Regiospecific Analysis of Diricinoleoylacylglycerols in Castor (<i>Ricinus communis</i> L.) Oil by Electrospray Ionization−Mass Spectrometry

Lin, Jiann‐Tsyh; Arcinas, Arthur

doi:10.1021/jf063105f

Cited by 33 publications

(65 citation statements)

References 16 publications

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“…3, Fig. 4 [3,4,10] from the cleavage between C-11 and C-12 of the ricinoleoyl chain for TAG containing ricinoleate. The proposed fragmentation pathway of this ion at m/z 207.1 is shown as Fig.…”

Section: Resultsmentioning

confidence: 99%

“…Castor oil is the only commercial source of ricinoleate. We have previously identified and quantified 14 molecular species of AG containing ricinoleate in castor oil using high-performance liquid chromatography (HPLC) and mass spectrometry (MS) methods [1][2][3][4]. We report here, the identification of 12 molecular species of AG containing dihydroxy fatty acids in castor oil.…”

Section: Introductionmentioning

confidence: 99%

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Identification of Acylglycerols Containing Dihydroxy Fatty Acids in Castor Oil by Mass Spectrometry

Lin

Arcinas

Harden

2008

Lipids

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Ricinoleate, a monohydroxy fatty acid, in castor oil has many industrial uses. Dihydroxy fatty acids can also be used in industry. The C(18) HPLC fractions of castor oil were analyzed by electrospray ionization mass spectrometry of lithium adducts to identify the acylglycerols containing dihydroxy fatty acids and the dihydroxy fatty acids. Four diacylglycerols identified were diOH18:1-diOH18:1, diOH18:2-OH18:1, diOH18:1-OH18:1 and diOH18:0-OH18:1. Eight triacylglycerols identified were diOH18:1-diOH18:1-diOH18:1, diOH18:1-diOH18:1-diOH18:0, diOH18:2-diOH18:1-OH18:1, diOH18:1-diOH18:1-OH18:1, diOH18:1-diOH18:0-OH18:1, diOH18:2-OH18:1-OH18:1, diOH18:1-OH18:1-OH18:1 and diOH18:0-OH18:1-OH18:1. The locations of fatty acids on the glycerol backbone were not determined. The structures of these three newly identified dihydroxy fatty acids were proposed as 11,12-dihydroxy-9-octadecenoic acid, 11,12-dihydroxy-9,13-octadecadienoic acid and 11,12-dihydroxyoctadecanoic acid. These individual acylglycerols were at the levels of about 0.5% or less in castor oil and can be isolated from castor oil or overproduced in a transgenic oil seed plant for future industrial uses.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Identification of Acylglycerols Containing Dihydroxy Fatty Acids in Castor Oil by Mass Spectrometry

Lin

Arcinas

Harden

2008

Lipids

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“…Major triacylglycerol product ions observed under these conditions include [M ϩ NH 4 -(RCOONH 4 ϩ -precursor ions of triacylglycerols utilizing an ion trap instrument showed comparable product ions, including [M ϩ H] ϩ -ions formed by direct loss of ammonia from the precursor ion allowing also MS n -measurements (n ϭ 3) of various first generation product ions but still not enabling positional determination of fatty acid substituents [15,19]. Triacylglycerols obtained from castor bean oil as well as some synthetic species were also analyzed as [M ϩ Li] ϩ -precursor ions by tandem mass spectrometry utilizing ion trap- [18] and triple quadrupole instrumentation [14], respectively, allowing positional isomer determination in favorable cases.…”

Section: Usually [M ϩ H]mentioning

confidence: 99%

“…R ecent advances in the analysis of complex triacylglycerol mixtures as well as detailed structural analysis thereof have been achieved by atmospheric pressure chemical ionization (APCI)- [1][2][3][4][5][6][7][8][9][10], electrospray ionization (ESI)- [11][12][13][14][15][16][17][18][19][20], fast atom bombardment (FAB)- [21][22][23][24][25][26], plasma desorption (PD) [27], and vacuum matrix-assisted laser desorption/ionization (vMALDI) mass spectrometry [28 -39] with and without prior chromatographic separation. Various types of mass spectrometric analyzers (single quadrupole, triple quadrupole, ion trap, sector, tandem sector, reflectron time-of-flight, and various hybrid instruments) were utilized for these analytes, enabling various tandem mass spectrometric experiments (tandemin-time, tandem-in-space) at different energy regimes for ion activation from low-energy (tens of eVs) to high-energy (up to 25 keV) collision-induced dissociation (CID) by selecting either [M ϩ H] ϩ -ions as well as [M ϩ NH 4 ] ϩ -or [M ϩ Na] ϩ -adduct ions as precursors ions.…”

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confidence: 99%

The renaissance of high-energy CID for structural elucidation of complex lipids: MALDI-TOF/RTOF-MS of alkali cationized triacylglycerols

Pittenauer

Allmaier

2009

J. Am. Soc. Mass Spectrom.

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Triacylglycerols were analyzed as cationized species (Li ϩ , Na ϩ , K ϩ ) by high-energy CID at 20 keV collisions utilizing MALDI-TOF/RTOF mass spectrometry. Precursor ions, based on [M ϩ Li] ϩ -adduct ions exhibited incomplete fragmentation in the high and low m/z region whereas [M ϩ K] ϩ -adducts did not show useful fragmentation. Only sodiated precursor ions yielded product ion spectra with structurally diagnostic product ions across the whole m/z range. The high m/z region of the CID spectra is dominated by abundant charge-remote fragmentation of the fatty acid substituents. In favorable cases also positions of double bonds or of hydroxy groups of the fatty acid alkyl chains could be determined. A-type product ions represent the end products of these charge-remote fragmentations. B-and C-type product ions yield the fatty acid composition of individual triacylglycerol species based on loss of either one neutral fatty acid or one sodium carboxylate residue, respectively. Product ions allowing fatty acid substituent positional determination were present in the low m/z range enabling identification of either the sn-1/sn-3 substituents (E-, F-, and G-type ions) or the sn-2 substituent (J-type ion). These findings were demonstrated with synthetic triacylglycerols and plant oils such as cocoa butter, olive oil, and castor bean oil. Typical features of 20 keV CID spectra of sodiated triacylglycerols obtained by MALDI-TOF/RTOF MS were an even distribution of product ions over the entire m/z range and a mass accuracy of Ϯ0.1 to 0.

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“…By contrast, tandem quadrupole [4] and quadrupole ion-trap [5] product-ion spectra from the [M + Li] + ions of TAG is readily applicable for identification of the fatty acid substituents and location their position on the glycerol backbone. Skimmer CAD on the lithiated adduct ion of TAG, followed by tandem quadrupole mass spectrometry on the dilithiated adduct ions of fatty acid substituents generated by skimmer CAD are applicable for location of double bonds.…”

Section: Introductionmentioning

confidence: 99%

Electrospray ionization multiple-stage linear ion-trap mass spectrometry for structural elucidation of triacylglycerols: Assignment of fatty acyl groups on the glycerol backbone and location of double bonds

Hsu

Turk

2010

J. Am. Soc. Mass Spectrom.

117

108

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Linear ion-trap multiple-stage mass spectrometric approach (MS n ) towards nearly complete structural elucidation of triacylglycerol (TAG) including (1) assignment the fatty acid substituents on the glycerol backbone and (2) 3) gives rise to the ion series locating the double bonds along the fatty acid chain. These ions arise from charge-remote fragmentations involving ␤-cleavage with ␥-H shift, analogous to those seen for the unsaturated long-chain fatty acids characterized as initiated ions. Significant differences in abundances in the ion pairs reflecting the additional losses of the fatty acid moieties, respectively, were also seen in the MS 3 spectra of the H igh-energy CAD with a tandem sector instrument permits structural characterization of triacylglycerol (or triacylglyceride) (TAG) as sodiated adducts desorbed by FAB, leading to identify each fatty acid substituent and positions of fatty acid substituents on the glycerol backbone. However, the sensitivity is poor and the application in elucidation of the location of double bond(s) for the unsaturated fatty acid substituents has not been demonstrated [1]. Highenergy CAD product-ion spectra of the sodiated adducts of TAG obtained with tandem sector instrument coupled with ESI were unsatisfactory for structural characterization, but those from the [M ϩ NH 4 ] ϩ ions identified the fatty acid substituents, nevertheless, are not informative for assignment of the fatty acid substituents on the glycerol backbone [1]. Similarly, tandem quadrupole mass spectra of the [M ϩ Na] ϩ ions of TAG did not contain structurally informative fragment ions, but those from [M ϩ NH 4 ] ϩ ions contained fragment ions that identify the fatty acid groups [2]. Neither the positions of the fatty acid substituents on the glycerol backbone nor the locations of double bonds in unsaturated fatty acid chains could be determined from these spectra [2]. Recently, Pittenauer and Allmaier demonstrated high-energy CAD using MALDI-TOF/RTOF-MS for characterization of TAGs as alkali adduct ions. The product ions from [M ϩ Na] ϩ ions of TAG afford determination of the position of fatty acid substituents on the glycerol backbone and in some favorable cases the location of double bonds or hydroxy groups. However, the method is limited by the insufficient precursor ion gating after MS 1 (gating window of 4 Da), and ion species differed by 2 Da cannot be separated [3].

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Regiospecific Analysis of Diricinoleoylacylglycerols in Castor (Ricinus communis L.) Oil by Electrospray Ionization−Mass Spectrometry

Cited by 33 publications

References 16 publications

Identification of Acylglycerols Containing Dihydroxy Fatty Acids in Castor Oil by Mass Spectrometry

Identification of Acylglycerols Containing Dihydroxy Fatty Acids in Castor Oil by Mass Spectrometry

The renaissance of high-energy CID for structural elucidation of complex lipids: MALDI-TOF/RTOF-MS of alkali cationized triacylglycerols

Electrospray ionization multiple-stage linear ion-trap mass spectrometry for structural elucidation of triacylglycerols: Assignment of fatty acyl groups on the glycerol backbone and location of double bonds

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