title: An investigation of the coordination chemistry of N,N`-disubstituted sulfonylthiourea ligands with d⁶ and d⁸ transition metal centres.

authors: Risi, Matthew

abstract: The coordination chemistry of both square-planar and piano-stool metal complexes derived from an array of disubstituted sulfonylthiourea ligands with the d⁸ and d⁶ transition metal centres of nickel(II), palladium(II), platinum(II), gold(III) and ruthenium(II) was investigated. It was found that these ligands coordinate to the metal centre through both the S and N atoms of the thiourea moiety in a bidentate fashion, which is reminiscent of the coordination chemistry of traditional thiourea complexes. Square-planar d⁸ metal complexes derived from sulfonylthioureas were characterised by both single crystal XRD and ³¹P{¹H} NMR aided by ¹⁹⁵Pt coupling, to be in the distal isomer with no isomerisation detected. This is to say that the non-coordinated nitrogen atom of the core thiourea bears the sulfonyl group and is positioned away from the metal centre. This is in contrast to the coordination observed for the analogous acylthiourea complexes which tend to favour a bidentate S and O coordination mode through the acyl oxygen. This indicates the coordination mode observed for square-planar sulfonylthiourea complexes more closely resembles that of unsubstituted thioureas. Interestingly, single crystal XRD analysis of the piano-stool ruthenium complexes reveals the sulfonylthiourea ligand coordinated to the ruthenium metal centre in the unexpected proximal isomer. Comparison of this structure to some analogous piano-stool acylthiourea complexes show extremely similar structure and coordination and may indicate piano-stool structures derived from sulfonylthioureas resemble those of acylthioureas which in-turn is similar to the coordination mode adopted by simple thioureas. Moreover, through monitoring of the observed decomposition of Ni(II) and Pd(II) sulfonylthiourea complexes by ESI-MS and ³¹P NMR and the attempted synthesis of monodentate Au(I) phosphine sulfonylthiourea complexes, it was discovered that these complexes have a tendency to form stable trinuclear aggregates of the formula [M₃S₂L₃]⁺ (L = bidentate chelating ligand). The formation of these sulfide complexes is theorised to be a result of a hydroxide induced S-C bond cleavage promoted by the electron withdrawing sulfonyl subsistent. This observation matches closely to the well-known ability of thioureas to act as a source of sulfide upon reactions with metal ions.

text: An investigation of the coordination chemistry of N,N`-disubstituted sulfonylthiourea ligands with d⁶ and d⁸ transition metal centres. The coordination chemistry of both square-planar and piano-stool metal complexes derived from an array of disubstituted sulfonylthiourea ligands with the d⁸ and d⁶ transition metal centres of nickel(II), palladium(II), platinum(II), gold(III) and ruthenium(II) was investigated. It was found that these ligands coordinate to the metal centre through both the S and N atoms of the thiourea moiety in a bidentate fashion, which is reminiscent of the coordination chemistry of traditional thiourea complexes. Square-planar d⁸ metal complexes derived from sulfonylthioureas were characterised by both single crystal XRD and ³¹P{¹H} NMR aided by ¹⁹⁵Pt coupling, to be in the distal isomer with no isomerisation detected. This is to say that the non-coordinated nitrogen atom of the core thiourea bears the sulfonyl group and is positioned away from the metal centre. This is in contrast to the coordination observed for the analogous acylthiourea complexes which tend to favour a bidentate S and O coordination mode through the acyl oxygen. This indicates the coordination mode observed for square-planar sulfonylthiourea complexes more closely resembles that of unsubstituted thioureas. Interestingly, single crystal XRD analysis of the piano-stool ruthenium complexes reveals the sulfonylthiourea ligand coordinated to the ruthenium metal centre in the unexpected proximal isomer. Comparison of this structure to some analogous piano-stool acylthiourea complexes show extremely similar structure and coordination and may indicate piano-stool structures derived from sulfonylthioureas resemble those of acylthioureas which in-turn is similar to the coordination mode adopted by simple thioureas. Moreover, through monitoring of the observed decomposition of Ni(II) and Pd(II) sulfonylthiourea complexes by ESI-MS and ³¹P NMR and the attempted synthesis of monodentate Au(I) phosphine sulfonylthiourea complexes, it was discovered that these complexes have a tendency to form stable trinuclear aggregates of the formula [M₃S₂L₃]⁺ (L = bidentate chelating ligand). The formation of these sulfide complexes is theorised to be a result of a hydroxide induced S-C bond cleavage promoted by the electron withdrawing sulfonyl subsistent. This observation matches closely to the well-known ability of thioureas to act as a source of sulfide upon reactions with metal ions.

year: 2020

title: The effectiveness of a CBT app vs. an ACT app  in changing negative self-thought

authors: Berthelsen, Tamsyn

abstract: Negative self-thought is associated with the deterioration of many mental health issues, such as depression, anxiety, self-esteem, and social isolation. Due to the impact negative thinking about oneself has on many individuals, there is a need for an accessible and cost-effective intervention. Cognitive Behavioural Therapy (CBT) focuses on insight and recognising the connection between thoughts, feelings, and behaviours surrounding an event. Acceptance and Commitment Therapy (ACT) focuses on being in the moment and accepting all thoughts that come up. In this study, I used a single-subject single-treatment design (A-B-A or A-C-A) to compare the effectiveness of two iHealth applications; iCBT™ and ACT Companion™ application in reducing negative thinking about oneself. Both approaches significantly reduced the mean daily negative thinking about oneself, however, the ACT Companion™ app was overall more effective. I found a significant increase in mean psychological flexibility, and the need for self-reflection and insight. Overall, both applications are promising forms of treatment for individuals struggling with some level of negative thinking about oneself. Overall, the ACT Companion™ application has shown to be an effective way of reducing negative thinking about oneself, in a relatively short period of time, and at the user’s own discretion.

text: The effectiveness of a CBT app vs. an ACT app  in changing negative self-thought Negative self-thought is associated with the deterioration of many mental health issues, such as depression, anxiety, self-esteem, and social isolation. Due to the impact negative thinking about oneself has on many individuals, there is a need for an accessible and cost-effective intervention. Cognitive Behavioural Therapy (CBT) focuses on insight and recognising the connection between thoughts, feelings, and behaviours surrounding an event. Acceptance and Commitment Therapy (ACT) focuses on being in the moment and accepting all thoughts that come up. In this study, I used a single-subject single-treatment design (A-B-A or A-C-A) to compare the effectiveness of two iHealth applications; iCBT™ and ACT Companion™ application in reducing negative thinking about oneself. Both approaches significantly reduced the mean daily negative thinking about oneself, however, the ACT Companion™ app was overall more effective. I found a significant increase in mean psychological flexibility, and the need for self-reflection and insight. Overall, both applications are promising forms of treatment for individuals struggling with some level of negative thinking about oneself. Overall, the ACT Companion™ application has shown to be an effective way of reducing negative thinking about oneself, in a relatively short period of time, and at the user’s own discretion.

year: 2019

title: Mapping Māori knowledge from the past to inform marine management futures

authors: Paul-Burke, Kura

subjects: mātauranga Māori

abstract: This article provides an overview of research which used mātauranga moana (Māori marine knowledge systems) to inform and assist Western science field research methods and surveys. Place-based Māori marine knowledge identified the traditional distribution range and sizing of taonga (culturally important) species in traditional coastal areas which had been fished and managed by consecutive generations of Māori; kina, Evechinus chloroticus, sea urchin; koura, Jasus edwardsii, red rock lobster; kūtai, Perna canaliculus, green lipped mussel; and pāua, Haliotis iris, abalone. This knowledge was then mapped and used as the baseline for sub-tidal marine science field research surveys. Findings from the transdisciplinary marine research was used to develop management actions to assist Māori and Government entities for improving, enhancing and safeguarding marine taonga species into the future. This article critically discusses and demonstrates the relevance and complementarity of mātauranga Māori and Western science, and the importance of kaupapa Māori strategies for empowering Māori collaboration and voices in marine research co-development, implementation and communication.

text: Mapping Māori knowledge from the past to inform marine management futures This article provides an overview of research which used mātauranga moana (Māori marine knowledge systems) to inform and assist Western science field research methods and surveys. Place-based Māori marine knowledge identified the traditional distribution range and sizing of taonga (culturally important) species in traditional coastal areas which had been fished and managed by consecutive generations of Māori; kina, Evechinus chloroticus, sea urchin; koura, Jasus edwardsii, red rock lobster; kūtai, Perna canaliculus, green lipped mussel; and pāua, Haliotis iris, abalone. This knowledge was then mapped and used as the baseline for sub-tidal marine science field research surveys. Findings from the transdisciplinary marine research was used to develop management actions to assist Māori and Government entities for improving, enhancing and safeguarding marine taonga species into the future. This article critically discusses and demonstrates the relevance and complementarity of mātauranga Māori and Western science, and the importance of kaupapa Māori strategies for empowering Māori collaboration and voices in marine research co-development, implementation and communication.

year: 2020