Functional Group Analysis of α-Pinene Oxidation Products Using Derivatization Reactions and High-Resolution Electrospray Ionization Collision-Induced Dissociation Mass Spectrometry

J Am Soc Mass Spectrom. 2024 Apr 3;35(4):728-737. doi: 10.1021/jasms.3c00415. Epub 2024 Mar 1.

Abstract

Oxidation products of monoterpenes (C10H16) play a significant role as precursors for secondary organic aerosol formation. They contain several structural isomers with multifunctional groups. However, only a few of these isomers have been identified experimentally. We describe a measurement technique for identifying oxygen-containing functional groups (carbonyl, carboxyl, and hydroxyl groups) included in monoterpene oxidation products. This technique involves (i) three derivatization reactions (oximation of carbonyls by O-(2,3,4,5,6-pentafluorobenzyl) hydroxylamine, methyl esterification of carboxylic acids by trimethylsilyl diazomethane, and acylation of alcohols by acetic anhydride), (ii) no preseparation high-resolution electrospray ionization mass spectrometry, and (iii) collision-induced dissociation. This technique was applied to functional group analysis of ozonolysis products for α-pinene. Multifunctional groups of known ozonolysis products were accurately identified. Furthermore, we successfully estimated the multifunctional groups of products that have not been previously reported.

Keywords: collision-induced dissociation; derivatization; functional group; high-resolution electrospray mass spectrometry; oxidation; α-pinene.