title: Dinuclear platinum(II) complexes containing ferrocenylalkyl–thiolate and –selenolate ligands

authors: Devoy, Sarah M.

subjects: thiolate

abstract: Alkylation reactions of [Pt₂(μ-S)₂(PPh₃)₄] with haloalkylferrocenes FcCH₂Cl, Fc(CH₂)₆Br and Fc(CH₂)₁₁Br [Fc = (η⁵-C₅H₅)Fe(η⁵-C₅H₄)] gave the cationic μ-thiolate complexes [Pt₂(μ-S){μ-S(CH₂)nFc}(PPh₃)₄]⁺ (n = 1, 6, 11), isolated as PF₆⁻ and/or BPh₄⁻ salts, and characterised by ESI mass spectrometry, NMR spectroscopy, microelemental analysis, and by an X-ray structure determination on [Pt₂(μ-S){μ-SCH₂Fc}(PPh₃)₄]PF₆. The complex contains the typical folded {Pt₂(μ-S)₂} core with an axial ferrocenylmethylthiolate ligand. The corresponding selenolate complex [Pt₂ (μ-Se){μ-SeCH₂Fc}(PPh₃)₄]⁺ was similarly obtained by alkylation of [Pt₂(μ-Se)₂ (PPh₃)₄] with FcCH₂Cl, and isolated as PF₆⁻ and BPh₄⁻ salts. The attempted liberation of FcCH₂SH from [Pt₂(μ-S){μ-SCH₂Fc}(PPh₃)₄]+ using Na₂S was not successful.

text: Dinuclear platinum(II) complexes containing ferrocenylalkyl–thiolate and –selenolate ligands Alkylation reactions of [Pt₂(μ-S)₂(PPh₃)₄] with haloalkylferrocenes FcCH₂Cl, Fc(CH₂)₆Br and Fc(CH₂)₁₁Br [Fc = (η⁵-C₅H₅)Fe(η⁵-C₅H₄)] gave the cationic μ-thiolate complexes [Pt₂(μ-S){μ-S(CH₂)nFc}(PPh₃)₄]⁺ (n = 1, 6, 11), isolated as PF₆⁻ and/or BPh₄⁻ salts, and characterised by ESI mass spectrometry, NMR spectroscopy, microelemental analysis, and by an X-ray structure determination on [Pt₂(μ-S){μ-SCH₂Fc}(PPh₃)₄]PF₆. The complex contains the typical folded {Pt₂(μ-S)₂} core with an axial ferrocenylmethylthiolate ligand. The corresponding selenolate complex [Pt₂ (μ-Se){μ-SeCH₂Fc}(PPh₃)₄]⁺ was similarly obtained by alkylation of [Pt₂(μ-Se)₂ (PPh₃)₄] with FcCH₂Cl, and isolated as PF₆⁻ and BPh₄⁻ salts. The attempted liberation of FcCH₂SH from [Pt₂(μ-S){μ-SCH₂Fc}(PPh₃)₄]+ using Na₂S was not successful.

year: 2013

title: Surrogate modeling a computational fluid dynamics-based wind turbine wake simulation using machine learning

authors: Wilson, Brett

subjects: computer science

abstract: The Wind Farm Layout Optimization problem involves finding the optimal positions for wind turbines on a wind farm site. Current Metahueristic based methods make use of a combination of turbine specifications and parameters, mathematical models and empirically produced power production equations to estimate the energy output of a real wind farm [15]. The overarching variable in any optimisation function is wind speed - this is what used to determine the power generated. Therefore, accurate predictions of wind speeds at specific points across the volume of the site are needed. In this paper, Computational Fluid Dynamics (CFD) was used to simulate a full scale rotating wind turbine blade with fluid (air) at various wind speeds flowing past the turbine. The wake effect can be observed and leads to decrease in wind speeds, as expected. Wind speed at specific x,y and z (3D) coordinates were sampled and used as input to common Machine Learning regression algorithms to create different surrogate models. This was needed as each individual CFD experiment takes approximately 8 hours to complete, so it is not feasible to continuously repeat these simulations inside a metaheuristic optimiser.

text: Surrogate modeling a computational fluid dynamics-based wind turbine wake simulation using machine learning The Wind Farm Layout Optimization problem involves finding the optimal positions for wind turbines on a wind farm site. Current Metahueristic based methods make use of a combination of turbine specifications and parameters, mathematical models and empirically produced power production equations to estimate the energy output of a real wind farm [15]. The overarching variable in any optimisation function is wind speed - this is what used to determine the power generated. Therefore, accurate predictions of wind speeds at specific points across the volume of the site are needed. In this paper, Computational Fluid Dynamics (CFD) was used to simulate a full scale rotating wind turbine blade with fluid (air) at various wind speeds flowing past the turbine. The wake effect can be observed and leads to decrease in wind speeds, as expected. Wind speed at specific x,y and z (3D) coordinates were sampled and used as input to common Machine Learning regression algorithms to create different surrogate models. This was needed as each individual CFD experiment takes approximately 8 hours to complete, so it is not feasible to continuously repeat these simulations inside a metaheuristic optimiser.

year: 2017

title: Cultural Theory Made Critical: Towards a Theory of the Indigenous Intellectual

authors: Hireme, Hemi Te Rere

abstract: Despite the fact that Western critical theory has provided us with theories of the power relations that operate within our lives, I argue that the indigenous element is nonetheless understated within these theories. To this end, my thesis is precisely that we must make the "cultural" critical. I argue that various theories of cognitive and moral submissiveness must be supplemented with a theory of submissiveness at the indigenous level in order for issues of latent power to be addressed. This thesis is therefore about developing a theory that for tangata whenua seeks to overcome one of the most debilitating effects of colonial domination - a loss of critical consciousness. I advocate the need for a new type of intellectual - the indigenous intellectual. 
I present my thesis in two parts. Part One examines Western critical theory to understand the processes that contribute to colonial domination. Here, I identify relations and processes of power that have contributed to a continuing assault on tangata whenua cultural continuity and well-being. Of particular significance are Foucault's study of governmentalisation and normalisation and Gramsci's notion of hegemony and the traditional and organic intellectuals. 
Part Two records not only how this understanding is put into action by way of the introduction of a "critical theory" component in programmes at Te Whare Wananga 0 Awanuiarangi over a number of years, but also offers a critical cultural theory in the form of the indigenous intellectual. While it acknowledges the extreme value of Western critical theory in allowing tangata whenua to understand the relations of power and the effects of colonial domination, the programme also identifies the many voids and spaces within Western critical theory that leave unanswered the oppressiveness and hegemony of cultural and ideological colonisation. I conclude my thesis by arguing that, whilst many in leadership positions claim allegiance to Gramsci' s concept of the organic intellectual, their ideological stance is anything but organic. By examining why they do not represent indigenous interests "organically", I argue that a new concept is needed to expose the sham of much of our contemporary "inorganic" politics: that our cultural needs are better served by a concept of the "indigenous" intellectual.

text: Cultural Theory Made Critical: Towards a Theory of the Indigenous Intellectual Despite the fact that Western critical theory has provided us with theories of the power relations that operate within our lives, I argue that the indigenous element is nonetheless understated within these theories. To this end, my thesis is precisely that we must make the "cultural" critical. I argue that various theories of cognitive and moral submissiveness must be supplemented with a theory of submissiveness at the indigenous level in order for issues of latent power to be addressed. This thesis is therefore about developing a theory that for tangata whenua seeks to overcome one of the most debilitating effects of colonial domination - a loss of critical consciousness. I advocate the need for a new type of intellectual - the indigenous intellectual. 
I present my thesis in two parts. Part One examines Western critical theory to understand the processes that contribute to colonial domination. Here, I identify relations and processes of power that have contributed to a continuing assault on tangata whenua cultural continuity and well-being. Of particular significance are Foucault's study of governmentalisation and normalisation and Gramsci's notion of hegemony and the traditional and organic intellectuals. 
Part Two records not only how this understanding is put into action by way of the introduction of a "critical theory" component in programmes at Te Whare Wananga 0 Awanuiarangi over a number of years, but also offers a critical cultural theory in the form of the indigenous intellectual. While it acknowledges the extreme value of Western critical theory in allowing tangata whenua to understand the relations of power and the effects of colonial domination, the programme also identifies the many voids and spaces within Western critical theory that leave unanswered the oppressiveness and hegemony of cultural and ideological colonisation. I conclude my thesis by arguing that, whilst many in leadership positions claim allegiance to Gramsci' s concept of the organic intellectual, their ideological stance is anything but organic. By examining why they do not represent indigenous interests "organically", I argue that a new concept is needed to expose the sham of much of our contemporary "inorganic" politics: that our cultural needs are better served by a concept of the "indigenous" intellectual.

year: 2002