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Simultaneous Detection of Cysteine Sulfenate, Sulfinate, and Sulfonate during Cysteine Interfacial Ozonolysis

Enami, Shinichi and Hoffmann, M. R. and Colussi, A. J. (2009) Simultaneous Detection of Cysteine Sulfenate, Sulfinate, and Sulfonate during Cysteine Interfacial Ozonolysis. Journal of Physical Chemistry B, 113 (28). pp. 9356-9358. ISSN 1520-6106. https://resolver.caltech.edu/CaltechAUTHORS:20090821-081122871

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Abstract

Sulfenic acids (RSOH) are reactive intermediates in the oxidation of protein cysteines. Among cysteine oxoforms, RSOH represent redox-reversible species that can thus participate in regulation and signaling mechanisms and play key roles in enzyme catalysis and antioxidant activity. How the cysteine (CyS) thiol groups of the human surfactant protein that lines the lung epithelium react with inhaled ozone is deemed critical in preserving structural integrity and immune functions. Here we report the simultaneous detection, by online thermospray ionization mass spectrometry, of cysteine sulfenate (CySO^−) and the overoxidized cysteine sulfinate (CySO_2^−) and cysteine sulfonate (CySO_3^−) species on the surface of aqueous CyS microdroplets exposed to O_3(g) for <1 ms. These species are produced by rapid, sequential O-atom additions whose relative rates are herein quantified for the first time. From the pH-dependence of ozonation rates, we derive pK_a(CySOH) = 7.6 ± 0.3 < pKa(CyS) = 8.3.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/jp904316nDOIArticle
http://pubs.acs.org/doi/abs/10.1021/jp904316nPublisherArticle
ORCID:
AuthorORCID
Enami, Shinichi0000-0002-2790-7361
Hoffmann, M. R.0000-0001-6495-1946
Colussi, A. J.0000-0002-3400-4101
Additional Information:Copyright © 2009 American Chemical Society. Received: May 8, 2009; Revised Manuscript Received: June 9, 2009. Publication Date (Web): June 18, 2009. S.E. thanks the Japan Society for the Promotion of Sciences Postdoctoral Fellowship for Research Abroad. This project was supported by the National Science Foundation (ATM-0714329).
Funders:
Funding AgencyGrant Number
Japan Society for the Promotion of Science (JSPS)UNSPECIFIED
NSFATM-0714329
Issue or Number:28
Record Number:CaltechAUTHORS:20090821-081122871
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20090821-081122871
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:15208
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:09 Sep 2009 17:55
Last Modified:03 Mar 2020 13:01

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