title: Manganese carbonyl-mediated reactions of azabutadienes with phenylacetylene, methyl acrylate and other unsaturated molecules

authors: Mace, Wade

subjects: azabutadienes

abstract: Reaction of PhCH₂Mn(CO)₅ with l,4-di-aryl-1-aza-1,3-butadienes gave substituted pyrrolinonyl rings which were η⁴-coordinated to a Mn(CO)₃ group. These are formed by intramolecular CO insertion into a (non-isolated) cyclomanganated intermediate, followed by cyclisation. Other unsaturated reagents (PhC≡CH, CH2=CHCOOMe, PhNCO) gave products arising from insertion of these, including a structurally characterised tri-aryl-η⁵-azacyclohexadienyl-Mn(CO)₃ complex from the reaction with the alkyne.
PhCH₂Mn(CO)₅ reacts with l,4-di-aryl-1-aza-1,3-butadienes in the presence of unsaturated substrates to give products based on a cyclomanganated intermediate.

text: Manganese carbonyl-mediated reactions of azabutadienes with phenylacetylene, methyl acrylate and other unsaturated molecules Reaction of PhCH₂Mn(CO)₅ with l,4-di-aryl-1-aza-1,3-butadienes gave substituted pyrrolinonyl rings which were η⁴-coordinated to a Mn(CO)₃ group. These are formed by intramolecular CO insertion into a (non-isolated) cyclomanganated intermediate, followed by cyclisation. Other unsaturated reagents (PhC≡CH, CH2=CHCOOMe, PhNCO) gave products arising from insertion of these, including a structurally characterised tri-aryl-η⁵-azacyclohexadienyl-Mn(CO)₃ complex from the reaction with the alkyne.
PhCH₂Mn(CO)₅ reacts with l,4-di-aryl-1-aza-1,3-butadienes in the presence of unsaturated substrates to give products based on a cyclomanganated intermediate.

year: 2004-08-01

title: Astroenzymology – the environmental limits of enzyme activity

authors: Daniel, Roy M.

subjects: hydration

abstract: Using organisms from extreme terrestrial environments as models for extraterrestrial life may lead us to underestimate the range of environments that life may inhabit. An alternative approach is to inspect the range of conditions over which crucial biomolecules might function. Recent investigations of enzyme activity suggest that they have the potential to function over a wider range of environmental conditions than expected. Although the upper temperature limit for enzyme stability is unclear, some enzymes are active up to 130°C. The evidence is that the instability of enzymes is a functional requirement, rather then because of any restraint on achieving higher stability. There is no evidence that enzyme activity ceases at low temperatures; it declines in a predictable manner to the lowest temperature at which it has been possible to make measurements, -100°C. It has been generally accepted that dehydration stops enzyme activity but this acceptance may have arisen partly from the technical difficulty of assessing enzyme activity without a fluid medium for diffusion. Experiments using anhydrous organic solvents or gas phase substrates suggest activity occurs in enzymes at very low hydration.

text: Astroenzymology – the environmental limits of enzyme activity Using organisms from extreme terrestrial environments as models for extraterrestrial life may lead us to underestimate the range of environments that life may inhabit. An alternative approach is to inspect the range of conditions over which crucial biomolecules might function. Recent investigations of enzyme activity suggest that they have the potential to function over a wider range of environmental conditions than expected. Although the upper temperature limit for enzyme stability is unclear, some enzymes are active up to 130°C. The evidence is that the instability of enzymes is a functional requirement, rather then because of any restraint on achieving higher stability. There is no evidence that enzyme activity ceases at low temperatures; it declines in a predictable manner to the lowest temperature at which it has been possible to make measurements, -100°C. It has been generally accepted that dehydration stops enzyme activity but this acceptance may have arisen partly from the technical difficulty of assessing enzyme activity without a fluid medium for diffusion. Experiments using anhydrous organic solvents or gas phase substrates suggest activity occurs in enzymes at very low hydration.

year: 2003-02

title: New Zealand’s Performance Based Research Funding (PBRF) model undermines Maori research

authors: Roa, Tom

subjects: Performance Based Research Funding

abstract: The Performance Based Research Funding (PBRF) model was instigated in 2002 to increase “the quality of research through peer assessment and performance indicators” in New Zealand (Ministry of Education 2002: 17). It is used to allocate funding between universities, departments and researchers according to the putative quality and quantity of their research outputs over the preceding 6 years. PBRF is expected to incentivise improved research excellence and efficiency, and allow government to invest research funds where greatest returns will result. This is potentially a huge gain for Māori. However, “by changing the conditions of knowledge production, research assessment exercises may also alter the shape and direction of disciplines by diverting and channelling researchers’ intellectual attention and political engagement, influencing what they study, how they do it, and how they report and write” (Middleton 2009: 194). Indeed, universities repeatedly encourage researchers to focus on activities that will improve their PBRF rankings. We believe that an unintended consequence of PBRF is the creation of significant barriers to increasing the volume, scope and quality of environmental research for Māori.

text: New Zealand’s Performance Based Research Funding (PBRF) model undermines Maori research The Performance Based Research Funding (PBRF) model was instigated in 2002 to increase “the quality of research through peer assessment and performance indicators” in New Zealand (Ministry of Education 2002: 17). It is used to allocate funding between universities, departments and researchers according to the putative quality and quantity of their research outputs over the preceding 6 years. PBRF is expected to incentivise improved research excellence and efficiency, and allow government to invest research funds where greatest returns will result. This is potentially a huge gain for Māori. However, “by changing the conditions of knowledge production, research assessment exercises may also alter the shape and direction of disciplines by diverting and channelling researchers’ intellectual attention and political engagement, influencing what they study, how they do it, and how they report and write” (Middleton 2009: 194). Indeed, universities repeatedly encourage researchers to focus on activities that will improve their PBRF rankings. We believe that an unintended consequence of PBRF is the creation of significant barriers to increasing the volume, scope and quality of environmental research for Māori.

year: 2009