title: Parent materials of Yellow-brown loams in the Waikato-Coromandel district.

authors: Gibbs, H.S.

abstract: The yellow-brown loams of the Waikato-Coromandel region are derived from weathered airfall volcanic materials. These materials may be either direct airfall deposits, or erosion products of these deposits, described as reworked ash in some publications. In the erosion products small amounts of other rocks may be included in the parent materials, and these additions may modify to a slight degree the chemical and physical properties of the soil as a yellow-brown loam. In larger amounts these additions result in the formation of intergrades to yellow-brown earths or gley soils.

text: Parent materials of Yellow-brown loams in the Waikato-Coromandel district. The yellow-brown loams of the Waikato-Coromandel region are derived from weathered airfall volcanic materials. These materials may be either direct airfall deposits, or erosion products of these deposits, described as reworked ash in some publications. In the erosion products small amounts of other rocks may be included in the parent materials, and these additions may modify to a slight degree the chemical and physical properties of the soil as a yellow-brown loam. In larger amounts these additions result in the formation of intergrades to yellow-brown earths or gley soils.

year: 1982-01-01

title: The synthesis and metal ion catalysed hydrolysis of methyl 4,5-diaminopentanoate

authors: Beresford, Geoffrey Derrick

abstract: The diamino acid ester, methyl 4, 5-diaminopentanoate has been prepared for the first time. The successful five step synthesis starting from 4-hydroxybutanoic acid lactone, and two other possible pathways via ethyl 3-formylpropanoate, are described. 
pKₐ values for 4,5-diaminopentanoic acid dihydrochloride and its a methyl ester dihydrochloride (determined by potentiometric titration at 25°C and I= 0.10molℓ⁻¹) are discussed in relation to those for other 1,2-diamines.
Stability constants of Cu(II) complexes of 4,5-diaminopentanoic acid and its methyl ester were evaluated from potentiometric titration data by the program SCOGS on a PDP 11/70 computer. Both compounds form high stability constant 1:1 and 1:2 complexes with Cu(II). (For 4,5-diaminopentanoic acid log K₁ = 10.94, log K₂ = 9.40 and for methyl 4,5-diaminopentanoate log K₁ = 9.84, log K₂ = 8.51, at 25°C and I= 0.10molℓ⁻¹). A variety of protonated complexes were also present at lower pH. 
pH-stat and spectrophotometric investigations showed that in the alkaline hydrolysis of methyl 4,5-diaminopentanoate, the simple Bᴀс2 reaction is slow and masked by a competing, extremely rapid, pair of intramolecular aminolysis (lactamisation) reactions. These involve competition between five and six membered lactam ring closure. Overall constants of the order 10³ℓmol⁻¹s⁻¹ at 25°C and I = 0.10molℓ⁻¹ are observed.
The Cu(II) catalysed hydrolysis of methyl 4,5-diaminopentanoate was studied at constant pH using a pH-stat. The kinetics of hydrolysis of solutions containing a 1:2 mole ratio of Cu(II): ester are consistent with the two consecutive second order (pseudo-first-order at constant pH) reactions (1) and (2) (where E is the ester and A⁻ the anion, of 4 ,5-diaminopentanoic acid).
CuE₂²⁺ + OH⁻ → CuEA⁺ + CH₃OH 	1
CuEA⁺ + OH⁻ → CUA₂ + CH₃OH 		2
The relative values for the two rate constants obtained (k (CuE₂²⁺) = 2.41ℓmol⁻¹s⁻¹ and k (CuEA⁺) = 0.80ℓmol⁻¹s⁻¹ at 25°C and I = 0.10molℓ⁻¹) can be explained by charge and statistical effects. The value of k(CuEA⁺) was confirmed independently from studies on solutions containing a 2.5:1:4 mole ratio of Cu(II): ester: acid. The value of k(CuEen²⁺) = 0.96ℓmol⁻¹s⁻¹ obtained from solutions containing Cu(II): ester: 1,2-diaminoethane = 2.5:1:4 is approximately k(CuE₂²⁺)/2 as expected statistically. 1:1 Solutions of Cu(II) and methyl 4,5-diaminopentanoate disproportionate, so no values for k(CuE²⁺) could be measured.
The absolute values for the Cu(II) catalysed rate constants are discussed in comparison with those for methyl 2,3-diaminopropanoate and other diamino acid esters. The results for methyl 4,5-diaminopentanoate can be explained by the attenuation of inductive and positive charge effects of the metal ion by the additional methylene groups of the methyl 4,5-diaminopentanoate alkyl chain. Direct methoxycarbonyl-metal ion interaction, presumably absent in methyl 4,5-diaminopentanoate must, therefore, be unimportant in the Cu(II) catalysed hydrolysis of methyl 2,3-diarninopropanoate.

text: The synthesis and metal ion catalysed hydrolysis of methyl 4,5-diaminopentanoate The diamino acid ester, methyl 4, 5-diaminopentanoate has been prepared for the first time. The successful five step synthesis starting from 4-hydroxybutanoic acid lactone, and two other possible pathways via ethyl 3-formylpropanoate, are described. 
pKₐ values for 4,5-diaminopentanoic acid dihydrochloride and its a methyl ester dihydrochloride (determined by potentiometric titration at 25°C and I= 0.10molℓ⁻¹) are discussed in relation to those for other 1,2-diamines.
Stability constants of Cu(II) complexes of 4,5-diaminopentanoic acid and its methyl ester were evaluated from potentiometric titration data by the program SCOGS on a PDP 11/70 computer. Both compounds form high stability constant 1:1 and 1:2 complexes with Cu(II). (For 4,5-diaminopentanoic acid log K₁ = 10.94, log K₂ = 9.40 and for methyl 4,5-diaminopentanoate log K₁ = 9.84, log K₂ = 8.51, at 25°C and I= 0.10molℓ⁻¹). A variety of protonated complexes were also present at lower pH. 
pH-stat and spectrophotometric investigations showed that in the alkaline hydrolysis of methyl 4,5-diaminopentanoate, the simple Bᴀс2 reaction is slow and masked by a competing, extremely rapid, pair of intramolecular aminolysis (lactamisation) reactions. These involve competition between five and six membered lactam ring closure. Overall constants of the order 10³ℓmol⁻¹s⁻¹ at 25°C and I = 0.10molℓ⁻¹ are observed.
The Cu(II) catalysed hydrolysis of methyl 4,5-diaminopentanoate was studied at constant pH using a pH-stat. The kinetics of hydrolysis of solutions containing a 1:2 mole ratio of Cu(II): ester are consistent with the two consecutive second order (pseudo-first-order at constant pH) reactions (1) and (2) (where E is the ester and A⁻ the anion, of 4 ,5-diaminopentanoic acid).
CuE₂²⁺ + OH⁻ → CuEA⁺ + CH₃OH 	1
CuEA⁺ + OH⁻ → CUA₂ + CH₃OH 		2
The relative values for the two rate constants obtained (k (CuE₂²⁺) = 2.41ℓmol⁻¹s⁻¹ and k (CuEA⁺) = 0.80ℓmol⁻¹s⁻¹ at 25°C and I = 0.10molℓ⁻¹) can be explained by charge and statistical effects. The value of k(CuEA⁺) was confirmed independently from studies on solutions containing a 2.5:1:4 mole ratio of Cu(II): ester: acid. The value of k(CuEen²⁺) = 0.96ℓmol⁻¹s⁻¹ obtained from solutions containing Cu(II): ester: 1,2-diaminoethane = 2.5:1:4 is approximately k(CuE₂²⁺)/2 as expected statistically. 1:1 Solutions of Cu(II) and methyl 4,5-diaminopentanoate disproportionate, so no values for k(CuE²⁺) could be measured.
The absolute values for the Cu(II) catalysed rate constants are discussed in comparison with those for methyl 2,3-diaminopropanoate and other diamino acid esters. The results for methyl 4,5-diaminopentanoate can be explained by the attenuation of inductive and positive charge effects of the metal ion by the additional methylene groups of the methyl 4,5-diaminopentanoate alkyl chain. Direct methoxycarbonyl-metal ion interaction, presumably absent in methyl 4,5-diaminopentanoate must, therefore, be unimportant in the Cu(II) catalysed hydrolysis of methyl 2,3-diarninopropanoate.

year: 1977

title: Te mana o ngā toa: Māori experiences of Ngāti Tūmatauenga, the New Zealand Army

authors: Kohere, Cheyenne Atairehia Mere

subjects: Kaupapa Māori

abstract: Diverse realities impact Māori people and their capacity to flourish. It is well- established that Māori are significant contributors to the New Zealand Defence Force (NZDF), and especially the New Zealand Army. Noteworthy participation in major conflicts, especially WWI and WWII create a whakapapa of military tradition which contributed to institutional change within the Army in the 1990s. The inclusion of Māori cultural training in the New Zealand Army can contribute to morale and the effectiveness of the organisation (Hohaia, 2016). This master’s thesis aims to deepen understandings of the experiences of Māori personnel in the Army by exploring the role of the New Zealand Army in the health and wellbeing of Māori soldiers, as well as how the Army can be a career pathway for Māori and their whānau to flourish.
This research employs the use qualitative methods such as Kaupapa Māori theory, phenomenology, and pūrākau as a form of narrative analysis. Semi-structured interviews with five participants (three retired personnel and two currently serving) explores these factors that contribute to the flourishing of Māori soldiers in the New Zealand Army. Each pūrākau developed from interview data is an acknowledgment of the personal journeys of the five participants and contains philosophical thought, epistemological constructs, cultural codes, and worldviews (Lee, 2009).
The findings of the research highlight the complexities that arise when considering the health and wellbeing of Māori soldiers. A range of interconnected factors conceptualised within five themes contributes to participants’ ability to flourish. These five themes include hauora (health), whanaungatanga (relationships), manaakitanga (support), whanonga pono (values) and whakapāwera (hardships). These results suggest that flourishing for Māori personnel is complex, and there is not a simple route to enable Māori to flourish. There are many ‘trade-offs’ for Māori and their experiences. However, Māori service provides opportunities and obstacles for an individual, as well as their whānau, hapū and iwi.

text: Te mana o ngā toa: Māori experiences of Ngāti Tūmatauenga, the New Zealand Army Diverse realities impact Māori people and their capacity to flourish. It is well- established that Māori are significant contributors to the New Zealand Defence Force (NZDF), and especially the New Zealand Army. Noteworthy participation in major conflicts, especially WWI and WWII create a whakapapa of military tradition which contributed to institutional change within the Army in the 1990s. The inclusion of Māori cultural training in the New Zealand Army can contribute to morale and the effectiveness of the organisation (Hohaia, 2016). This master’s thesis aims to deepen understandings of the experiences of Māori personnel in the Army by exploring the role of the New Zealand Army in the health and wellbeing of Māori soldiers, as well as how the Army can be a career pathway for Māori and their whānau to flourish.
This research employs the use qualitative methods such as Kaupapa Māori theory, phenomenology, and pūrākau as a form of narrative analysis. Semi-structured interviews with five participants (three retired personnel and two currently serving) explores these factors that contribute to the flourishing of Māori soldiers in the New Zealand Army. Each pūrākau developed from interview data is an acknowledgment of the personal journeys of the five participants and contains philosophical thought, epistemological constructs, cultural codes, and worldviews (Lee, 2009).
The findings of the research highlight the complexities that arise when considering the health and wellbeing of Māori soldiers. A range of interconnected factors conceptualised within five themes contributes to participants’ ability to flourish. These five themes include hauora (health), whanaungatanga (relationships), manaakitanga (support), whanonga pono (values) and whakapāwera (hardships). These results suggest that flourishing for Māori personnel is complex, and there is not a simple route to enable Māori to flourish. There are many ‘trade-offs’ for Māori and their experiences. However, Māori service provides opportunities and obstacles for an individual, as well as their whānau, hapū and iwi.

year: 2022