title: An investigation of beryllium coordination chemistry using electrospray ionisation mass spectrometry

authors: Raymond, Onyekachi

subjects: Electrospray ionisation mass spectrometry

abstract: The electrospray ionisation mass spectrometric behaviour of various complexes of beryllium have been investigated in this thesis. These beryllium complexes were prepared in situ on a small scale by preparing appropriate molar mixtures of the Be²⁺ ion with ligands in a range of solvent systems. In view of the toxicity of beryllium compounds, this combinatorial type screening, involving miniscule amounts of material in solution, proved to be a safe strategy to pursue the coordination chemistry of beryllium. 
          Starting from simple beryllium compounds which include the metal salts (Chapter 2), the speciation and hydrolysis of beryllium ions in aqueous solution have been studied over a pH range of 2.5-6.0 using electrospray ionisation mass spectrometry (ESI-MS). Ions observed by ESI-MS revealed that the speciation of beryllium with hydroxide ligands in solution was preserved into the gas phase via charge reduction by ion pairing with the salt anion. The pH-dependent hydrolytic tendencies of the Be²⁺ cation presented as an ESI-MS speciation diagram for beryllium hydrolysis is in good agreement with previous speciation data which indicates the ability of ESI-MS as a quick, sensitive and safe screening technique for observing beryllium speciation with ligands of interest at low concentrations. Collision induced dissociation patterns further confirmed that the trimer [Be₃(OH)₃]³⁺ is the most stable beryllium hydroxido-aggregate arrangement while the pronounced ion pairing of the beryllium cation with the sulfato ligand yielded additional beryllium ion cluster arrangements such as Be₃ (μ₃-O) aggregate and mixed sulfato-/hydroxido- species. These ions were further investigated using computational techniques simulated in the gas and aqueous environment which allowed for the first time, the molecular dynamics simulations of the ligand exchange processes of the Be²⁺ cation (Chapter 3). A major finding from the ab initio molecular simulations was that hydrogen bonding was relevant in stabilising the tetraaquaberyllium complex in beryllium solutions. Therefore, in the gas phase where the solvation shell of such beryllium species is very much compromised, the formation of inner-sphere complexes is commonplace as observed from the ion signal assignment in the ESI mass spectra. While these extraneous species may not be an exact representation of the solution state, these ions provided insight into plausible modes of beryllium aggregation that are not otherwise easily investigated. 
          Building on these results, a variety of beryllium complexes was generated with various ligands in solutions and subjected to detailed characterisation by ESIMS. These ligands containing functional groups or architecture of interest, varied from simple monodentate ligands such as the acetate ion to more common beryllium chelators including 1,3-diketone, hydroxy keto, malonic acid, chromotropic acid and crown ethers (Chapter 4). Generally, there was an excellent correlation between the species observed in the mass spectrum and those confirmed to exist in solution by other techniques. This lent strong credence to the ESI-MS methodology used as an efficient analytical technique for the easy screening of a diverse range of potential ligands for the divalent beryllium ion.  
          A fundamental issue in beryllium research is the search for suitable chelating ligands for environmental and biomedical application. Therefore, the ESIMS methodology was further employed to investigate several multidentate aminopolycarboxylic acids which are well-known commercial and biomedical chelating agents (Chapter 5). Notable among these are the nitrilotripropionic acid (NTP) and related tetradentate ligands designed towards the full encapsulation of the Be²⁺ cation. Stoichiometric information which was readily obtained from the ESI mass spectra was found to be effective for the preliminary screening of potential encapsulation by tetradentate coordination from a single ligand. Lastly, to corroborate ESI-MS speciation results, beryllium complexes with these class of ligands were synthesised on a larger scale and characterised by ⁹Be NMR and single-crystal X-ray crystallography.

text: An investigation of beryllium coordination chemistry using electrospray ionisation mass spectrometry The electrospray ionisation mass spectrometric behaviour of various complexes of beryllium have been investigated in this thesis. These beryllium complexes were prepared in situ on a small scale by preparing appropriate molar mixtures of the Be²⁺ ion with ligands in a range of solvent systems. In view of the toxicity of beryllium compounds, this combinatorial type screening, involving miniscule amounts of material in solution, proved to be a safe strategy to pursue the coordination chemistry of beryllium. 
          Starting from simple beryllium compounds which include the metal salts (Chapter 2), the speciation and hydrolysis of beryllium ions in aqueous solution have been studied over a pH range of 2.5-6.0 using electrospray ionisation mass spectrometry (ESI-MS). Ions observed by ESI-MS revealed that the speciation of beryllium with hydroxide ligands in solution was preserved into the gas phase via charge reduction by ion pairing with the salt anion. The pH-dependent hydrolytic tendencies of the Be²⁺ cation presented as an ESI-MS speciation diagram for beryllium hydrolysis is in good agreement with previous speciation data which indicates the ability of ESI-MS as a quick, sensitive and safe screening technique for observing beryllium speciation with ligands of interest at low concentrations. Collision induced dissociation patterns further confirmed that the trimer [Be₃(OH)₃]³⁺ is the most stable beryllium hydroxido-aggregate arrangement while the pronounced ion pairing of the beryllium cation with the sulfato ligand yielded additional beryllium ion cluster arrangements such as Be₃ (μ₃-O) aggregate and mixed sulfato-/hydroxido- species. These ions were further investigated using computational techniques simulated in the gas and aqueous environment which allowed for the first time, the molecular dynamics simulations of the ligand exchange processes of the Be²⁺ cation (Chapter 3). A major finding from the ab initio molecular simulations was that hydrogen bonding was relevant in stabilising the tetraaquaberyllium complex in beryllium solutions. Therefore, in the gas phase where the solvation shell of such beryllium species is very much compromised, the formation of inner-sphere complexes is commonplace as observed from the ion signal assignment in the ESI mass spectra. While these extraneous species may not be an exact representation of the solution state, these ions provided insight into plausible modes of beryllium aggregation that are not otherwise easily investigated. 
          Building on these results, a variety of beryllium complexes was generated with various ligands in solutions and subjected to detailed characterisation by ESIMS. These ligands containing functional groups or architecture of interest, varied from simple monodentate ligands such as the acetate ion to more common beryllium chelators including 1,3-diketone, hydroxy keto, malonic acid, chromotropic acid and crown ethers (Chapter 4). Generally, there was an excellent correlation between the species observed in the mass spectrum and those confirmed to exist in solution by other techniques. This lent strong credence to the ESI-MS methodology used as an efficient analytical technique for the easy screening of a diverse range of potential ligands for the divalent beryllium ion.  
          A fundamental issue in beryllium research is the search for suitable chelating ligands for environmental and biomedical application. Therefore, the ESIMS methodology was further employed to investigate several multidentate aminopolycarboxylic acids which are well-known commercial and biomedical chelating agents (Chapter 5). Notable among these are the nitrilotripropionic acid (NTP) and related tetradentate ligands designed towards the full encapsulation of the Be²⁺ cation. Stoichiometric information which was readily obtained from the ESI mass spectra was found to be effective for the preliminary screening of potential encapsulation by tetradentate coordination from a single ligand. Lastly, to corroborate ESI-MS speciation results, beryllium complexes with these class of ligands were synthesised on a larger scale and characterised by ⁹Be NMR and single-crystal X-ray crystallography.

year: 2018

title: Systematic evidence map of disparities in police outcomes: final report

authors: Tompson, Lisa

subjects: police

abstract: To support the New Zealand Police Understanding Policing Delivery (UPD) project, we were tasked with completing an academic literature review on bias in policing. However, the vastness and complexity of the relevant research, and the short timeframe for completion meant that it was not possible to complete a single literature review that accurately reflected the evidence base; indeed, it would be difficult to do justice to this literature in a single review under any circumstances. Thus, rather than attempting a traditional literature review, we developed an evidence and gap map of the international research on bias in policing. In this report, we present the rationale, methods used, and key features of the studies on the evidence and gap map (referred to as the ‘evidence map’). This evidence map serves several purposes. Its overarching purpose is to be a resource for more targeted work on specific areas of apparent disparity in policing, including areas prioritised by New Zealand Police as part of the UPD project: decisions about stops, charges, and the use of force. Researchers will be able to use the map to easily identify a) the extent of research in the area of interest, and b) the key features of the research that has been conducted in that area, as a basis. The map will guide rapid evidence reviews and future primary research, both of which can be used to design police practice-based interventions to reduce police-generated disparities in New Zealand.

text: Systematic evidence map of disparities in police outcomes: final report To support the New Zealand Police Understanding Policing Delivery (UPD) project, we were tasked with completing an academic literature review on bias in policing. However, the vastness and complexity of the relevant research, and the short timeframe for completion meant that it was not possible to complete a single literature review that accurately reflected the evidence base; indeed, it would be difficult to do justice to this literature in a single review under any circumstances. Thus, rather than attempting a traditional literature review, we developed an evidence and gap map of the international research on bias in policing. In this report, we present the rationale, methods used, and key features of the studies on the evidence and gap map (referred to as the ‘evidence map’). This evidence map serves several purposes. Its overarching purpose is to be a resource for more targeted work on specific areas of apparent disparity in policing, including areas prioritised by New Zealand Police as part of the UPD project: decisions about stops, charges, and the use of force. Researchers will be able to use the map to easily identify a) the extent of research in the area of interest, and b) the key features of the research that has been conducted in that area, as a basis. The map will guide rapid evidence reviews and future primary research, both of which can be used to design police practice-based interventions to reduce police-generated disparities in New Zealand.

year: 2021

title: Archetypes and the unthought: The projection of the King’s Court in New Zealand television media

authors: Mataira, Kelvin

abstract: This thesis explores archetypal projections of conflict in Television New Zealand’s news and current affairs as an unthought. The television news and current affairs programmes identified in the thesis relate to issues of conflict between the Maori people of New Zealand, and the Government and Crown agencies of New Zealand. The unresolved issues of conflict are manifest in what has become popularly known as the Treaty of Waitangi settlement process.

The thesis is informed by Foucault’s conviction that the unthought is the power that is linked to every mode of knowledge. The thesis argues that knowledge in relation to thought is limited because the knowledge is surrounded by an immense region of shadow. In an ontology based on thought only it is shown how the Shadow and the King’s Court archetypes conceal and prevent human beings from comprehending other discourses.

It is argued that Foucault’s concern with the unthought is reflected in Carl Gustav Jung’s convictions about the collective unconscious. Jung’s theory of the quarternio: thinking, sensing, intuition and feeling that describe the four functions of the mind, inform the theory and the methodology for the thesis. It is proposed that the discursive activities of television media can be understood in relation to Hermes the Greek God of magic, lies and illusion. It is further proposed that the images that are projected from television media can be informed by mythical accounts of Hermes’ behaviour and activity in relation to Zeus, Apollo, Dionysus, and Ares.

In the thesis, the quarternio and the Greek Gods are represented by the archetypes of the King’s Court. The Ruler archetype represents Zeus and Apollo as the thinking function of the mind. The Sage archetype is shown to be located in close proximity to the Ruler. The Warrior archetype represents Dionysus as the sensing function of the mind. The Magician archetype represents Hermes as the intuitive function of the mind. The Fool archetype represents Ares as the feeling function of the mind. The Destroyer archetype as the inferior and rejected contents of the collective unconscious represents the archetypal Shadow that undermines the activities of the King’s Court. 

It is maintained in the thesis that television media projections of the King’s Court are a metaphor of the mind, and in particular of the contents of the collective unconscious. The King’s Court as a mythical and archetypal metaphor invites an inspection of the unthought through the epistemology of image. The thesis furnishes a methodology based on the epistemology of television. Through an analysis of popular contemporary films such as the Star Wars Trilogy that are shown to be heavily invested with archetypal motif, discourses for each of the King’s Court archetypes are presented. Foucault’s notion of the rituals and gestures that constitute the true discourse in a regime of truth informs the definition of discourse in the thesis. Discourse in the thesis is to be understood as verbal and non-verbal modes of communication.

Foucault’s notion of disciplinary power provides a method for analysing television news and current affairs programmes as an order of discourse. Disciplinary power enables an understanding of the power relations in television media as the power that circulates in an inquisition between the examiner and the confessor. The archetypes of the King’s Court are projected through the rituals of inquisition in television media.

In the analysis all of the archetypes of the King’s Court are seen except for the Magician. Television it is argued represents the Magician. The Destroyer, the Ruler the Sage, the Warrior and the Fool on television media are controlled by the Magician. The Magician shows that the Ruler’s discourse reflected through the King’s Court represents the regime of truth. The competing discourse of the Destroyer as archetypal foe is located outside of the King’s Court and in opposition to the Ruler’s discourse. The Ruler’s discourse is Apollonine. The Ruler projects the image of control, peace, reconciliation, rationality, serenity, authority, and wealth. The Sage as the intellectual and the Fool as the archetypal Trickster are shown to actively facilitate the power of the Ruler. The Warrior who is projected as a powerful leader may be alienated from the King’s Court.

text: Archetypes and the unthought: The projection of the King’s Court in New Zealand television media This thesis explores archetypal projections of conflict in Television New Zealand’s news and current affairs as an unthought. The television news and current affairs programmes identified in the thesis relate to issues of conflict between the Maori people of New Zealand, and the Government and Crown agencies of New Zealand. The unresolved issues of conflict are manifest in what has become popularly known as the Treaty of Waitangi settlement process.

The thesis is informed by Foucault’s conviction that the unthought is the power that is linked to every mode of knowledge. The thesis argues that knowledge in relation to thought is limited because the knowledge is surrounded by an immense region of shadow. In an ontology based on thought only it is shown how the Shadow and the King’s Court archetypes conceal and prevent human beings from comprehending other discourses.

It is argued that Foucault’s concern with the unthought is reflected in Carl Gustav Jung’s convictions about the collective unconscious. Jung’s theory of the quarternio: thinking, sensing, intuition and feeling that describe the four functions of the mind, inform the theory and the methodology for the thesis. It is proposed that the discursive activities of television media can be understood in relation to Hermes the Greek God of magic, lies and illusion. It is further proposed that the images that are projected from television media can be informed by mythical accounts of Hermes’ behaviour and activity in relation to Zeus, Apollo, Dionysus, and Ares.

In the thesis, the quarternio and the Greek Gods are represented by the archetypes of the King’s Court. The Ruler archetype represents Zeus and Apollo as the thinking function of the mind. The Sage archetype is shown to be located in close proximity to the Ruler. The Warrior archetype represents Dionysus as the sensing function of the mind. The Magician archetype represents Hermes as the intuitive function of the mind. The Fool archetype represents Ares as the feeling function of the mind. The Destroyer archetype as the inferior and rejected contents of the collective unconscious represents the archetypal Shadow that undermines the activities of the King’s Court. 

It is maintained in the thesis that television media projections of the King’s Court are a metaphor of the mind, and in particular of the contents of the collective unconscious. The King’s Court as a mythical and archetypal metaphor invites an inspection of the unthought through the epistemology of image. The thesis furnishes a methodology based on the epistemology of television. Through an analysis of popular contemporary films such as the Star Wars Trilogy that are shown to be heavily invested with archetypal motif, discourses for each of the King’s Court archetypes are presented. Foucault’s notion of the rituals and gestures that constitute the true discourse in a regime of truth informs the definition of discourse in the thesis. Discourse in the thesis is to be understood as verbal and non-verbal modes of communication.

Foucault’s notion of disciplinary power provides a method for analysing television news and current affairs programmes as an order of discourse. Disciplinary power enables an understanding of the power relations in television media as the power that circulates in an inquisition between the examiner and the confessor. The archetypes of the King’s Court are projected through the rituals of inquisition in television media.

In the analysis all of the archetypes of the King’s Court are seen except for the Magician. Television it is argued represents the Magician. The Destroyer, the Ruler the Sage, the Warrior and the Fool on television media are controlled by the Magician. The Magician shows that the Ruler’s discourse reflected through the King’s Court represents the regime of truth. The competing discourse of the Destroyer as archetypal foe is located outside of the King’s Court and in opposition to the Ruler’s discourse. The Ruler’s discourse is Apollonine. The Ruler projects the image of control, peace, reconciliation, rationality, serenity, authority, and wealth. The Sage as the intellectual and the Fool as the archetypal Trickster are shown to actively facilitate the power of the Ruler. The Warrior who is projected as a powerful leader may be alienated from the King’s Court.

year: 2000