title: Identification of β-hydroxy fatty acid esters and primary, secondary-alkanediol esters in cuticular waxes of the moss Funaria hygrometrica.
abstract: The plant cuticle, a multi-layered membrane that covers plant aerial surfaces to prevent desiccation, consists of the structural polymer cutin and surface-sealing waxes. Cuticular waxes are complex mixtures of ubiquitous, typically monofunctional fatty acid derivatives and taxon-specific, frequently bifunctional specialty compounds. To further our understanding of the chemical diversity of specialty compounds, the waxes on the aerial structures of the leafy gametophyte, sporophyte capsule, and calyptra of the moss Funaria hygrometrica were surveyed. Respective moss surfaces were extracted, and resulting lipid mixtures were analyzed by gas chromatography-mass spectrometry (GC-MS). The extracts contained ubiquitous wax compound classes along with two prominent, unidentified classes of compounds that exhibited some characteristics of bifunctional structures. Microscale transformations led to derivatives with characteristic MS fragmentation patterns suggesting possible structures for these compounds. To confirm the tentative structure assignments, one compound in each of the suspected homologous series was synthesized. Based on GC-MS comparison with the authentic standards, the first series of compounds was identified as containing esters formed by β-hydroxy fatty acids and wax alcohols, with ester chain lengths varying from C42 to C50 and the most prominent homolog being C46. The second series consisted of fatty acid esters of 1,7-alkanediols, linked via the primary hydroxyl group, with ester chain lengths C40-C52 also dominated by the C46 homolog. The β-hydroxy acid esters were restricted to the sporophyte capsule, and the diol esters to the leafy gametophyte and calyptra. Based on their homolog and isomer distributions, and the presence of free 1,7-triacontanediol, possible biosynthetic reactions leading to these compounds are discussed.
authors.affiliation: Department of Chemistry, University of British Columbia, 2036 Main Mall, Vancouver, BC V6T 1Z1, Canada.
authors.forename: Lucas
authors.initials: L
authors.lastname: Busta
authors.affiliation: Department of Plant Biology, University of California - Davis, One Shields Ave., Davis, CA 95616, USA.
authors.forename: Jessica M
authors.initials: JM
authors.lastname: Budke
authors.affiliation: Department of Chemistry, University of British Columbia, 2036 Main Mall, Vancouver, BC V6T 1Z1, Canada; Department of Botany, University of British Columbia, 6270 University Boulevard, Vancouver, BC V6T 1Z4, Canada. Electronic address: jetter@mail.ubc.ca.
authors.forename: Reinhard
authors.initials: R
authors.lastname: Jetter
mesh_terms: D000438:Alcohols / Q000737:chemistry; D044002:Bryophyta / Q000737:chemistry*; D004952:Esters / Q000737:chemistry; D005227:Fatty Acids / Q000032:analysis*; D008401:Gas Chromatography-Mass Spectrometry; D008055:Lipids / Q000032:analysis; D015394:Molecular Structure; D018515:Plant Leaves / Q000737:chemistry; D014885:Waxes / Q000737:chemistry*
chemical_list: D000438:Alcohols; D004952:Esters; D005227:Fatty Acids; D008055:Lipids; D014885:Waxes
keywords: Bryophyta; Calyptra; Cuticular wax; Esters; Funaria hygrometrica; Gametophyte; Sporophyte; Structure elucidation; Very-long-chain