O and OH chemical ionization of some fatty acid methyl esters and triacylglycerols

Abstract
O and OH react with fatty acid methyl esters (FAMES) under chemical ionization conditions both as Bronsted bases to form [M - H] and as nucleophiles to form the carboxylate ion RCOO. O shows a much greater tendency to react as a nucleophile than does OH. The [M - H] ions fragment by elimination of CH3OH, with unsaturation in certain positions in the fatty acid hydrocarbon chain promoting this elimination for unknown reasons. The reaction of O and OH with triacylglycerols leads to [M - H], characteristic of the molecular mass, and to carboxylate ions characteristic of the fatty acid(s) present in the lipid. The presence of the three ester functions in the lipids greatly enhances the formation of carboxylate ions compared to the FAMES.

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