title: Indole diterpenoid secondary metabolites produced by the Epichloë festucae var. lolii – Lolium perenne symbiosis.

authors: Kaufononga, Sangata Ana Fiealu

abstract: The indole diterpenoid intermediates of lolitrems in a crude extract of Lolium perenne (L. perenne) seed infected with Epichloë festucae var. lolii (E. festucae var. lolii) and their biological activity against porina larvae were investigated.

Liquid-liquid partitioning of the crude extract, together with a series of bench columns (normal and reversed phase) and semi-preparative High Performance Liquid Chromatography (HPLC) yielded the novel compounds A – D (64 – 67).

Mass spectrometry (MS) and Nuclear Magnetic Resonance (NMR) spectroscopy were used to determine the structures of these alkaloids. The indole moiety of known indole diterpenoids was modified to a six-membered ring in the novel compounds A – D (64 – 67), with the right side of these molecules similar to that of lolitrem B (3) and terpendole C (49). Compounds A – D (64 – 67) differ in the stereochemistry and substituent at C-2. The structural features of these compounds are very unusual. These contain a spiro centre that fuses the modified indole region to the right side, indicating that they may be artefacts rather than naturally occurring, which in turn, could explain why they are not detectable in the Liquid Chromatography Mass Spectrometry (LC-MS) analysis of fresh extract. However, further work would be required to confirm this. 

The known alkaloids, terpendole D (50), 13-desoxypaxilline (37) and paspaline (42) were also isolated, together with a potential emindole analogue. This is the first report of terpendole D (50) from this ryegrass-endophyte association. The presence of an emindole analogue suggested that further intermediates are yet to be isolated from this association as indicated in the LC MS analysis of the crude extract. However, due to the scarcity of the emindole analogue, complete structural confirmation was not possible.

The biological activity of paxilline (36), lolitrem B (3), 13-desoxypaxilline (37), paspaline (42), terpendole D (50) and compounds A (64) and B (65) on porina larvae was determined using a semi-synthetic diet feeding bioassay. These compounds had not been previously tested on porina. Paxilline (36) had a dose-dependent effect on both food consumption and larval weight. Diet consumption and weight gain of porina larvae were significantly reduced by paxilline at concentrations of  2.5, 5 and 10 μg/g but not at concentrations of 1.0 μg/g, compared to dimethyl sulfoxide (DMSO) solvent control diet. Lolitrem B (3) had a similar effect on consumption and weight gain to that of paxilline (36) at concentrations of 5 and 10 μg/g but there was no indication that 13-desoxypaxilline (37), terpendole D (50), paspaline (42), compound A (64) or compound B (65) reduced feeding by porina larvae.

text: Indole diterpenoid secondary metabolites produced by the Epichloë festucae var. lolii – Lolium perenne symbiosis. The indole diterpenoid intermediates of lolitrems in a crude extract of Lolium perenne (L. perenne) seed infected with Epichloë festucae var. lolii (E. festucae var. lolii) and their biological activity against porina larvae were investigated.

Liquid-liquid partitioning of the crude extract, together with a series of bench columns (normal and reversed phase) and semi-preparative High Performance Liquid Chromatography (HPLC) yielded the novel compounds A – D (64 – 67).

Mass spectrometry (MS) and Nuclear Magnetic Resonance (NMR) spectroscopy were used to determine the structures of these alkaloids. The indole moiety of known indole diterpenoids was modified to a six-membered ring in the novel compounds A – D (64 – 67), with the right side of these molecules similar to that of lolitrem B (3) and terpendole C (49). Compounds A – D (64 – 67) differ in the stereochemistry and substituent at C-2. The structural features of these compounds are very unusual. These contain a spiro centre that fuses the modified indole region to the right side, indicating that they may be artefacts rather than naturally occurring, which in turn, could explain why they are not detectable in the Liquid Chromatography Mass Spectrometry (LC-MS) analysis of fresh extract. However, further work would be required to confirm this. 

The known alkaloids, terpendole D (50), 13-desoxypaxilline (37) and paspaline (42) were also isolated, together with a potential emindole analogue. This is the first report of terpendole D (50) from this ryegrass-endophyte association. The presence of an emindole analogue suggested that further intermediates are yet to be isolated from this association as indicated in the LC MS analysis of the crude extract. However, due to the scarcity of the emindole analogue, complete structural confirmation was not possible.

The biological activity of paxilline (36), lolitrem B (3), 13-desoxypaxilline (37), paspaline (42), terpendole D (50) and compounds A (64) and B (65) on porina larvae was determined using a semi-synthetic diet feeding bioassay. These compounds had not been previously tested on porina. Paxilline (36) had a dose-dependent effect on both food consumption and larval weight. Diet consumption and weight gain of porina larvae were significantly reduced by paxilline at concentrations of  2.5, 5 and 10 μg/g but not at concentrations of 1.0 μg/g, compared to dimethyl sulfoxide (DMSO) solvent control diet. Lolitrem B (3) had a similar effect on consumption and weight gain to that of paxilline (36) at concentrations of 5 and 10 μg/g but there was no indication that 13-desoxypaxilline (37), terpendole D (50), paspaline (42), compound A (64) or compound B (65) reduced feeding by porina larvae.

year: 2019

title: Educational research and the philosophy of context

authors: Peters, Michael A.

abstract: Editorial. Wittgenstein, the Austrian counter-Enlightenment philosopher who developed two distinctive philosophies and influenced the turn towards language (‘the linguistic turn’) was perhaps the preeminent philosopher of context. The work know as the Philosophical Investigations (Wittgenstein, 1953), published posthumously, asserted a doctrine of ‘meaning as use’ and helps to supply a pragmatic account of meaning that simultaneously took on both cultural and historic aspects leading to a radical semantic, cultural and epistemological contextualism.

text: Educational research and the philosophy of context Editorial. Wittgenstein, the Austrian counter-Enlightenment philosopher who developed two distinctive philosophies and influenced the turn towards language (‘the linguistic turn’) was perhaps the preeminent philosopher of context. The work know as the Philosophical Investigations (Wittgenstein, 1953), published posthumously, asserted a doctrine of ‘meaning as use’ and helps to supply a pragmatic account of meaning that simultaneously took on both cultural and historic aspects leading to a radical semantic, cultural and epistemological contextualism.

year: 2012

title: He tangi mai i te puehu: He whakatewhatewha i te mahi whakamāori me te reo ā-tuhi a ngā tūpuna

authors: Apiata, Hāwea

subjects: Māori spirituality

abstract: Kei te pūtahi o tēnei tuhinga whakapae ko te whakatewhatewha i te whakapapa o te whakaaro Māori (Māori intellectual history) mā ēnei pātai e rua: He aha ā te Māori i tuhituhi ai i te tōmuatanga o te rautau rua tekau? Ā, he pēhea tāna wetewete i ngā huatau whakawairua nō waho i te ao Māori? 

Ina koa, ko tā te tuhinga whakapae nei he whakaaranga, he whakaatu hoki i ētahi huarahi e toru hei rangahau i ngā whakapapa o te whakaaro taketake: ko te ketuketu rua mahara (archival research); ko te tātari ariā (conceptual analysis); me te reo e whakamahia ana kia wetewete i te kaupapa. Mā te mahi ketuketu rua mahara e āhei ai ki te wānanga i ngā whakaputanga a Wiremu Takana, he kaituhi, he kaiwhakamāori nō Ngāti Kahungunu. Ka whakaputaina tāna tuhinga tuatahi i te tau 1915. Ā, e rua anō i whakaputaina e ia i te tau whai muri mai i 1916. Ko ēnei tuhinga āna e whakatewhatewha ana i te whakamāoritanga o te rongopai me te āheinga o ngā pūrākau Māori kia whakamārama i ngā whakaakoranga Moromona. Kāore anō kia āta tātaritia, kia āta rangahaua āna pukapuka e tētahi atu o mua. Ko te huarahi rangahau tuarua ko te tātari i te whakamāoritanga o ētahi ariā whakawairua e kitea ana i roto i ngā karaipiture o te Hāhi o Ihu Karaiti o te Hunga Tapu o ngā Rā o Muri nei. E toru ngā ariā kua tīpakongia hei tirotiro, arā, ko heaven, hell me baptism. Ā, hei whakawhānui atu i te titiro ki tēnei kaupapa, ka huritaongia ngā hua o te tuhinga reo Māori, arā, ka matapakina ngā take kia tuhituhi i te mahi rangahau i roto i te reo Māori.

I te mutunga iho, mā te āta wānanga i ngā whakaputanga reo Māori a te Hāhi o Ihu Karaiti (LDS) e whakawhānuitia ai tō tātou māramatanga ki te hītori o te mahi whakaputa pukapuka i roto i te Hāhi, te mahi punenga a te Māori, te whakareretanga o ngā tuhituhinga reo Māori, me te hītori o te Hāhi o Ihu Karaiti i Aotearoa nei.

text: He tangi mai i te puehu: He whakatewhatewha i te mahi whakamāori me te reo ā-tuhi a ngā tūpuna Kei te pūtahi o tēnei tuhinga whakapae ko te whakatewhatewha i te whakapapa o te whakaaro Māori (Māori intellectual history) mā ēnei pātai e rua: He aha ā te Māori i tuhituhi ai i te tōmuatanga o te rautau rua tekau? Ā, he pēhea tāna wetewete i ngā huatau whakawairua nō waho i te ao Māori? 

Ina koa, ko tā te tuhinga whakapae nei he whakaaranga, he whakaatu hoki i ētahi huarahi e toru hei rangahau i ngā whakapapa o te whakaaro taketake: ko te ketuketu rua mahara (archival research); ko te tātari ariā (conceptual analysis); me te reo e whakamahia ana kia wetewete i te kaupapa. Mā te mahi ketuketu rua mahara e āhei ai ki te wānanga i ngā whakaputanga a Wiremu Takana, he kaituhi, he kaiwhakamāori nō Ngāti Kahungunu. Ka whakaputaina tāna tuhinga tuatahi i te tau 1915. Ā, e rua anō i whakaputaina e ia i te tau whai muri mai i 1916. Ko ēnei tuhinga āna e whakatewhatewha ana i te whakamāoritanga o te rongopai me te āheinga o ngā pūrākau Māori kia whakamārama i ngā whakaakoranga Moromona. Kāore anō kia āta tātaritia, kia āta rangahaua āna pukapuka e tētahi atu o mua. Ko te huarahi rangahau tuarua ko te tātari i te whakamāoritanga o ētahi ariā whakawairua e kitea ana i roto i ngā karaipiture o te Hāhi o Ihu Karaiti o te Hunga Tapu o ngā Rā o Muri nei. E toru ngā ariā kua tīpakongia hei tirotiro, arā, ko heaven, hell me baptism. Ā, hei whakawhānui atu i te titiro ki tēnei kaupapa, ka huritaongia ngā hua o te tuhinga reo Māori, arā, ka matapakina ngā take kia tuhituhi i te mahi rangahau i roto i te reo Māori.

I te mutunga iho, mā te āta wānanga i ngā whakaputanga reo Māori a te Hāhi o Ihu Karaiti (LDS) e whakawhānuitia ai tō tātou māramatanga ki te hītori o te mahi whakaputa pukapuka i roto i te Hāhi, te mahi punenga a te Māori, te whakareretanga o ngā tuhituhinga reo Māori, me te hītori o te Hāhi o Ihu Karaiti i Aotearoa nei.

year: 2021