title: Asymmetric Ligands Derived from Carbohydrates

authors: Jarman, Bevan Peter

subjects: Carbohydrates

abstract: This thesis describes the incorporation of carbohydrate groups in thiourea, 1, or iminophosphorane, 2, ligands. Several carbohydrate acyl thioureas, 3, were synthesised from the reaction of protected and unprotected D‐glucosamine with acyl isothiocyanates, RCONCS. Internal hydrogen‐bonding forms a planar six‐membered ring, which locks the thiourea into an Z,E,Z‐anti conformation as shown by 1H NMR spectroscopy and confirmed by X‐ray structure determination of two examples. As neutral ligands to Rh(III), Rh(I), Ru(II), Pd(II), Pt(II) and Au(I) they bond through the sulfur atom with retention of the six‐membered ring and the Z,E,Z‐anti conformation. This was confirmed by two X‐ray structure determinations on Rh(III) and Pd(II) examples which also showed the new hydrogen‐bond formed by HN2 to a halide on the metal. 
Deprotonation of the ligands 3 with NaOAc gave anionic species which formed bidentate chelating complexes with metals. When attached to Rh(III), Ru(II) or with two thiourea bonding to Pd(II) it forms a four‐membered ring through the S and N2 atoms which retains the hydrogen‐bond. If Rh(I) or (C,Ndimethylbenzylamine‐ Pd) is used a six‐membered ring is formed through the S and O atoms which disrupts the hydrogen‐bond. This disruption of the hydrogenbond is apparent from the chemical shift of HN1. For examples where coordination led to a chiral metal complex (e.g. for Cp*RhCl(N,S‐thiourea)) NMR measurements showed that the natural chirality of the ligand did not provide any selectivity with equal proportions of the two diastereoisomers formed.
Iminophosphoranes were produced by the reaction of protected sugar azides with phosphines via the Staudinger reaction. Cyclometalated complexes, 4, could not be formed directly which an X‐ray structure determination suggested was because of steric crowding of the nitrogen. An indirect transmetalation route was developed where the sugar azides were reacted with the mercurated diphosphine, Hg(2‐C₆H₄PPh₂)₂, and the resulting iminophosphoranes transmetalated with [NMe₄][AuCl₄] to produce cyclometalated Au(III) dichloride complexes. Two X‐ray structure determinations showed that the five‐membered metalocyclic ring was in an envelope conformation. The chlorides were labile and able to be displaced by PPh3 and thiosalicylic acid.
A series of N‐sugar and N‐phenyl iminophosphorane Au(III) complexes were shown to catalyse the addition of 2‐methyl furan to methyl vinyl ketone.

text: Asymmetric Ligands Derived from Carbohydrates This thesis describes the incorporation of carbohydrate groups in thiourea, 1, or iminophosphorane, 2, ligands. Several carbohydrate acyl thioureas, 3, were synthesised from the reaction of protected and unprotected D‐glucosamine with acyl isothiocyanates, RCONCS. Internal hydrogen‐bonding forms a planar six‐membered ring, which locks the thiourea into an Z,E,Z‐anti conformation as shown by 1H NMR spectroscopy and confirmed by X‐ray structure determination of two examples. As neutral ligands to Rh(III), Rh(I), Ru(II), Pd(II), Pt(II) and Au(I) they bond through the sulfur atom with retention of the six‐membered ring and the Z,E,Z‐anti conformation. This was confirmed by two X‐ray structure determinations on Rh(III) and Pd(II) examples which also showed the new hydrogen‐bond formed by HN2 to a halide on the metal. 
Deprotonation of the ligands 3 with NaOAc gave anionic species which formed bidentate chelating complexes with metals. When attached to Rh(III), Ru(II) or with two thiourea bonding to Pd(II) it forms a four‐membered ring through the S and N2 atoms which retains the hydrogen‐bond. If Rh(I) or (C,Ndimethylbenzylamine‐ Pd) is used a six‐membered ring is formed through the S and O atoms which disrupts the hydrogen‐bond. This disruption of the hydrogenbond is apparent from the chemical shift of HN1. For examples where coordination led to a chiral metal complex (e.g. for Cp*RhCl(N,S‐thiourea)) NMR measurements showed that the natural chirality of the ligand did not provide any selectivity with equal proportions of the two diastereoisomers formed.
Iminophosphoranes were produced by the reaction of protected sugar azides with phosphines via the Staudinger reaction. Cyclometalated complexes, 4, could not be formed directly which an X‐ray structure determination suggested was because of steric crowding of the nitrogen. An indirect transmetalation route was developed where the sugar azides were reacted with the mercurated diphosphine, Hg(2‐C₆H₄PPh₂)₂, and the resulting iminophosphoranes transmetalated with [NMe₄][AuCl₄] to produce cyclometalated Au(III) dichloride complexes. Two X‐ray structure determinations showed that the five‐membered metalocyclic ring was in an envelope conformation. The chlorides were labile and able to be displaced by PPh3 and thiosalicylic acid.
A series of N‐sugar and N‐phenyl iminophosphorane Au(III) complexes were shown to catalyse the addition of 2‐methyl furan to methyl vinyl ketone.

year: 2011

title: Delinquent hositility: The effect of Borstal Training, and it's relationship to authoritarian attitudes

authors: Simcock, Robert Malcolm

abstract: This study was based on the assumption that it is not psychologically useful to research all criminals whether detected or not, as one group. It is argued that the group usually referred to as delinquent, is made up of a relatively homogeneous collection of law breakers, and further, that the essential characteristic of this group is a high degree of hostility. 
Previous work has indicated that prison staff tend to be highly authoritarian, and the theory concerning authoritarian people suggests that they are highly hostile, although this has not been emperically verified. It was therefore decided to investigate the relationship between these factors in the present study. 
Because it is considered that hostility is central to delinquency, it is likely that any significant effect of Borstal Training would show itself in a change of hostility levels. Both the frustration and modelling based theories of hostility, seem to suggest that the Borstal is unlikely to reduce hostility, particularly if, as is argued , most staff are of the authoritarian personality type.
The study used four measures, one verbal and one non-verbal measure of authoritarianism, and one verbal and one mainly non-verbal measure of hostility. As expected the non-verbal tests gave better results with the delinquent samples. The results of the analysis of authoritarianism and its relationship with hostility were at best inconclusive and no significant change in authoritarian attitudes occurred as the result of Borstal Training. 
The hypothesis that delinquency is related to hostility was supported by an analysis of hostility scores and their relationship to four indices of delinquency. It was found that Borstal Training was associated with a very significant increase in fantasy hostility.
The verbal measure of hostility gave few significant results, but neither did it suggest any conclusions contrary to those suggested by the non-verbal measure. Overall the two tests correlated with one another significantly. The non-verbal measure, the Rosenzweig Picture-Frustration Study scored according to the method devised by Chorost, proved a very sensitive instrument showing good correlations with the indices of delinquency and a highly significant increase after Borstal Training. 
The staff sample was found to be highly authoritarian as expected, and there was no evidence that the level of authoritarianism was decreasing. It was concluded that hostility is a basic factor in delinquency and that Borstal Training as it now operates increases hostility. It was also concluded that the employment of less authoritarian staff will not be sufficient to bring a change, because such staff are unlikely to remain long in the job as presently defined.

text: Delinquent hositility: The effect of Borstal Training, and it's relationship to authoritarian attitudes This study was based on the assumption that it is not psychologically useful to research all criminals whether detected or not, as one group. It is argued that the group usually referred to as delinquent, is made up of a relatively homogeneous collection of law breakers, and further, that the essential characteristic of this group is a high degree of hostility. 
Previous work has indicated that prison staff tend to be highly authoritarian, and the theory concerning authoritarian people suggests that they are highly hostile, although this has not been emperically verified. It was therefore decided to investigate the relationship between these factors in the present study. 
Because it is considered that hostility is central to delinquency, it is likely that any significant effect of Borstal Training would show itself in a change of hostility levels. Both the frustration and modelling based theories of hostility, seem to suggest that the Borstal is unlikely to reduce hostility, particularly if, as is argued , most staff are of the authoritarian personality type.
The study used four measures, one verbal and one non-verbal measure of authoritarianism, and one verbal and one mainly non-verbal measure of hostility. As expected the non-verbal tests gave better results with the delinquent samples. The results of the analysis of authoritarianism and its relationship with hostility were at best inconclusive and no significant change in authoritarian attitudes occurred as the result of Borstal Training. 
The hypothesis that delinquency is related to hostility was supported by an analysis of hostility scores and their relationship to four indices of delinquency. It was found that Borstal Training was associated with a very significant increase in fantasy hostility.
The verbal measure of hostility gave few significant results, but neither did it suggest any conclusions contrary to those suggested by the non-verbal measure. Overall the two tests correlated with one another significantly. The non-verbal measure, the Rosenzweig Picture-Frustration Study scored according to the method devised by Chorost, proved a very sensitive instrument showing good correlations with the indices of delinquency and a highly significant increase after Borstal Training. 
The staff sample was found to be highly authoritarian as expected, and there was no evidence that the level of authoritarianism was decreasing. It was concluded that hostility is a basic factor in delinquency and that Borstal Training as it now operates increases hostility. It was also concluded that the employment of less authoritarian staff will not be sufficient to bring a change, because such staff are unlikely to remain long in the job as presently defined.

year: 1972

title: He raraunga inamata, he toronga ānamata, he huanga āke tonu atu: A multifaceted approach to improving quality of life for upper limb amputees

authors: August, Luke

subjects: Prosthesis

abstract: This thesis investigates innovative approaches to enhance the quality of life for upper limb amputees, integrating advanced prosthetic design, neurocontrol systems, and Māori knowledge systems. With the prevalence of prosthetic rejection and limitations in current designs affecting amputees' daily functionality and psychological well-being, a multifaceted strategy is essential. This research aims to address these challenges by improving prosthetic functionality, user control mechanisms, and incorporating cultural perspectives into prosthetic development.
The study first focuses on the design, development, and evaluation of four low-cost prosthetic hands. Assessing their Degrees of Freedom (DoF), Range of Motion (RoM), and Kapandji scores. The research proposes a novel hybrid coupled-tendon system. This system aims to combine the adaptability of underactuated designs with the precision control of coupled mechanisms, enhancing the prosthetic hands' functionality and grasp versatility.
In exploring control mechanisms, an EEG-based control system was developed to improve the intuitiveness of prosthetic control. Through comparative analysis of motor execution and action observation training regimes, facilitated by a digital twin, the study evaluates the efficacy of these methods in enhancing users' control over the prosthetics. The research identifies limitations in the classification of multiple active grasps and suggests potential improvements through augmented and virtual reality training environments. 
This thesis incorporates Māori perspectives by examining how mātauranga Māori can inform and enrich prosthetic design and usage. Through the analysis of pūrākau Māori, this work highlights the importance of considering the mauri, whakapapa of materials in prosthetic manufacturing and the implications of tapu on control systems. This inclusion aims to create culturally resonant devices that acknowledge and integrate the spiritual and cultural dimensions of the user's identity, offering a holistic approach to prosthetic development.
This interdisciplinary research contributes to the field by proposing a comprehensive framework that not only advances prosthetic technology but also aligns with cultural values and practices. By addressing the technical, psychological, and cultural needs of upper limb amputees, the project underscores the potential of combining engineering innovation with cultural wisdom to significantly improve amputees' autonomy and well-being. The findings advocate for a more inclusive and holistic approach to prosthetic development, emphasizing the importance of user-centric design and cultural competency in enhancing the quality of life for individuals with limb loss.

text: He raraunga inamata, he toronga ānamata, he huanga āke tonu atu: A multifaceted approach to improving quality of life for upper limb amputees This thesis investigates innovative approaches to enhance the quality of life for upper limb amputees, integrating advanced prosthetic design, neurocontrol systems, and Māori knowledge systems. With the prevalence of prosthetic rejection and limitations in current designs affecting amputees' daily functionality and psychological well-being, a multifaceted strategy is essential. This research aims to address these challenges by improving prosthetic functionality, user control mechanisms, and incorporating cultural perspectives into prosthetic development.
The study first focuses on the design, development, and evaluation of four low-cost prosthetic hands. Assessing their Degrees of Freedom (DoF), Range of Motion (RoM), and Kapandji scores. The research proposes a novel hybrid coupled-tendon system. This system aims to combine the adaptability of underactuated designs with the precision control of coupled mechanisms, enhancing the prosthetic hands' functionality and grasp versatility.
In exploring control mechanisms, an EEG-based control system was developed to improve the intuitiveness of prosthetic control. Through comparative analysis of motor execution and action observation training regimes, facilitated by a digital twin, the study evaluates the efficacy of these methods in enhancing users' control over the prosthetics. The research identifies limitations in the classification of multiple active grasps and suggests potential improvements through augmented and virtual reality training environments. 
This thesis incorporates Māori perspectives by examining how mātauranga Māori can inform and enrich prosthetic design and usage. Through the analysis of pūrākau Māori, this work highlights the importance of considering the mauri, whakapapa of materials in prosthetic manufacturing and the implications of tapu on control systems. This inclusion aims to create culturally resonant devices that acknowledge and integrate the spiritual and cultural dimensions of the user's identity, offering a holistic approach to prosthetic development.
This interdisciplinary research contributes to the field by proposing a comprehensive framework that not only advances prosthetic technology but also aligns with cultural values and practices. By addressing the technical, psychological, and cultural needs of upper limb amputees, the project underscores the potential of combining engineering innovation with cultural wisdom to significantly improve amputees' autonomy and well-being. The findings advocate for a more inclusive and holistic approach to prosthetic development, emphasizing the importance of user-centric design and cultural competency in enhancing the quality of life for individuals with limb loss.

year: 2024