title: Preparation and characterisation of decoloured Novatein and modified PLA blends

authors: Izuchukwu, Sandra C.P.

abstract: Modified Poly (lactic acid) (PLA) was blended with Decoloured Novatein® (DNTP), a thermoplastic protein material using reactive extrusion to produce a degradable material with improved properties compared to neat Decoloured Novatein®. PLA was modified through free radical grafting of itaconic anhydride to create reactive side-chain groups. Varying ratios of DNTP/ PLA-g-IA or PLA were prepared. Blending DNTP with PLA was found to increase tensile strength  between 22% to 538% and modulus between 201 GPa to 3193 GPa, whereas the strain at break decreased between 80% to 94% depending on the blend ratio. The glass transition temperature of the blends which was measured as the tan δ peak, also revealed an increase when compared to neat DNTP.  Scanning electron microscope revealed an enhanced interfacial adhesion between the two phases in the blends with PLA-g-IA suggesting a more homogenous microstructure. WAXS result revealed an insignificant decrease in the crystallinity of the blends compared to neat DNTP, indicating that blending with PLA had no structural effect on DNTP. The results show the possibility and feasibility of blending DNTP with PLA for use in agricultural and packaging applications.

text: Preparation and characterisation of decoloured Novatein and modified PLA blends Modified Poly (lactic acid) (PLA) was blended with Decoloured Novatein® (DNTP), a thermoplastic protein material using reactive extrusion to produce a degradable material with improved properties compared to neat Decoloured Novatein®. PLA was modified through free radical grafting of itaconic anhydride to create reactive side-chain groups. Varying ratios of DNTP/ PLA-g-IA or PLA were prepared. Blending DNTP with PLA was found to increase tensile strength  between 22% to 538% and modulus between 201 GPa to 3193 GPa, whereas the strain at break decreased between 80% to 94% depending on the blend ratio. The glass transition temperature of the blends which was measured as the tan δ peak, also revealed an increase when compared to neat DNTP.  Scanning electron microscope revealed an enhanced interfacial adhesion between the two phases in the blends with PLA-g-IA suggesting a more homogenous microstructure. WAXS result revealed an insignificant decrease in the crystallinity of the blends compared to neat DNTP, indicating that blending with PLA had no structural effect on DNTP. The results show the possibility and feasibility of blending DNTP with PLA for use in agricultural and packaging applications.

year: 2017

title: Regioisomeric preferences in the orthomanganation of meta-substituted acetophenones and isopropyl benzoates, and application of iodo-demanganation with iodine chloride to the synthesis of 2-iodo-3-O-substituted and other ortho-iodo arylcarbonyl compounds

authors: Cooney, Janine M.

subjects: Manganese

abstract: Synthesis is reported of regioisomeric ortho-[Mn(CO)4] derivatives of aryl ketones (2-chlorothioxanthen-9-one and 3′,4′-methylenedioxyacetophenone) and esters (isopropyl 3-methoxy- and 3-acetoxy-benzoate), as well as of the single ortho-[Mn(CO)4] products from methyl 4-methoxy- and 3,5-dimethoxy-benzoate. Factors influencing the preference for manganation at the crowded positions ortho to the C=O in meta-substituted aryl ketones and esters are considered. The frequency of the lowest energy metal carbonyl stretching mode is useful in the structural assignment of the regioisomers. Isopropyl 2-iodo-3-methoxy- and 2-iodo-3-acetoxy-benzoates are obtained by reaction of iodine chloride to replace the Mn(CO)4 group at the crowded 2-position of the corresponding orthomanganated 3-O-substituted benzoate esters. ortho-Iodoacetophenones were prepared likewise, without α-iodination, some with iodine in crowded positions (2′-iodo-3′-methoxy-, -3′,4′-methylenedioxy- and -3′,4′,5′-trimethoxy-acetophenone), others with O-protected 2′-hydroxy groups (2′-benzyloxy- and 2′-t-butyldimethylsilyloxy-3′,4′-dimethoxy-6′-iodobenzene and 2′-t-butyldimethylsiloxy-6′-iodobenzene). Potential general synthetic routes to derivatives of 2-iodo-3-hydroxy-, 2-iodo-3,4-dihydroxy-, and 2-iodo-6-hydroxy-aryl carbonyl compounds are indicated. The corresponding routes to 3-iodo-4-acetyl-2,5-dimethylthiophene and 3-iodo-2-acetylthiophene are also reported.

text: Regioisomeric preferences in the orthomanganation of meta-substituted acetophenones and isopropyl benzoates, and application of iodo-demanganation with iodine chloride to the synthesis of 2-iodo-3-O-substituted and other ortho-iodo arylcarbonyl compounds Synthesis is reported of regioisomeric ortho-[Mn(CO)4] derivatives of aryl ketones (2-chlorothioxanthen-9-one and 3′,4′-methylenedioxyacetophenone) and esters (isopropyl 3-methoxy- and 3-acetoxy-benzoate), as well as of the single ortho-[Mn(CO)4] products from methyl 4-methoxy- and 3,5-dimethoxy-benzoate. Factors influencing the preference for manganation at the crowded positions ortho to the C=O in meta-substituted aryl ketones and esters are considered. The frequency of the lowest energy metal carbonyl stretching mode is useful in the structural assignment of the regioisomers. Isopropyl 2-iodo-3-methoxy- and 2-iodo-3-acetoxy-benzoates are obtained by reaction of iodine chloride to replace the Mn(CO)4 group at the crowded 2-position of the corresponding orthomanganated 3-O-substituted benzoate esters. ortho-Iodoacetophenones were prepared likewise, without α-iodination, some with iodine in crowded positions (2′-iodo-3′-methoxy-, -3′,4′-methylenedioxy- and -3′,4′,5′-trimethoxy-acetophenone), others with O-protected 2′-hydroxy groups (2′-benzyloxy- and 2′-t-butyldimethylsilyloxy-3′,4′-dimethoxy-6′-iodobenzene and 2′-t-butyldimethylsiloxy-6′-iodobenzene). Potential general synthetic routes to derivatives of 2-iodo-3-hydroxy-, 2-iodo-3,4-dihydroxy-, and 2-iodo-6-hydroxy-aryl carbonyl compounds are indicated. The corresponding routes to 3-iodo-4-acetyl-2,5-dimethylthiophene and 3-iodo-2-acetylthiophene are also reported.

year: 2001-09-01

title: Kaupapa Māori Science

authors: Stewart, Georgina Marjorie

subjects: Kaupapa Maori

abstract: This thesis investigates how Māori knowledge and language articulate with current discourses of Pūtaiao education, and possible alternative articulations. A Kaupapa Māori version of critical discourse analysis methodology is developed and applied to discourses relevant to Pūtaiao, or Māori-medium science education. This topic represents an intersection between language, science, education, and culture - fields which are all highly politically charged. Therefore, it is essential that a politically robust Kaupapa Māori position be taken in relation to the research topic. Not only the issues being investigated but the underlying research paradigm must be interrogated using Kaupapa Māori theory at each stage of the project.

The goal is to study the range of possible meanings for the notions of 'Pūtaiao' and 'Māori science' by exploring the relevant dialectical issues, critiquing the assumptions and positions taken on language, knowledge, identity and ethos, in order to inform further Pūtaiao curriculum development. The research project is a narration of the larger story of Pūtaiao education: what is the current situation, how did it come about, what theoretical issues have been influential in this process, and what possibilities are there for further development of Pūtaiao curriculum and pedagogy? 

The thesis research consists of a series of discourse analyses of varying levels of focus and intersection with Pūtaiao:
Wāhanga 1: Translated NCEA L1 science and mathematics examinations, and a traditional Taitokerau oral text;
Wāhanga 2: Māori science curriculum policy;
Wāhanga 3: Multicultural science education research;
Wāhanga 4: Curriculum politics, preventive linguistics, language of science;
Wāhanga 5: Mātauranga, rationality, philosophy of science.

Each analysis takes the form of a narrative history, based on a selected corpus of previously published scholarship (in Wāhanga 1, including numerical data and oral tradition) on the issue under examination, from a Kaupapa Māori perspective. Mainly in the first two chapters, analysis at times also draws on 'personal narrative' accounts of previously unpublished details relating to Pūtaiao.
 
Additionally, an investigation of various qualified notions of 'science' is undertaken, beginning in Wāhanga 2, concluding in Wāhanga 5, in order to explore the nature and boundaries of science as a system of knowledge, and its relationship to other types or systems of knowledge. 

Synopses are included of the following concepts and theoretical issues impacting on the discourses under analysis: 
Wāhanga 1: Ethnicity, 'race', critical theory, Kaupapa Māori theory. 
Wāhanga 2: Science, scientism, science ideology and anti-science.
Wāhanga 4: Identity, linguistic purism, the Sapir-Whorf hypothesis.

Informed by this research, in Wāhanga 5 an original model for the relationship between mātauranga and science is proposed, and the notion of Kaupapa Māori science/epistemology is explored. An analogy between the Sapir-Whorf hypothesis and multicultural science is used to draw together the cultural debates in language and knowledge, which are surmised to intersect at the level of discourse. 

The final chapter presents a re-articulation of Pūtaiao as the notion of Kaupapa Māori science education, and some recommendations for language and content knowledge in further development of Pūtaiao curriculum policy.

text: Kaupapa Māori Science This thesis investigates how Māori knowledge and language articulate with current discourses of Pūtaiao education, and possible alternative articulations. A Kaupapa Māori version of critical discourse analysis methodology is developed and applied to discourses relevant to Pūtaiao, or Māori-medium science education. This topic represents an intersection between language, science, education, and culture - fields which are all highly politically charged. Therefore, it is essential that a politically robust Kaupapa Māori position be taken in relation to the research topic. Not only the issues being investigated but the underlying research paradigm must be interrogated using Kaupapa Māori theory at each stage of the project.

The goal is to study the range of possible meanings for the notions of 'Pūtaiao' and 'Māori science' by exploring the relevant dialectical issues, critiquing the assumptions and positions taken on language, knowledge, identity and ethos, in order to inform further Pūtaiao curriculum development. The research project is a narration of the larger story of Pūtaiao education: what is the current situation, how did it come about, what theoretical issues have been influential in this process, and what possibilities are there for further development of Pūtaiao curriculum and pedagogy? 

The thesis research consists of a series of discourse analyses of varying levels of focus and intersection with Pūtaiao:
Wāhanga 1: Translated NCEA L1 science and mathematics examinations, and a traditional Taitokerau oral text;
Wāhanga 2: Māori science curriculum policy;
Wāhanga 3: Multicultural science education research;
Wāhanga 4: Curriculum politics, preventive linguistics, language of science;
Wāhanga 5: Mātauranga, rationality, philosophy of science.

Each analysis takes the form of a narrative history, based on a selected corpus of previously published scholarship (in Wāhanga 1, including numerical data and oral tradition) on the issue under examination, from a Kaupapa Māori perspective. Mainly in the first two chapters, analysis at times also draws on 'personal narrative' accounts of previously unpublished details relating to Pūtaiao.
 
Additionally, an investigation of various qualified notions of 'science' is undertaken, beginning in Wāhanga 2, concluding in Wāhanga 5, in order to explore the nature and boundaries of science as a system of knowledge, and its relationship to other types or systems of knowledge. 

Synopses are included of the following concepts and theoretical issues impacting on the discourses under analysis: 
Wāhanga 1: Ethnicity, 'race', critical theory, Kaupapa Māori theory. 
Wāhanga 2: Science, scientism, science ideology and anti-science.
Wāhanga 4: Identity, linguistic purism, the Sapir-Whorf hypothesis.

Informed by this research, in Wāhanga 5 an original model for the relationship between mātauranga and science is proposed, and the notion of Kaupapa Māori science/epistemology is explored. An analogy between the Sapir-Whorf hypothesis and multicultural science is used to draw together the cultural debates in language and knowledge, which are surmised to intersect at the level of discourse. 

The final chapter presents a re-articulation of Pūtaiao as the notion of Kaupapa Māori science education, and some recommendations for language and content knowledge in further development of Pūtaiao curriculum policy.

year: 2007