Evidence that Criegee intermediates drive autoxidation in unsaturated lipids

Zeng, Meirong; Heine, Nadja; Wilson, Kevin R.

doi:10.1073/pnas.1920765117

Evidence that Criegee intermediates drive autoxidation in unsaturated lipids

Journal Article · Tue Feb 18 00:00:00 EST 2020 · Proceedings of the National Academy of Sciences of the United States of America

DOI:https://doi.org/10.1073/pnas.1920765117· OSTI ID:1600086

Zeng, Meirong ^[1]; Heine, Nadja ^[1]; ^[1]

Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94720

Significance

Autoxidation leads to the slow persistent destruction of organic molecules causing oxidative stress and associated disease. The prevailing autoxidation mechanism of unsaturated lipids involves chain reactions initiated and propagated by H-atom abstraction, mediated by peroxy radicals and other reactive oxygen species. Here we report experimental evidence for an autoxidation mechanism initiated by OH, which is unanticipated and proceeds by OH addition followed by pathways involving Criegee intermediates (CIs). Although CIs are routinely encountered in atmospheric and synthetic organic chemistry, their role in autoxidation is unexpected. Our results suggest that in all likelihood these exotic species play a much more prominent and general role in the chemistry of cells, food, petrochemicals, and the environment beyond what is currently believed.

View Journal Article

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1600086

Alternate ID(s):: OSTI ID: 1983885

Journal Information:: Proceedings of the National Academy of Sciences of the United States of America, Journal Name: Proceedings of the National Academy of Sciences of the United States of America Journal Issue: 9 Vol. 117; ISSN 0027-8424

Publisher:: Proceedings of the National Academy of SciencesCopyright Statement

Country of Publication:: United States

Language:: English

References (29)

Mechanism of Ozonolysis Criegee, Rudolf Angewandte Chemie International Edition in English, Vol. 14, Issue 11 https://doi.org/10.1002/anie.197507451	journal	November 1975
The real radical generator other than main-product hydroperoxide in lipid autoxidation Morita, Makio; Tokita, Masako Lipids, Vol. 41, Issue 1 https://doi.org/10.1007/s11745-006-5075-9	journal	January 2006
A pulse radiolysis study of the reactions of OH/O− with linoleic acid in oxygen-free aqueous solution Heijman, M. G. J.; Heitzman, A. J. P.; Nauta, H. Radiation Physics and Chemistry (1977), Vol. 26, Issue 1 https://doi.org/10.1016/0146-5724(85)90037-8	journal	January 1985
What is oxidative stress? Betteridge, D. John Metabolism, Vol. 49, Issue 2 https://doi.org/10.1016/S0026-0495(00)80077-3	journal	February 2000
Sulfur Dioxide Accelerates the Heterogeneous Oxidation Rate of Organic Aerosol by Hydroxyl Radicals Richards-Henderson, Nicole K.; Goldstein, Allen H.; Wilson, Kevin R. Environmental Science & Technology, Vol. 50, Issue 7 https://doi.org/10.1021/acs.est.5b05369	journal	March 2016
Connecting the Elementary Reaction Pathways of Criegee Intermediates to the Chemical Erosion of Squalene Interfaces during Ozonolysis Heine, Nadja; Houle, Frances A.; Wilson, Kevin R. Environmental Science & Technology, Vol. 51, Issue 23 https://doi.org/10.1021/acs.est.7b04197	journal	November 2017
An Extended Computational Study of Criegee Intermediate–Alcohol Reactions Watson, Nathan A. I.; Black, Joshua A.; Stonelake, Thomas M. The Journal of Physical Chemistry A, Vol. 123, Issue 1 https://doi.org/10.1021/acs.jpca.8b09349	journal	December 2018
Large Enhancement in the Heterogeneous Oxidation Rate of Organic Aerosols by Hydroxyl Radicals in the Presence of Nitric Oxide Richards-Henderson, Nicole K.; Goldstein, Allen H.; Wilson, Kevin R. The Journal of Physical Chemistry Letters, Vol. 6, Issue 22 https://doi.org/10.1021/acs.jpclett.5b02121	journal	October 2015
Criegee Intermediate Reactions with Carboxylic Acids: A Potential Source of Secondary Organic Aerosol in the Atmosphere Chhantyal-Pun, Rabi; Rotavera, Brandon; McGillen, Max R. ACS Earth and Space Chemistry, Vol. 2, Issue 8 https://doi.org/10.1021/acsearthspacechem.8b00069	journal	June 2018
Free Radical Lipid Peroxidation: Mechanisms and Analysis Yin, Huiyong; Xu, Libin; Porter, Ned A. Chemical Reviews, Vol. 111, Issue 10 https://doi.org/10.1021/cr200084z	journal	October 2011
Advances in Radical-Trapping Antioxidant Chemistry in the 21st Century: A Kinetics and Mechanisms Perspective Ingold, Keith U.; Pratt, Derek A. Chemical Reviews, Vol. 114, Issue 18 https://doi.org/10.1021/cr500226n	journal	September 2014
Environmental Implications of Hydroxyl Radicals ( ^• OH) Gligorovski, Sasho; Strekowski, Rafal; Barbati, Stephane Chemical Reviews, Vol. 115, Issue 24 https://doi.org/10.1021/cr500310b	journal	December 2015
Thermal Vaporization of Biological Nanoparticles: Fragment-Free Vacuum Ultraviolet Photoionization Mass Spectra of Tryptophan, Phenylalanine−Glycine−Glycine, and β-Carotene Wilson, Kevin R.; Jimenez-Cruz, Michael; Nicolas, Christophe The Journal of Physical Chemistry A, Vol. 110, Issue 6 https://doi.org/10.1021/jp0543734	journal	February 2006
Role of Tunable Acid Catalysis in Decomposition of α-Hydroxyalkyl Hydroperoxides and Mechanistic Implications for Tropospheric Chemistry Kumar, Manoj; Busch, Daryle H.; Subramaniam, Bala The Journal of Physical Chemistry A, Vol. 118, Issue 41 https://doi.org/10.1021/jp505100x	journal	October 2014
Autoxidation of Linoleic Acid BergstrÖM, Sune Nature, Vol. 156, Issue 3972 https://doi.org/10.1038/156717b0	journal	December 1945
Neurodegenerative diseases and oxidative stress Barnham, Kevin J.; Masters, Colin L.; Bush, Ashley I. Nature Reviews Drug Discovery, Vol. 3, Issue 3 https://doi.org/10.1038/nrd1330	journal	March 2004
Targeting cancer cells by ROS-mediated mechanisms: a radical therapeutic approach? Trachootham, Dunyaporn; Alexandre, Jerome; Huang, Peng Nature Reviews Drug Discovery, Vol. 8, Issue 7 https://doi.org/10.1038/nrd2803	journal	May 2009
Quantifying the reactive uptake of OH by organic aerosols in a continuous flow stirred tank reactor Che, Dung L.; Smith, Jared D.; Leone, Stephen R. Physical Chemistry Chemical Physics, Vol. 11, Issue 36 https://doi.org/10.1039/b904418c	journal	January 2009
The direct observation of secondary radical chain chemistry in the heterogeneous reaction of chlorine atoms with submicron squalane droplets Liu, Chen-Lin; Smith, Jared D.; Che, Dung L. Physical Chemistry Chemical Physics, Vol. 13, Issue 19 https://doi.org/10.1039/c1cp20236g	journal	January 2011
Kinetics of olefin oxidation Bolland, J. L. Quarterly Reviews, Chemical Society, Vol. 3, Issue 1 https://doi.org/10.1039/qr9490300001	journal	January 1949
Cholesterol provides nonsacrificial protection of membrane lipids from chemical damage at air–water interface Zhang, Xinxing; Barraza, Kevin M.; Beauchamp, J. L. Proceedings of the National Academy of Sciences, Vol. 115, Issue 13 https://doi.org/10.1073/pnas.1722323115	journal	March 2018
Unimolecular reaction of acetone oxide and its reaction with water in the atmosphere Long, Bo; Bao, Junwei Lucas; Truhlar, Donald G. Proceedings of the National Academy of Sciences, Vol. 115, Issue 24 https://doi.org/10.1073/pnas.1804453115	journal	May 2018
DNA Base Damage by Reactive Oxygen Species, Oxidizing Agents, and UV Radiation Cadet, J.; Wagner, J. R. Cold Spring Harbor Perspectives in Biology, Vol. 5, Issue 2 https://doi.org/10.1101/cshperspect.a012559	journal	February 2013
Direct Measurements of Conformer-Dependent Reactivity of the Criegee Intermediate CH3CHOO Taatjes, C. A.; Welz, O.; Eskola, A. J. Science, Vol. 340, Issue 6129 https://doi.org/10.1126/science.1234689	journal	April 2013
Infrared-driven unimolecular reaction of CH3CHOO Criegee intermediates to OH radical products Liu, F.; Beames, J. M.; Petit, A. S. Science, Vol. 345, Issue 6204 https://doi.org/10.1126/science.1257158	journal	September 2014
Skin Lipids: Their Biochemical Uniqueness Nicolaides, N. Science, Vol. 186, Issue 4158 https://doi.org/10.1126/science.186.4158.19	journal	October 1974
Resonance-stabilized hydrocarbon-radical chain reactions may explain soot inception and growth Johansson, K. O.; Head-Gordon, M. P.; Schrader, P. E. Science, Vol. 361, Issue 6406 https://doi.org/10.1126/science.aat3417	journal	September 2018
Criegee Intermediates: What Direct Production and Detection Can Teach Us About Reactions of Carbonyl Oxides Taatjes, Craig A. Annual Review of Physical Chemistry, Vol. 68, Issue 1 https://doi.org/10.1146/annurev-physchem-052516-050739	journal	May 2017
The Haber-Weiss cycle – 70 years later Koppenol, W. H. Redox Report, Vol. 6, Issue 4 https://doi.org/10.1179/135100001101536373	journal	August 2001

Similar Records

Coupling of Lipid Peroxidation and Criegee Intermediate Mediated Autoxidation in the Heterogeneous Oxidation of Linoleic Acid Aerosols

Journal Article · Wed Apr 30 20:00:00 EDT 2025 · Environmental Science and Technology · OSTI ID:2584846

Evaluating Possible Formation Mechanisms of Criegee Intermediates during the Heterogeneous Autoxidation of Squalene

Journal Article · Wed Jun 19 20:00:00 EDT 2024 · Environmental Science and Technology · OSTI ID:2499765

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Criegee intermediate
autoxidation
unsaturated lipids

Evidence that Criegee intermediates drive autoxidation in unsaturated lipids

Citation Formats

References (29)

Similar Records

Related Subjects