title: Big brother is watching you - now in a doubleplusgood way

authors: Sterling, Corey

subjects: computer science

abstract: This paper reports on the progress made with our X Marks The Spot (XMTS) system. In XMTS we make a fundamental change to the compositing operation in a desktop manager, storing all text-display events and their related raster-draw events. This means we can provide the user with a search interface that allows them to go back in time and view how their desktop used to look. Because XMTS is aware of what text was drawn into which window and at what position, the provided snapshot is semi-interactive in that the user can bring individual windows forwards and backwards, and copy text from them. In previous work we demonstrated the approach is technically feasible. In this paper we detail infrastructural advances we have made and showcase its new search interface.

text: Big brother is watching you - now in a doubleplusgood way This paper reports on the progress made with our X Marks The Spot (XMTS) system. In XMTS we make a fundamental change to the compositing operation in a desktop manager, storing all text-display events and their related raster-draw events. This means we can provide the user with a search interface that allows them to go back in time and view how their desktop used to look. Because XMTS is aware of what text was drawn into which window and at what position, the provided snapshot is semi-interactive in that the user can bring individual windows forwards and backwards, and copy text from them. In previous work we demonstrated the approach is technically feasible. In this paper we detail infrastructural advances we have made and showcase its new search interface.

year: 2017

title: A study of novel ferrocenyl-phosphorus compounds

authors: Goodwin, Nicholas J.

abstract: The intent of this investigation was to use the distinctive characteristics of hydroxymethylphosphine chemistry in order to create new ferrocenyl-phosphorus compounds, as well as carry out investigations into both their electrochemistry and their potential for the production of ferrocene-containing polymers. 

The compound FcCH₂P(CH₂OH)₂ 1 (Fe = ferrocenyl) was prepared by the reaction of P(CH₂OH)₃ with [FcCH₂NMe₃]I, and FcCH₂PPh₂ 2 was prepared by a similar reaction. The compounds FcCH₂P(O)(CH₂OH)₂ 3, FcCH₂P(S)(CH₂OH)₂ 4, FcCH₂P(CH₂CH₂CN)₂ 5, FcCH₂P(CH₂NEt₂)₂ 6, FcCH₂P(O)(CH₂Net₂)₂ 7, [FcCH₂P(Me)(CH₂OH)₂]I 8, FcCH₂P(Me)CH₂OH 9, [(FcCH₂)₂P(CH₂OH)₂]Cl 10, (FcCH₂)₂PCH₂OH 11, FcCH₂P(H)PPh₂ 14 and FcCH₂P(O)PPh₂ 15 were prepared and characterised, and the compounds [FcCH₂P(Bz)(CH₂OH)₂]Br (Bz = benzyl) 12 and FcCH₂P(Bz)CH₂OH 13 were investigated though not fully characterised. The ferrocenylphosphine complexes cis- PtCl₂[FcCH₂P(CH₂OH)₂]₂ 16, PdCl₂[FcCH₂P(CH₂OH)₂]₂ 17, [Au{FcCH₂P(CH₂OH)₂}₂]Cl 18, RuCl₂(η⁶-C₁₀H₁₄)[FcCH₂P(CH₂OH)₂] 19 and RuCl₂ (η⁶-C₁₀H₁₄)(FcCH₂PPh₂) 20 were also prepared. X-ray crystal structure determinations were carried out for the compounds 1, 2, 4, 8, 18 and 20, and the solid-state hydrogen-bonding interactions present in the case of 1, 4, 8 and 18 were deduced. 

Hydrogen-bonding in the crystal structures of compounds Ph₂P(O)CH₂OH 21, Ph₂P(S)CH₂OH 22 and Ph₂P(Se)CH₂OH 23 was also investigated. Results were explained in terms of the positioning of hydrogen bonds in line with the direction of lone-pairs on the phosphine chalcogenide heteroatoms. 

The reaction of 1 with sodium metabisulfite in varying amounts was used to produce the compounds FcCH₂PH₂ 24, FcCH₂P(H)CH₂OH 25 and FcCH₂P(O)(OH)CH₂OH 26. The primary phosphine 24 was found to be remarkably air-stable, and was used to prepare the complexes Mo(CO)₅(FcCH₂PH₂) 27, Mo(CO)₄(FcCH₂PH₂)₂ 28, RuCl₂(η⁶-C₁₀H₁₄)(FcCH₂PH₂) 29, Ru₃(μ²-H)₂(CO)₉(μ³-PCH₂Fc) 30 and Ru₄(CO)₁₀(μ²-CO)(μ³-PCH₂Fc)₂ 31. Confirmation of the structures of 24, 27, 28 and 30 was obtained using X-ray crystallography. 

Cyclic voltammetric analysis of the electrochemical behaviour of 1, 2, 5, 24, 2S and FcCH(Me)P(CH₂OH)₂ 32 showed that these compounds exhibit a reversible one-electron oxidation followed by a chemical reaction, which leads to formation of a product which undergoes another reversible one-electron oxidation at higher potential. The rate-determining step for the reaction is intermolecular. BE (bulk electrolysis) of 1, 2 and 5 gave similar results in each case, with one-electron oxidation appearing to initially oxidise the ferrocene centre; in the case of 2 and 5 a green colour characteristic of ferrocenium species is seen during BE, but disappears with time. The conclusion was reached that this initial ferrocenium charge is transferred to another part of the molecule. Evidence from NMR and electrospray mass spectrometric analysis of BE products for 1 and 2 suggests the formation of unusual dimeric species is the end result of oxidation. The ferrocenylphosphine 11 shows simpler electrochemical behaviour consistent with previous literature. Compounds 3, 4, 8, 10, 14, 15, 16, 17, 18 and 30 showed very simple electrochemical behaviour consistent with one chemically and electrochemically reversible ferrocene redox couple. Cyclic voltammetry of the complexes 19, 20 and 29 showed both ferrocene and ruthenium redox processes. The electrochemistry of 7 was complex and not intensively investigated.  

Reaction of 1 with multi-functional secondary amines was used to produce a number of polymeric materials which were investigated using cyclic voltammetry of DMF solutions carbon paste electrodes and drop-coated electrodes. Attempts to covalently bind one of these, polymers to a glassy carbon electrode were unsuccessful. The most electrochemically stable form of electrode investigated was the carbon paste electrode, although the materials did not appear to show great promise for use in such applications, due to irreversible chemical changes in the polymers and quick decay of the ferrocene redox signal upon subjection to cyclic voltammetry.

text: A study of novel ferrocenyl-phosphorus compounds The intent of this investigation was to use the distinctive characteristics of hydroxymethylphosphine chemistry in order to create new ferrocenyl-phosphorus compounds, as well as carry out investigations into both their electrochemistry and their potential for the production of ferrocene-containing polymers. 

The compound FcCH₂P(CH₂OH)₂ 1 (Fe = ferrocenyl) was prepared by the reaction of P(CH₂OH)₃ with [FcCH₂NMe₃]I, and FcCH₂PPh₂ 2 was prepared by a similar reaction. The compounds FcCH₂P(O)(CH₂OH)₂ 3, FcCH₂P(S)(CH₂OH)₂ 4, FcCH₂P(CH₂CH₂CN)₂ 5, FcCH₂P(CH₂NEt₂)₂ 6, FcCH₂P(O)(CH₂Net₂)₂ 7, [FcCH₂P(Me)(CH₂OH)₂]I 8, FcCH₂P(Me)CH₂OH 9, [(FcCH₂)₂P(CH₂OH)₂]Cl 10, (FcCH₂)₂PCH₂OH 11, FcCH₂P(H)PPh₂ 14 and FcCH₂P(O)PPh₂ 15 were prepared and characterised, and the compounds [FcCH₂P(Bz)(CH₂OH)₂]Br (Bz = benzyl) 12 and FcCH₂P(Bz)CH₂OH 13 were investigated though not fully characterised. The ferrocenylphosphine complexes cis- PtCl₂[FcCH₂P(CH₂OH)₂]₂ 16, PdCl₂[FcCH₂P(CH₂OH)₂]₂ 17, [Au{FcCH₂P(CH₂OH)₂}₂]Cl 18, RuCl₂(η⁶-C₁₀H₁₄)[FcCH₂P(CH₂OH)₂] 19 and RuCl₂ (η⁶-C₁₀H₁₄)(FcCH₂PPh₂) 20 were also prepared. X-ray crystal structure determinations were carried out for the compounds 1, 2, 4, 8, 18 and 20, and the solid-state hydrogen-bonding interactions present in the case of 1, 4, 8 and 18 were deduced. 

Hydrogen-bonding in the crystal structures of compounds Ph₂P(O)CH₂OH 21, Ph₂P(S)CH₂OH 22 and Ph₂P(Se)CH₂OH 23 was also investigated. Results were explained in terms of the positioning of hydrogen bonds in line with the direction of lone-pairs on the phosphine chalcogenide heteroatoms. 

The reaction of 1 with sodium metabisulfite in varying amounts was used to produce the compounds FcCH₂PH₂ 24, FcCH₂P(H)CH₂OH 25 and FcCH₂P(O)(OH)CH₂OH 26. The primary phosphine 24 was found to be remarkably air-stable, and was used to prepare the complexes Mo(CO)₅(FcCH₂PH₂) 27, Mo(CO)₄(FcCH₂PH₂)₂ 28, RuCl₂(η⁶-C₁₀H₁₄)(FcCH₂PH₂) 29, Ru₃(μ²-H)₂(CO)₉(μ³-PCH₂Fc) 30 and Ru₄(CO)₁₀(μ²-CO)(μ³-PCH₂Fc)₂ 31. Confirmation of the structures of 24, 27, 28 and 30 was obtained using X-ray crystallography. 

Cyclic voltammetric analysis of the electrochemical behaviour of 1, 2, 5, 24, 2S and FcCH(Me)P(CH₂OH)₂ 32 showed that these compounds exhibit a reversible one-electron oxidation followed by a chemical reaction, which leads to formation of a product which undergoes another reversible one-electron oxidation at higher potential. The rate-determining step for the reaction is intermolecular. BE (bulk electrolysis) of 1, 2 and 5 gave similar results in each case, with one-electron oxidation appearing to initially oxidise the ferrocene centre; in the case of 2 and 5 a green colour characteristic of ferrocenium species is seen during BE, but disappears with time. The conclusion was reached that this initial ferrocenium charge is transferred to another part of the molecule. Evidence from NMR and electrospray mass spectrometric analysis of BE products for 1 and 2 suggests the formation of unusual dimeric species is the end result of oxidation. The ferrocenylphosphine 11 shows simpler electrochemical behaviour consistent with previous literature. Compounds 3, 4, 8, 10, 14, 15, 16, 17, 18 and 30 showed very simple electrochemical behaviour consistent with one chemically and electrochemically reversible ferrocene redox couple. Cyclic voltammetry of the complexes 19, 20 and 29 showed both ferrocene and ruthenium redox processes. The electrochemistry of 7 was complex and not intensively investigated.  

Reaction of 1 with multi-functional secondary amines was used to produce a number of polymeric materials which were investigated using cyclic voltammetry of DMF solutions carbon paste electrodes and drop-coated electrodes. Attempts to covalently bind one of these, polymers to a glassy carbon electrode were unsuccessful. The most electrochemically stable form of electrode investigated was the carbon paste electrode, although the materials did not appear to show great promise for use in such applications, due to irreversible chemical changes in the polymers and quick decay of the ferrocene redox signal upon subjection to cyclic voltammetry.

year: 1998

title: Kei hea te tangi a te Tūī? An exploration of Kaitiakitanga in urban spaces

authors: Walker, Erana

subjects: Kaitiakitanga

abstract: Indigenous people’s connection to the natural world differs from place to place. In Aotearoa, New Zealand, Māori connection to nature is often articulated through the concept of kaitiakitanga whilst intertwining concepts of whakapapa, wairua, mana, mauri and place. Kaitiakitanga captures the relationships, narratives and practices that Māori utilise to protect kin of the natural environment as well as Māori communities in general. Over recent decades increase use of kaitiakitanga with respect to resource management has been linked to ideas of guardianship and stewardship, departing from important aspects such as place, whakapapa, intergenerational knowledge, spirituality and resource use. Calls to recognise the diverse ways kaitiakitanga has and can be expressed by Māori have echoed through academic literature, encouraging wider perspectives and application of the concept to develop. This has reinvigorated not only the need for natures protection but also the recognition of cultural knowledges and concepts in practicing kaitiakitanga. 
 
As with most indigenous people, Māori have experienced urbanisation that has spanned across generations of whānau and hapū. Urbanisation has the ability to challenge health outcomes, cultural practices and cultural knowledge, and more importantly, relationships to nature. Growing urbanisation and environmental degradation continue to challenge people and our relationships to nature. There is now a need to understand how urban spaces may also challenge the concepts that encourage connections to nature like kaitiakitanga. Moreover, there is a need to understand if such cultural concepts can become challenged when transient Māori reside in another tribal group’s boundaries. This research provides a deeper analysis of kaitiakitanga by understanding its application within the urban space of Kirikiriroa/Hamilton. From data gathered through a survey, focus groups and interviews, this research project illustrates the experiences of Māori in the urban space who know and practice kaitiakitanga in Kirikiriroa/Hamilton. More importantly, this study posits the integral role of place connection and mana in supporting and shaping kaitiakitanga practices in urban spaces.

The data from participants shows a clear narrative of kaitiakitanga from both local and transient Māori exist and indicates that kaitiakitanga is practiced in accordance with their location and whakapapa to their area of residence. The study has found that kaitiakitanga practices have adapted to suit urban spaces allowing for both transient and local knowledges to exist within the urban space. The key findings of this research show many influences that impact kaitiakitanga practices like the recognition of childhood spaces and experiences, ideas of kinship, cultural knowledges, spirituality, mobility, nature as well as modernisation. Through exploring participants use and knowledge of kaitiakitanga, this research provides a new lens in which to view this concept and bring to the fore, the various experiences and ways that participants connect to place, people, culture and most importantly, nature.

text: Kei hea te tangi a te Tūī? An exploration of Kaitiakitanga in urban spaces Indigenous people’s connection to the natural world differs from place to place. In Aotearoa, New Zealand, Māori connection to nature is often articulated through the concept of kaitiakitanga whilst intertwining concepts of whakapapa, wairua, mana, mauri and place. Kaitiakitanga captures the relationships, narratives and practices that Māori utilise to protect kin of the natural environment as well as Māori communities in general. Over recent decades increase use of kaitiakitanga with respect to resource management has been linked to ideas of guardianship and stewardship, departing from important aspects such as place, whakapapa, intergenerational knowledge, spirituality and resource use. Calls to recognise the diverse ways kaitiakitanga has and can be expressed by Māori have echoed through academic literature, encouraging wider perspectives and application of the concept to develop. This has reinvigorated not only the need for natures protection but also the recognition of cultural knowledges and concepts in practicing kaitiakitanga. 
 
As with most indigenous people, Māori have experienced urbanisation that has spanned across generations of whānau and hapū. Urbanisation has the ability to challenge health outcomes, cultural practices and cultural knowledge, and more importantly, relationships to nature. Growing urbanisation and environmental degradation continue to challenge people and our relationships to nature. There is now a need to understand how urban spaces may also challenge the concepts that encourage connections to nature like kaitiakitanga. Moreover, there is a need to understand if such cultural concepts can become challenged when transient Māori reside in another tribal group’s boundaries. This research provides a deeper analysis of kaitiakitanga by understanding its application within the urban space of Kirikiriroa/Hamilton. From data gathered through a survey, focus groups and interviews, this research project illustrates the experiences of Māori in the urban space who know and practice kaitiakitanga in Kirikiriroa/Hamilton. More importantly, this study posits the integral role of place connection and mana in supporting and shaping kaitiakitanga practices in urban spaces.

The data from participants shows a clear narrative of kaitiakitanga from both local and transient Māori exist and indicates that kaitiakitanga is practiced in accordance with their location and whakapapa to their area of residence. The study has found that kaitiakitanga practices have adapted to suit urban spaces allowing for both transient and local knowledges to exist within the urban space. The key findings of this research show many influences that impact kaitiakitanga practices like the recognition of childhood spaces and experiences, ideas of kinship, cultural knowledges, spirituality, mobility, nature as well as modernisation. Through exploring participants use and knowledge of kaitiakitanga, this research provides a new lens in which to view this concept and bring to the fore, the various experiences and ways that participants connect to place, people, culture and most importantly, nature.

year: 2021