title: Cis-trans ring substituent isomerism in cyano-substituted metallathietane-3,3-dioxide complexes of platinum(II) and palladium(II)

authors: Dowling-Mitchell, Sacha A.M.

abstract: Reactions of the platinum complexes cis-[PtCl₂(PPh₃)₂ ], [PtCl₂(dppf)], or [PtCl₂(dppe)], and the palladium complexes, [PdCl₂(PPh₃)₂] or [PdCl₂(dppe)], with bis(cyanomethyl)sulfone NCCH₂SO₂ CH₂CN  in methanol with added trimethylamine base gave the new cyano-substituted metallathietane-3,3- dioxide complexes [M{CH(CN)SO₂ CH(CN)}L₂ ] (M = Pd, Pt) in good yields and purities. ¹H and ³¹P{¹H} NMR spectroscopy indicates that (in the majority of cases) the products are formed as a mixture of cis and trans isomers, with regard to the disposition of the cyano groups across the four-membered ring. An X-ray structure determination on a crystal of [Pd{CH(CN)SO₂CH(CN)}(PPh₃)₂] showed it to be of the cis isomer, the ﬁrst structurally characterized cis isomer of this type of complex. The four-membered palladacyclic ring is highly planar, in contrast to other metallathietane-3,3-dioxide complexes that have puckered rings. Factors inﬂuencing the relative abundances of the two isomers of [Pd{CH(CN)SO₂CH(CN)}(PR₃)₂] have been investigated by means of NMR spectroscopy and DFT calculations.

text: Cis-trans ring substituent isomerism in cyano-substituted metallathietane-3,3-dioxide complexes of platinum(II) and palladium(II) Reactions of the platinum complexes cis-[PtCl₂(PPh₃)₂ ], [PtCl₂(dppf)], or [PtCl₂(dppe)], and the palladium complexes, [PdCl₂(PPh₃)₂] or [PdCl₂(dppe)], with bis(cyanomethyl)sulfone NCCH₂SO₂ CH₂CN  in methanol with added trimethylamine base gave the new cyano-substituted metallathietane-3,3- dioxide complexes [M{CH(CN)SO₂ CH(CN)}L₂ ] (M = Pd, Pt) in good yields and purities. ¹H and ³¹P{¹H} NMR spectroscopy indicates that (in the majority of cases) the products are formed as a mixture of cis and trans isomers, with regard to the disposition of the cyano groups across the four-membered ring. An X-ray structure determination on a crystal of [Pd{CH(CN)SO₂CH(CN)}(PPh₃)₂] showed it to be of the cis isomer, the ﬁrst structurally characterized cis isomer of this type of complex. The four-membered palladacyclic ring is highly planar, in contrast to other metallathietane-3,3-dioxide complexes that have puckered rings. Factors inﬂuencing the relative abundances of the two isomers of [Pd{CH(CN)SO₂CH(CN)}(PR₃)₂] have been investigated by means of NMR spectroscopy and DFT calculations.

year: 2012

title: Spatial equity and realised access to healthcare - a geospatial analysis of general practitioner enrolments in Waikato, New Zealand

authors: Whitehead, Jesse

subjects: Science & Technology

abstract: Introduction:  Geographic measures of accessibility can quantify inequitable distributions of health care. Although closest distance measures are often used in Aotearoa New Zealand these may not reflect patient use of health care. This research examines patterns of patient enrolment in general practitioner (GP) services from a geospatial perspective.
Methods:  Patient enrolment records (n=137 596) from one primary health organisation were examined and geographic information systems used to determine whether patients enrolled with their closest GP service. A binomial logistic regression was performed to examine factors associated with the bypass of GP services closer to patients’ homes.
Results:  Overall 68.1% of patients in the sample bypassed the GP service closest to their home, while rates of GP bypass varied across the Waikato region and between rural and urban areas. A binary logistic regression analysis revealed that rurality of patient residence, patient ethnicity, patient age, area-level socioeconomic deprivation, sex, distance to the closest GP clinic, clinic after-hours availability, Māori service provider status, GP and nurse full time equivalent hours, and clinic fees were statistically significant predictors of increased closest-GP bypass. While residents of major urban areas had high rates of GP bypass, this was followed by patients living in rural areas – patients living more than 20 km from the closest GP service had exceptionally high rates of GP bypass.
Conclusion:  This study suggests that most patients in the Waikato region do not enrol with the GP service closest to their home and it outlines several factors, including rurality of residence, associated with the GP bypass. Closest distance accessibility measures may be inappropriate in mixed urban–rural settings, and researchers should consider other approaches to quantifying spatial equity. Health services should also be designed to better reflect the realities of the populations they serve.

text: Spatial equity and realised access to healthcare - a geospatial analysis of general practitioner enrolments in Waikato, New Zealand Introduction:  Geographic measures of accessibility can quantify inequitable distributions of health care. Although closest distance measures are often used in Aotearoa New Zealand these may not reflect patient use of health care. This research examines patterns of patient enrolment in general practitioner (GP) services from a geospatial perspective.
Methods:  Patient enrolment records (n=137 596) from one primary health organisation were examined and geographic information systems used to determine whether patients enrolled with their closest GP service. A binomial logistic regression was performed to examine factors associated with the bypass of GP services closer to patients’ homes.
Results:  Overall 68.1% of patients in the sample bypassed the GP service closest to their home, while rates of GP bypass varied across the Waikato region and between rural and urban areas. A binary logistic regression analysis revealed that rurality of patient residence, patient ethnicity, patient age, area-level socioeconomic deprivation, sex, distance to the closest GP clinic, clinic after-hours availability, Māori service provider status, GP and nurse full time equivalent hours, and clinic fees were statistically significant predictors of increased closest-GP bypass. While residents of major urban areas had high rates of GP bypass, this was followed by patients living in rural areas – patients living more than 20 km from the closest GP service had exceptionally high rates of GP bypass.
Conclusion:  This study suggests that most patients in the Waikato region do not enrol with the GP service closest to their home and it outlines several factors, including rurality of residence, associated with the GP bypass. Closest distance accessibility measures may be inappropriate in mixed urban–rural settings, and researchers should consider other approaches to quantifying spatial equity. Health services should also be designed to better reflect the realities of the populations they serve.

year: 2019

title: The appropriate use of Te Reo Maori in the names of new species discovered in Aotearoa New Zealand

authors: Papa, Judy Wiki

subjects: Te Reo Maori

abstract: Language is the key to understanding
Ko te reo te taikura o te whakaao-mārama
In this thesis I investigate the naming of new species that are being discovered in and around the waters of the coastline, across the vast landscape and in remote areas of Aotearoa New Zealand. These native species often endemic to Aotearoa New Zealand are often named with no reference to the native landscape and wear names that pay homage to or represent ancestors and traditions of another culture.   Few of these species have been given scientific names that include Te Reo Māori and this study sought to explore why this was the case and how Te Reo Māori should be included in these names.
This study investigated the background, methods and the knowledge associated with matauranga Māori and scientific naming protocols and how these could be incorporated into the naming of new species of Aotearoa New Zealand.  Data were gathered from historical manuscripts that mention naming or classification of species in Aotearoa New Zealand, literature about classification, and eight interviews with people knowledgeable in the Māori and western scientific naming traditions of nomenclature and classification.  The interview data was transcribed and analysed using these themes drawn both from the literature and the data.  The study considered the rightful place of Māori knowledge and western scientific systems of naming new species, including the appropriate use of Te Reo Māori in a uniquely Aotearoa New Zealand way.
My findings indicate that the practice of naming species in Aotearoa New Zealand by scientists is governed by international protocols and that any incorporation of Te Reo Māori varied, and this variation depended on individual researchers that have developed their own method of using Te Reo Māori in the names of new species.  The findings indicate however that Te Reo Māori is of utmost importance to a Māori cultural context and must be used appropriately for the benefit of future generations of Māori.  
In my conclusions I acknowledge the two systems of biological classification and matauranga Māori and their historical importance in the classification of species in Aotearoa New Zealand and on the international stage.  I also recommend a set of guidelines derived from the research findings on the appropriate use of Te Reo Māori in naming new species.

text: The appropriate use of Te Reo Maori in the names of new species discovered in Aotearoa New Zealand Language is the key to understanding
Ko te reo te taikura o te whakaao-mārama
In this thesis I investigate the naming of new species that are being discovered in and around the waters of the coastline, across the vast landscape and in remote areas of Aotearoa New Zealand. These native species often endemic to Aotearoa New Zealand are often named with no reference to the native landscape and wear names that pay homage to or represent ancestors and traditions of another culture.   Few of these species have been given scientific names that include Te Reo Māori and this study sought to explore why this was the case and how Te Reo Māori should be included in these names.
This study investigated the background, methods and the knowledge associated with matauranga Māori and scientific naming protocols and how these could be incorporated into the naming of new species of Aotearoa New Zealand.  Data were gathered from historical manuscripts that mention naming or classification of species in Aotearoa New Zealand, literature about classification, and eight interviews with people knowledgeable in the Māori and western scientific naming traditions of nomenclature and classification.  The interview data was transcribed and analysed using these themes drawn both from the literature and the data.  The study considered the rightful place of Māori knowledge and western scientific systems of naming new species, including the appropriate use of Te Reo Māori in a uniquely Aotearoa New Zealand way.
My findings indicate that the practice of naming species in Aotearoa New Zealand by scientists is governed by international protocols and that any incorporation of Te Reo Māori varied, and this variation depended on individual researchers that have developed their own method of using Te Reo Māori in the names of new species.  The findings indicate however that Te Reo Māori is of utmost importance to a Māori cultural context and must be used appropriately for the benefit of future generations of Māori.  
In my conclusions I acknowledge the two systems of biological classification and matauranga Māori and their historical importance in the classification of species in Aotearoa New Zealand and on the international stage.  I also recommend a set of guidelines derived from the research findings on the appropriate use of Te Reo Māori in naming new species.

year: 2012