期刊
ANALYTICAL CHEMISTRY
卷 92, 期 19, 页码 13470-13477出版社
AMER CHEMICAL SOC
DOI: 10.1021/acs.analchem.0c02896
关键词
-
资金
- National Natural Science Foundation of China [21722506]
The Paterno-Buchi (PB) reaction is a photochemical reaction involving [2 + 2] cycloaddition between electronically excited carbonyl and carbon-carbon double bond (C=C). It has been established as a lipid derivatization strategy, leading to confident assignment of C=C locations in lipids when coupled with tandem mass spectrometry (MS/MS). Although acetone and several aryl-containing ketones or aldehydes have been explored as PB reagents, the chemical properties critical to achieving efficient conversion and minimum side reactions remain unclear. Herein, we investigated a set of acetophenone (AP) derivatives, aiming to provide insights into the development of new PB reagents with enhanced performance for lipid analysis. For AP derivatives, we found that electron-withdrawing groups (e.g., -F and -CF3) on the benzene ring improved the overall conversion, while a bulky group at the ortho-position decreased the conversion. Norrish Type I cleavage was largely diminished; however, the Norrish Type II side reaction was more competitive, producing products isomeric to the PB reaction products. Among all AP derivatives tested, 2',4',6'-trifluoroacetophenone (triFAP) showed the best performance. It offered a relatively high PB yield (20-30%) for different types of C=C, high sensitivity (sub-nM) for C=C identification, and accurate isomer quantitation. Due to the significantly reduced chemical interferences in shotgun analysis, triFAP provided better performance than that from acetone PB-MS/MS. An offline triFAP PB reaction was implemented in a liquid chromatography analysis workflow, which enabled the large-scale identification of phospholipids including C=C location isomers from a complex lipid extract.
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