title: Synthesis and characterization of new trimetallic complexes with {Pt₂Au(μ-S) ₂} ⁿ⁺ (n=2, 3) cores containing C, N and N, N donor ligands

authors: White, Bradley C.

subjects: Biological activity

abstract: Reactions of the dinuclear platinum(II) sulfide complex [Pt ₂(μ-S) ₂(PPh ₃) ₄] with a range of gold(III) dichloride complexes [AuLCl ₂] containing C, N- or N, N-cycloaurated ligands L gives a new series of dicationic adducts [Pt ₂(μ-S) ₂(PPh ₃) ₄AuL] ²⁺, isolated as their PF ₆ - salts. The complexes investigated are [Au{C₆₋H ₄(CH ₂NMe ₂)-2}Cl ₂], [Au{C ₆H ₃(CH ₂NMe ₂)-2-(OMe)-5}Cl ₂], [Au{NC ₅H ₄(CH ₂C ₆H ₄)-2}Cl ₂], [Au{NC ₅H ₄(COC ₆H ₄)-2}Cl ₂] and [Au{NC ₅H ₄(CONH)-2}Cl ₂]. An X-ray structure determination on the picolinamide-derived complex [Pt ₂(μ-S) ₂(PPh ₃) ₄Au{NC ₅H ₄(CONH)-2}](PF₆) ₂ was not of sufficiently high quality for detailed discussion, but confirmed the atom connectivity. Reactions of [Pt ₂(μ-S) ₂(PPh ₃) ₄] with [AuCl ₂(bipy)]PF ₆ (L=bipy=2,2'-bipyridine) and [AuCl ₂(phen)]Cl (L=phen=1,10-phenanthroline) gives the corresponding tricationic adducts [Pt ₂(μ-S) ₂(PPh ₃) ₄AuL] ³⁺, also isolated as their PF ₆⁻ salts. The complexes are characterised by NMR spectroscopy, electrospray mass spectrometry and microelemental analyses. Biological assay data of a selection of these new complexes towards the P388 murine leukemia cell line, as well as a range of antimicrobial tests, reveals overall low activity compared to other cycloaurated gold(III) complexes.

text: Synthesis and characterization of new trimetallic complexes with {Pt₂Au(μ-S) ₂} ⁿ⁺ (n=2, 3) cores containing C, N and N, N donor ligands Reactions of the dinuclear platinum(II) sulfide complex [Pt ₂(μ-S) ₂(PPh ₃) ₄] with a range of gold(III) dichloride complexes [AuLCl ₂] containing C, N- or N, N-cycloaurated ligands L gives a new series of dicationic adducts [Pt ₂(μ-S) ₂(PPh ₃) ₄AuL] ²⁺, isolated as their PF ₆ - salts. The complexes investigated are [Au{C₆₋H ₄(CH ₂NMe ₂)-2}Cl ₂], [Au{C ₆H ₃(CH ₂NMe ₂)-2-(OMe)-5}Cl ₂], [Au{NC ₅H ₄(CH ₂C ₆H ₄)-2}Cl ₂], [Au{NC ₅H ₄(COC ₆H ₄)-2}Cl ₂] and [Au{NC ₅H ₄(CONH)-2}Cl ₂]. An X-ray structure determination on the picolinamide-derived complex [Pt ₂(μ-S) ₂(PPh ₃) ₄Au{NC ₅H ₄(CONH)-2}](PF₆) ₂ was not of sufficiently high quality for detailed discussion, but confirmed the atom connectivity. Reactions of [Pt ₂(μ-S) ₂(PPh ₃) ₄] with [AuCl ₂(bipy)]PF ₆ (L=bipy=2,2'-bipyridine) and [AuCl ₂(phen)]Cl (L=phen=1,10-phenanthroline) gives the corresponding tricationic adducts [Pt ₂(μ-S) ₂(PPh ₃) ₄AuL] ³⁺, also isolated as their PF ₆⁻ salts. The complexes are characterised by NMR spectroscopy, electrospray mass spectrometry and microelemental analyses. Biological assay data of a selection of these new complexes towards the P388 murine leukemia cell line, as well as a range of antimicrobial tests, reveals overall low activity compared to other cycloaurated gold(III) complexes.

year: 2013

title: The comfort zone: Reflection on a taken-for-granted model

authors: Brown, Mike

subjects: outdoor adventure education

abstract: Reference to the comfort zone model is widespread within outdoor adventure education. It is based on the belief that when placed in a stressful situation people will respond by overcoming their hesitancy and grow. This model is often presented to students prior to activities with a perceived sense of risk and challenge which arouses strong emotional and physical responses to novel tasks (e.g., a ropes course). Students are encouraged to ‘stretch themselves’, to move outside their comfort zone and expand their preconceived limits and by inference learn. This article briefly explores the theories that underpin the comfort zone model and suggests that it is time to rethink how it is used.

text: The comfort zone: Reflection on a taken-for-granted model Reference to the comfort zone model is widespread within outdoor adventure education. It is based on the belief that when placed in a stressful situation people will respond by overcoming their hesitancy and grow. This model is often presented to students prior to activities with a perceived sense of risk and challenge which arouses strong emotional and physical responses to novel tasks (e.g., a ropes course). Students are encouraged to ‘stretch themselves’, to move outside their comfort zone and expand their preconceived limits and by inference learn. This article briefly explores the theories that underpin the comfort zone model and suggests that it is time to rethink how it is used.

year: 2008

title: Waata Kukutai: Rangatira o Ngaati Tiipa 1822-1867

authors: Ewe, Denise Te Tuhi

subjects: Biography

abstract: This thesis examines the life of Ngaati Tiipa rangatira Waata Kukutai (1822-1867), and critiques historical perspectives that have narrowly identified him as merely a Kuupapa loyalist. This study argues that Kukutai’s choices and leadership were driven first and foremost by those things he viewed as crucial to Ngaati Tiipa autonomy and wellbeing. Kukutai was an articulate and well-educated leader of Ngaati Tiipa. Waata was governed by principles of rangatiratanga (chieftainship), mana motuhake (independence) and loyalty to Ngaati Tiipa and to the whenua. He was deeply religious and courageous and was an entrepreneur who sought to protect his people by securing economic independence. This thesis shows how he negotiated colonial structures by forming strategic alliances, and in the process led his people through one of the most turbulent periods in New Zealand history.  

Waata was an enigma shaped by loss, vision and hope for a new future in extraordinary times in New Zealand’s history. Waata was a polarising personality who held fast to his life principles. He withstood immense pressure from other Waikato chiefs during the Waikato invasion. During the Waikato War Waata was most active, carrying letters, food and supplies to colonial soldiers and earned himself and his tribe of Ngaati Tiipa the label of kuupapa. While Waata was not the only ‘friendly chief’ during colonial times he has been the most pillorised in Waikato. Seemingly ignored by many historians is at the same time Waata ensued that Ngaati Tiipa land was never invaded by the colonial troops. Waata’s actions protected his people and his land and maintained his mana motuhake, his sovereignty over his district.

text: Waata Kukutai: Rangatira o Ngaati Tiipa 1822-1867 This thesis examines the life of Ngaati Tiipa rangatira Waata Kukutai (1822-1867), and critiques historical perspectives that have narrowly identified him as merely a Kuupapa loyalist. This study argues that Kukutai’s choices and leadership were driven first and foremost by those things he viewed as crucial to Ngaati Tiipa autonomy and wellbeing. Kukutai was an articulate and well-educated leader of Ngaati Tiipa. Waata was governed by principles of rangatiratanga (chieftainship), mana motuhake (independence) and loyalty to Ngaati Tiipa and to the whenua. He was deeply religious and courageous and was an entrepreneur who sought to protect his people by securing economic independence. This thesis shows how he negotiated colonial structures by forming strategic alliances, and in the process led his people through one of the most turbulent periods in New Zealand history.  

Waata was an enigma shaped by loss, vision and hope for a new future in extraordinary times in New Zealand’s history. Waata was a polarising personality who held fast to his life principles. He withstood immense pressure from other Waikato chiefs during the Waikato invasion. During the Waikato War Waata was most active, carrying letters, food and supplies to colonial soldiers and earned himself and his tribe of Ngaati Tiipa the label of kuupapa. While Waata was not the only ‘friendly chief’ during colonial times he has been the most pillorised in Waikato. Seemingly ignored by many historians is at the same time Waata ensued that Ngaati Tiipa land was never invaded by the colonial troops. Waata’s actions protected his people and his land and maintained his mana motuhake, his sovereignty over his district.

year: 2020