Rapid transesterification and mass spectrometric approach to seed oil analysis

Ayorinde, Folahan O.; Clifton, James R; Afolabi, Olajide Joseph; Shepard, Robert L.

doi:10.1007/bf02544516

Cited by 41 publications

(31 citation statements)

References 4 publications

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“…11 Our rationale for carrying out base catalysis was to create milder reaction conditions so as to preserve the end groups of the parent polymer. Table 1 shows the relationship between the concentration of the sodium methoxide and the size of the resulting oligomers.…”

Section: Base-catalyzed Transesterificationmentioning

confidence: 99%

Characterization of partially transesterified poly(β-hydroxyalkanoate)s using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry

Saeed

Ayorinde

Eribo

et al. 1999

Rapid Commun. Mass Spectrom.

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Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOFMS) was used for the characterization of a partially transesterified poly(beta-hydroxyalkanoate), PHA, polymer produced by the bacterial strain Alcaligenes eutrophus using saponified vegetable oils as the sole carbon sources. The transesterification was carried out separately under acidic and basic conditions to obtain PHA oligomers weighing less than 10 kDa. The intact oligomers were detected in their cationized [M + Na](+) and [M + K](+) forms by MALDI-TOFMS. A composition analysis, using the MALDI-TOF spectra, indicate that the oligomers obtained via acid catalysis were terminated with a methyl 3-hydroxybutyrate end group, and those obtained by base catalysis had a methyl crotonate (olefinic) termination. In addition to HB (hydroxy butyrate), the oligomers were found to contain a small percentage of HV (hydroxy valerate). This was independently confirmed using gas chromatography/mass spectrometry (GC/MS). In comparison, the analysis of a commercial PHA polymer, transesterified under identical conditions, only showed the presence of HB, i.e. a pure PHB homopolymer. Copyright 1999 John Wiley & Sons, Ltd.

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Section: Base-catalyzed Transesterificationmentioning

confidence: 99%

Characterization of partially transesterified poly(β-hydroxyalkanoate)s using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry

Saeed

Ayorinde

Eribo

et al. 1999

Rapid Commun. Mass Spectrom.

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“…Also, the base-catalyzed methanolysis (14) of the oil resulted only in transesterification to give epoxidized methyl ester. Consequently, we were interested in studying the effect of a nucleophilic agent such as LAH on the epoxy functionality.…”

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confidence: 99%

“…The products from this reaction could constitute potential intermediates in the synthesis of oleochemicals from Vernonia galamensis seed oil, since it has been recognized as a potential oil seed crop (11,12). The initial interest was due to the unique fatty acid composition of its seed oil, which contains epoxidized triacylglycerols, of which trivernolin has been shown to be the major triacylglycerol (13,14).Previous work in our laboratory indicated that the epoxy functionality in VO was reactive toward nucleophilic reagents only under acidic conditions (12), whereas aminolysis (15) of the oil gave epoxy-containing amides with no indication of epoxy opening. Also, the base-catalyzed methanolysis (14) of the oil resulted only in transesterification to give epoxidized methyl ester.…”

mentioning

confidence: 99%

Synthesis of cis‐12, 13‐epoxy‐cis‐9‐octadecenol and 12(13)‐hydroxy‐cis‐9‐octadecenol from vernonia oil using lithium aluminum hydride

Elhilo

Anderson

Ayorinde

2000

J Americ Oil Chem Soc

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Reduction of vernonia oil methyl esters (VOME) into epoxy fatty alcohol and diols was achieved with lithium aluminum hydride (LAH), under reflux and room temperature conditions, by using hexane and tetrahydrofuran (THF) as solvents . The reactions of VOME with LAH in hexane produced cis-12,13-epoxy-cis-9-octadecenol as a major product with an isolated yield of 73.62%, whereas the reactions with LAH in THF gave isomers of 12(13)-hydroxy-cis-9-octadecenol as the major products with an isolated yield of 95.1%. LAH was similarly reacted with vernonia oil (VO) to give the same products in lower yields. 1 H nuclear magnetic resonance (NMR), 13 C NMR, gas chromatography-mass spectrometry, and infrared were used to characterize these products.This study demonstrates the ability to control the reactivity of the epoxy functionality in VO or VOME with the choice of polar or nonpolar solvents, and extends the range of oleochemicals that can be derived from vernonia oil.The most extensively used oleochemicals, after fatty acids, are fatty alcohols, and there are growing efforts aimed at developing new derivatives and applications for the alcohols (1). Current laboratory methodology for their synthesis involves direct reduction of fatty esters with lithium aluminum hydride (LAH) (2). LAH is among the most powerful complex metal hydride reducing agents, with the ability to reduce carbonyl functionality in aldehydes, ketones, and esters to corresponding alcohols, while leaving the carbon-carbon double bond or carbon-carbon triple linkages untouched (3-5). In the case of the reaction of LAH with esters (2), the reduction of the ester functionality proceeds by nucleophilic attack of the hydride ion on the carbonyl group, leading to the formation of intermediate alkoxide salts from which the alcohol is generated upon acidification. Micovic and coworkers (6) reported on the production of corresponding alcohols resulting from the LAH reduction of tripalmitin and triolein, olive oil, lard, and oil of chaulmoogra glycerides. In another study, Walborsky and Colombini (7) reported on the syntheses of alcohol mixtures by the LAH reduction of glycidic esters. Ernest and coworkers (8,9) have also demonstrated the ability of LAH to reduce epoxides to alcohols.Therefore, we were interested in studying the reaction between LAH and vernonia oil (VO), which is a naturally epoxidized vegetable oil (10). The products from this reaction could constitute potential intermediates in the synthesis of oleochemicals from Vernonia galamensis seed oil, since it has been recognized as a potential oil seed crop (11,12). The initial interest was due to the unique fatty acid composition of its seed oil, which contains epoxidized triacylglycerols, of which trivernolin has been shown to be the major triacylglycerol (13,14).Previous work in our laboratory indicated that the epoxy functionality in VO was reactive toward nucleophilic reagents only under acidic conditions (12), whereas aminolysis (15) of the oil gave epoxy-containing amides with no indication of epo...

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“…Vernolic acid offers potential application in the formulation of additives, coatings, and lubricant additives. Vernonia oil has become a unique renewable candidate for industrial feedstock due to its use as raw material and its potential derivatization into value-added products [1,[6][7][8][9].…”

Section: Introductionmentioning

confidence: 99%

“…Our group have recently reported the synthesis of epoxy fatty acid esters of cassava starch by reacting cassava starch with vernonia oil methyl ester (epoxy ester) using 1-butyl-3-methylimidazolium hexafluorophosphate, 6 ] ionic liquid (IL) as a reaction medium and DMSO as co-solvent [1]. Similarly we have also reported the successful preparation of epoxy fatty acid esters of cassava starch (starch vernolates) by reacting cassava starch with vernonia oil methyl ester using only 1-butyl-3-methylimidazolium chloride, [C 4 C 1 im]Cl, ionic liquid as a reaction medium and an inexpensive base such as pyridine as a catalyst [50].…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Characterization of Starch Vernolates in Organic Solvents

Desalegn¹,

Segne²,

Chebude³

2016

AJAC

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Abstract:In this study the synthesis of epoxy fatty acid esters of starch (starch vernolates) by the reaction of cassava starch with vernonia oil methyl ester (epoxy ester) using basic catalyst K 2 CO 3 and organic solvent, DMSO as a reaction medium is presented. Under current reaction conditions, a high degree of substitution of 1.24 was achieved, at a reaction temperature of 110°C and 12 hours of reaction time. The new starch vernolates were characterized by Scanning electron microscopy (SEM) and X-ray diffraction (XRD) indicated that the new product is an amorphous material with a continuous and shapeless morphology. The melting point measured by differential scanning calorimetry (DSC) was 118°C. The new synthetic method makes the synthesis of starch vernolates less time consuming and more inexpensive. The differences in melting point and degree of substitution with previously synthesized starch vernolates using enzymatic and chemical catalysis suggest a difference in reaction selectivity via this new reaction path.

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Rapid transesterification and mass spectrometric approach to seed oil analysis

Cited by 41 publications

References 4 publications

Characterization of partially transesterified poly(β-hydroxyalkanoate)s using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry

Characterization of partially transesterified poly(β-hydroxyalkanoate)s using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry

Synthesis of cis‐12, 13‐epoxy‐cis‐9‐octadecenol and 12(13)‐hydroxy‐cis‐9‐octadecenol from vernonia oil using lithium aluminum hydride

Synthesis and Characterization of Starch Vernolates in Organic Solvents

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