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Title: Evidence that Criegee intermediates drive autoxidation in unsaturated lipids

Abstract

Autoxidation is an autocatalytic free-radical chain reaction responsible for the oxidative destruction of organic molecules in biological cells, foods, plastics, petrochemicals, fuels, and the environment. In cellular membranes, lipid autoxidation (peroxidation) is linked with oxidative stress, age-related diseases, and cancers. The established mechanism of autoxidation proceeds via H-atom abstraction through a cyclic network of peroxy–hydroperoxide-mediated free-radical chain reactions. For a series of model unsaturated lipids, we present evidence for an autoxidation mechanism, initiated by hydroxyl radical (OH) addition to C=C bonds and propagated by chain reactions involving Criegee intermediates (CIs). This mechanism leads to unexpectedly rapid autoxidation even in the presence of water, implying that as reactive intermediates, CI could play a much more prominent role in chemistries beyond the atmosphere.

Authors:
; ; ORCiD logo
Publication Date:
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1600086
Grant/Contract Number:  
[AC02-05CH11231]
Resource Type:
Published Article
Journal Name:
Proceedings of the National Academy of Sciences of the United States of America
Additional Journal Information:
[Journal Name: Proceedings of the National Academy of Sciences of the United States of America Journal Volume: 117 Journal Issue: 9]; Journal ID: ISSN 0027-8424
Publisher:
Proceedings of the National Academy of Sciences
Country of Publication:
United States
Language:
English

Citation Formats

Zeng, Meirong, Heine, Nadja, and Wilson, Kevin R. Evidence that Criegee intermediates drive autoxidation in unsaturated lipids. United States: N. p., 2020. Web. doi:10.1073/pnas.1920765117.
Zeng, Meirong, Heine, Nadja, & Wilson, Kevin R. Evidence that Criegee intermediates drive autoxidation in unsaturated lipids. United States. doi:10.1073/pnas.1920765117.
Zeng, Meirong, Heine, Nadja, and Wilson, Kevin R. Tue . "Evidence that Criegee intermediates drive autoxidation in unsaturated lipids". United States. doi:10.1073/pnas.1920765117.
@article{osti_1600086,
title = {Evidence that Criegee intermediates drive autoxidation in unsaturated lipids},
author = {Zeng, Meirong and Heine, Nadja and Wilson, Kevin R.},
abstractNote = {Autoxidation is an autocatalytic free-radical chain reaction responsible for the oxidative destruction of organic molecules in biological cells, foods, plastics, petrochemicals, fuels, and the environment. In cellular membranes, lipid autoxidation (peroxidation) is linked with oxidative stress, age-related diseases, and cancers. The established mechanism of autoxidation proceeds via H-atom abstraction through a cyclic network of peroxy–hydroperoxide-mediated free-radical chain reactions. For a series of model unsaturated lipids, we present evidence for an autoxidation mechanism, initiated by hydroxyl radical (OH) addition to C=C bonds and propagated by chain reactions involving Criegee intermediates (CIs). This mechanism leads to unexpectedly rapid autoxidation even in the presence of water, implying that as reactive intermediates, CI could play a much more prominent role in chemistries beyond the atmosphere.},
doi = {10.1073/pnas.1920765117},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
number = [9],
volume = [117],
place = {United States},
year = {2020},
month = {2}
}

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Works referenced in this record:

Large Enhancement in the Heterogeneous Oxidation Rate of Organic Aerosols by Hydroxyl Radicals in the Presence of Nitric Oxide
journal, October 2015

  • Richards-Henderson, Nicole K.; Goldstein, Allen H.; Wilson, Kevin R.
  • The Journal of Physical Chemistry Letters, Vol. 6, Issue 22
  • DOI: 10.1021/acs.jpclett.5b02121

Advances in Radical-Trapping Antioxidant Chemistry in the 21st Century: A Kinetics and Mechanisms Perspective
journal, September 2014

  • Ingold, Keith U.; Pratt, Derek A.
  • Chemical Reviews, Vol. 114, Issue 18
  • DOI: 10.1021/cr500226n

Connecting the Elementary Reaction Pathways of Criegee Intermediates to the Chemical Erosion of Squalene Interfaces during Ozonolysis
journal, November 2017

  • Heine, Nadja; Houle, Frances A.; Wilson, Kevin R.
  • Environmental Science & Technology, Vol. 51, Issue 23
  • DOI: 10.1021/acs.est.7b04197

Neurodegenerative diseases and oxidative stress
journal, March 2004

  • Barnham, Kevin J.; Masters, Colin L.; Bush, Ashley I.
  • Nature Reviews Drug Discovery, Vol. 3, Issue 3
  • DOI: 10.1038/nrd1330

Cholesterol provides nonsacrificial protection of membrane lipids from chemical damage at air–water interface
journal, March 2018

  • Zhang, Xinxing; Barraza, Kevin M.; Beauchamp, J. L.
  • Proceedings of the National Academy of Sciences, Vol. 115, Issue 13
  • DOI: 10.1073/pnas.1722323115

Resonance-stabilized hydrocarbon-radical chain reactions may explain soot inception and growth
journal, September 2018


Sulfur Dioxide Accelerates the Heterogeneous Oxidation Rate of Organic Aerosol by Hydroxyl Radicals
journal, March 2016

  • Richards-Henderson, Nicole K.; Goldstein, Allen H.; Wilson, Kevin R.
  • Environmental Science & Technology, Vol. 50, Issue 7
  • DOI: 10.1021/acs.est.5b05369

Thermal Vaporization of Biological Nanoparticles:  Fragment-Free Vacuum Ultraviolet Photoionization Mass Spectra of Tryptophan, Phenylalanine−Glycine−Glycine, and β-Carotene
journal, February 2006

  • Wilson, Kevin R.; Jimenez-Cruz, Michael; Nicolas, Christophe
  • The Journal of Physical Chemistry A, Vol. 110, Issue 6
  • DOI: 10.1021/jp0543734

A pulse radiolysis study of the reactions of OH/O− with linoleic acid in oxygen-free aqueous solution
journal, January 1985

  • Heijman, M. G. J.; Heitzman, A. J. P.; Nauta, H.
  • Radiation Physics and Chemistry (1977), Vol. 26, Issue 1
  • DOI: 10.1016/0146-5724(85)90037-8

Crystallization of designed protein variants
journal, August 1990


DNA Base Damage by Reactive Oxygen Species, Oxidizing Agents, and UV Radiation
journal, February 2013


Mechanism of Ozonolysis
journal, November 1975

  • Criegee, Rudolf
  • Angewandte Chemie International Edition in English, Vol. 14, Issue 11
  • DOI: 10.1002/anie.197507451

Role of Tunable Acid Catalysis in Decomposition of α-Hydroxyalkyl Hydroperoxides and Mechanistic Implications for Tropospheric Chemistry
journal, October 2014

  • Kumar, Manoj; Busch, Daryle H.; Subramaniam, Bala
  • The Journal of Physical Chemistry A, Vol. 118, Issue 41
  • DOI: 10.1021/jp505100x

An Extended Computational Study of Criegee Intermediate–Alcohol Reactions
journal, December 2018

  • Watson, Nathan A. I.; Black, Joshua A.; Stonelake, Thomas M.
  • The Journal of Physical Chemistry A, Vol. 123, Issue 1
  • DOI: 10.1021/acs.jpca.8b09349

Criegee Intermediates: What Direct Production and Detection Can Teach Us About Reactions of Carbonyl Oxides
journal, May 2017


Skin Lipids: Their Biochemical Uniqueness
journal, October 1974


Kinetics of olefin oxidation
journal, January 1949


Quantifying the reactive uptake of OH by organic aerosols in a continuous flow stirred tank reactor
journal, January 2009

  • Che, Dung L.; Smith, Jared D.; Leone, Stephen R.
  • Physical Chemistry Chemical Physics, Vol. 11, Issue 36
  • DOI: 10.1039/b904418c

The direct observation of secondary radical chain chemistry in the heterogeneous reaction of chlorine atoms with submicron squalane droplets
journal, January 2011

  • Liu, Chen-Lin; Smith, Jared D.; Che, Dung L.
  • Physical Chemistry Chemical Physics, Vol. 13, Issue 19
  • DOI: 10.1039/c1cp20236g

Environmental Implications of Hydroxyl Radicals ( OH)
journal, December 2015

  • Gligorovski, Sasho; Strekowski, Rafal; Barbati, Stephane
  • Chemical Reviews, Vol. 115, Issue 24
  • DOI: 10.1021/cr500310b

The heterogeneous reaction of hydroxyl radicals with sub-micron squalane particles: a model system for understanding the oxidative aging of ambient aerosols
journal, January 2009

  • Smith, J. D.; Kroll, J. H.; Cappa, C. D.
  • Atmospheric Chemistry and Physics Discussions, Vol. 9, Issue 1
  • DOI: 10.5194/acpd-9-3945-2009

Autoxidation of Linoleic Acid
journal, December 1945


The Haber-Weiss cycle – 70 years later
journal, August 2001


Direct Measurements of Conformer-Dependent Reactivity of the Criegee Intermediate CH3CHOO
journal, April 2013


The real radical generator other than main-product hydroperoxide in lipid autoxidation
journal, January 2006


Infrared-driven unimolecular reaction of CH3CHOO Criegee intermediates to OH radical products
journal, September 2014


Free Radical Lipid Peroxidation: Mechanisms and Analysis
journal, October 2011

  • Yin, Huiyong; Xu, Libin; Porter, Ned A.
  • Chemical Reviews, Vol. 111, Issue 10
  • DOI: 10.1021/cr200084z

Unimolecular reaction of acetone oxide and its reaction with water in the atmosphere
journal, May 2018

  • Long, Bo; Bao, Junwei Lucas; Truhlar, Donald G.
  • Proceedings of the National Academy of Sciences, Vol. 115, Issue 24
  • DOI: 10.1073/pnas.1804453115

Targeting cancer cells by ROS-mediated mechanisms: a radical therapeutic approach?
journal, May 2009

  • Trachootham, Dunyaporn; Alexandre, Jerome; Huang, Peng
  • Nature Reviews Drug Discovery, Vol. 8, Issue 7
  • DOI: 10.1038/nrd2803

Criegee Intermediate Reactions with Carboxylic Acids: A Potential Source of Secondary Organic Aerosol in the Atmosphere
journal, June 2018