title: Examination of the Molecular Mass of Polyhydroxypolyamides

authors: Faville, Martyn

subjects: Polyhydroxypolyamides

abstract: The work described in this thesis investigated the use of size exclusion chromatography (SEC) to fractionate a variety of different polyhydroxypolyamide (PHPA) samples for analysis by matrix assisted laser desorption ionisation-time of flight spectrometry (MALDI-TOF). The molecular weights obtained via MALDI-TOF were then compared to those obtained by 1H nuclear magnetic resonance (NMR) end-group analysis.
Deionised water was used as the solvent for SEC fractionation using KS sugar columns KS-804 and 805 in series. An issue with PHPA is the possibility that they may hydrolyse in water and also under elevated temperature. Since deionised water was used to prepare each sample and they were run through columns which were under elevated temperatures (50˚C) hydrolysis could occur during fractionation by SEC. Through 1H NMR degradation experiments at room temperature and at 50˚C, it was observed that degradation would not be a problem.
Analysis of each PHPA sample on each KS sugar column showed fractions in the V0 region. These fractions make up the majority of the composition of unfractionated PHPA samples. There are two possible explanations for these fractions in this region, these are; 1) smaller ionised molecular weight PHPA polymers and 2) extremely high molecular weight PHPA polymer fractions. From the resulting SEC, MALDI and 1H NMR T2 relaxation rate measurements, it was concluded that these fractions are extremely high molecular weight polymer fractions.
The size of these PHPA fractions means molecular weights cannot be determined for these fractions and for unfractionated PHPA samples due to the limitations of MALDI-TOF spectrometry and 1H NMR end group analysis. However MALDI-TOF and 1H NMR end-group analysis do give good predictions for low molecular weight PHPA fractions which are in agreement with each other.

text: Examination of the Molecular Mass of Polyhydroxypolyamides The work described in this thesis investigated the use of size exclusion chromatography (SEC) to fractionate a variety of different polyhydroxypolyamide (PHPA) samples for analysis by matrix assisted laser desorption ionisation-time of flight spectrometry (MALDI-TOF). The molecular weights obtained via MALDI-TOF were then compared to those obtained by 1H nuclear magnetic resonance (NMR) end-group analysis.
Deionised water was used as the solvent for SEC fractionation using KS sugar columns KS-804 and 805 in series. An issue with PHPA is the possibility that they may hydrolyse in water and also under elevated temperature. Since deionised water was used to prepare each sample and they were run through columns which were under elevated temperatures (50˚C) hydrolysis could occur during fractionation by SEC. Through 1H NMR degradation experiments at room temperature and at 50˚C, it was observed that degradation would not be a problem.
Analysis of each PHPA sample on each KS sugar column showed fractions in the V0 region. These fractions make up the majority of the composition of unfractionated PHPA samples. There are two possible explanations for these fractions in this region, these are; 1) smaller ionised molecular weight PHPA polymers and 2) extremely high molecular weight PHPA polymer fractions. From the resulting SEC, MALDI and 1H NMR T2 relaxation rate measurements, it was concluded that these fractions are extremely high molecular weight polymer fractions.
The size of these PHPA fractions means molecular weights cannot be determined for these fractions and for unfractionated PHPA samples due to the limitations of MALDI-TOF spectrometry and 1H NMR end group analysis. However MALDI-TOF and 1H NMR end-group analysis do give good predictions for low molecular weight PHPA fractions which are in agreement with each other.

year: 2010

title: Fa’afatāmanu talafeagai mo lesona fa’asaienisi: O le tu’ualalo mo a’oga a faia’oga saienisi fa’aōliōli. A culturally appropriate formative assessment in science lessons: Implications for initial science teacher education.

authors: Lee-Hang, Desmond Mene

subjects: culturally appropriate

abstract: This study set out to find the views of Samoan teachers on formative assessment and to document any cultural aspects of the fa’aSamoa (or Samoan culture) that could hinder the use of formative assessment in science classrooms. In addition, the research was also an opportunity for professional development of teachers on doing formative assessment. The culturally constructed le-tautala or pupil silence in the classrooms that was mentioned by teachers seemed to hinder formative interactions in classrooms. Written worksheets from this study seemed to be culturally appropriate for doing formative assessment because it provided a way to overcome le-tautala, since the worksheets solicited responses from all pupils. At the same time these written formative assessment worksheets have the potential to enhance Samoan pupils learning of science concepts because of the opportunity provided for feedback and feedforward.

text: Fa’afatāmanu talafeagai mo lesona fa’asaienisi: O le tu’ualalo mo a’oga a faia’oga saienisi fa’aōliōli. A culturally appropriate formative assessment in science lessons: Implications for initial science teacher education. This study set out to find the views of Samoan teachers on formative assessment and to document any cultural aspects of the fa’aSamoa (or Samoan culture) that could hinder the use of formative assessment in science classrooms. In addition, the research was also an opportunity for professional development of teachers on doing formative assessment. The culturally constructed le-tautala or pupil silence in the classrooms that was mentioned by teachers seemed to hinder formative interactions in classrooms. Written worksheets from this study seemed to be culturally appropriate for doing formative assessment because it provided a way to overcome le-tautala, since the worksheets solicited responses from all pupils. At the same time these written formative assessment worksheets have the potential to enhance Samoan pupils learning of science concepts because of the opportunity provided for feedback and feedforward.

year: 2011

title: Reha Aperahama: a Ngati Rahiri rangatira

authors: Hart, Philip

abstract: Reha Aperahama had an illustrious whakapapa and was affiliated to several hapu. His father was notable as one of the most loyal rangatira (from the Crown’s perspective) in Hauraki, and Reha followed his lead, probably in part because of the financial rewards he received from selling land to settlers. He tried to maximize his income from this source, spending several years pleading for permission to sell his Te Kawana block (near Te Aroha). After opposing Ngati Haua ambitions to acquire the Aroha block, by 1878 he was willing to encourage road building. 
Reha was regularly before the courts because of his inability or reluctance to pay his debts, occasionally perjuring himself to avoid liability. In his later years he had little money. Despite occasionally being drunk and even violent, he was an important figure in Maori society, with a leadership role in his hapu and in the Mormon church. He was also notable for his marital complications.

text: Reha Aperahama: a Ngati Rahiri rangatira Reha Aperahama had an illustrious whakapapa and was affiliated to several hapu. His father was notable as one of the most loyal rangatira (from the Crown’s perspective) in Hauraki, and Reha followed his lead, probably in part because of the financial rewards he received from selling land to settlers. He tried to maximize his income from this source, spending several years pleading for permission to sell his Te Kawana block (near Te Aroha). After opposing Ngati Haua ambitions to acquire the Aroha block, by 1878 he was willing to encourage road building. 
Reha was regularly before the courts because of his inability or reluctance to pay his debts, occasionally perjuring himself to avoid liability. In his later years he had little money. Despite occasionally being drunk and even violent, he was an important figure in Maori society, with a leadership role in his hapu and in the Mormon church. He was also notable for his marital complications.

year: 2016