title: Cycloauration of pyridyl sulphonamides

authors: Kilpin, Kelly Joan

subjects: Gold

abstract: The pyridyl-2-alkylsulfonamides C₅H₄N(CH₂)nNHSO₂R (n = 1,2; R = Me, Ph or p-C₆H₄Me) and 8-(p-tosylamino)quinoline undergo facile cycloauration reactions with H[AuCl₄] in water, giving metallacyclic complexes coordinated through the pyridyl (or quinolyl) nitrogen atom and the deprotonated nitrogen of the sulfonamide group. The complexes have been fully characterised by NMR spectroscopy, ESI mass spectrometry and elemental analysis. The X-ray crystal structures of two derivatives reveal the presence of non-planar sulfonamide nitrogen atoms. The complexes show low activity against P388 murine leukaemia cells, possibly as a result of their ease of reduction with mild reducing agents.

text: Cycloauration of pyridyl sulphonamides The pyridyl-2-alkylsulfonamides C₅H₄N(CH₂)nNHSO₂R (n = 1,2; R = Me, Ph or p-C₆H₄Me) and 8-(p-tosylamino)quinoline undergo facile cycloauration reactions with H[AuCl₄] in water, giving metallacyclic complexes coordinated through the pyridyl (or quinolyl) nitrogen atom and the deprotonated nitrogen of the sulfonamide group. The complexes have been fully characterised by NMR spectroscopy, ESI mass spectrometry and elemental analysis. The X-ray crystal structures of two derivatives reveal the presence of non-planar sulfonamide nitrogen atoms. The complexes show low activity against P388 murine leukaemia cells, possibly as a result of their ease of reduction with mild reducing agents.

year: 2008

title: Computational Nanobiosensing – Drawing Analogies Between Optimisation and Nanobiosensing for Smart Tumour Targeting

authors: Zhang, Lisa

abstract: Nanotechnology has been rapidly developing for early diagnosis and treatment of cancer, with nanoparticles being a large focus. However, traditional drug delivery mechanisms are passive and inefficient, with only 0.7% of nanoparticles reaching the tumour through blood vasculature. In vivo computation, also known as computational nanobiosensing (CONA), replaces nanoparticles with swarms of externally manipulable nanorobots whose movement is controlled by an external actuating system. The biological problem of smart tumour targeting is viewed from the computational perspective as an optimisation problem: nanorobot swarms (computational agents) explore the blood vasculature of high-risk tissue (search space) to locate the tumour (global optimum). Tumour biological gradient fields (BGF) create a fitness landscape, which can be analysed with fitness landscape analysis (FLA) to select and tune appropriate search algorithms for in vivo computation.

Key limitations of previous work for in vivo computation are a lack of realistic BGFs that reflect the tumour microenvironment to test search algorithms on; and for FLA, no available measures that consider physical constraints of the in vivo environment.

Two realistic tumour BGF models were created using COMSOL Multiphysics software (CFD Module), one highly vascularised, the other less vascularised. The vascular architecture was based on in vivo blood vessel networks in healthy and tumour regions, and blood velocity was used as a BGF. Blood velocity was found to be lowest in the tumour region, not exceeding 100 µm/s, confirming its applicability as a BGF for search algorithm testing.

Three new FLA measures were created and validated with numerical simulations on two possible tumour vascular landscapes. These measures addressed the physical constraints of discrete search space, unidirectional blood flow, and nanorobot steering imperfections when using a uniform magnetic field. The less vascularized landscape was found to be more discrete, more heterogeneous, and contain a smaller countercurrent frequency of search direction. This indicated it would be more challenging to solve for than the highly vascularised landscape.

These advancements of the CONA framework allow the in vivo search environment to be better visualised and understood for algorithmic development, as well as provide realistic BGFs to test these search algorithms on.

text: Computational Nanobiosensing – Drawing Analogies Between Optimisation and Nanobiosensing for Smart Tumour Targeting Nanotechnology has been rapidly developing for early diagnosis and treatment of cancer, with nanoparticles being a large focus. However, traditional drug delivery mechanisms are passive and inefficient, with only 0.7% of nanoparticles reaching the tumour through blood vasculature. In vivo computation, also known as computational nanobiosensing (CONA), replaces nanoparticles with swarms of externally manipulable nanorobots whose movement is controlled by an external actuating system. The biological problem of smart tumour targeting is viewed from the computational perspective as an optimisation problem: nanorobot swarms (computational agents) explore the blood vasculature of high-risk tissue (search space) to locate the tumour (global optimum). Tumour biological gradient fields (BGF) create a fitness landscape, which can be analysed with fitness landscape analysis (FLA) to select and tune appropriate search algorithms for in vivo computation.

Key limitations of previous work for in vivo computation are a lack of realistic BGFs that reflect the tumour microenvironment to test search algorithms on; and for FLA, no available measures that consider physical constraints of the in vivo environment.

Two realistic tumour BGF models were created using COMSOL Multiphysics software (CFD Module), one highly vascularised, the other less vascularised. The vascular architecture was based on in vivo blood vessel networks in healthy and tumour regions, and blood velocity was used as a BGF. Blood velocity was found to be lowest in the tumour region, not exceeding 100 µm/s, confirming its applicability as a BGF for search algorithm testing.

Three new FLA measures were created and validated with numerical simulations on two possible tumour vascular landscapes. These measures addressed the physical constraints of discrete search space, unidirectional blood flow, and nanorobot steering imperfections when using a uniform magnetic field. The less vascularized landscape was found to be more discrete, more heterogeneous, and contain a smaller countercurrent frequency of search direction. This indicated it would be more challenging to solve for than the highly vascularised landscape.

These advancements of the CONA framework allow the in vivo search environment to be better visualised and understood for algorithmic development, as well as provide realistic BGFs to test these search algorithms on.

year: 2024

title: Listening to the voices of Year 13 Māori students: A case study in a New Zealand secondary school

authors: Kay, Joan-Marie

subjects: Maori Achievement

abstract: This research focuses on listening to the voices of Year 13 academically successful Māori students in a large, urban, mainstream, co-educational, decile 4, New Zealand secondary school. Traditionally, researchers have tended to emphasise the poor academic performance of Māori students in New Zealand. In contrast, this qualitative case study, however, seeks to understand what influences and motivates the academically successful Year 13 Māori students who have gained the National Certificate of Educational Achievement (NCEA) Level 2 and who returned to school to study for NCEA Level 3.

Semi structured interviews as conversations with all thirteen Māori students who had achieved NCEA Level 2 formed the basis of this research. Five of their parents, seven of their teachers and the principal were also interviewed.

The findings show that these students all stress the importance of their family, in particular, one family member or significant adult in their lives who valued education and supported the student, influencing and encouraging their motivation and self-efficacy. Building positive relationships with their teachers was the next strongest influence on their academic success followed closely by the positive influence of their friends. Self-motivation was mainly extrinsic. The students perceived that the principal had little effect on their individual achievement.

The teachers also acknowledge the importance of building positive relationships with their students and acknowledge the benefits of the reflective practice provided by the Te Kotahitanga project in highlighting this factor.

The findings suggest the excellent initiatives currently taking place in the school need to be continued or strengthened and that further interventions which target particular Māori students, rather than are global across the school, should be introduced.

text: Listening to the voices of Year 13 Māori students: A case study in a New Zealand secondary school This research focuses on listening to the voices of Year 13 academically successful Māori students in a large, urban, mainstream, co-educational, decile 4, New Zealand secondary school. Traditionally, researchers have tended to emphasise the poor academic performance of Māori students in New Zealand. In contrast, this qualitative case study, however, seeks to understand what influences and motivates the academically successful Year 13 Māori students who have gained the National Certificate of Educational Achievement (NCEA) Level 2 and who returned to school to study for NCEA Level 3.

Semi structured interviews as conversations with all thirteen Māori students who had achieved NCEA Level 2 formed the basis of this research. Five of their parents, seven of their teachers and the principal were also interviewed.

The findings show that these students all stress the importance of their family, in particular, one family member or significant adult in their lives who valued education and supported the student, influencing and encouraging their motivation and self-efficacy. Building positive relationships with their teachers was the next strongest influence on their academic success followed closely by the positive influence of their friends. Self-motivation was mainly extrinsic. The students perceived that the principal had little effect on their individual achievement.

The teachers also acknowledge the importance of building positive relationships with their students and acknowledge the benefits of the reflective practice provided by the Te Kotahitanga project in highlighting this factor.

The findings suggest the excellent initiatives currently taking place in the school need to be continued or strengthened and that further interventions which target particular Māori students, rather than are global across the school, should be introduced.

year: 2008