title: Metal complexes of sporidesmin D and dimethylgliotoxin, investigated by electrospray ionisation mass spectrometry

authors: Woodcock, Jane C.

subjects: Electrospray mass spectrometry

abstract: Electrospray ionisation mass spectrometry (ES-MS) has been used to probe the coordination chemistry of metabolites such as sporidesmin D (spdD), found in the saprophytic fungus Pithomyces chartarum, and the related bisdethiobis(methylthio)gliotoxin (dimethylgliotoxin, Megtx). SpdD forms complexes of the type [spdD+M(MeCN)]+ and [2spdD+M]+ (M=Cu, Ag) and, at higher cone voltages, [spdD+M]+. The bis(ligand) ion [2spdD+M]+ was observed at very high cone voltages, indicating it has appreciable stability; the proposed structure of this species has a four-coordinate metal ion with two bidentate spdD ligands, coordinated through their SMe groups. 1H NMR titrations of spdD with K+, Ag+ and Cu+ provided additional evidence for complex formation with the soft metals. SpdD forms only relatively weak complexes with Zn2+, Cd2+, Co2+ and Mn2+, in keeping with the known reduced tendency of these metals to form stable thioether complexes. ES-MS studies of Megtx showed similar results to spdD, with stable adducts formed with Cu+ and Ag+ ions. The X-ray crystal structure of spdD is also reported.

text: Metal complexes of sporidesmin D and dimethylgliotoxin, investigated by electrospray ionisation mass spectrometry Electrospray ionisation mass spectrometry (ES-MS) has been used to probe the coordination chemistry of metabolites such as sporidesmin D (spdD), found in the saprophytic fungus Pithomyces chartarum, and the related bisdethiobis(methylthio)gliotoxin (dimethylgliotoxin, Megtx). SpdD forms complexes of the type [spdD+M(MeCN)]+ and [2spdD+M]+ (M=Cu, Ag) and, at higher cone voltages, [spdD+M]+. The bis(ligand) ion [2spdD+M]+ was observed at very high cone voltages, indicating it has appreciable stability; the proposed structure of this species has a four-coordinate metal ion with two bidentate spdD ligands, coordinated through their SMe groups. 1H NMR titrations of spdD with K+, Ag+ and Cu+ provided additional evidence for complex formation with the soft metals. SpdD forms only relatively weak complexes with Zn2+, Cd2+, Co2+ and Mn2+, in keeping with the known reduced tendency of these metals to form stable thioether complexes. ES-MS studies of Megtx showed similar results to spdD, with stable adducts formed with Cu+ and Ag+ ions. The X-ray crystal structure of spdD is also reported.

year: 2001-04-01

title: Seismic resilience vs. functional recovery of buildings: A critical review

authors: Li, L

abstract: Achieving functional recovery means that buildings can be safely reoccupied in a reasonable amount of time and with minimal repair following a major earthquake. It requires a paradigm shift of building standards and design practice from life-safety-centred to resilience-oriented. This paper presents a critical review of the existing methodologies and frameworks for assessing buildings' seismic resilience and modelling functional recovery. In particular, the insights about how seismic resilience contributes to functional recovery and vice versa were drawn from a comparison of these two concepts. This paper can be helpful in future research to determine the resiliency targets and identify the missing gaps to formulate a framework for functional recovery to be used in the New Zealand engineering and building sector.

text: Seismic resilience vs. functional recovery of buildings: A critical review Achieving functional recovery means that buildings can be safely reoccupied in a reasonable amount of time and with minimal repair following a major earthquake. It requires a paradigm shift of building standards and design practice from life-safety-centred to resilience-oriented. This paper presents a critical review of the existing methodologies and frameworks for assessing buildings' seismic resilience and modelling functional recovery. In particular, the insights about how seismic resilience contributes to functional recovery and vice versa were drawn from a comparison of these two concepts. This paper can be helpful in future research to determine the resiliency targets and identify the missing gaps to formulate a framework for functional recovery to be used in the New Zealand engineering and building sector.

year: 2022

title: Accommodating multiculturalism and biculturalism in Aotearoa New Zealand: implication for language education.

authors: May, Stephen

subjects: bilingual education

abstract: The field of language education in Aotearoa New Zealand, as elsewhere, has developed significantly since its early and almost exclusive focus on the acquisition of English literacy in schools. As the field has expanded, so too has the range of language education sectors addressed and the theoretical approaches and understandings employed in relation to language and literacy education. Both developments have resulted in a more coordinated literacy education policy - exemplified to date most clearly in the New Zealand Literacy Taskforce - and a more situated, less monolithic understanding of the widely different literacies available to learners. Despite these developments, however, one area still remains noticeably under-theorised and marginalized in relation to the ongoing development of language and literacy education policy in Aotearoa New Zealand - the place of second language learners within it. This paper explores this lacuna and the potential policy implications of addressing and integrating first and second language educational concerns within an evolving national literacy education policy. This has particular implications for the further development of bilingual education - both for Maori and, possibly, other minority groups - and for the related possibilities of multicultural education. It also requires a wider and clearer recognition of minority language education rights, as developed within both international law and political theory, in order to apply these rights appropriately to an Aotearoa New Zealand context which is currently witnessing rapid and extensive demographic (and linguistic) change.

text: Accommodating multiculturalism and biculturalism in Aotearoa New Zealand: implication for language education. The field of language education in Aotearoa New Zealand, as elsewhere, has developed significantly since its early and almost exclusive focus on the acquisition of English literacy in schools. As the field has expanded, so too has the range of language education sectors addressed and the theoretical approaches and understandings employed in relation to language and literacy education. Both developments have resulted in a more coordinated literacy education policy - exemplified to date most clearly in the New Zealand Literacy Taskforce - and a more situated, less monolithic understanding of the widely different literacies available to learners. Despite these developments, however, one area still remains noticeably under-theorised and marginalized in relation to the ongoing development of language and literacy education policy in Aotearoa New Zealand - the place of second language learners within it. This paper explores this lacuna and the potential policy implications of addressing and integrating first and second language educational concerns within an evolving national literacy education policy. This has particular implications for the further development of bilingual education - both for Maori and, possibly, other minority groups - and for the related possibilities of multicultural education. It also requires a wider and clearer recognition of minority language education rights, as developed within both international law and political theory, in order to apply these rights appropriately to an Aotearoa New Zealand context which is currently witnessing rapid and extensive demographic (and linguistic) change.

year: 2002