Plant wax compounds preserved in lake sediments are used as proxies for paleohydrologic reconstructions. Despite their presence in lake sediments, little is known about their transport from plants to their deposition in lake sediments. By drawing on the leaf and pollen taphonomy literature combined with sediment focusing models, it is possible to develop several working hypotheses for the transport and deposition of plant waxes in lake sediments. An improved understanding of plant wax transport and deposition into lake sediments is necessary to increase the accuracy of paleohydrologic reconstructions.
To better understand the controls on plant wax transport and deposition in lake sediment, we analyzed the sedimentary plant waxes from 3 lakes in the Adirondack Mountains of New York. These lakes were chosen to capture a range of basin-specific properties to evaluate their influences on the transport and deposition of plant wax compounds in surface sediments. We spatially characterized sediment properties with surface sediment samples and high-resolution underwater imaging, acoustically profiled the sub-bottom, and measured temperature profiles. From each site, we measured n-alkanes, bulk organic content (loss-on-ignition), bulk carbon and nitrogen concentrations, C:N ratios, and bulk carbon isotopes.
Preliminary n-alkane concentrations and chain length distributions, as well as bulk carbon isotopes, are variable within each lake basin suggesting a mix of aquatic and terrestrial sources. The bulk carbon isotope values for two of the three lakes show a similar range of -2‰ compared to a range of -6.3‰ at the third lake. Likewise, the range of total n-alkane concentrations is much higher in the third lake suggesting that the controls on the distribution of n-alkanes and organic carbon are different between lakes. For terrestrial plant waxes, we find low n-alkane concentrations in sandy nearshore sediments relative to higher n-alkane concentrations in deeper fine-grained sediments. Combined, this information suggests that littoral processes focus organic compounds and fine sediments towards the main depo-center of the lake. These and other observations highlight important relationships between basin-specific properties and processes controlling the transport and deposition of plant wax compounds.
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Fatty alcohol oxidase 3 (FAO3) and FAO4b connect the alcohol- and alkane-forming pathways in Arabidopsis stem wax biosynthesis
The alcohol- and alkane-forming pathways in cuticular wax biosynthesis are well characterized in Arabidopsis. However, potential interactions between the two pathways remain unclear. Here, we reveal that mutation of CER4, the key gene in the alcohol-forming pathway, also led to a deficiency in the alkane-forming pathway in distal stems. To trace the connection between the two pathways, we characterized two homologs of fatty alcohol oxidase (FAO), FAO3 and FAO4b, which were highly expressed in distal stems and localized to the endoplasmic reticulum. The amounts of waxes from the alkane-forming pathway were significantly decreased in stems of fao4b and much lower in fao3 fao4b plants, indicative of an overlapping function for the two proteins in wax synthesis. Additionally, overexpression of FAO3 and FAO4b in Arabidopsis resulted in a dramatic reduction of primary alcohols and significant increases of aldehydes and related waxes. Moreover, expressing FAO3 or FAO4b led to significantly decreased amounts of C18–C26 alcohols in yeast co-expressing CER4 and FAR1. Collectively, these findings demonstrate that FAO3 and FAO4b are functionally redundant in suppressing accumulation of primary alcohols and contributing to aldehyde production, which provides a missing and long-sought-after link between these two pathways in wax biosynthesis.
more » « less- NSF-PAR ID:
- 10367435
- Publisher / Repository:
- Oxford University Press
- Date Published:
- Journal Name:
- Journal of Experimental Botany
- Volume:
- 73
- Issue:
- 9
- ISSN:
- 0022-0957
- Page Range / eLocation ID:
- p. 3018-3029
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Abstract In plants,
N ‐acylethanolamines (NAEs) are most abundant in desiccated seeds and their levels decline during germination and early seedling establishment. However, endogenous NAE levels rise in seedlings when ABA or environmental stress is applied, and this results in an inhibition of further seedling development. When the most abundant, polyunsaturated NAEs of linoleic acid (18:2) and linolenic acid (18:3) were exogenously applied, seedling development was affected in an organ‐specific manner. NAE 18:2 primarily affected primary root elongation and NAE 18:3 primarily affected cotyledon greening and expansion and overall seedling growth. The molecular components and signaling mechanisms involved in this pathway are not well understood. In addition, the bifurcating nature of this pathway provides a unique system in which to study the spatial aspects and interaction of these lipid‐specific and organ‐targeted signaling pathways. Using whole transcriptome sequencing (RNA‐seq) and differential expression analysis, we identified early (1–3 hr) transcriptional changes induced by the exogenous treatment of NAE 18:2 and NAE 18:3 in cotyledons, roots, and seedlings. These two treatments led to a significant enrichment in ABA‐response and chitin‐response genes in organs where the treatments led to changes in development. InArabidopsis seedlings, NAE 18:2 treatment led to the repression of genes involved in cell wall biogenesis and organization in roots and seedlings. In addition, cotyledons, roots, and seedlings treated with NAE 18:3 also showed a decrease in transcripts that encode proteins involved in growth processes. NAE 18:3 also led to changes in the abundance of transcripts involved in the modulation of chlorophyll biosynthesis and catabolism in cotyledons. Overall, NAE 18:2 and NAE 18:3 treatment led to lipid‐type and organ‐specific gene expression changes that include overlapping and non‐overlapping gene sets. These data will provide future, rich opportunities to examine the genetic pathways involved in transducing early signals into downstream physiological changes in seedling growth. -
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Abstract Understanding gene regulatory networks is essential to elucidate developmental processes and environmental responses. Here, we studied regulation of a maize (Zea mays) transcription factor gene using designer transcription activator-like effectors (dTALes), which are synthetic Type III TALes of the bacterial genus Xanthomonas and serve as inducers of disease susceptibility gene transcription in host cells. The maize pathogen Xanthomonas vasicola pv. vasculorum was used to introduce 2 independent dTALes into maize cells to induced expression of the gene glossy3 (gl3), which encodes a MYB transcription factor involved in biosynthesis of cuticular wax. RNA-seq analysis of leaf samples identified, in addition to gl3, 146 genes altered in expression by the 2 dTALes. Nine of the 10 genes known to be involved in cuticular wax biosynthesis were upregulated by at least 1 of the 2 dTALes. A gene previously unknown to be associated with gl3, Zm00001d017418, which encodes aldehyde dehydrogenase, was also expressed in a dTALe-dependent manner. A chemically induced mutant and a CRISPR-Cas9 mutant of Zm00001d017418 both exhibited glossy leaf phenotypes, indicating that Zm00001d017418 is involved in biosynthesis of cuticular waxes. Bacterial protein delivery of dTALes proved to be a straightforward and practical approach for the analysis and discovery of pathway-specific genes in maize.
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Harmata, Michael (Ed.)Several years ago, a small family of diterpenoid natural products attracted our attention as novel targets for synthesis studies. Initially, four compounds were independently characterized by the research teams of Vidari1 and Steglich.2 Trichoaurantianolides AeD (1e4 of Fig. 9.1) were isolated from fruiting bodies of the mushrooms Tricholoma aurantium and Tricholoma fracticum in 1995. Subsequent efforts of Stermer and coworkers3 described the isolation of the closely related lepistal (5) and lepistol (6) of Fig. 9.2 as the corresponding C8 deoxygenated compounds of this family. In addition, the corresponding acetate of trichoaurantianolide B was discovered and named as 6-O-aetyl- trichoaurantin (7).2 Structure assignments were based upon extensive nuclear magnetic resonance (NMR) studies, and the features of relative stereo- chemistry were confirmed by an X-ray crystallographic analysis of trichoaurantianolide B (2).1b,2 These original investigators described the trichoaurantianolides as examples of a new class of diterpenes named as neodolastanes that signified a structural relationship to the tricyclic metabo- lites of marine origins known as dolastanes as represented by dolatriol (8)4 and the clavularane 95 of Fig. 9.2. Neodolastanes were defined as substances in which the bridgehead methyl substituent appears in a vicinal relationship with respect to the isopropyl group as exemplified in 4,5-deoxyneodolabelline (10) of Fig. 9.2, a related class of marine natural products.6 Steglich and coworkers2 also indicated an assignment of absolute stereo- chemistry for 2 that was based on Hamilton’s applications of linear-hypothesis testing of crystallographic data. This seldom-used technique was in agreement with the proposed absolute configuration of 2 that was advanced by Vidari, based on an assessment of the observed Cotton effects in CD spectroscopy. In 2003, Ohta and coworkers7 reported the discovery of related neodolastanes tricholomalides A, B, and C (structures 11, 12, and 13 of Fig. 9.3) from Tricholoma sp. They concluded that the tricholomalides possessed the opposite absolute configuration claimed for the trichoaurantianolides. This conclusion was based upon the independent analysis of their circular dichroism studies. By application of the octant rule for substituent effects on cisoid a,b- unsaturated ketones,8 Ohta and coworkers suggested a revision of the prior assignment of absolute configuration for the trichoaurantianolides. This asser- tion was advanced in spite of the consistently positive specific rotations recorded in different solvents for trichoaurantianolides A, B, and C1,2 versus the negative values of tricholomalides A (11) and B (12) (compare values in Figs. 9.1 and 9.3). Note that tricholomalide C (13) only differs from trichoaurantianolide B (2) as a C-8 diastereomeric alcohol, presented in the antipodal series. The specific rotation of 13 was of little value since it was recorded as [a]0 (c 0.01, MeOH).7 In 2006, Danishefsky described a pathway for the total synthesis of racemic tricholomalides A and B, and this effort led to a revision of the relative C-2 stereochemistry (Fig. 9.3; revised structures 14 and 15).9 It seemed rather unusual that genetically similar fungi would produce closely related metabolites as enantiomers, but certainly this is not unprecedented. As a starting point, this issue lacked clarity, and we concluded that our synthesis plans must unambig- uously address the issues of absolute configuration. The chemistry of dolabellane and dolastane diterpenes has been reviewed.10 The proposed pathway for biosynthesis of the trichoaurantianolides and related compounds (Fig. 9.4) follows an established sequence from geranyl- geranyl pyrophosphate (16), which undergoes p-cation cyclization to initially form the eleven-membered ring of 17. The event is followed by a second cyclization to form the dolabellane cation 18, and this [9.3.0]cyclotetradecane skeleton is central to several families of natural products. Direct capture or elimination from 18 leads to the 3,7-dolabelladiene 19, which presents the most common pattern of unsaturation within this class. Compounds within this group are traditionally numbered beginning with C-1 as the bridgehead carbon bearing the methyl group rather than following the connectivity presented in ger- anylgeranyl 16. The cation 18 also undergoes a 1,2-hydrogen migration and elimination, which leads to a transannular cyclization yielding the 5e7e6 tri- cyclic dolastane 20. The secodolastanes, represented by 21, are a small collec- tion of marine natural products, which arise from oxidative cleavage of C10eC14 in the parent tricycle 20. In analogous fashion, the neodolabellane structure 22 is produced from 18 by stereospecific backbone migrations that result in the vicinal placement of the bridgehead methyl and isopropyl substituents. Transannular cyclizations, stemming from 22, yield the class of neodolastane diterpenes (23). Trichoaurantianolides and the related lepistal A (5) are the result of oxidations and cleavage of the C-ring (C4eC5) of 23, which leads to the features of an unusual butyrolactone system. The guanacastepenes, such as 24,11 and heptemerones, such as 25,12 are primary examples of the 5e7e6 neodolastane family, and these metabolites have also been isolated from fungi sources. A characteristic structural feature is the vicinal, syn-relationship of the bridgehead methyl and isopropyl sub- stituents as compared with the 1,3-trans relationship found in dolastanes (Fig. 9.2, structures 8 and 9). Guanacastepenes have proven to be attractive targets for synthesis studies.11,13 However, these fungal metabolites exhibit the antipodal, absolute stereochemistry as compared with neodolastanes from marine origins, such as sphaerostanol (26) (Fig. 9.5).14more » « less
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Abstract Sedimentary plant wax
δ 2H values are common proxies for hydrology, a poorly constrained variable in the Arctic. However, it can be difficult to distinguish plant waxes derived from aquatic versus terrestrial plants, causing uncertainty in climate interpretations. We test the hypothesis that Arctic lake sediment mid‐ and long‐chain plant waxes derive from aquatic and terrestrial plants, respectively. We comparen ‐alkanoic acid andn ‐alkane chain‐length distributions andn ‐alkanoic acidδ 2H andδ 13C values of the 29 most abundant modern plant taxa to those for soils, water filtrates, and lake sediments in the Qaupat Lake (QPT) catchment, Nunavut, Canada. Chain length distributions are variable among terrestrial plants, but similar and dominated by mid‐chain waxes among submerged/floating aquatic plants. Sedimentary wax distributions are similar to those in submerged/floating aquatic plants and toSalix spp., which are among the most abundant terrestrial plants in the QPT catchment. Mid‐chainn‐ alkanoic acidδ 2H values are similar in sediments and submerged/floating aquatic plants, but 50‰ lower thanSalix spp. In contrast, sedimentary long‐chainn ‐alkanoic acidδ 2H values fall between those for submerged/floating aquatic plants andSalix spp. We therefore infer that mid‐chain waxes in QPT are primarily from aquatic plants, whereas long‐chain waxes are from a mix of terrestrial and aquatic plants. In Arctic lakes like QPT, terrestrial wax transport via leaf litter and surface flow is limited by low‐lying topography and sparse vegetation. If these lakes also have abundant aquatic plants growing near the sediment‐water interface, the aquatic plants can contribute large portions of sedimentary waxes.
