title: Ab initio molecular dynamics investigation of beryllium complexes

authors: Raymond, Onyekachi

subjects: Science & Technology

abstract: Structures of aqueous [Be(H₂O)₄]²⁺, its outer-sphere and inner-sphere complexes with F⁻, Cl⁻, and SO₄²⁻, and dinuclear complexes with a [Be₂(κ-OH)(κ-SO₄)]⁺ core have been studied through Car–Parrinello molecular dynamics (CPMD) simulations with the BLYP functional. According to constrained CPMD/BLYP simulations and pointwise thermodynamic integration, the free energy of deprotonation of [Be(H₂O)₄]²⁺ and its binding free energy with F⁻ are 9.6 and −6.2 kcal/mol, respectively, in good accord with available experimental data. The computed activation barriers for replacing a water ligand in [Be(H₂O)₄]²⁺ with F⁻ and SO₄²⁻, 10.9 and 13.6 kcal/mol, respectively, are also in good qualitative agreement with available experimental data. These ligand-substitution reactions are indicated to follow associative interchange mechanisms with backside (SN2-like) attack of the anion relative to the aquo ligand it is displacing. Outperforming static density functional theory computations of the salient kinetic and thermodynamic quantities involving simple polarizable continuum solvent models, CPMD simulations are validated as a promising tool for studying the structures and speciation of beryllium complexes in aqueous solution.

text: Ab initio molecular dynamics investigation of beryllium complexes Structures of aqueous [Be(H₂O)₄]²⁺, its outer-sphere and inner-sphere complexes with F⁻, Cl⁻, and SO₄²⁻, and dinuclear complexes with a [Be₂(κ-OH)(κ-SO₄)]⁺ core have been studied through Car–Parrinello molecular dynamics (CPMD) simulations with the BLYP functional. According to constrained CPMD/BLYP simulations and pointwise thermodynamic integration, the free energy of deprotonation of [Be(H₂O)₄]²⁺ and its binding free energy with F⁻ are 9.6 and −6.2 kcal/mol, respectively, in good accord with available experimental data. The computed activation barriers for replacing a water ligand in [Be(H₂O)₄]²⁺ with F⁻ and SO₄²⁻, 10.9 and 13.6 kcal/mol, respectively, are also in good qualitative agreement with available experimental data. These ligand-substitution reactions are indicated to follow associative interchange mechanisms with backside (SN2-like) attack of the anion relative to the aquo ligand it is displacing. Outperforming static density functional theory computations of the salient kinetic and thermodynamic quantities involving simple polarizable continuum solvent models, CPMD simulations are validated as a promising tool for studying the structures and speciation of beryllium complexes in aqueous solution.

year: 2020

title: Sustainability, hegemony and the dialectics of change

authors: Roper, Juliet

abstract: Given that at its centre lies a concern for enduring global social and environmental welfare, for many sustainability appears to be a common sense concept. However, in an economic system that is based upon continued economic growth, the notion that social and environmental imperatives should be at least equal in priority across all sectors of society (government, business and civil society) means that sustainability is inherently fraught with tensions. A recent review of business and society literature reveals that little analysis has been published on the nature of these tensions within and between organisations and sectors, including government (Van der Byl & Slawinski, 2015). Further, little critical examination is available of why and how, given what is at stake, economic imperatives continue to be favoured over social and environmental ones.

text: Sustainability, hegemony and the dialectics of change Given that at its centre lies a concern for enduring global social and environmental welfare, for many sustainability appears to be a common sense concept. However, in an economic system that is based upon continued economic growth, the notion that social and environmental imperatives should be at least equal in priority across all sectors of society (government, business and civil society) means that sustainability is inherently fraught with tensions. A recent review of business and society literature reveals that little analysis has been published on the nature of these tensions within and between organisations and sectors, including government (Van der Byl & Slawinski, 2015). Further, little critical examination is available of why and how, given what is at stake, economic imperatives continue to be favoured over social and environmental ones.

year: 2016

title: Hā Ora: secondary care barriers and enablers to early diagnosis of lung cancer for Māori communities.

authors: Kidd, Jacquie

subjects: Barriers

abstract: BACKGROUND: Lung Cancer is the leading cause of cancer deaths in Aotearoa New Zealand. Māori communities in particular have higher incidence and mortality rates from Lung Cancer. Diagnosis of lung cancer at an early stage can allow for curative treatment. This project aimed to document the barriers to early diagnosis and treatment of lung cancer in secondary care for Māori communities. 
METHODS: This project used a kaupapa Māori approach. Nine community hui (focus groups) and nine primary healthcare provider hui were carried out in five rural localities in the Midland region. Community hui included cancer patients, whānau (families), and other community members. Healthcare provider hui comprised staff members at the local primary healthcare centre, including General Practitioners and nurses. Hui data were thematically analysed. 
RESULTS: Barriers and enablers to early diagnosis of lung cancer were categorised into two broad themes: Specialist services and treatment, and whānau journey. The barriers and enablers that participants experienced in specialist services and treatment related to access to care, engagement with specialists, communication with specialist services and cultural values and respect, whereas barriers and enablers relating to the whānau journey focused on agency and the impact on whānau. 
CONCLUSIONS: The study highlighted the need to improve communication within and across healthcare services, the importance of understanding the cultural needs of patients and whānau and a health system strategy that meets these needs. Findings also demonstrated the resilience of Māori and the active efforts of whānau as carers to foster health literacy in future generations.

text: Hā Ora: secondary care barriers and enablers to early diagnosis of lung cancer for Māori communities. BACKGROUND: Lung Cancer is the leading cause of cancer deaths in Aotearoa New Zealand. Māori communities in particular have higher incidence and mortality rates from Lung Cancer. Diagnosis of lung cancer at an early stage can allow for curative treatment. This project aimed to document the barriers to early diagnosis and treatment of lung cancer in secondary care for Māori communities. 
METHODS: This project used a kaupapa Māori approach. Nine community hui (focus groups) and nine primary healthcare provider hui were carried out in five rural localities in the Midland region. Community hui included cancer patients, whānau (families), and other community members. Healthcare provider hui comprised staff members at the local primary healthcare centre, including General Practitioners and nurses. Hui data were thematically analysed. 
RESULTS: Barriers and enablers to early diagnosis of lung cancer were categorised into two broad themes: Specialist services and treatment, and whānau journey. The barriers and enablers that participants experienced in specialist services and treatment related to access to care, engagement with specialists, communication with specialist services and cultural values and respect, whereas barriers and enablers relating to the whānau journey focused on agency and the impact on whānau. 
CONCLUSIONS: The study highlighted the need to improve communication within and across healthcare services, the importance of understanding the cultural needs of patients and whānau and a health system strategy that meets these needs. Findings also demonstrated the resilience of Māori and the active efforts of whānau as carers to foster health literacy in future generations.

year: 2021