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Comparison of derivatization/ionization techniques for liquid chromatography tandem mass spectrometry analysis of oxylipins

Meckelmann, Sven W., Hellhake, Stefan, Steuck, Maryvonne, Krohn, Michael and Schebb, Nils Helge 2017. Comparison of derivatization/ionization techniques for liquid chromatography tandem mass spectrometry analysis of oxylipins. Prostaglandins & Other Lipid Mediators 130 , pp. 8-15.

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Abstract

The performance of two derivatization and ionization techniques for the quantitative reversed phase liquid chromatography (LC)- mass spectrometry (MS) analysis of hydroxy fatty acids (OH-PUFA) in plasma was evaluated: One used AMPP (N-(4-aminomethylphenyl)pyridinium chloride) leading to a positive charged amid-derivate which can be detected by electrospray ionization (ESI)-MS. Second yielded penta fluorobenzyl bromide (PFB) ester derivates allowing detection in electron capture atmospheric pressure chemical ionization (ecAPCI)-MS. The sensitivity of detection of a comprehensive set of hydroxy fatty acids of n6- and n3- poly unsaturated fatty acids was investigated. On the SCIEX3200 MS the applied PFB derivatization led to poor limits of detection (LOD) of 10–100 nM (0.1–1 pmol/0.03–0.3 ng on column). By contrast, AMPP derivatization led to a similar sensitivity compared to the standard ESI(-) of non derivatized analytes (LOD about 1 nM (10 fmol/3 pg on column)). For several analytes, including 9-HETE, 11-HETE and 17-HDHA the AMPP derivatization improved sensitivity enabling their detection in human plasma. However, precision was reduced by AMPP derivatization and variation in IS recovery indicated a strong matrix influence on the MS-signal. In sum, with the instrumentation used, neither of these derivatization methods improves in our hands the LC–MS based quantification of oxylipins.

Item Type: Article
Date Type: Publication
Status: Published
Schools: Medicine
Publisher: Elsevier
ISSN: 1098-8823
Date of Acceptance: 14 February 2017
Last Modified: 18 Oct 2017 14:06
URI: http://orca.cf.ac.uk/id/eprint/105595

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