title: Antifungal terpenoid and troponoid analogues for wood durability enhancement

authors: Torr, Kirk

abstract: Aspects of the development of novel analogues of terpenoid and tropolone natural products with antifungal properties against important wood deteriorating fungi are reported. Antifungal wood extractives and essential oil components provided valuable leads in chemical syntheses toward novel compounds with potential as wood bio-protectants.

Analogues of antifungal monoterpenoid and diterpenoid wood extractives were synthesised and tested for activity against wood damaging fungi. 1-Methyl-4-nonylcyclohexan-1-ol, an analogue of β-terpineol and 2-isopropyl-4-nonylphenol, an analogue of thymol were prepared from p-n-nonylanisole by multi-step syntheses. 2-Isopropyl-1-naphthol, a simplified analogue of totarol was prepared by C-isopropylation of β-naphthoxide. In antifungal activity assays, these terpenoid analogues showed good to moderate activity against the brown rot fungus Coniophora puteana but were, in general, only weakly active against the other test decay and staining fungi.

A bio-activity led investigation of oxygenated sesquiterpenoids from the foliage essential oils of three New Zealand native softwoods, totara, rimu and kahikatea, identified caryophyllene oxide, humulene oxide II, globulol and a-cadinol as major components of fungistatic oil fractions. Based on these findings simple synthetic compounds with epoxide (4-nonylcyclohexan-1,2-epoxide) and tertiary alcohol functionalities (4-ethyl-1-methyl-1,2,3,4-tetrahydronaphth-1-ol and 5,9-dimethyl-6,7,8,9-tetrahydrobenzocyclohepten-5-ol) were synthesised by multi-step pathways. Bioassays against wood decay and sapstain fungi revealed these compounds possessed efficacies equal to, or in some cases superior to, the natural sesquiterpenoids.

A range of known and novel tropolone compounds was prepared by adapted literature methods. 3-Carboxy-4-carboxymethyltropolone, prepared by oxidation of purpurogallin, was a key intermediate in the synthesis of 4-alkylcarboxytropolones, an alkyl δ-lactone tropolone, 4-alkenyl and 4-alkyltropolones and 4-styryltropolones. A new synthetic pathway to β-thujaplicin via oxidation of 1-methyl-3,4,6-trihydroxy-(5H)-benzocyclohepten-5-one was proposed and investigated, but proved unsuccessful. A series of novel 3-alkyltropolones were prepared by direct alkylation of tropolone and β-thujaplicin with diethyl acetals. 3-(1-Formylmethyl)tropolone, prepared by condensation of trans-hex-2-enal diethyl acetal with tropolone, proved a useful intermediate to tropolones with secondary functional groups. A selection of these synthetic tropolones exhibited potent antifungal properties against four wood damaging fungi, in particular Coniophora puteana. Efficacies were comparable to and, in certain cases, superior to the commercial wood preservative tri-n-butyltin napththenate (TBTN). The best performing of the tropolones was 3-(1-ethyl)butyltropolone. This compound exhibited greater fungitoxicity than TBTN against the white rot and soft rot test fungi and was of comparable activity to the commercial antisapstain agent 3-iodo-2-propynyl butyl carbamate against the sapstain fungus Sphaeropsis sapinea.

text: Antifungal terpenoid and troponoid analogues for wood durability enhancement Aspects of the development of novel analogues of terpenoid and tropolone natural products with antifungal properties against important wood deteriorating fungi are reported. Antifungal wood extractives and essential oil components provided valuable leads in chemical syntheses toward novel compounds with potential as wood bio-protectants.

Analogues of antifungal monoterpenoid and diterpenoid wood extractives were synthesised and tested for activity against wood damaging fungi. 1-Methyl-4-nonylcyclohexan-1-ol, an analogue of β-terpineol and 2-isopropyl-4-nonylphenol, an analogue of thymol were prepared from p-n-nonylanisole by multi-step syntheses. 2-Isopropyl-1-naphthol, a simplified analogue of totarol was prepared by C-isopropylation of β-naphthoxide. In antifungal activity assays, these terpenoid analogues showed good to moderate activity against the brown rot fungus Coniophora puteana but were, in general, only weakly active against the other test decay and staining fungi.

A bio-activity led investigation of oxygenated sesquiterpenoids from the foliage essential oils of three New Zealand native softwoods, totara, rimu and kahikatea, identified caryophyllene oxide, humulene oxide II, globulol and a-cadinol as major components of fungistatic oil fractions. Based on these findings simple synthetic compounds with epoxide (4-nonylcyclohexan-1,2-epoxide) and tertiary alcohol functionalities (4-ethyl-1-methyl-1,2,3,4-tetrahydronaphth-1-ol and 5,9-dimethyl-6,7,8,9-tetrahydrobenzocyclohepten-5-ol) were synthesised by multi-step pathways. Bioassays against wood decay and sapstain fungi revealed these compounds possessed efficacies equal to, or in some cases superior to, the natural sesquiterpenoids.

A range of known and novel tropolone compounds was prepared by adapted literature methods. 3-Carboxy-4-carboxymethyltropolone, prepared by oxidation of purpurogallin, was a key intermediate in the synthesis of 4-alkylcarboxytropolones, an alkyl δ-lactone tropolone, 4-alkenyl and 4-alkyltropolones and 4-styryltropolones. A new synthetic pathway to β-thujaplicin via oxidation of 1-methyl-3,4,6-trihydroxy-(5H)-benzocyclohepten-5-one was proposed and investigated, but proved unsuccessful. A series of novel 3-alkyltropolones were prepared by direct alkylation of tropolone and β-thujaplicin with diethyl acetals. 3-(1-Formylmethyl)tropolone, prepared by condensation of trans-hex-2-enal diethyl acetal with tropolone, proved a useful intermediate to tropolones with secondary functional groups. A selection of these synthetic tropolones exhibited potent antifungal properties against four wood damaging fungi, in particular Coniophora puteana. Efficacies were comparable to and, in certain cases, superior to the commercial wood preservative tri-n-butyltin napththenate (TBTN). The best performing of the tropolones was 3-(1-ethyl)butyltropolone. This compound exhibited greater fungitoxicity than TBTN against the white rot and soft rot test fungi and was of comparable activity to the commercial antisapstain agent 3-iodo-2-propynyl butyl carbamate against the sapstain fungus Sphaeropsis sapinea.

year: 2002

title: Diurnal changes in the heterotrophic uptake of glycolate and glucose in two lakes

authors: Rawley, Brian Andrew

subjects: Antarctica

abstract: A study was made of diurnal changes in the heterotrophic uptake kinetics of both ¹⁴C-glucose and ¹⁴C- glycolate in two small stratified lakes, Lake Rotomanuka in New Zealand and Lake Fryxell in Antarctica. The purpose of the investigation was to study the effect that diurnal changes in the extracellular release of certain substrates by algae might have on the uptake of those substrates by aquatic microheterotrophs. The heterotrophic uptake technique of Parsons and Strickland.(196l) was modified to provide a technique which was more convenient for field-work. In an effort to exclude the effects of migration and heterogeneous population distribution on substrate uptake, the microbial population in each lake was observed using a combination of (a) direct counts of bacteria (using acridine orange staining and epi-fluorescent microscopy); (b) measurement of chlorophyll α and bacterio-chlorophyll and (c) measurement of the reduction of INT dye. The natural concentration of glycolate was measured on some occasions using a modification of the technique of Shah and Wright (1974).

text: Diurnal changes in the heterotrophic uptake of glycolate and glucose in two lakes A study was made of diurnal changes in the heterotrophic uptake kinetics of both ¹⁴C-glucose and ¹⁴C- glycolate in two small stratified lakes, Lake Rotomanuka in New Zealand and Lake Fryxell in Antarctica. The purpose of the investigation was to study the effect that diurnal changes in the extracellular release of certain substrates by algae might have on the uptake of those substrates by aquatic microheterotrophs. The heterotrophic uptake technique of Parsons and Strickland.(196l) was modified to provide a technique which was more convenient for field-work. In an effort to exclude the effects of migration and heterogeneous population distribution on substrate uptake, the microbial population in each lake was observed using a combination of (a) direct counts of bacteria (using acridine orange staining and epi-fluorescent microscopy); (b) measurement of chlorophyll α and bacterio-chlorophyll and (c) measurement of the reduction of INT dye. The natural concentration of glycolate was measured on some occasions using a modification of the technique of Shah and Wright (1974).

year: 1982

title: Implementation framework for chronic disease intervention effectiveness in Maori and other indigenous communities

authors: Oetzel, John G.

subjects: Science & Technology

abstract: Background: About 40% of all health burden in New Zealand is due to cancer, cardiovascular disease, and type 2 diabetes/obesity. Outcomes for Māori (indigenous people) are significantly worse than non-Maori; these inequities mirror those found in indigenous communities elsewhere. Evidence-based interventions with established efficacy may not be effective in indigenous communities without addressing specific implementation challenges. We present an implementation framework for interventions to prevent and treat chronic conditions for Māori and other indigenous communities.
Theoretical framework: The He Pikinga Waiora Implementation Framework has indigenous self-determination at its core and consists of four elements: cultural-centeredness, community engagement, systems thinking, and integrated knowledge translation. All elements have conceptual fit with Kaupapa Māori aspirations (i.e., indigenous knowledge creation, theorizing, and methodology) and all have demonstrated evidence of positive implementation outcomes.
Applying the framework: A coding scheme derived from the Framework was applied to 13 studies of diabetes prevention in indigenous communities in Australia, Canada, New Zealand, and the United States from a systematic review. Cross-tabulations demonstrated that culture-centeredness (p = .008) and community engagement (p = .009) explained differences in diabetes outcomes and community engagement (p = .098) explained difference in blood pressure outcomes.
Implications and conclusions: The He Pikinga Waiora Implementation Framework appears to be well suited to advance implementation science for indigenous communities in general and Māori in particular. The framework has promise as a policy and planning tool to evaluate and design effective interventions for chronic disease prevention in indigenous communities.

text: Implementation framework for chronic disease intervention effectiveness in Maori and other indigenous communities Background: About 40% of all health burden in New Zealand is due to cancer, cardiovascular disease, and type 2 diabetes/obesity. Outcomes for Māori (indigenous people) are significantly worse than non-Maori; these inequities mirror those found in indigenous communities elsewhere. Evidence-based interventions with established efficacy may not be effective in indigenous communities without addressing specific implementation challenges. We present an implementation framework for interventions to prevent and treat chronic conditions for Māori and other indigenous communities.
Theoretical framework: The He Pikinga Waiora Implementation Framework has indigenous self-determination at its core and consists of four elements: cultural-centeredness, community engagement, systems thinking, and integrated knowledge translation. All elements have conceptual fit with Kaupapa Māori aspirations (i.e., indigenous knowledge creation, theorizing, and methodology) and all have demonstrated evidence of positive implementation outcomes.
Applying the framework: A coding scheme derived from the Framework was applied to 13 studies of diabetes prevention in indigenous communities in Australia, Canada, New Zealand, and the United States from a systematic review. Cross-tabulations demonstrated that culture-centeredness (p = .008) and community engagement (p = .009) explained differences in diabetes outcomes and community engagement (p = .098) explained difference in blood pressure outcomes.
Implications and conclusions: The He Pikinga Waiora Implementation Framework appears to be well suited to advance implementation science for indigenous communities in general and Māori in particular. The framework has promise as a policy and planning tool to evaluate and design effective interventions for chronic disease prevention in indigenous communities.

year: 2017