Oxidative stress leads to the formation of esterified erythro- and threo-dihydroxy-fatty acids in HepG2 cells

Oxidative stress plays a central role in pathophysiology. To assess oxidative stress, sensitive methods are required to monitor the cellular damage caused by reactive oxygen species. Phospholipid-bound isoprostanes, such as 5-iPF2α-VI determined by liquid chromatography-tandem mass spectrometry (LC-...

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Main Authors: Lilli Scholz, Luca M. Wende, Michel A. Chromik, Nadja Kampschulte, Nils Helge Schebb
Format: Article
Language:English
Published: Elsevier 2025-05-01
Series:Redox Biology
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Online Access:http://www.sciencedirect.com/science/article/pii/S2213231725001028
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author Lilli Scholz
Luca M. Wende
Michel A. Chromik
Nadja Kampschulte
Nils Helge Schebb
author_facet Lilli Scholz
Luca M. Wende
Michel A. Chromik
Nadja Kampschulte
Nils Helge Schebb
author_sort Lilli Scholz
collection DOAJ
description Oxidative stress plays a central role in pathophysiology. To assess oxidative stress, sensitive methods are required to monitor the cellular damage caused by reactive oxygen species. Phospholipid-bound isoprostanes, such as 5-iPF2α-VI determined by liquid chromatography-tandem mass spectrometry (LC-MS/MS) are currently the best markers for oxidative stress. Here, we describe erythro- and threo-dihydroxy-polyunsaturated fatty acids (PUFA), the hydrolysis products of trans- and cis-epoxy-PUFA, as new biomarkers of oxidative stress in cells. This is demonstrated in four oxidative stress models in HepG2 cells using radical-forming tert-butyl hydroperoxide, glutathione peroxidase 4 inhibiting RSL-3, the redox cycling agent paraquat or rotenone blocking the electron transport chain. LC-MS/MS analysis following the liberation of esterified oxylipins by saponification unveiled in all oxidative stress models a strong formation of erythro- and threo-dihydroxy-PUFA. The levels increased concentration-dependently and correlated to isoprostane 5-iPF2α-VI formation. Among the positional isomers derived from linoleic acid, arachidonic acid and docosahexaenoic acid, those bearing the dihydroxy-group closest to the carboxy terminus were predominantly formed. Thus, the highest concentrations were found of erythro-5,6-DiHETrE and erythro-4,5-DiHDPE, which allowed a more sensitive detection of oxidative stress compared to 5-iPF2α-VI levels. The (erythro-) dihydroxy-PUFA are a new set of markers, which enable a more comprehensive analysis of oxidative stress, particularly when combined with simultaneous LC-MS/MS quantification of trans-epoxy-PUFA and isoprostanes.
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spelling doaj-art-8fbf64b98227480dae0da0353f2afc462025-08-20T03:14:52ZengElsevierRedox Biology2213-23172025-05-018210358910.1016/j.redox.2025.103589Oxidative stress leads to the formation of esterified erythro- and threo-dihydroxy-fatty acids in HepG2 cellsLilli Scholz0Luca M. Wende1Michel A. Chromik2Nadja Kampschulte3Nils Helge Schebb4Chair of Food Chemistry, Faculty of Mathematics and Natural Sciences, University of Wuppertal, Gaussstrasse 20, 42119, Wuppertal, GermanyChair of Food Chemistry, Faculty of Mathematics and Natural Sciences, University of Wuppertal, Gaussstrasse 20, 42119, Wuppertal, GermanyChair of Food Chemistry, Faculty of Mathematics and Natural Sciences, University of Wuppertal, Gaussstrasse 20, 42119, Wuppertal, GermanyChair of Food Chemistry, Faculty of Mathematics and Natural Sciences, University of Wuppertal, Gaussstrasse 20, 42119, Wuppertal, GermanyCorresponding author.; Chair of Food Chemistry, Faculty of Mathematics and Natural Sciences, University of Wuppertal, Gaussstrasse 20, 42119, Wuppertal, GermanyOxidative stress plays a central role in pathophysiology. To assess oxidative stress, sensitive methods are required to monitor the cellular damage caused by reactive oxygen species. Phospholipid-bound isoprostanes, such as 5-iPF2α-VI determined by liquid chromatography-tandem mass spectrometry (LC-MS/MS) are currently the best markers for oxidative stress. Here, we describe erythro- and threo-dihydroxy-polyunsaturated fatty acids (PUFA), the hydrolysis products of trans- and cis-epoxy-PUFA, as new biomarkers of oxidative stress in cells. This is demonstrated in four oxidative stress models in HepG2 cells using radical-forming tert-butyl hydroperoxide, glutathione peroxidase 4 inhibiting RSL-3, the redox cycling agent paraquat or rotenone blocking the electron transport chain. LC-MS/MS analysis following the liberation of esterified oxylipins by saponification unveiled in all oxidative stress models a strong formation of erythro- and threo-dihydroxy-PUFA. The levels increased concentration-dependently and correlated to isoprostane 5-iPF2α-VI formation. Among the positional isomers derived from linoleic acid, arachidonic acid and docosahexaenoic acid, those bearing the dihydroxy-group closest to the carboxy terminus were predominantly formed. Thus, the highest concentrations were found of erythro-5,6-DiHETrE and erythro-4,5-DiHDPE, which allowed a more sensitive detection of oxidative stress compared to 5-iPF2α-VI levels. The (erythro-) dihydroxy-PUFA are a new set of markers, which enable a more comprehensive analysis of oxidative stress, particularly when combined with simultaneous LC-MS/MS quantification of trans-epoxy-PUFA and isoprostanes.http://www.sciencedirect.com/science/article/pii/S2213231725001028Liquid chromatographyTandem mass spectrometryOxylipinsIsoprostaneEicosanoids
spellingShingle Lilli Scholz
Luca M. Wende
Michel A. Chromik
Nadja Kampschulte
Nils Helge Schebb
Oxidative stress leads to the formation of esterified erythro- and threo-dihydroxy-fatty acids in HepG2 cells
Redox Biology
Liquid chromatography
Tandem mass spectrometry
Oxylipins
Isoprostane
Eicosanoids
title Oxidative stress leads to the formation of esterified erythro- and threo-dihydroxy-fatty acids in HepG2 cells
title_full Oxidative stress leads to the formation of esterified erythro- and threo-dihydroxy-fatty acids in HepG2 cells
title_fullStr Oxidative stress leads to the formation of esterified erythro- and threo-dihydroxy-fatty acids in HepG2 cells
title_full_unstemmed Oxidative stress leads to the formation of esterified erythro- and threo-dihydroxy-fatty acids in HepG2 cells
title_short Oxidative stress leads to the formation of esterified erythro- and threo-dihydroxy-fatty acids in HepG2 cells
title_sort oxidative stress leads to the formation of esterified erythro and threo dihydroxy fatty acids in hepg2 cells
topic Liquid chromatography
Tandem mass spectrometry
Oxylipins
Isoprostane
Eicosanoids
url http://www.sciencedirect.com/science/article/pii/S2213231725001028
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AT lucamwende oxidativestressleadstotheformationofesterifiederythroandthreodihydroxyfattyacidsinhepg2cells
AT michelachromik oxidativestressleadstotheformationofesterifiederythroandthreodihydroxyfattyacidsinhepg2cells
AT nadjakampschulte oxidativestressleadstotheformationofesterifiederythroandthreodihydroxyfattyacidsinhepg2cells
AT nilshelgeschebb oxidativestressleadstotheformationofesterifiederythroandthreodihydroxyfattyacidsinhepg2cells