Gynocardin from Baileyoxylon lanceolatum and a revision of cyanogenic glycosides in Achariaceae

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Abstract

The cyclopentenone cyanhydrin glycoside gynocardin was the only cyanogen isolated from foliage of monotypic Australian rainforest tree, Baileyoxylon lanceolatum (Achariaceae). The presence of cyanogenic compounds in plants can have considerable taxonomic utility. A review of previous reports of cyanogenesis in the recently revised Achariaceae revealed distinct taxonomic patterns as well as inconsistencies in the reporting of cyanogenic compounds. This variation appears to be due to tissue level localisation of cyanogenic compounds as well as discrepancies in results obtained from different detection methods. Recommendations are made for future investigations.

Introduction

The presence of endogenous cyanide-containing compounds in plants was first described over 200 years ago and is now recognised in over 3000 species representing more than 550 genera and 130 families (Lechtenberg and Nahrstedt, 1999, Møller and Seigler, 1999, Poulton, 1990). Plants producing cyanogenic glycosides are particularly common in certain families (Seigler, 1976, Seigler, 1991, Thomsen and Brimer, 1997) and the identification of cyanogenic constituents has been used as an informative taxonomic marker (Spencer and Seigler, 1985b, Spencer et al., 1985). Despite their taxonomic utility, the specific cyanogens have been characterised in less than 20% of species in which cyanogenesis has been documented (Lechtenberg and Nahrstedt, 1999, Poulton, 1990, Seigler, 1991). Moreover, it is not always easy to draw out patterns in taxonomic distributions of cyanogenic glycosides due to partitioning of different cyanogenic compounds among tissue within the same plant (e.g. Dicenta et al., 2002), variation in the accuracy and methodology of procedures for detecting and identifying cyanogenic compounds (Brimer, 1988, Brinker and Seigler, 1989, Seigler, 1975), and the use of less than ideal tissue for studying cyanogenesis (e.g. Spencer and Seigler, 1985a).

Reports of one group of cyanogenic glycosides, the cyclopentenone cyanhydrin glycosides derived from the non-protein amino acid 2-(2-cyclopentenyl)glycine, are restricted to 5 of 39 families within the Malpighiales: Achariaceae, Malesherbiaceae, Passifloraceae, Salicaceae and Turneraceae (Cabalion et al., 1980, Chase et al., 2002, Lechtenberg and Nahrstedt, 1999, Spencer and Seigler, 1985a, Thorne, 2002). Initial reports of cyclopentenyl glycosides in the Caricaceae (Goldstein and Spencer, 1985, Lechtenberg and Nahrstedt, 1999, Spencer, 1988, Spencer and Seigler, 1984) now appear incorrect (Olafsdottir et al., 2002, Seigler et al., 2002). The structures of 15 distinct cyclopentenoid cyanogens have been documented (Lechtenberg and Nahrstedt, 1999) and these compounds have been proposed as phylogenetic markers in a number of chemotaxonomic studies at both the family (Saupe, 1981, Spencer and Seigler, 1985b, Spencer et al., 1985) and generic (Jaroszewski et al., 2002) level.

In their recent revision of Flacourtiaceae sensu lato, Chase et al. (2002) assigned 30 genera, and the majority of cyanogenic taxa, to Achariaceae. One of these species was the monotypic Baileyoxylon lanceolatum C.T.White, a tree endemic to Australian tropical rainforests. Preliminary positive reports for cyanogenesis using fresh tissue of B. lanceolatum (Webber, 2005) conflicted with previous negative tests based on herbarium material (Spencer and Seigler, 1985a). Therefore, in this paper we investigate cyanogenesis in B. lanceolatum and review the knowledge on the presence of cyanogenic glycosides in the Achariaceae sensu Chase et al. (2002). More specifically, our aims were to (1) identify the cyanogenic constituent(s) in B. lanceolatum foliage; and (2) review previous literature on cyanogenic glycoside reports in the Achariaceae to draw out patterns and inconsistencies. This will be the first revision of cyanogenesis in the Achariaceae sensu Chase et al. (2002) and was undertaken for two reasons. First, to correct both mistaken claims that tests for cyanogenesis in some taxa did not exist (e.g. Andersen et al., 2001), and also errors in the reporting of cyanogenic constituents (e.g. Spencer and Seigler, 1985a, Spencer et al., 1982 corrected by Jaroszewski and Olafsdottir, 1987, Seigler and Spencer, 1989). Second, a comparison of the distribution of cyanogenic compounds within and between genera and between tissue types will be invaluable for future taxonomic work on Achariaceae. This revision will build on the early reviews of Greshoff, 1906a, Greshoff, 1906b, Rosenthaler, 1919, Farnsworth et al., 1958, Hegnauer, 1966, Hegnauer, 1989 and Tjon Sie Fat (1979) on cyanogenic glycosides in Flacourtiaceous species.

Section snippets

Plant material

Baileyoxylon lanceolatum C.T.White (Achariaceae; Flacourtiaceae pro parte) is a canopy rainforest tree (to 30 m) endemic to north east Queensland, Australia. Leaf samples (fully expanded mature leaves without significant damage or epiphyll colonisation) were obtained from 4 mature trees growing in tropical rainforest on the Atherton Tableland, Queensland, Australia in April 2005. After sampling, foliar tissue was snap-frozen in liquid N2, freeze dried, ground to a fine homogeneous powder using

Cyanogenesis in Baileyoxylon lanceolatum

The concentration of cyanogenic glycosides in the ground tissue ranged from 0.67 to 2.65 mg CN g−1 dry wt (mean ± SE 1.44 ± 0.42) across the four trees. Cyanogenic constituents were extracted from field-collected leaf material and purified using HP-TLC. Fractionation of the leaf methanol extract by HP-TLC identified a single band (Rf = 0.22; CHCl3:MeOH, 3:1 v/v) of cyanogenic activity, co-migrating with gynocardin, the cyanogenic glycoside from Ryparosa kurrangii B.L.Webber (Webber et al., 2007). The

Cyanogenesis in Baileyoxylon lanceolatum

The identification of gynocardin (1) from B. lanceolatum leaf tissue is in accordance with other studies on Achariaceae taxa in which gynocardin was the only cyanogenic glycoside documented in foliar tissue (Jensen and Nielsen, 1986, Spencer and Seigler, 1985a, Webber et al., 2007). Gynocardin was the first cyclopentenoid glycoside to be discovered (Power and Barrowcliff, 1905a, Power and Gornall, 1904b, Power and Lees, 1905) and have its chemical structure determined (Coburn and Long, 1966,

Acknowledgements

We thank Rigel Jensen for his assistance with fieldwork, Sue Zmarzty (Royal Botanic Gardens, Kew) for expert taxonomic advice, Jim Solomon (Missouri Botanical Garden) for checking current determinations on herbarium material from the Spencer & Seigler study, David Harman and Wilford Lie (School of Chemistry, University of Wollongong, Wollongong) for assistance with MS and NMR analyses and many generous colleagues for help with locating and translating old manuscripts.

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    Current address: School of Biological Sciences, Monash University, Victoria 3800, Australia.

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