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. 2020 Jan 17;11:375. doi: 10.1038/s41467-019-14180-4

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© The Author(s) 2020

Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons license and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/.

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Fig. 1 — a The chemical structure of PC 18:1(9Z)/16:0. b Schematic of the experimental setup for online derivatization of unsaturated GPs by coupling 254 nm irradiation with nanoESI-MS. c MS spectrum of PC 16:0/18:1(9Z) after 30 s reaction. d MS³ spectrum of PC 16:0/18:1(9Z) without PB derivatization. Sodiated lipid precursors were first fragmented to generate product ions after headgroup loss (−183 Da). Product ion at m/z 599.5 was further fragmented to release sn-1-specific diagnostic ions at m/z 319 (C16:0) and 345 (C18:1). e Comparison the relative abundance of sn-position and C=C location specific ions of PC 16:0/18:1(9Z) without and with PB derivatization using different PB reagents (Bza: benzaldehyde, APh: acetophenone, BPh: benzophenone, AP: acetylpyridine). Error bar represents the standard deviation, n = 3. f, g PB-MS³ spectra of PC 16:0/18:1(9Z) (f) and PC 18:1(9Z)/16:0 (g). Product ions at m/z 489 and 578 were C=C-specific diagnostic ions due to oxetane cleavage, indicated C=C at Δ9 in C18:1. Product ion at m/z 466 was specific for C16:0 at sn-2. Product ion at m/z 396 was specific for C18:1 at sn-2. h, i PB-MS³ spectra of PC 16:0/18:2(9Z, 12Z) (h) and PC 18:0/20:4(5Z, 8Z, 11Z, 14Z) (i). Refer to insets for detailed fragmentation pathways responsible for generating diagnostic ions. Peaks labeled in red and blue are C=C-specific and sn-specific diagnostic ions, respectively. Source data are provided in a Source Data file.