title: Leaf-level coordination principles propagate to the ecosystem scale.

authors: Gomarasca, Ulisse

subjects: Ecosystem

abstract: Fundamental axes of variation in plant traits result from trade-offs between costs and benefits of resource-use strategies at the leaf scale. However, it is unclear whether similar trade-offs propagate to the ecosystem level. Here, we test whether trait correlation patterns predicted by three well-known leaf- and plant-level coordination theories - the leaf economics spectrum, the global spectrum of plant form and function, and the least-cost hypothesis - are also observed between community mean traits and ecosystem processes. We combined ecosystem functional properties from FLUXNET sites, vegetation properties, and community mean plant traits into three corresponding principal component analyses. We find that the leaf economics spectrum (90 sites), the global spectrum of plant form and function (89 sites), and the least-cost hypothesis (82 sites) all propagate at the ecosystem level. However, we also find evidence of additional scale-emergent properties. Evaluating the coordination of ecosystem functional properties may aid the development of more realistic global dynamic vegetation models with critical empirical data, reducing the uncertainty of climate change projections.

text: Leaf-level coordination principles propagate to the ecosystem scale. Fundamental axes of variation in plant traits result from trade-offs between costs and benefits of resource-use strategies at the leaf scale. However, it is unclear whether similar trade-offs propagate to the ecosystem level. Here, we test whether trait correlation patterns predicted by three well-known leaf- and plant-level coordination theories - the leaf economics spectrum, the global spectrum of plant form and function, and the least-cost hypothesis - are also observed between community mean traits and ecosystem processes. We combined ecosystem functional properties from FLUXNET sites, vegetation properties, and community mean plant traits into three corresponding principal component analyses. We find that the leaf economics spectrum (90 sites), the global spectrum of plant form and function (89 sites), and the least-cost hypothesis (82 sites) all propagate at the ecosystem level. However, we also find evidence of additional scale-emergent properties. Evaluating the coordination of ecosystem functional properties may aid the development of more realistic global dynamic vegetation models with critical empirical data, reducing the uncertainty of climate change projections.

year: 2023-07-04

title: Kinetic studies of redox and related reactions of some new isoalloxazines

authors: Gumbley, Stewart John

abstract: This thesis describes the synthesis of three new isoalloxazines with special structural characteristics which we hoped would, and in fact did, modify their chemical reactivity so as to improve our understanding of mechanisms of flavin reactions generally: kinetic studies of their reactions with a dithiol, reduced nicotinamide and sulphite were made.

A new general synthesis is described for the preparation of o-nitro-(N-alkylamino) aromatic compounds via nucleophilic displacement by alkylamine of a methoxy group ortho to a nitro group. Two new compounds, the isomers 1-(2'-hydroxyethylamino)-2-nitronaphthalene and 2-(2'-hydroxyethylamino)-1-nitronaphthalene, were prepared by this method.

These compounds were used to synthesize two isoalloxazines which each have an additional benzene ring fused either at the 6,7-bond of the isoalloxazine nucleus (7-(2'-hydroxyethyl)-10-methylnaphtho[1,2-g]pteridine- 9,11(7H,10H)-dione; isoalloxazine A) or at the 8,9-bond (12-(2'-hydroxyethyl)-9-methylnaphtho[2,1-g]pteridine- 8,10(9H,12H)-dione; isoalloxazine B). The third new isoalloxazine (10-(2'-hydroxyethyl)-3-methylbenzo[g]pteridine- 2,4(3H,10H)-dione; isoalloxazine C) was prepared by a conventional route.

Kinetic studies, the first recorded for isoalloxazines of the type of A and B, were undertaken for reactions with 1,3-dithio-2-propanol, with NADH and with sulphite.

In the case of the dithiopropanol reaction, a linear free-energy relationship was observed between the logarithm of the second order rate constant and the polarographic half-wave potential, E⅟₂ (slope 26 ± 1 V⁻¹). The conclusion drawn from this is that, if the redox reaction occurs through an addition-elimination sequence, the 5-, 6- and 8-positions are not essential centres for thiol oxidation.

In the case of the reaction with NADH, direct evidence was obtained for the formation of a kinetically important complex between the isoalloxazine and NADH from the observation of saturation kinetics. This is the first reported instance of the observation of such direct evidence for complex formation with NADH. The rate constants for the three isoalloxazines follow the reverse order expected from the E⅟₂ values and from the rates of reaction with DTP. The equilibrium constants (Kₑ) for the complexing of tryptophan with the isoalloxazines were measured by fluorescence quenching. A linear free-energy relationship was not observed between the logarithm of Kₑ and the logarithm of the rate constant for NADH oxidation. It was concluded that the unexpectedly high rate of reaction of A relative to that of B was due to the formation by A of a complex with NADH closer to the hydride acceptor site, the 5-position, than is the case for isoalloxazine B; and that the productivity of the complex therefore is markedly determined by the orientation of the NADH molecule with respect to the isoalloxazine within the complex.

The anaerobic nucleophilic addition reaction of sulphite with isoalloxazines A and C is a two step process of the form X⇌Y→Z, whereas the reaction with B is a single equilibrium step. The reduced isoalloxazine products from A and C are oxidized by molecular oxygen to new isoalloxazines but that from B is not. The new isoalloxazine from C reacts further with sulphite to yield a reduced species different from that of the anaerobic reaction, while the product from A does not react further. These observations provide support for the mechanism previously suggested in the literature for the reaction of sulphite with isoalloxazines. A small rate depression was observed for A relative to B and C in a plot of logarithm of rate constant against E ⅟₂. This is interpreted as being due to steric crowding at the 5-position caused by the α-hydrogen on the naphthalene moiety, an effect not observed in the dithiol reaction which more likely involves nucleophilic addition at the 4a- rather than the 5-position.

text: Kinetic studies of redox and related reactions of some new isoalloxazines This thesis describes the synthesis of three new isoalloxazines with special structural characteristics which we hoped would, and in fact did, modify their chemical reactivity so as to improve our understanding of mechanisms of flavin reactions generally: kinetic studies of their reactions with a dithiol, reduced nicotinamide and sulphite were made.

A new general synthesis is described for the preparation of o-nitro-(N-alkylamino) aromatic compounds via nucleophilic displacement by alkylamine of a methoxy group ortho to a nitro group. Two new compounds, the isomers 1-(2'-hydroxyethylamino)-2-nitronaphthalene and 2-(2'-hydroxyethylamino)-1-nitronaphthalene, were prepared by this method.

These compounds were used to synthesize two isoalloxazines which each have an additional benzene ring fused either at the 6,7-bond of the isoalloxazine nucleus (7-(2'-hydroxyethyl)-10-methylnaphtho[1,2-g]pteridine- 9,11(7H,10H)-dione; isoalloxazine A) or at the 8,9-bond (12-(2'-hydroxyethyl)-9-methylnaphtho[2,1-g]pteridine- 8,10(9H,12H)-dione; isoalloxazine B). The third new isoalloxazine (10-(2'-hydroxyethyl)-3-methylbenzo[g]pteridine- 2,4(3H,10H)-dione; isoalloxazine C) was prepared by a conventional route.

Kinetic studies, the first recorded for isoalloxazines of the type of A and B, were undertaken for reactions with 1,3-dithio-2-propanol, with NADH and with sulphite.

In the case of the dithiopropanol reaction, a linear free-energy relationship was observed between the logarithm of the second order rate constant and the polarographic half-wave potential, E⅟₂ (slope 26 ± 1 V⁻¹). The conclusion drawn from this is that, if the redox reaction occurs through an addition-elimination sequence, the 5-, 6- and 8-positions are not essential centres for thiol oxidation.

In the case of the reaction with NADH, direct evidence was obtained for the formation of a kinetically important complex between the isoalloxazine and NADH from the observation of saturation kinetics. This is the first reported instance of the observation of such direct evidence for complex formation with NADH. The rate constants for the three isoalloxazines follow the reverse order expected from the E⅟₂ values and from the rates of reaction with DTP. The equilibrium constants (Kₑ) for the complexing of tryptophan with the isoalloxazines were measured by fluorescence quenching. A linear free-energy relationship was not observed between the logarithm of Kₑ and the logarithm of the rate constant for NADH oxidation. It was concluded that the unexpectedly high rate of reaction of A relative to that of B was due to the formation by A of a complex with NADH closer to the hydride acceptor site, the 5-position, than is the case for isoalloxazine B; and that the productivity of the complex therefore is markedly determined by the orientation of the NADH molecule with respect to the isoalloxazine within the complex.

The anaerobic nucleophilic addition reaction of sulphite with isoalloxazines A and C is a two step process of the form X⇌Y→Z, whereas the reaction with B is a single equilibrium step. The reduced isoalloxazine products from A and C are oxidized by molecular oxygen to new isoalloxazines but that from B is not. The new isoalloxazine from C reacts further with sulphite to yield a reduced species different from that of the anaerobic reaction, while the product from A does not react further. These observations provide support for the mechanism previously suggested in the literature for the reaction of sulphite with isoalloxazines. A small rate depression was observed for A relative to B and C in a plot of logarithm of rate constant against E ⅟₂. This is interpreted as being due to steric crowding at the 5-position caused by the α-hydrogen on the naphthalene moiety, an effect not observed in the dithiol reaction which more likely involves nucleophilic addition at the 4a- rather than the 5-position.

year: 1976

title: Ko wai tēnei e tū ake nei? Activating collectivity and accountability through grounded positioning

authors: Rata, Arama

abstract: Building on conference conversations about positionality—about who we are and how our identities shape our views of the world, about the connections and disconnections experienced between us, and about our proximities to place, power, and privilege—this piece brings together four conference participants to continue to reflect on what positionality means, on why it is important, and on how to practice it in non-performative, well-developed, and mutually nourishing ways. Their dialogue reflects active and critical positioning in process and practice, creating opportunities for acknowledging our relationships and activating both collectivity and accountability in the various spaces where we live, work, create, and hope.

text: Ko wai tēnei e tū ake nei? Activating collectivity and accountability through grounded positioning Building on conference conversations about positionality—about who we are and how our identities shape our views of the world, about the connections and disconnections experienced between us, and about our proximities to place, power, and privilege—this piece brings together four conference participants to continue to reflect on what positionality means, on why it is important, and on how to practice it in non-performative, well-developed, and mutually nourishing ways. Their dialogue reflects active and critical positioning in process and practice, creating opportunities for acknowledging our relationships and activating both collectivity and accountability in the various spaces where we live, work, create, and hope.

year: 2021-12