Beyond lipid peroxidation: Distinct mechanisms observed for POPC and POPG oxidation initiated by UV‐enhanced Fenton reactions at the air–water interface. (10th August 2020)

• Record Type: Journal Article
• Authors: Zhang, Dongmei; Gong, Chu; Wang, Jie; Mu, Chaonan; Wang, Wei; Zhang, Xinxing
• Other Names: Chu Ivan K. guestEditor.; O'Hair Richard A. J. guestEditor.; Siu K. W. Michael guestEditor.; Jiang Guibin guestEditor.; Wada Yoshinao guestEditor.; Siu‐Kwan Sze Newman guestEditor.; Oh Han Bin guestEditor.; Shiea Jentaie guestEditor.; Armentrout Peter B. guestEditor.
• Is Part Of: Journal of mass spectrometry. Volume 56:Number 4(2021)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2020-08-10
• Subjects: air–water interface -- Fenton reaction -- field‐induced droplet ionization mass spectrometry -- lipid monolayer -- lipid oxidation; Mass spectrometry -- Periodicals; 543.65
• DOI: 10.1002/jms.4626
• Languages: English
• ISSNs: 1076-5174

Abstract

Abstract: Fenton or Fenton‐like reactions are ubiquitous in nature, and the hydroxyl radicals (·OH) generated in these reactions are accountable for a plethora of oxidation processes both in the environment and in vivo. Among these oxidation reactions, lipid oxidation initiated by ·OH radicals has long been oversimplified as a peroxidation mechanism, but in reality, it is a highly complicated process that can result in a large variety of products. Using the unique field‐induced droplet ionization mass spectrometry (FIDI‐MS) methodology that is capable of selective sampling of amphiphilic molecules that reside at the air–water interface, here, we show distinct mechanisms from the ultraviolet (UV)‐enhanced Fenton oxidations of two phospholipids, POPC and POPG, even though these two lipids possess the same functional groups that are vulnerable to ·OH attack. We postulate that it is the different packing densities that determine the permeability of ambient NO molecules into the monolayers, resulting in highly distinct reaction pathways and products. We anticipate that this work will be a wake‐up call that the lipid peroxidation mechanism is sometimes taken for granted and that lipid oxidation can be subtly affected by various factors that deserves deeper investigations.