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Subtle Changes in Lipid Environment Have Profound Effects on Membrane Oxidation Chemistry

Zhang, Xinxing and Barraza, Kevin M. and Upton, Kathleen T. and Beauchamp, J. L. (2018) Subtle Changes in Lipid Environment Have Profound Effects on Membrane Oxidation Chemistry. Journal of the American Chemical Society, 140 (50). pp. 17492-17498. ISSN 0002-7863. http://resolver.caltech.edu/CaltechAUTHORS:20181121-102917366

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Abstract

Nature carefully designs the components of amphiphile-composed monolayer and bilayer membranes to deliver specific functions. The compositions of these interfacial layered structures are so delicate that minute modifications can result in huge changes in function. Great effort has been expended to understand membrane physical properties, with only minimum attention given to associated chemical properties. Here we report the first examples of the delicate chemistry associated with membrane amphiphilic components by studying OH-mediated oxidation of six different unsaturated lipids/surfactants and their mixtures at the air–water interface using field-induced droplet ionization mass spectrometry (FIDI-MS). When the packing is loose or perturbed to be loose by other components or prior chemical modification, the double bond is oxidized without cleavage by adding oxygen functionality. In contrast, compact packing results in double bond cleavage through a Criegee intermediate mechanism. We postulate that constrained environments imposed by lipid packing limit the conformations of the reaction intermediates, controlling reaction pathways.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1021/jacs.8b08610DOIArticle
https://pubs.acs.org/doi/suppl/10.1021/jacs.8b08610PublisherSupporting Information
ORCID:
AuthorORCID
Barraza, Kevin M.0000-0003-1849-5219
Upton, Kathleen T.0000-0003-4292-7616
Beauchamp, J. L.0000-0001-8839-4822
Additional Information:© 2018 American Chemical Society. Received: August 10, 2018; Published: November 21, 2018. This work was supported by the Beckman Institute at Caltech and by NSF grant CHE-1508825 (J.L.B.). The authors declare no completing financial interest.
Funders:
Funding AgencyGrant Number
Caltech Beckman InstituteUNSPECIFIED
NSFCHE-1508825
Record Number:CaltechAUTHORS:20181121-102917366
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20181121-102917366
Official Citation:Subtle Changes in Lipid Environment Have Profound Effects on Membrane Oxidation Chemistry. Xinxing Zhang, Kevin M. Barraza, Kathleen T. Upton, and J. L. Beauchamp. Journal of the American Chemical Society 2018 140 (50), 17492-17498. DOI: 10.1021/jacs.8b08610
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:91134
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:21 Nov 2018 18:55
Last Modified:20 Dec 2018 17:13

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