title: Applications of Hydroxymethylphosphines

authors: Wyllie, Megan Jane

subjects: Hydroxymethylphosphine

abstract: Hydroxymethylphosphines are compounds containing P-CH₂-OH functional groups. They have numerous applications, of which three types were explored in this project.
The cross-linking ability of tris(hydroxymethyl)phosphine (THP) was investigated for use as a fixative for biological samples for visualisation by scanning electron microscopy (SEM). THP has similar cross-linking ability to glutaraldehyde, the most commonly used fixative for SEM samples. Samples fixed with THP were compared with samples fixed with glutaraldehyde and an unfixed sample, under the SEM. THP appears to have a similar effect on the preservation of the samples, and seems to be successful as a fixative.
The bonding between Ph₂P(S)CH₂OH and diiodine was investigated. The resulting adduct was unable to be crystallised. It was partially characterised by ³¹P NMR and IR spectroscopy. The related compound, Ph₃PS.I₂ was synthesised successfully and characterised by ³¹P NMR and IR spectroscopy.
The ability of THP to immobilise compounds to solid supports, in the interest of immobilising fluorescent compounds was investigated. THP was used to immobilise N-(2-aminoethyl)-1,8-naphthalimide onto aminopropyl silica, and analysed under UV light. The resulting solid however, fluoresced only slightly. The reaction between Ph₂P(CH₂OH) ₂Cl and N-(2-aminoethyl)-1,8-naphthalimide was also investigated, but the product was unable to be crystallised.

text: Applications of Hydroxymethylphosphines Hydroxymethylphosphines are compounds containing P-CH₂-OH functional groups. They have numerous applications, of which three types were explored in this project.
The cross-linking ability of tris(hydroxymethyl)phosphine (THP) was investigated for use as a fixative for biological samples for visualisation by scanning electron microscopy (SEM). THP has similar cross-linking ability to glutaraldehyde, the most commonly used fixative for SEM samples. Samples fixed with THP were compared with samples fixed with glutaraldehyde and an unfixed sample, under the SEM. THP appears to have a similar effect on the preservation of the samples, and seems to be successful as a fixative.
The bonding between Ph₂P(S)CH₂OH and diiodine was investigated. The resulting adduct was unable to be crystallised. It was partially characterised by ³¹P NMR and IR spectroscopy. The related compound, Ph₃PS.I₂ was synthesised successfully and characterised by ³¹P NMR and IR spectroscopy.
The ability of THP to immobilise compounds to solid supports, in the interest of immobilising fluorescent compounds was investigated. THP was used to immobilise N-(2-aminoethyl)-1,8-naphthalimide onto aminopropyl silica, and analysed under UV light. The resulting solid however, fluoresced only slightly. The reaction between Ph₂P(CH₂OH) ₂Cl and N-(2-aminoethyl)-1,8-naphthalimide was also investigated, but the product was unable to be crystallised.

year: 2015

title: Robust regression for highly corrupted response by shifting outliers

authors: Jung, Yoonsuh

abstract: Outlying observations are often disregarded at the sacrifice of degrees of freedom or downsized via robust loss functions (e.g., Huber's loss) to reduce the undesirable impact on data analysis. In this article, we treat the outlying status of each observation as a parameter and propose a penalization method to automatically adjust the outliers. The proposed method shifts the outliers towards the fitted values, while preserve the non-outlying observations. We also develop a generally applicable algorithm in the iterative fashion to estimate model parameters and demonstrate the connection with the maximum likelihood based estimation procedure in the case of least squares estimation. We establish asymptotic property of the resulting parameter estimators under the condition that the proportion of outliers does not vanish as sample size increases. We apply the proposed outlier adjustment method to ordinary least squares and lasso-type penalization procedure and demonstrate its empirical value via numeric studies. Furthermore, we study applicability of the proposed method to two robust estimators, Huber's robust estimator and Huberized lasso, and demonstrate its noticeable improvement of model fit in the presence of extremely large outliers.

text: Robust regression for highly corrupted response by shifting outliers Outlying observations are often disregarded at the sacrifice of degrees of freedom or downsized via robust loss functions (e.g., Huber's loss) to reduce the undesirable impact on data analysis. In this article, we treat the outlying status of each observation as a parameter and propose a penalization method to automatically adjust the outliers. The proposed method shifts the outliers towards the fitted values, while preserve the non-outlying observations. We also develop a generally applicable algorithm in the iterative fashion to estimate model parameters and demonstrate the connection with the maximum likelihood based estimation procedure in the case of least squares estimation. We establish asymptotic property of the resulting parameter estimators under the condition that the proportion of outliers does not vanish as sample size increases. We apply the proposed outlier adjustment method to ordinary least squares and lasso-type penalization procedure and demonstrate its empirical value via numeric studies. Furthermore, we study applicability of the proposed method to two robust estimators, Huber's robust estimator and Huberized lasso, and demonstrate its noticeable improvement of model fit in the presence of extremely large outliers.

year: 2016-01-22

title: Ko Te Kawa Tūpanapana i ngā Hau Tūpua a Tāwhiri-mātea : The validation, revitalisation and enhancement of Māori environment knowledge of weather and climate

authors: Skipper, Apanui Sonny

subjects: Maori Environmental knowledge

abstract: KO TE KAWA TŪPANAPANA I NGĀ HAU TŪPUA A TĀWHIRI-MĀTEA – THE RITUALISTIC FORMS GOVERNING THE SUPERNATURAL WINDS OF TĀWHIRI-MĀTEA
Mankind has always gazed skyward observing the im immense power generated by forked lightning when it strikes the land. The resounding thunder booming across the landscape never failed to capture the awe and imagination of a people. Māori were no different. The legacy of their Polynesian ancestors, who populated most of the Islands of Te Moana-nui-a-Kiwa, the largest ocean on the planet, based on belief, courage, and navigational expertise, honed over many millenia, reached Aotearoa approximately in the 12 century. These highly skilled ancestors from the tropics applied a formalised process of settling a new land. It also required their own weatherlore to be recalibrated to the local conditions, in order to survive in a much harsher, colder climate.

Over the centuries the descendants of these early Polynesian settlers, developed an extensive localised knowledge of weather, climate, and seasonal indicators to accurately predict daily weather, monthly or annual climate conditions. The ongoing lessons learned especially after experiencing a fatality were incorporated into cultural practices of important everyday activities such as ahuwhenua, te mahi hī ika, kohi rongoā, whakaako tamariki, gathering pounamu, whakatū rāhui, and kaitiakitanga, in order to minimise further loss of life.

Formal recognition of these contributions was made at the inaugural Māori Climate Forum in Wellington in 2003, where a number of Māori elders highlighted the importance of giving a greater account of Māori knowledge of environmental change. Among the many priorities identified for research at this forum, an opportunity based on a challenge from a Māori elder led to the development of a pilot project to explore traditional Māori understandings of weather–climate variability and change. 

One of the key outcomes from this work was the identification of Māori environmental indicators to anticipate local weather and climate conditions and thereby manage the risk associated with weather-climate extremes. However, in spite of the work achieved, there remain unanswered questions about the use and ongoing efficacy of environmental indicators to forecast and monitor weather and climate risks, including how new opportunities might be created to promote learning about subtle signals in nature that can reveal much about changes in weather and climate conditions. 

Due to the fact that many of the elders that provided the basis of this thesis have passed away, a great sense of responsibility has remained with me to complete this research. To identify the gaps in the previous research, to ground-truth it, to consolidate and carefully document the level of localised environmental knowledge of weather and climate specifically with iwi from Tainui-Hauraki, Te Whānau-a-Apanui, and Ngāi Tahu. A total of 56 interviews and 17 group wānanga were conducted during 2009-2016. Examples of Māori Environmental Knowledge were also sourced from numerous personal conversations with knowledge holders from 1989-2003, adding to the body of knowledge that was analysed to provide further context. A conceptual framework coined `Ngā Whenu Tapu e Waru’ was created from identifying the key themes of the interviews to inform how Māori Environmental Knowledge was described in the three regions. This study has yielded understandings of wind, rain, thunder, lightning, and cloud classifications; weather and climate indicators; spiritual signs of misfortune and death; memory techniques; longitudinal weather predictions, and lunar calendars in each region.

This thesis is underpinned by a Kaupapa Māori theory and research methodology that links to a body of transformative research and literature conducted by Māori scholars based on the knowledge and experience of tūpuna  Māori. 

Heoti anō rā kei ngā kākahi whakairoiro, kei ngā matataiko, nau piki mai, nau kake mai ki tēnei wānanga nui whakaharahara.

text: Ko Te Kawa Tūpanapana i ngā Hau Tūpua a Tāwhiri-mātea : The validation, revitalisation and enhancement of Māori environment knowledge of weather and climate KO TE KAWA TŪPANAPANA I NGĀ HAU TŪPUA A TĀWHIRI-MĀTEA – THE RITUALISTIC FORMS GOVERNING THE SUPERNATURAL WINDS OF TĀWHIRI-MĀTEA
Mankind has always gazed skyward observing the im immense power generated by forked lightning when it strikes the land. The resounding thunder booming across the landscape never failed to capture the awe and imagination of a people. Māori were no different. The legacy of their Polynesian ancestors, who populated most of the Islands of Te Moana-nui-a-Kiwa, the largest ocean on the planet, based on belief, courage, and navigational expertise, honed over many millenia, reached Aotearoa approximately in the 12 century. These highly skilled ancestors from the tropics applied a formalised process of settling a new land. It also required their own weatherlore to be recalibrated to the local conditions, in order to survive in a much harsher, colder climate.

Over the centuries the descendants of these early Polynesian settlers, developed an extensive localised knowledge of weather, climate, and seasonal indicators to accurately predict daily weather, monthly or annual climate conditions. The ongoing lessons learned especially after experiencing a fatality were incorporated into cultural practices of important everyday activities such as ahuwhenua, te mahi hī ika, kohi rongoā, whakaako tamariki, gathering pounamu, whakatū rāhui, and kaitiakitanga, in order to minimise further loss of life.

Formal recognition of these contributions was made at the inaugural Māori Climate Forum in Wellington in 2003, where a number of Māori elders highlighted the importance of giving a greater account of Māori knowledge of environmental change. Among the many priorities identified for research at this forum, an opportunity based on a challenge from a Māori elder led to the development of a pilot project to explore traditional Māori understandings of weather–climate variability and change. 

One of the key outcomes from this work was the identification of Māori environmental indicators to anticipate local weather and climate conditions and thereby manage the risk associated with weather-climate extremes. However, in spite of the work achieved, there remain unanswered questions about the use and ongoing efficacy of environmental indicators to forecast and monitor weather and climate risks, including how new opportunities might be created to promote learning about subtle signals in nature that can reveal much about changes in weather and climate conditions. 

Due to the fact that many of the elders that provided the basis of this thesis have passed away, a great sense of responsibility has remained with me to complete this research. To identify the gaps in the previous research, to ground-truth it, to consolidate and carefully document the level of localised environmental knowledge of weather and climate specifically with iwi from Tainui-Hauraki, Te Whānau-a-Apanui, and Ngāi Tahu. A total of 56 interviews and 17 group wānanga were conducted during 2009-2016. Examples of Māori Environmental Knowledge were also sourced from numerous personal conversations with knowledge holders from 1989-2003, adding to the body of knowledge that was analysed to provide further context. A conceptual framework coined `Ngā Whenu Tapu e Waru’ was created from identifying the key themes of the interviews to inform how Māori Environmental Knowledge was described in the three regions. This study has yielded understandings of wind, rain, thunder, lightning, and cloud classifications; weather and climate indicators; spiritual signs of misfortune and death; memory techniques; longitudinal weather predictions, and lunar calendars in each region.

This thesis is underpinned by a Kaupapa Māori theory and research methodology that links to a body of transformative research and literature conducted by Māori scholars based on the knowledge and experience of tūpuna  Māori. 

Heoti anō rā kei ngā kākahi whakairoiro, kei ngā matataiko, nau piki mai, nau kake mai ki tēnei wānanga nui whakaharahara.

year: 2020