scholarly journals Computational metabolomics illuminates the lineage-specific diversification of resin glycoside acylsugars in the morning glory (Convolvulaceae) family

2021 ◽  
Author(s):  
Lars H. Kruse ◽  
Alexandra A. Bennett ◽  
Elizabeth H. Mahood ◽  
Elena Lazarus ◽  
Se Jin Park ◽  
...  
Keyword(s):  
Structural Diversity ◽  
Morning Glory ◽  
Resonance Spectroscopy ◽  
Leaf Extracts ◽  
Evolutionary Mechanisms ◽  
Defense Compounds ◽  
Resin Glycoside ◽  
Ring Structures ◽  
Acyl Chains ◽  
Fragmentation Patterns

AbstractAcylsugars are a class of plant defense compounds produced across many distantly related families. Members of the horticulturally important morning glory (Convolvulaceae) family produce a diverse sub-class of acylsugars called resin glycosides (RGs), which comprise oligosaccharide cores, hydroxyacyl chain(s), and decorating aliphatic and aromatic acyl chains. While many RG structures are characterized, the extent of structural diversity of this class in different genera and species is not known. In this study, we asked whether there has been lineage-specific diversification of RG structures in different Convolvulaceae species that may suggest diversification of the underlying biosynthetic pathways. Liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS) was performed from root and leaf extracts of 26 species sampled in a phylogeny-guided manner. LC-MS/MS revealed thousands of peaks with signature RG fragmentation patterns with one species producing over 300 signals, mirroring the diversity in Solanaceae-type acylsugars. A novel RG from Dichondra argentea was characterized using Nuclear Magnetic Resonance spectroscopy, supporting previous observations of RGs with open hydroxyacyl chains instead of closed macrolactone ring structures. Substantial lineage-specific differentiation in utilization of sugars, hydroxyacyl chains, and decorating acyl chains was discovered, especially among Ipomoea and Convolvulus – the two largest genera in Convolvulaceae. Adopting a computational, knowledge-based strategy, we further developed a high-recall workflow that successfully explained ~72% of the MS/MS fragments, predicted the structural components of 11/13 previously characterized RGs, and partially annotated ~45% of the RGs. Overall, this study improves our understanding of phytochemical diversity and lays a foundation for characterizing the evolutionary mechanisms underlying RG diversification.

Repeated rearrangement of the GSL‐AOP locus contributed to spatio‐temporal variation in defense chemistry in Arabidopsis

2020 ◽  
Author(s):  
Konrad Weber ◽  
Lucasz Krych ◽  
Meike Burow
Keyword(s):  
Flowering Time ◽  
Regulatory Networks ◽  
Structural Diversity ◽  
Sequence Information ◽  
Sequencing Data ◽  
Defense Compounds ◽  
Caucasus Region ◽  
Time Control ◽  
Spatio Temporal ◽  
Flowering Time Control

Abstract Plants coordinate metabolic and developmental processes with the help of genetically variable, interconnected regulatory networks. The GSL-AOP locus in Arabidopsis thaliana encodes enzymes involved in the biosynthesis of glucosinolate defense compounds and has been attributed regulatory functions e.g. in flowering time control. To correlate genetic and phenotypic variation linked to GSL-AOP, we conducted a phylogenetic analysis across 1135 accessions and found that the available short-read sequencing data does not fully resolve the structural diversity in the locus. We analyzed a selection of 74 accessions for glucosinolate profiles and flowering time under different conditions and acquired long-read sequence information for glucosinolate and flowering time loci. Especially in the Caucasus region, structural variation in GSL-AOP was associated with conditional, tissue-specific glucosinolate profiles. Variation in FLC among the Caucasian accessions correlated with variation in the flowering time response to vernalization, suggesting that local adaptation has shaped defense and development in an orchestrated manner.

scholarly journals Identification of unusual phospholipids from bovine heart mitochondria by HPLC-MS/MS

2020 ◽  
Vol 61 (12) ◽  
pp. 1707-1719
Author(s):  
Junhwan Kim ◽  
Charles L. Hoppel
Keyword(s):  
Acyl Chain ◽  
Heart Mitochondria ◽  
Ether Linkage ◽  
Molecular Weights ◽  
Bovine Heart ◽  
Class Separation ◽  
Normal Phase Hplc ◽  
Acyl Chains ◽  
Clear Identification ◽  
Fragmentation Patterns

Phospholipids, including ether phospholipids, are composed of numerous isomeric and isobaric species that have the same backbone and acyl chains. This structural resemblance results in similar fragmentation patterns by collision-induced dissociation of phospholipids regardless of class, yielding complicated MS/MS spectra when isobaric species are analyzed together. Furthermore, the presence of isobaric species can lead to misassignment of species when made solely based on their molecular weights. In this study, we used normal-phase HPLC for ESI-MS/MS analysis of phospholipids from bovine heart mitochondria. Class separation by HPLC eliminates chances for misidentification of isobaric species from different classes of phospholipids. Chromatography yields simple MS/MS spectra without interference from isobaric species, allowing clear identification of peaks corresponding to fragmented ions containing monoacylglycerol backbone derived from losing one acyl chain. Using these fragmented ions, we characterized individual and isomeric species in each class of mitochondrial phospholipids, including unusual species, such as PS, containing an ether linkage and species containing odd-numbered acyl chains in cardiolipin, PS, PI, and PG. We also characterized monolysocardiolipin and dilysocardiolipin, the least abundant but nevertheless important mitochondrial phospholipids. The results clearly show the power of HPLC-MS/MS for identification and characterization of phospholipids, including minor species.

Interaction between lipid bilayers and a new class of antineoplastic agents derived from arylchloroethylurea: a 2H solid-state NMR study

1998 ◽  
Vol 76 (2-3) ◽  
pp. 465-471 ◽  
Author(s):  
Audrey Saint-Laurent ◽  
Nadine Boudreau ◽  
René C.-Gaudreault ◽  
Patrick Poyet ◽  
Michèle Auger
Keyword(s):  
Lipid Bilayer ◽  
Lipid Bilayers ◽  
Antineoplastic Agents ◽  
Acyl Chain ◽  
Resonance Spectroscopy ◽  
Interfacial Region ◽  
Molar Ratios ◽  
New Class ◽  
Nmr Study ◽  
Acyl Chains

We have investigated the interaction between a new class of antineoplastic agents derived from arylchloroethylurea (CEU) and model membrane of dimyristoylphosphatidylcholine by deuterium nuclear magnetic resonance spectroscopy. The results indicate that the drug incorporates in the bilayer and causes an increase of the lipid acyl chain order, this effect being greater close to the interfacial region of the lipid bilayer. The increase in ordering is dependent on the nature (degree of ramification, length of the alkyl chain, and presence of a sulfur atom) as well as on the position of the R substituent and is correlated with the cytotoxicity of the drugs. More specifically, the more cytotoxic drugs, such as 4-sec-butyl CEU, are those having a bulky ramified substituent and those for which the ordering effect on the lipid bilayer is the smallest. On the other hand, the ordering effect is greater and seen all along the lipid acyl chains for the long-chain CEUs, such as n-hexadecyl CEU, which have been shown to have very weak cytotoxic activity. Finally, the results obtained as a function of the drug concentration indicate that the ordering effect is seen for lipid to drug molar ratios as low as 20:1.Key words: deuterium, NMR, membrane, arylchloroethylurea, liposome.

Resin Glycoside Constituents ofIpomoea pes-caprae(Beach Morning Glory)

2008 ◽  
Vol 71 (12) ◽  
pp. 1998-2003 ◽  
Author(s):  
Hongwen Tao ◽  
Xiaojiang Hao ◽  
Jinggen Liu ◽  
Jian Ding ◽  
Yuchun Fang ◽  
...  
Keyword(s):  
Morning Glory ◽  
Resin Glycoside

scholarly journals Epilipidomics platform for holistic profiling of oxidized complex lipids in blood plasma of obese individuals

2021 ◽  
Author(s):  
Angela Criscuolo ◽  
Palina Nepachalovich ◽  
Diego Fernando Garcia-del Rio ◽  
Mike Lange ◽  
Zhixu Ni ◽  
...  
Keyword(s):  
Type Ii Diabetes ◽  
Metabolic Disorders ◽  
Neutral Lipids ◽  
Structural Diversity ◽  
Oxidized Lipids ◽  
Lipid Modifications ◽  
Specific Manner ◽  
Acyl Chains ◽  
Complex Lipids ◽  
Regulatory Significance

Lipids are a structurally diverse class of biomolecules which can undergo a variety of chemical modifications. Among them, lipid (per)oxidation attracts most of the attention due to its significance in regulation of inflammation, cell proliferation and death programs. Despite their apparent regulatory significance, the molecular repertoire of oxidized lipids remains largely elusive as accurate annotation of lipid modifications is challenged by their low abundance and largely unknown, biological context-dependent structural diversity. Here we provide a holistic workflow based on the combination of bioinformatics and LC-MS/MS technologies to support identification and relative quantification of oxidized complex lipids in a modification type- and position-specific manner. The developed methodology was used to identify epilipidomics signatures of lean and obese individuals with and without type II diabetes. Characteristic signature of lipid modifications in lean individuals, dominated by the presence of modified octadecanoid acyl chains in phospho- and neutral lipids, was drastically shifted towards lipid peroxidation-driven accumulation of oxidized eicosanoids, suggesting significant alteration of endocrine signalling by oxidized lipids in metabolic disorders.

scholarly journals Diversity of secoiridoid glycosides in leaves of UK and Danish ash provide new insight for ash dieback management

2020 ◽  
Vol 10 (1) ◽  
Author(s):  
John D. Sidda ◽  
Lijiang Song ◽  
Jack L. Parker ◽  
David J. Studholme ◽  
Christine Sambles ◽  
...  
Keyword(s):  
Emerald Ash Borer ◽  
Structural Diversity ◽  
Feeding Deterrents ◽  
Leaf Extracts ◽  
Ash Dieback ◽  
Sample Group ◽  
Ash Trees ◽  
Secoiridoid Glycosides ◽  
The Uk ◽  
European Ash

Abstract Secoiridoid glycosides are anti-feeding deterrents of the Oleaceae family recently highlighted as potential biomarkers in Danish ash trees to differentiate between those tolerant and susceptible to the fungal disease ash dieback. With the knowledge that emerald ash borer has recently entered Europe from Russia, and that extensive selection trials are ongoing in Europe for ash dieback tolerant European ash (Fraxinus excelsior), we undertook comprehensive screening of secoiridoid glycosides in leaf extracts of trees tolerant and susceptible to ash dieback sampled from sites in the UK and Denmark. Here we report an unexpected diversity of secoiridoid glycosides in UK trees and higher levels of secoiridoid glycosides in the UK sample group. While it is unlikely that secoiridoid glycosides generally can serve as reliable markers for ash dieback susceptibility, there are differences between tolerant and susceptible groups for specific secoiridoids. We predict that the high levels—and structural diversity—of secoiridoids present in the UK group may provide a robust reservoir of anti-feeding deterrents to mitigate future herbivore threats such as the Emerald ash borer.

scholarly journals Evolution of host range in Coleosporium ipomoeae, a plant pathogen with multiple hosts

2016 ◽  
Vol 113 (19) ◽  
pp. 5346-5351 ◽  
Author(s):  
Thomas M. Chappell ◽  
Mark D. Rausher
Keyword(s):  
Natural Selection ◽  
Host Range ◽  
Plant Pathogen ◽  
Host Species ◽  
Local Community ◽  
Morning Glory ◽  
Direct Selection ◽  
Evolutionary Mechanisms ◽  
Community Evolution ◽  
Selection For

Plants and their pathogens coevolve locally. Previous investigations of one host–one pathogen systems have demonstrated that natural selection favors pathogen genotypes that are virulent on a broad range of host genotypes. In the present study, we examine a system consisting of one pathogen species that infects three host species in the morning glory genus Ipomoea. We show that many pathogen genotypes can infect two or three of the host species when tested on plants from nonlocal communities. By contrast, pathogen genotypes are highly host-specific, infecting only one host species, when tested on host species from the local community. This pattern indicates that within-community evolution narrows the host breadth of pathogen genotypes. Possible evolutionary mechanisms include direct selection for narrow host breadth due to costs of virulence and evolution of ipomoea resistance in the host species.

Unambiguous structural and nuclear magnetic resonance spectral characterization of two triterpenoids of Maprouneaguianensis by two-dimensional nuclear magnetic resonance spectroscopy

1987 ◽  
Vol 65 (11) ◽  
pp. 2519-2525 ◽  
Author(s):  
Stewart McLean ◽  
Marion Perpick-Dumont ◽  
William F. Reynolds ◽  
Helen Jacobs ◽  
Sagar Singh Lachmansing
Keyword(s):  
Nuclear Magnetic Resonance ◽  
Magnetic Resonance ◽  
Resonance Spectroscopy ◽  
Two Dimensional ◽  
Mass Spectral Fragmentation ◽  
Mass Spectral ◽  
Alternative Approaches ◽  
Fragmentation Patterns ◽  
Nuclear Magnetic

It is shown that 1H–13C shift-correlated two-dimensional spectra obtained for polarization transfer via two-bond and three-bond 13C–1H coupling can, in conjunction with related experiments, be used to assign unambiguously the molecular skeletons of two of the less common triterpenes, moretenone and 3-acetylaleuritolic acid. It is concluded that this is a technique of considerable generality for assigning structures of triterpenes and is more reliable than alternative approaches such as mass spectral fragmentation patterns. It has the additional benefit of simultaneously providing reliable 13C and 1H spectral assignments for these compounds.

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