title: Detection and structural elucidation of esterified oxylipids in human synovial fluid by electrospray ionization-fourier transform ion-cyclotron mass spectrometry and liquid chromatography-ion trap-MS(3): detection of esterified hydroxylated docosapentaenoic acid containing phospholipids.
abstract: Here, we present the application of a cross-platform approach, combining rapid direct infusion high-resolution/accurate mass electrospray ionization Fourier transform ion-cyclotron mass spectrometry (ESI-FTICRMS) with in-depth data-dependent LC-MS(2) and LC-MS(3) analysis for lipid profiling. The analytical approach as well as the subsequent data handling is described. The method was applied to human synovial fluid samples from osteo- and rheumatoid arthritis patients. Multivariate statistical analysis revealed esterified oxylipids as molecular features in a subset of the patient samples. Employing LC-MS(2) and LC-MS(3) analysis of these species, we were able to clarify the hypothesized lipid structures initially based on the accurate mass measurements performed on the ESI-FTICRMS platform. LC-MS(3) analysis of intact esterified oxy-lipids and LC-MS(2) analysis of the hydrolysis products allowed for the detection of positional isomers. The approach led to the structural elucidation of hydroxylated docosapentaenoic acid-containing diacyl-phosphatidylcholine type phospholipids in human synovial fluid.
authors.affiliation: Leiden University Medical Center (LUMC), Center for Proteomics and Metabolomics, Albinusdreef 2, 2300RC Leiden, The Netherlands.
authors.forename: Hulda S
authors.initials: HS
authors.lastname: Jónasdóttir
authors.forename: Simone
authors.initials: S
authors.lastname: Nicolardi
authors.forename: Willem
authors.initials: W
authors.lastname: Jonker
authors.forename: Rico
authors.initials: R
authors.lastname: Derks
authors.forename: Magnus
authors.initials: M
authors.lastname: Palmblad
authors.forename: Andreea
authors.initials: A
authors.lastname: Ioan-Facsinay
authors.forename: René
authors.initials: R
authors.lastname: Toes
authors.forename: Yuri E M
authors.initials: YE
authors.lastname: van der Burgt
authors.forename: André M
authors.initials: AM
authors.lastname: Deelder
authors.forename: Oleg A
authors.initials: OA
authors.lastname: Mayboroda
authors.forename: Martin
authors.initials: M
authors.lastname: Giera
mesh_terms: D002853:Chromatography, Liquid / Q000379:methods; D017357:Cyclotrons; D004951:Esterification; D005231:Fatty Acids, Unsaturated / Q000032:analysis* / Q000737:chemistry; D006801:Humans; D006900:Hydroxylation; D010743:Phospholipids / Q000032:analysis* / Q000737:chemistry; D021241:Spectrometry, Mass, Electrospray Ionization / Q000379:methods*; D017550:Spectroscopy, Fourier Transform Infrared / Q000379:methods; D013582:Synovial Fluid / Q000737:chemistry*
chemical_list: D005231:Fatty Acids, Unsaturated; D010743:Phospholipids; C026219:docosapentaenoic acid