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J Am Soc Mass Spectrom. 2018 Mar;29(3):481-489. doi: 10.1007/s13361-017-1861-2. Epub 2017 Dec 12.

UV Lamp as a Facile Ozone Source for Structural Analysis of Unsaturated Lipids Via Electrospray Ionization-Mass Spectrometry.

Journal of the American Society for Mass Spectrometry

Craig A Stinson, Wenpeng Zhang, Yu Xia

Affiliations

  1. Department of Chemistry, Purdue University, West Lafayette, IN, 47907-2084, USA.
  2. Intel Corporation, Hillsboro, OR, 97214, USA.
  3. Department of Chemistry, Tsinghua University, Beijing, 100084, China.
  4. Department of Chemistry, Purdue University, West Lafayette, IN, 47907-2084, USA. [email protected].
  5. Department of Chemistry, Tsinghua University, Beijing, 100084, China. [email protected].

PMID: 29235039 PMCID: PMC5839981 DOI: 10.1007/s13361-017-1861-2

Abstract

Ozonolysis of alkene functional groups is a type of highly specific and effective chemical reaction, which has found increasing applications in structural analysis of unsaturated lipids via coupling with mass spectrometry (MS). In this work, we utilized a low-pressure mercury lamp (6 W) to initiate ozonolysis inside electrospray ionization (ESI) sources. By placing the lamp near a nanoESI emitter that partially transmits 185 nm ultraviolet (UV) emission from the lamp, dissolved dioxygen in the spray solution was converted into ozone, which subsequently cleaved the double bonds within fatty acyls of lipids. Solvent conditions, such as presence of water and acid solution pH, were found to be critical in optimizing ozonolysis yields. Fast (on seconds time scale) and efficient (50%-100% yield) ozonolysis was achieved for model unsaturated phospholipids and fatty acids with UV lamp-induced ozonolysis incorporated on a static and an infusion nanoESI source. The method was able to differentiate double bond location isomers and identify the geometry of the double bond based on yield. The analytical utility of UV lamp-induced ozonolysis was further demonstrated by implementation on a liquid chromatography (LC)-MS platform. Ozonolysis was effected in a flow microreactor that was made from ozone permeable tubing, so that ambient ozone produced by the lamp irradiation could diffuse into the reactor and induce online ozonolysis post-LC separation and before ESI-MS. Graphical Abstract ᅟ.

Keywords: Electrospray ionization; LC-ms; Lipidomics; Ozonolysis; Unsaturated lipid

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