Enami, Shinichi and Hoffmann, Michael R. and Colussi, Agustín J. (2015) OH-Radical Specific Addition to Glutathione S-Atom at the Air–Water Interface: Relevance to the Redox Balance of the Lung Epithelial Lining Fluid. Journal of Physical Chemistry Letters, 6 (19). pp. 3935-3943. ISSN 1948-7185 . http://resolver.caltech.edu/CaltechAUTHORS:20151030-124958894
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Antioxidants in epithelial lining fluids (ELF) prevent inhaled air pollutants from reaching lung tissue. This process, however, may upset ELF’s redox balance, which is deemed to be expressed by the ratio of the major antioxidant glutathione (GSH) to its putative oxidation product GSSG. Previously, we found that at physiological pH O_3(g) rapidly oxidizes GS2–(aq) (but not GSH–) to GSO_3– rather than GSSG. Here, we report that in moderately acidic pH ≤ 5 media ·OH(g) oxidizes GSH–(aq) to sulfenic GSOH–, sulfinic GSO_2–, and sulfonic GSO_3– acids via ·OH specific additions to reduced S-atoms. The remarkable specificity of ·OH on water versus its lack of selectivity in bulk water implicates an unprecedented steering process during [OH···GSH] interfacial encounters. Thus, both O_3 and ·OH oxidize GSH to GSOH– under most conditions, and since GSOH– is reduced back to GSH in vivo by NADPH, redox balance may be in fact signaled by GSH/GSOH ratios.
|Additional Information:||© 2015 American Chemical Society. ACS AuthorChoice - This is an open access article published under an ACS AuthorChoice License, which permits copying and redistribution of the article or any adaptations for non-commercial purposes. Received: August 19, 2015; Accepted: September 14, 2015; Published: September 14, 2015. We gratefully acknowledge Dr. Tao Cheng and Prof. Bill Goddard of Caltech for helpful discussions. S. E. is grateful to the Research Foundation for Opto-Science and Technology, the Kurita Water and Environment Foundation, and the Japan Science and Technology Agency (JST) PRESTO program. S. E. also thanks Prof. Hiroshi Masuhara for stimulating discussions. M. R. H. and A. J. C. acknowledge support from the National Science Foundation (U.S.A.) Grant AC-1238977. The authors declare no competing financial interest.|
|Official Citation:||OH-Radical Specific Addition to Glutathione S-Atom at the Air–Water Interface: Relevance to the Redox Balance of the Lung Epithelial Lining Fluid Shinichi Enami, Michael R. Hoffmann, and Agustín J. Colussi The Journal of Physical Chemistry Letters 2015 6 (19), 3935-3943 DOI: 10.1021/acs.jpclett.5b01819|
|Usage Policy:||No commercial reproduction, distribution, display or performance rights in this work are provided.|
|Deposited By:||Tony Diaz|
|Deposited On:||02 Nov 2015 23:50|
|Last Modified:||02 Nov 2015 23:50|
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