Identification of carbon-carbon double bond stereochemistry in unsaturated fatty acids by charge-remote fragmentation of fixed-charge derivatives

Journal article


Young, Reuben, Flakelar, Clare, Narreddula, Venkateswara, Jekimovs, Lachlan, Menzel, Jan, Poad, Berwyck and Blanksby, Stephen. (2022). Identification of carbon-carbon double bond stereochemistry in unsaturated fatty acids by charge-remote fragmentation of fixed-charge derivatives. Analytical Chemistry. 94(46), pp. 16180-16188. https://doi.org/10.1021/acs.analchem.2c03625
AuthorsYoung, Reuben, Flakelar, Clare, Narreddula, Venkateswara, Jekimovs, Lachlan, Menzel, Jan, Poad, Berwyck and Blanksby, Stephen
Abstract

Separation and identification of fatty acid (FA) isomers in biological samples represents a challenging problem for lipid chemists. Notably, FA regio- and stereo-isomers differing in the location or (cis/trans) geometry of carbon-carbon double bonds are often incompletely separated and ambiguously assigned in conventional chromatography-mass spectrometry analyses. To address this challenge, FAs have been derivatized with the charge-switch derivatization reagents N-methyl-pyridinium-3-methanamine and N-(4-aminomethylphenyl)pyridinium and subjected to reversed-phase liquid chromatography-tandem mass spectrometry. Charge-remote fragmentation of the fixed-charge derivatives leads to characteristic product ions arising from dissociation at allylic positions that enable assignment of position(s) of unsaturation, while a newly discovered dihydrogen neutral loss was found to be dominant for double bonds with cis-stereochemistry. The structure of the [M - 2]+ product ions was probed by gas-phase ozonolysis revealing the presence of two new carbon-carbon bonds on either side of the initial position of unsaturation consistent with an electrocyclic mechanism of 1,4-dihydrogen elimination. Charge-remote fragmentation pathways diagnostic of double bond position and stereochemistry were found to be generalized for FAs of different carbon-chain lengths, double bond positions, and degrees of unsaturation and were effective in the unequivocal assignment of the FA structure in complex mixtures of FA isomers, including bovine milk powder.

Year2022
JournalAnalytical Chemistry
Journal citation94 (46), pp. 16180-16188
PublisherAmerican Chemical Society
ISSN0003-2700
Digital Object Identifier (DOI)https://doi.org/10.1021/acs.analchem.2c03625
Scopus EID2-s2.0-85141669104
Page range16180-16188
FunderResearch Training Program Scholarship (RTP), Australian Government
Australian Catholic University (ACU)
Australian Research Council (ARC)
Publisher's version
License
All rights reserved
File Access Level
Controlled
Output statusPublished
Publication dates
Online07 Nov 2022
Publication process dates
Accepted24 Oct 2022
Deposited27 Jan 2023
ARC Funded ResearchThis output has been funded, wholly or partially, under the Australian Research Council Act 2001
Grant IDLP180100238
DP190101486
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