid profile of New Zealand manuka (Leptospermum scoparium) honey, a honey which is internationally recognised for its unique medicinal properties. While all honeys are antibacterial due to the production of peroxides, manuka is unique because it exhibits an additional non-peroxide antibacterial activity due to high levels of methylglyoxal. The established extraction method, which utilises Amberlite XAD-2 resin to extract phenolics from honey, has been modified to permit extraction of phenolics from samples as small as five grams, with no measurable loss of extraction reproducibility. This development opens up a much larger collection of honey samples to flavonoid profiling. Measurement of the recovery rates for this extraction method has been further developed in this study in an attempt to account for the matrix effects of the high carbohydrate and phenolic acid content, relative to the flavonoids, of honey. This was achieved by extraction of flavonoid standards from an artificial honey matrix. The recovery rates of 10   6%, 16   7% and 19   9% for quercetin, chrysin and kaempferol respectively, were significantly lower than rates (28-60%) measured using the accepted procedure of extracting flavonoids from a simple solution. However, it should be noted that the recovery rates measured for extraction from solution were lower than those reported by other research groups. This has been partly attributed to an additional filtration step using a sacrificial HPLC column which was implemented to protect the analytical HPLC system from an unknown contaminant in the phenolic extracts.
Having evaluated the reproducibility and reliability of the modified extraction method, it was then applied to the analysis of 31 manuka honeys and 8 other non-manuka honeys from New Zealand. The results have shown that the honeys studied have a common flavonoid profile consisting mainly of the flavanone pinocembrin and the dihydroflavonol pinobanksin. These flavonoids are derived from propolis and are a common feature of honeys from temperate regions of the Northern Hemisphere. The manuka honeys analysed had total flavonoid content ranging between 0.59-2.24mg/100g of honey, with an average level of 1.16   0.16mg per 100g of honey. The flavonoid profile of these samples consisted mainly of pinobanksin (0.27   0.04mg/100g honey), pinocembrin (0.17   0.02mg/100g honey), luteolin (0.14   0.02mg/100g honey) and chrysin (0.13   0.02mg/100g honey), together accounting for 61% of the total flavonoid content. Manuka honey was distinguishable from the other honeys studied by its high total flavonoid content, high luteolin content (greater than 0.05mg/100g honey) and high levels of an unidentified (unknown compound 01) which was found to elute with the flavonoids on HPLC but did not appear to be a flavonoid from its UV spectrum. Statistical analysis showed that a positive correlation existed between the levels of unknown compound 01 in manuka honeys and their non-peroxide antibacterial activity. A similar correlation was also observed for luteolin. The progress of this research has been hampered by the limited range of flavonoid standards available for comparison with HPLC chromatogram peaks. A total of eight flavonoids were found in manuka honey, and a further seven in the non-manuka honeys, which did not coincide with any of the flavonoid standards available. Two of unknown flavonoids were subsequently extracted from fifteen kilograms of manuka honey using Amberlite XAD-2 resin and liquid-liquid extraction, and isolated by a combination of Sephadex-LH20 column chromatography and HPLC. Characterisation of these flavonoids was achieved using a combination of UV absorption spectroscopy, 1H, 13C and HMBC NMR spectroscopy, and LDI-TOF mass spectrometry. The isolated flavonoids were identified as pinobanksin and 8-methoxykaempferol, both flavonoids which have been previously found in honeys.

text: The Flavonoid Profile of New Zealand Manuka Honey Flavonoids are a class of natural products derived from plants which are incorporated into honeys through propolis, nectar and pollen. Research has shown that many honeys possess characteristic flavonoid profiles which can be used as markers for the geographical and floral origin of honey. The objective of this study has been to determine the flavonoid profile of New Zealand manuka (Leptospermum scoparium) honey, a honey which is internationally recognised for its unique medicinal properties. While all honeys are antibacterial due to the production of peroxides, manuka is unique because it exhibits an additional non-peroxide antibacterial activity due to high levels of methylglyoxal. The established extraction method, which utilises Amberlite XAD-2 resin to extract phenolics from honey, has been modified to permit extraction of phenolics from samples as small as five grams, with no measurable loss of extraction reproducibility. This development opens up a much larger collection of honey samples to flavonoid profiling. Measurement of the recovery rates for this extraction method has been further developed in this study in an attempt to account for the matrix effects of the high carbohydrate and phenolic acid content, relative to the flavonoids, of honey. This was achieved by extraction of flavonoid standards from an artificial honey matrix. The recovery rates of 10   6%, 16   7% and 19   9% for quercetin, chrysin and kaempferol respectively, were significantly lower than rates (28-60%) measured using the accepted procedure of extracting flavonoids from a simple solution. However, it should be noted that the recovery rates measured for extraction from solution were lower than those reported by other research groups. This has been partly attributed to an additional filtration step using a sacrificial HPLC column which was implemented to protect the analytical HPLC system from an unknown contaminant in the phenolic extracts.
Having evaluated the reproducibility and reliability of the modified extraction method, it was then applied to the analysis of 31 manuka honeys and 8 other non-manuka honeys from New Zealand. The results have shown that the honeys studied have a common flavonoid profile consisting mainly of the flavanone pinocembrin and the dihydroflavonol pinobanksin. These flavonoids are derived from propolis and are a common feature of honeys from temperate regions of the Northern Hemisphere. The manuka honeys analysed had total flavonoid content ranging between 0.59-2.24mg/100g of honey, with an average level of 1.16   0.16mg per 100g of honey. The flavonoid profile of these samples consisted mainly of pinobanksin (0.27   0.04mg/100g honey), pinocembrin (0.17   0.02mg/100g honey), luteolin (0.14   0.02mg/100g honey) and chrysin (0.13   0.02mg/100g honey), together accounting for 61% of the total flavonoid content. Manuka honey was distinguishable from the other honeys studied by its high total flavonoid content, high luteolin content (greater than 0.05mg/100g honey) and high levels of an unidentified (unknown compound 01) which was found to elute with the flavonoids on HPLC but did not appear to be a flavonoid from its UV spectrum. Statistical analysis showed that a positive correlation existed between the levels of unknown compound 01 in manuka honeys and their non-peroxide antibacterial activity. A similar correlation was also observed for luteolin. The progress of this research has been hampered by the limited range of flavonoid standards available for comparison with HPLC chromatogram peaks. A total of eight flavonoids were found in manuka honey, and a further seven in the non-manuka honeys, which did not coincide with any of the flavonoid standards available. Two of unknown flavonoids were subsequently extracted from fifteen kilograms of manuka honey using Amberlite XAD-2 resin and liquid-liquid extraction, and isolated by a combination of Sephadex-LH20 column chromatography and HPLC. Characterisation of these flavonoids was achieved using a combination of UV absorption spectroscopy, 1H, 13C and HMBC NMR spectroscopy, and LDI-TOF mass spectrometry. The isolated flavonoids were identified as pinobanksin and 8-methoxykaempferol, both flavonoids which have been previously found in honeys.

year: 2009

title: Lithostratigraphy and depositional episodes of the Oligocene carbonate-rich Tikorangi Formation, Taranaki Basin, New Zealand

authors: Hood, Steven D.

subjects: carbonate

abstract: The subsurface Oligocene Tikorangi Formation is a unique and important oil producer in the onshore Waihapa-Ngaere Field, Taranaki Basin, being the only carbonate and fracture-producing reservoir within the basin. Core sample data from seven onshore wells (foredeep megafacies) and a single offshore well (basinal megafacies) are correlated with a suite of sonic and gamma-ray geophysical well log data to derive interpretative carbonate facies for the Tikorangi Formation. Four mixed siliciclastic-carbonate to carbonate facies have been defined: facies A-calcareous siliciclastite (<25% carbonate); facies B-very calcareous siliciclastite (25-50% carbonate); facies C-muddy limestone (50-75% carbonate); and facies D-coarse limestone (>75% carbonate). Single or interbedded combinations of these facies form the basis for identifying nine major lithostratigraphic units in the Tikorangi Formation that are correlatable between the eight wells in this study.The Tikorangi Formation accumulated across a shelf-slope-basin margin within a tectonically diversified basin setting, notably involving considerable off-shelf redeposition of sediment into a bounding foredeep. Analysis of gamma, sonic, and resistivity well logs identifies five major episodes of sedimentary evolution. Episode I comprises retrogradational siliciclastic-dominated redeposited units associated with foredeep subsidence. Episode II is a continuation of episode I retrogradation, but with increased mass-redeposited carbonate influx during accelerated foredeep subsidence and relative sea-level rise, the top marking the maximum flooding surface. Episode III involves a progradational sequence comprising relatively pure redeposited carbonate units associated with declining subsidence rates and minimal siliciclastic input, with movement of facies belts basinward. Episode IV consists of prograding aggradation involving essentially static facies belts dominated by often thick, periodically mass-emplaced, carbonate-rich units separated by thin background siliciclastic shale-like units. Episode V is a retrogradational sequence marking the reintroduction of siliciclastic material into the basin following uplift of Mesozoic basement associated with accelerated compressional tectonics along the Australia-Pacific plate boundary, initially diluting and ultimately extinguishing carbonate production factories and terminating deposition of the Tikorangi Formation.

text: Lithostratigraphy and depositional episodes of the Oligocene carbonate-rich Tikorangi Formation, Taranaki Basin, New Zealand The subsurface Oligocene Tikorangi Formation is a unique and important oil producer in the onshore Waihapa-Ngaere Field, Taranaki Basin, being the only carbonate and fracture-producing reservoir within the basin. Core sample data from seven onshore wells (foredeep megafacies) and a single offshore well (basinal megafacies) are correlated with a suite of sonic and gamma-ray geophysical well log data to derive interpretative carbonate facies for the Tikorangi Formation. Four mixed siliciclastic-carbonate to carbonate facies have been defined: facies A-calcareous siliciclastite (<25% carbonate); facies B-very calcareous siliciclastite (25-50% carbonate); facies C-muddy limestone (50-75% carbonate); and facies D-coarse limestone (>75% carbonate). Single or interbedded combinations of these facies form the basis for identifying nine major lithostratigraphic units in the Tikorangi Formation that are correlatable between the eight wells in this study.The Tikorangi Formation accumulated across a shelf-slope-basin margin within a tectonically diversified basin setting, notably involving considerable off-shelf redeposition of sediment into a bounding foredeep. Analysis of gamma, sonic, and resistivity well logs identifies five major episodes of sedimentary evolution. Episode I comprises retrogradational siliciclastic-dominated redeposited units associated with foredeep subsidence. Episode II is a continuation of episode I retrogradation, but with increased mass-redeposited carbonate influx during accelerated foredeep subsidence and relative sea-level rise, the top marking the maximum flooding surface. Episode III involves a progradational sequence comprising relatively pure redeposited carbonate units associated with declining subsidence rates and minimal siliciclastic input, with movement of facies belts basinward. Episode IV consists of prograding aggradation involving essentially static facies belts dominated by often thick, periodically mass-emplaced, carbonate-rich units separated by thin background siliciclastic shale-like units. Episode V is a retrogradational sequence marking the reintroduction of siliciclastic material into the basin following uplift of Mesozoic basement associated with accelerated compressional tectonics along the Australia-Pacific plate boundary, initially diluting and ultimately extinguishing carbonate production factories and terminating deposition of the Tikorangi Formation.

year: 2003

title: Hoea te waka reo e 'Āti Rangi ē! He Kohinga Kōrero

authors: Fairhall, Tīahomarama Te Haana

subjects: Māori

abstract: He taonga tuku iho Te Reo Māori nō tāukiuki, nō tuawhakarere, nō onamata rānō, he kākano i ruia mai i Rangiātea. He taonga Te Reo Māori i raro i ngā tikanga o Te Tiriti o Waitangi, ā, nō te tau 1987 ka whakamanahia hai reo tūturu o Aotearoa. Ahakoa he reo tuku iho ki tērā whakatupuranga, ki tērā whakatupuranga, kai te tāmate te reo. He huhua noa ngā rautaki e whakarauora ai i te reo i roto i ngā kura, i ngā whānau, i ngā hapū, i ngā iwi anō hoki. 

Ko te tino o te tuhinga roa nei he āta titiro ki ngā momo rautaki a ngā uri e whakarauora nei i tō tātou reo ki roto o Ngāti Rangiwewehi kia kore ai ā mātou tamariki, ā mātou mokopuna e haere reo kore. Nō roto mai i te tuhinga nei ka āta whakatewhatewha te iwi o Ngāti Rangiwewehi o mua, kia mārama ai ki ōna āhua, ki ōna whenua, ki āna kōrero, ki ōna tāngata, ki ōna pūkōrero, ki tōna ahurei. Ka mutu, ka āta titiro, ka āta tātari, ka āta wetewete i ngā raraunga kōrero i kapo mai i ngā uiuinga, i kapo mai i ngā pātaitai, i kapo mai i ngā pukapuka kōrero ngā momo rautaki e whakarauora ai te reo o ngā uri o Ngāti Rangiwewehi. Hai āpitihanga, ka āta whakatakoto hoki i ngā piki me ngā heke o te reo ā tatauranga nei, ka kitea te ahunga mai i te wā i a koroua mā, i a kuia mā, ā, moroki noa nei.

Kai roto i ngā upoko o te tuhingaroa nei te tino ia o ngā kōrero, ā, e ono ngā upoko e whakatinana ai tēnei rangahau. Kai te upoko tuatahi e tino kōrerohia ana te iwi o Ngāti Rangiwewehi. Kātahi rā ka uru atu ki ngā whakamahukitanga o ngā mātāpono rangahau kai te upoko tuarua. Ka whakaara mai te upoko tuarua i ngā kaponga ariā me ngā rautaki reo hai tuarā mō te tuhingaroa nei. Kai te upoko tuawhā me te tuarima ngā pitopito kōrero, ngā putanga o te pākiki me ngā uiuinga. Ka mutu mai ki te upoko tuaono, ki te kupu whakamutunga o te tuhingaroa.

The Māori language is a taonga protected under the terms of Te Tiriti o Waitangi. An official language of New Zealand, since 1987. However, although a language passed down from generation to generation, the future of the language is not secure. Efforts are endless in providing many strategies of revitalization and ensuring that Te Reo Māori survives within kura, whare wānanga, whānau, hapū and iwi. The purpose of this research is to gather information pertaining to the tribe of Ngāti Rangiwewehi. This study will explore Ngāti Rangiwewehi in a traditional context, their traditional qualities and will also examine the contributions of the descendants in preserving Te Reo Māori. Furthermore, this study will also examine the ups and downs of the language and how Ngāti Rangiwewehi rates statisticaly in the national census under Te Reo Māori. This information will be gathered to examine strategy examples of Te reo that could benefit both present and future generations. As part of my research I will be interviewing key informants and conducting a survey. There are six chapters to this thesis. Chapter one is based on Ngāti Rangiwewehi as a iwi, past and present. Chapter two is based on the research methodology. Chapter three is the literature review, while Chapter four is the questionnaire. Chapter five are the interviews and lastly Chapter 6, the conclusion.

text: Hoea te waka reo e 'Āti Rangi ē! He Kohinga Kōrero He taonga tuku iho Te Reo Māori nō tāukiuki, nō tuawhakarere, nō onamata rānō, he kākano i ruia mai i Rangiātea. He taonga Te Reo Māori i raro i ngā tikanga o Te Tiriti o Waitangi, ā, nō te tau 1987 ka whakamanahia hai reo tūturu o Aotearoa. Ahakoa he reo tuku iho ki tērā whakatupuranga, ki tērā whakatupuranga, kai te tāmate te reo. He huhua noa ngā rautaki e whakarauora ai i te reo i roto i ngā kura, i ngā whānau, i ngā hapū, i ngā iwi anō hoki. 

Ko te tino o te tuhinga roa nei he āta titiro ki ngā momo rautaki a ngā uri e whakarauora nei i tō tātou reo ki roto o Ngāti Rangiwewehi kia kore ai ā mātou tamariki, ā mātou mokopuna e haere reo kore. Nō roto mai i te tuhinga nei ka āta whakatewhatewha te iwi o Ngāti Rangiwewehi o mua, kia mārama ai ki ōna āhua, ki ōna whenua, ki āna kōrero, ki ōna tāngata, ki ōna pūkōrero, ki tōna ahurei. Ka mutu, ka āta titiro, ka āta tātari, ka āta wetewete i ngā raraunga kōrero i kapo mai i ngā uiuinga, i kapo mai i ngā pātaitai, i kapo mai i ngā pukapuka kōrero ngā momo rautaki e whakarauora ai te reo o ngā uri o Ngāti Rangiwewehi. Hai āpitihanga, ka āta whakatakoto hoki i ngā piki me ngā heke o te reo ā tatauranga nei, ka kitea te ahunga mai i te wā i a koroua mā, i a kuia mā, ā, moroki noa nei.

Kai roto i ngā upoko o te tuhingaroa nei te tino ia o ngā kōrero, ā, e ono ngā upoko e whakatinana ai tēnei rangahau. Kai te upoko tuatahi e tino kōrerohia ana te iwi o Ngāti Rangiwewehi. Kātahi rā ka uru atu ki ngā whakamahukitanga o ngā mātāpono rangahau kai te upoko tuarua. Ka whakaara mai te upoko tuarua i ngā kaponga ariā me ngā rautaki reo hai tuarā mō te tuhingaroa nei. Kai te upoko tuawhā me te tuarima ngā pitopito kōrero, ngā putanga o te pākiki me ngā uiuinga. Ka mutu mai ki te upoko tuaono, ki te kupu whakamutunga o te tuhingaroa.

The Māori language is a taonga protected under the terms of Te Tiriti o Waitangi. An official language of New Zealand, since 1987. However, although a language passed down from generation to generation, the future of the language is not secure. Efforts are endless in providing many strategies of revitalization and ensuring that Te Reo Māori survives within kura, whare wānanga, whānau, hapū and iwi. The purpose of this research is to gather information pertaining to the tribe of Ngāti Rangiwewehi. This study will explore Ngāti Rangiwewehi in a traditional context, their traditional qualities and will also examine the contributions of the descendants in preserving Te Reo Māori. Furthermore, this study will also examine the ups and downs of the language and how Ngāti Rangiwewehi rates statisticaly in the national census under Te Reo Māori. This information will be gathered to examine strategy examples of Te reo that could benefit both present and future generations. As part of my research I will be interviewing key informants and conducting a survey. There are six chapters to this thesis. Chapter one is based on Ngāti Rangiwewehi as a iwi, past and present. Chapter two is based on the research methodology. Chapter three is the literature review, while Chapter four is the questionnaire. Chapter five are the interviews and lastly Chapter 6, the conclusion.

year: 2015