Content uploaded by Andrew Rozefelds
Author content
All content in this area was uploaded by Andrew Rozefelds on Feb 01, 2015
Content may be subject to copyright.
Chemistry of the Australian Gymnosperms—Part 5: Leaf Essential Oils of Some Endemic Tasmanian Gymnosperms: Diselma archeri, Lagarostrobos franklinii, Microcachrys tetragona and Phyllocladus aspleniifolius
Abstract
The steam volatile leaf oils of four endemic Tasmanian conifers have been analyzed. The leaf oil of Diselma archeri, produced in 0.6–0.8% yield, based on fresh leaves, contained α-pinene (45-73%), δ-3-carene (1-15%) and limonene as principal components. Lagarostrobos franklinii gave a leaf oil in 0.8–0.9% yield based on fresh leaves in which the major components were α-pinene (13-36%), δ-3-carene (1-17%), limonene (16-42%), 16-kaurene (3-7%), phyllocladene (4-10%) and sclarene (2-23%). A re-examination of the wood oil of this species showed it to contain methyl eugenol (74%), (E)-methyl isoeugenol (2%) and elemicin (24%). Microcachrys tetragona gave a leaf oil in 0.1–0.5% yield based on fresh leaves in which the principal components were α-pinene (44-50%) and limonene (10-13%). Phyllocladus aspleniifolius produced a leaf oil in 0.5–1% yield based on fresh leaves in which α-pinene (44-55%), phyllocladene (15-28%) and 8-β-hydroxyisopimarene (5-7%) were principal components.
... Diterpenes would be expected in a residue of a paint that contained the resin from a conifer such as Manoao colensoi (Podocarpaceae) (Briasco and Murray, 1952;Brophy et al., 2003;Carman et al., 1966;Molloy, 1995). These are the largest and most durable compounds in the water-insoluble resin, and the most likely to be preserved. ...
New Zealand was first settled by Māori soon after 1200 CE, however the age, and so the social and environmental contexts of the rock art they made remains uncertain. We report the first attempts at the direct dating of New Zealand rock art through radiocarbon analysis focusing on the return of an unexpectedly early date. Historical information and pigment testing indicates that the particular figures that returned the early date were retouched with modern crayons. We report the use of portable X-ray fluorescence to identify rock art figures that have been retouched in this way. Results emphasise the need to consider historical information in future assessments of material for dating Māori rock art.
... We also know that temperature (Jönsson et Anderbrant 1993) and wind (Adams et al. 1995) are parameters which influence the dispersal of odours and by consequence, the capture of insects. As for Brophy et al. (2003), they noted that B. tryoni is attracted by newlyfelled trees of Lagarostrobos (Dacridium) franklinii (Hook. f.) Queen (Gymnosperma, Podocarpaceae). ...
Les Mouches des fruits de la famille des Tephritidae sont parmi les ravageurs les plus importants des cultures fruitières et légumières dans le monde. La faune des Tephritidae compte 30 espèces en Nouvelle-Calédonie. Les espèces de la sous-famille des Dacinae sont les seules à attaquer les fruits cultivés. Les Dacinae comprennent deux genres en Nouvelle-Calédonie : Bactrocera et Dacus. Neuf espèces ont radié dans le genre Bactrocera et le genre Dacus est monospécifique. Une étude préliminaire de phylogénie moléculaire des Dacinae endémiques semble indiquer que les deux espèces polyphages endémiques Bactrocera curvipennis et B. psidii auraient des origines extérieures, australienne pour la première et du Pacifique pour la seconde. Trois espèces sont d'importance économique : les deux espèces endémiques précitées et la Mouche du Queensland, B. tryoni, introduite accidentellement à la fin des années 60. C'est sur ces trois espèces que se sont concentrées diverses études comportementales. Le rythme circadien et l'acoustique du comportement pré-copulatoire chez les mâles de ces trois espèces nuisibles ont été étudiés. Ensuite, une étude sur l'attractivité de huit couleurs sur des sphères a été menée. Puis, l'attractivité et la répulsion de 30 huiles essentielles ont été évaluées dans des pièges en conditions semi-naturelles. La lutte contre les Mouches des fruits est basée en partie sur la destruction des mâles par la méthode MAT ouMale Annihilation Technique par l'utilisation simultanée d'un puissant attractif odorant, le cue-lure et d'un insecticide de contact. L'attractivité du cue-lure a été évaluée et comparée entre les trois espèces d'importance économique. Enfin, l'étude des données de six années de piégeage dans deux types de vergers a permis de connaître les principaux facteurs influençant les fluctuations des populations de Mouches des fruits.
... In a recent paper on the oil chemistry of selected genera in the Podocarpaceae no qualitative differences in oil chemistry were detected between L. franklinii and M. colensoi (Hook.) Molloy, when compared with other genera in the family (Brophy et al. 2002). Differences in oil chemistry therefore provide no support for recognising two separate genera. ...
The endemic genera of Tasmania are a heterogenous assemblage of taxa, which are represented in families including Asteliaceae, Asteraceae, Campynemataceae, Cunoniaceae, Cupressaceae, Ericaceae, Haloragaceae sensu lato (including Tetracarpaea), Iridaceae, Malvaceae, Podocarpaceae, Proteaceae and Res tionaceae. Two informal groupings of genera are recognised, one group consists of old relictual genera (palaeoendemics) and a second group are relatively recent segregates (neoendemics). Palaeoendemics include the conifers, Athrotaxis, Diselma, Lagarostrobos and Microcachrys, and the flowering plants, Agastachys, Anodopetalum, Bellendena, Campynema, Cenarrhenes, Isophysis, Milligania, Prionotes, Planocarpa and Tetracarpaea. These genera are early offshoots in their respective clades and some are so phylogenetically isolated that their sister group relationships are only determinable at the subfamily level, and/or their closest relatives lie outside of Australia. Tasmania is therefore an extremely important refuge for a significant number of taxonomically isolated genera. The palaeoendemics are largely restricted to the western half of Tasmania, which has an aseasonal-wet climate. This biome typically includes the rainforest genera, although some, like Agastachys, Cenarrhenes and Milligania, occur in a range of plant communities. With the possible exception of Lagarostrobos and Microcachrys there is no fossil evidence to indicate that these palaeoendemics have occurred outside of the state. The neoendemics, Asterotrichion, Odixia and Stonesiella, are relatively recent segregates and occur in eastern Tasmania, often as undershrubs in Eucalyptus forests and they appear to have evolved in situ and in response to aridification of the Tasmanian climate from the Miocene onwards. The status of two endemics, Winifredia and Pterygopappus, is unclear. Tasmania is interpreted to be a composite area, and the history of the taxa and their systematic and biogeographical relationships are complex. Overall the biogeographical relationships of Tasmania's endemic genera are gondwanic with approximately 48% having links to mainland Australia. More distant links are recognised with New Zealand (5%), New Caledonia (5%), southern Africa (5%) and South America (10%). KANUNNAH Andrew C. Rozefelds 36 The aim of this paper is to compile a list of the genera endemic to Tasmania, review their phylogenetic relationships and assess the utility and limitations of these studies in understanding the evolutionary history of the Tasmanian flora. The distribution of endemic species in Tasmania, which would also include the endemic genera, has been studied by Kirkpatrick and Brown (1984a, b). There has been, however , no previous attempt to review the phylogenetic and biogeographical relationships of the en demic genera in the state. The study also aims to determine what, if any, generalised patterns might exist between these genera in terms of geographical distribution, habit, altitude and associations with particular plant communities and habitats. In this paper the phylogenetic and bio-geographical relationships of each genus are discussed using both morphological and molecular-based data. The plant communities in which these genera occur have been described by Jarman et al. (1994) and Kirkpatrick et al. (1995). Information on the distribution, habitat and altitudinal range of these plants is from Tasmanian Herbarium (HO) records, literature sources and additional advice provided by Greg Jordan (University of Tasmania).
... The leaf oil of N. pancheri is different from the two previous Callitris samples and characterised by a high level of sesquiterpenoids: germacrene D (6.6%), bicyclogermacrene (7.8%), spathulenol (49.0%), epi-α-muurolol (7.4%) and α-cadinol (11.6%). On the other hand, the leaves of C. sulcata, C. neocaledonica and N. pancheri do not accumulate volatile diterpenes, as seen in other members of the Cupressaceae family [16,[26][27][28][29]. ...
The volatile components obtained by hydrodistillation of leaves of C. neocaledonica Dummer, C. sulcata (Parlatore) Schlechter and N. pancheri (Carrière) de Laubenfels from New Caledonia were investigated for the first time by a combination of GC and GC-MS analysis, and compared with the heartwood oil compositions of the three species. The essential oils from C. sulcata and C. neocaledonica leaves contain a majority of monoterpenes while the leaf oil of N. pancheri is characterized by a high level of sesquiterpenoids. On the basis of the sesquiterpenoid composition of the wood- and leaf oils, N. pancheri is closely related to both New Caledonian Callitris spp. However, C. sulcata and C. neocaledonica oils remain distinct from N. pancheri and the Australian Callitris oils by the presence of compounds biosynthetically related to the bisabolyl cation, mainly barbatenes and thujopsene.
In this comprehensive commentary, Australian essential oils and their components are listed and discussed in the context of their value to industry and aesthetics. The historic and cultural significance of endemic essential oils is explained. Several promising candidates are identified that have commercial potential and will enter the marketplace in the not-too-distant future. This text elaborates on the current progress in research, and explains the up-to-date view of 'bioactive,' with reference to insect repellence, antimicrobial activity, anti-inflammatory activity, and potential toxicity. The concept of chemotypes and chemophenetics is explained in detail to justify why chemically variable species in Australia require standardisation practices to ensure reproducibility of their derived natural products: standardisation practice includes cultivar development and authentica-tion protocols. Thereafter, some of the more significant essential oils are defined and some background information provided. This review concludes with a comprehensive table of aromatic species that were studied by Joseph Brophy over the last 30 years, thereby providing the most comprehensive overview available, on the chemistry of Australian essential oil yielding species.
This comprehensive, extensively illustrated, critical review chapter addresses the biochemical pathways to two major plant metabolic classes, namely, the rather ubiquitous allyl/propenyl phenols and lignans, which are the subclasses of phenylpropanoids (C6C3). These substances are considered to have diverse physiological/ecological roles within plants, including defense against microbes and insects, as antioxidants, and also as pollinator attractants. Comprehensive analysis of their structural diversity in extant plant groups provides much needed insight into their evolution. In addition, what is known of their biosynthetic pathways is extensively discussed, including the genes/proteins known to be responsible for each biochemical step, their enzymatic kinetic behaviors, three-dimensional structures, and postulated chemical mechanisms. Lastly, many are historically important natural products, and their current and potential human uses in spices, medicines, nutrition, and other fields are broadly reviewed. The text is supported by more than 50 illustrations and schemes including more than 300 compounds, and about 550 key references are presented to the reader.
The leaf oil of Prumnopitys ladei, which was analyzed by a combination of GC and GC/MS, was found to contain significant amounts of mono-, sesqui- and diterpenes, with α-pinene (15–25%), β-caryophyllene (12–16%), rimuene (3–27%) and kaurene (5–29%) being the principal components.
The leaf oils of the 18 species and four subspecies of the genus Callitris endemic to Australia have been investigated by a combination of GC and GC/MS. All taxa produced oils in poor to moderate yields. Callitris baileyi produced a leaf oil in which α-pinene and limonene together, contributed the majority of the oil, while in Callitris canescens methyl citronellate also made significant contributions to the oil. In C. columellaris, limonene was the principal component, contributing up to 78% of the oil. Callitris drummondii gave a leaf oil which showed two chemical varieties. The samples from Western Australia contained large amounts of α-pinene (67–69%), while the sample from South Australia contained limonene (10.9%), bornyl acetate (24.2%) and geranyl acetate (14.9%) as significant components. In C. endlicheri the main components were limonene, α-pinene and bornyl acetate. Limonene and α-pinene were the principal components of the leaf oil of C. glaucophylla. Callitris gracilis ssp. gracilis gave an oil in which the principal components were α-pinene, myrcene and limonene, while in ssp. murrayensis a-pinene was the principal component. α-Pinene and limonene were the principal components of C. intratropica and C. macleayana. Callitris muelleri was found in two chemical forms, one monoterpenoid and one sesquiterpenoid, with either a-pinene or spathulenol being the principal component. In C. oblonga, which consists of three subspecies, α-pinene was the main component. In C. preissii the major components were α-pinene, myrcene, limonene and bornyl acetate. Callitris rhomboidea was distinguished from the vast majority of other Callitris species by containing significant amounts of neryl acetate, geranyl acetate and citronellyl acetate. Callitris roei contained significant amounts of sesquiterpenes in its leaf oil, with (E)-nerolidol being the principal component. In C. tuberculata α-pinene and limonene were the major components. α-Pinene, limonene and camphor were the major components in the leaf oil of C. verrucosa, while in Callitris sp. (Emerald Falls PI. Forster +PIF26357) α-pinene and limonene were the principal components with significant amounts of α-fenchyl acetate. The leaf oil of the putative introgressed populations of C. columellaris—C. verrucosa had α-pinene (25–46%), myrcene (9–19%), limonene (14–24%), α-fenchyl acetate (8–13%) and bornyl acetate (4–13%) as the most significant components. The oil does provide similarities to the oils of both putative parent species in that it contains camphor (1–3%), which is characteristic of C. verrucosa and bornyl acetate (2–13%) characteristic of C. glaucophylla.
Abstract This review discusses the occurrence and distribution (within a plant) of methyl eugenol in different plant species (> 450) from 80 families spanning many plant orders, as well as various roles this chemical plays in nature, especially in the interactions between tephritid fruit flies and plants.
A detailed investigation of the wood, leaf, branch and root oil of Eremophila mitchellii (Benth.) was carried out by a combination of GC-FID, GC-MS and NMR. The wood oil was composed predominantly of eremophilanes, a rare class of biologically active, bicyclic sesquiterpenoids. The root oil was also found to contain the eremophilanes together with the zizaene sesquiterpene, sesquithuriferone. 9-Hydroxy-1,7(11),9-eremophilatrien-8-one and the known 1(10),11-eremophiladien-9-one (eremophilone), 9-hydroxy-7(11),9-eremophiladien-8-one (2-hydroxyeremophilone), 8-hydroxy-11-eremophilen-9-one (santalcamphor), 8-hydroxy-10,11-eremophiladien-9-one, sesquithuriferone and 8-hydroxy-1,11-eremophiladien-9-one were purified and elucidated by NMR. Three approaches to the purification of the major eremophilanes from the wood oil are described. (+) Spathulenol, α-pinene, globulol, viridiflorene were the major constituents of the leaf oil. All of the essential oils and the eremophilanes exhibited cytotoxicity against P388D(1) mouse lymphoblast cells in-vitro.
Analysis of sequences of the chloroplast gene rbcL for
76 taxa of Podocarpaceae (representing all genera except
Parasitaxus) and five species of Phyllocladaceae were
undertaken with respect to their relationships to each other and to 28
coniferalean outgroup taxa from seven families. The results indicate that
Podocarpaceae are polyphyletic unless expanded to include Phyllocladaceae.
Within Podocarpaceae, Sundacarpus is placed in a clade
with Prumnopitys, and
Falcatifolium is paraphyletic as a basal grade to
Dacrydium. Phyllocladus is in an
unresloved clade with Halocarpus,
Manoao/Lagarostrobos and
Prumnopitys/Sundacarpus. The separation of
Afrocarpus from Podocarpus and its
placement instead as sister to Nageia and
Retrophyllum is supported.
Podocarpus s. str. is monophyletic, with both subgenera
identified, albeit poorly supported. The analysis placed
Lepidothamnus and Saxegothaea in
an unresolved basal polytomy within the family. There were no clear outgroup
relationships with the family. These results differ from the morphological
clades found by Kelch (1997), and disagree strongly with his
18S-sequence-based phylogeny (Kelch 1998). However, jackknife support values
indicate that although the genera are well supported, relationships both
within and between them are not, suggesting that intergeneric relationships in
the family require further study. There is also some congruence between our
results and those of the gymnosperm 18S study by Chaw
et al. (1997), although their study included only three
Podocarpaceae and one Phyllocladaceae species.
A survey of twenty-eight species of the Podocarpaceae and of nine related gymnosperms for diterpene hydrocarbons has been carried out by gas-liquid chromatography. The results have been used to clarify previously reported occurrences of diterpenes and to assess their taxonomic value.
(+)-Phyllocladene, (+)-rimuene, (+)-isokaurene, (–)-sandaracopimaradiene, and (+)-manoyl oxide have been identified in the diterpenoid fraction of the oil, which contains in addition a new diterpene alcohol, which has been shown to be (–)-8β-hydroxy-sandaracopimar-15-ene.
Dacrydium Sol. ex Lamb. emend. de Laub. is redefined to include only those species belonging to section B
(Florin 1931; de Laubenfels 1969). The remaining species are assigned to Lepidothamnus Phil. (two species
from New Zealand, one from Chile). Lagarostrobos gen. nov. (one species from New Zealand. one from
Tasmania) and Halocarpus gen. nov. (three species from New Zealand). Ovule orientation, one of the main
character-states used to define Dacrydium s.l., is reexamined and shown to be in accord with the new
taxonomic arrangement. Lepidothamnus fonkii Phil. is reinstated and seven new combinations are made, viz.
Lepidotharnnus intermedius (T. Kirk) C. J. Quinn, L. laxifolius (Hook. f.) C. J. Quinn, Halocarpus bidwillii
(Hook. f. exT. Kirk) C. J. Quinn, H. biformis (Hook.) C. J . Quinn, H. kirkii (F. Muell. ex Parl.) C. J. Quinn,
Lagarostrobos colensoi (Hook.) C. J . Quinn and L. franklinii (Hook. f.) C. J. Quinn. A key to the genera in
the Podocarpaceae is also given.