Characterization of Novel Triacylglycerol Estolides from the Seed Oil of <i>Mallotus philippensis</i> and <i>Trewia nudiflora</i>

Smith, Mark; Zhang, Haixia; Forseille, Li; Purves, Randy W.

doi:10.1007/s11745-012-3721-y

Cited by 21 publications

(13 citation statements)

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“…4d, 2 kV MS/MS with CID off). This observation is consistent with our previous study in which a sodium-mediated THAP matrix [15] was used for TAG-estolide analysis with the CID gas off. When the collision gas was switched on (either 1 kV or 2 kV method), intense low mass fragment ions (m/z \ 200, Fig.…”

Section: Effect Of Cations On Ms and Ms/ms Spectra Of Ergot Estolidessupporting

confidence: 93%

“…Various techniques have been reported for TAG-estolide analysis: these include separation by column chromatography [5], TLC [1], HPLC [6], GC [7], and supercritical fluid chromatography [9]; estolide linkage detection using NMR [1], refractive index [10], infrared [11], atmosphericpressure chemical ionization (APCI) [12], electrospray ionization-mass spectrometry (ESI-MS) [13], and matrixassisted laser desorption/ionization-mass spectrometry (MALDI-MS) [14,15]. The use of mass spectrometry [16][17][18] offers advantages of high mass resolution, excellent detection sensitivity, and very low sample consumption, as low as 100 fmol of trilaurin has been detected with MALDI-MS [19].…”

Section: Introductionmentioning

confidence: 99%

“…However, the detection of TAG-estolides using MS has received little attention, with the exception of a report by Lin and co-workers [13] who used LC-ESI-MS to detect TAG-estolides present as a minor component of castor oil. We previously reported the identification and characterization of abundant TAGestolides from plant and ergot oils using MALDI-MS [14,15]. Compared with ESI-MS, MALDI-MS has the advantages of a short analysis time, better salt/detergent tolerance, and the ability to re-examine the spot containing the analyte when required.…”

Section: Introductionmentioning

confidence: 99%

“…They reported that DHB and CHCA in the presence of TFA have poor shot-toshot reproducibility; dithranol had very low sensitivity, whereas the use of K 4 [Fe(CN) 6 ] matrix was not successful. We have also reported the analysis of TAG-estolides from fungal and plant oils using THAP [14] or DHB [15] with sodium chloride. Our results showed that both matrices had good performance for TAG-estolide analysis, with sodiated ions being the only TAG-estolide signals in the mass spectra, and informative MS/MS spectra were obtained for analyte determination.…”

Section: Introductionmentioning

confidence: 99%

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Optimization of Triacylglycerol‐estolide Analysis by Matrix‐Assisted Laser Desorption/Ionization‐Mass Spectrometry

Zhang

Smith

Purves

2014

J Americ Oil Chem Soc

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Acylglycerols containing more than three acyl groups (TAG-estolides) have been reported in plant seed oils and oil from ergot fungus. These TAG-estolides have considerable potential for industrial use, however, costs of producing synthetic TAG-estolides limits their use in largescale applications. Identification and structural characterization of additional natural sources of TAG-estolides has been restricted by their complexity and limitations of current analytical techniques. In this work, detection and characterization of TAG-estolides was optimized for use with MALDI-TOF-MS. Eight commonly used matrices were compared; 2,5-dihydroxybenzoic acid (DHB) and 2,4,6-trihydroxyacetophenone (THAP) gave good quality mass spectra. Matrix additives were examined and lithium was the most suitable, since MS/MS spectra of lithiated TAG-estolides provided the most informative fragmentation using an optimized method. The matrix solution pH was examined, and for THAP, replacing LiCl with 10-40 mM LiOH resulted in a slightly basic pH and significantly more intense TAG-estolide signals (up to eightfold higher). Since DHB is acidic, a larger amount of LiOH ([150 mM) was required for the matrix solution to become basic, leading to ion suppression and reduced signal intensities. Thus, for TAG-estolide analysis, THAP with *20 to 30 mM LiOH gives the highest quality spectra and the most informative MS/MS fragmentation. KeywordsTriacylglycerol Á Estolide Á Ergot oil Á MALDI-MS Á DHB Á THAP Abbreviations AG Acylglycerol(s) CHCA a-Cyano-4-hydroxycinnamic acid DHB 2,5-Dihydroxybenzoic acid ESI Electrospray ionization FA Fatty acid(s) O Oleic acid (octadec-9-cis-enoic acid, 18:1) M Molecular ion MALDI Matrix-assisted laser desorption/ionization-mass spectrometry P Palmitic acid (hexadecanoic acid, 16:0) R Ricinoleic acid (12-hydroxyoctadec-9-cis-enoic acid, 18:1-OH) S/N Signal-to-noise ratio TAG Triacylglycerol(s) THAP 2,4,6-Trihydroxyacetophenone Electronic supplementary material The online version of this article (

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Section: Effect Of Cations On Ms and Ms/ms Spectra Of Ergot Estolidessupporting

confidence: 93%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Optimization of Triacylglycerol‐estolide Analysis by Matrix‐Assisted Laser Desorption/Ionization‐Mass Spectrometry

Zhang

Smith

Purves

2014

J Americ Oil Chem Soc

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“…For MALDI‐TOF MS of intact seed lipids an AB Sciex 4800 MALDI TOF/TOF mass spectrometer (Applied Biosystems, Frederick, MD, USA) was employed, equipped with an Nd:YAG laser operating at a wavelength of 355 nm, a 3–7 pulse duration and a laser shot frequency of 200 Hz. The MALDI matrix was 2,5‐dihydroxybenzoic acid (Sigma–Aldrich), prepared in 20 mM NaCl to ensure that sodiated adducts ([M + Na] + ) were the predominant ions . 0.8 μL of matrix solution was deposited onto the 384‐well plate (Opti‐TOF insert, Applied Biosystems), followed by the application of 1.0 μL of the oil sample, which was prepared in hexane.…”

Section: Methodsmentioning

confidence: 99%

2‐Acetyl‐1,3‐Diacyl–sn‐Glycerols with Unusual Acyl Composition in Seed Oils of the Genus Polygala

Smith

Zhang

Burton

et al. 2018

Euro J Lipid Sci & Tech

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Seed oils containing unusual triacylglycerol (TAG) molecules, where one fatty acid of a TAG is substituted by an acetate group (Ac), are uncommon but of considerable interest as potential low‐viscosity biofuels and lubricants or reduced calorie food ingredients. Although the properties and pathway of biosynthesis of 3‐acetyl‐1,2‐diacyl‐sn‐glycerols (sn‐3‐acTAGs) have been described, little is known about the occurrence of 2‐acetyl‐1,3‐diacyl‐sn‐glycerols (sn‐2‐acTAGs). Prompted by a report of sn‐2‐acTAGs in the seeds of Polygala virgata, a study of the seed oil of seven members of this genus, and two related species is conducted. The presence of sn‐2‐acTAG and lesser amounts of conventional TAG is conclusively demonstrated in Polygala seed oil by Matrix‐Assisted Laser Desorption/Ionization Time‐of‐Flight Mass Spectrometry (MALDI‐TOF MS) and high resolution C13 nuclear magnetic resonance spectroscopy (C13 NMR). Analysis of seed fatty acids reveals a diversity of composition with oils from P. myrtifolia and P. fruticosa dominated by the medium‐chain fatty acid (MCFA) myristic acid (tetradecanoic acid) at an average of 79.8 and 74.1% of total seed fatty acids, respectively. In contrast, MCFAs are absent from oils from P. tenuifolia and P. virgata, with the very‐long‐chain fatty acid (VLCFA) gondoic acid (cis‐11‐eicosenoic acid) being most abundant. Polygala species therefore represent a rich source of sn‐2‐acTAGs and uncommon fatty acids. Practical applications: The seed oils of Polygala species contain a highly unusual combination of sn‐2‐acTAGs and uncommon fatty acids. These plants can serve as a unique genetic resource for the elucidation of the pathways of biosynthesis of these lipids and the identification of genes for the engineering of novel oils in transgenic plants. As Polygala is morphologically diverse genus ranging from annual herbs to small trees, identification of species with suitable seed production and agronomic characteristics may allow the commercial production of novel oils for specific higher value uses. Plant seed oils are generally composed primarily of triacylglycerol (TAG). In this article, the authors examine the seed oils of seven species in the genus Polygala and report the occurrence of an unusual lipid, 2‐acetyl‐1,3‐diacyl–sn‐glycerol (sn‐2 acTAG). These plants also produce unusual fatty acids in their seed oil, with Polygala tenuifolia being enriched in gondoic acid (cis‐11‐eicosenoic acid, 20:1Δ11) and Polygala myrtifolia containing myristic acid (tetradecanoic acid, 14:0). The genus Polygala represents a potential source of novel oil and a resource for the characterization of sn‐2 acTAG biosynthesis.

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Seeds as oil factories

Baud

2018

Plant Reprod

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Studying seed oil metabolism. The seeds of higher plants represent valuable factories capable of converting photosynthetically derived sugars into a variety of storage compounds, including oils. Oils are the most energy-dense plant reserves and fatty acids composing these oils represent an excellent nutritional source. They supply humans with much of the calories and essential fatty acids required in their diet. These oils are then increasingly being utilized as renewable alternatives to petroleum for the chemical industry and for biofuels. Plant oils therefore represent a highly valuable agricultural commodity, the demand for which is increasing rapidly. Knowledge regarding seed oil production is extensively exploited in the frame of breeding programs and approaches of metabolic engineering for oilseed crop improvement. Complementary aspects of this research include (1) the study of carbon metabolism responsible for the conversion of photosynthetically derived sugars into precursors for fatty acid biosynthesis, (2) the identification and characterization of the enzymatic actors allowing the production of the wide set of fatty acid structures found in seed oils, and (3) the investigation of the complex biosynthetic pathways leading to the production of storage lipids (waxes, triacylglycerols). In this review, we outline the most recent developments in our understanding of the underlying biochemical and molecular mechanisms of seed oil production, focusing on fatty acids and oils that can have a significant impact on the emerging bioeconomy.

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Characterization of Novel Triacylglycerol Estolides from the Seed Oil of Mallotus philippensis and Trewia nudiflora

Cited by 21 publications

References 21 publications

Optimization of Triacylglycerol‐estolide Analysis by Matrix‐Assisted Laser Desorption/Ionization‐Mass Spectrometry

Optimization of Triacylglycerol‐estolide Analysis by Matrix‐Assisted Laser Desorption/Ionization‐Mass Spectrometry

2‐Acetyl‐1,3‐Diacyl–sn‐Glycerols with Unusual Acyl Composition in Seed Oils of the Genus Polygala

Seeds as oil factories

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