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Reactions of Criegee Intermediates with Alcohols at Air-Aqueous Interfaces

Enami, Shinichi and Colussi, Agustín J. (2017) Reactions of Criegee Intermediates with Alcohols at Air-Aqueous Interfaces. Journal of Physical Chemistry A, 121 (27). pp. 5175-5182. ISSN 1089-5639. https://resolver.caltech.edu/CaltechAUTHORS:20170623-131349627

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Abstract

The fate of Criegee intermediates (CIs) from the gas-phase ozonolysis of unsaturated organic compounds in the troposphere is largely controlled by their reactions with water vapor. We recently found that against all expectations carboxylic acids compete at millimolar concentrations with water for CIs at the air–liquid interface of aqueous organic media. This outcome is consistent with both the low water concentration in the outermost interfacial layers and the enrichment of the competing acids therein. Here we show, via online electrospray mass spectrometric detection, that CIs generated in situ in the fast ozonolysis of sesquiterpenes (C_(15)H_(24)) on the surface of water:acetonitrile microjets react with n ≥ 4 linear alcohols C_nH_(2n+1)OH to produce high molecular weight C_(15+n) ethers in one step. The OH group of 1-octanol proved to be ∼25 times less reactive than that of n-octanoic toward CIs at the same bulk molar concentration, revealing that the reactivity of hydroxylic species depends on both acidities and interfacial affinities. CI interfacial reactions with surface-active hydroxylic species, by bypassing water, represent shortcuts to molecular complexity in atmospheric aerosols.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/acs.jpca.7b04272DOIArticle
http://pubs.acs.org/doi/abs/10.1021/acs.jpca.7b04272PublisherArticle
http://pubs.acs.org/doi/suppl/10.1021/acs.jpca.7b04272PublisherSupporting Information
ORCID:
AuthorORCID
Enami, Shinichi0000-0002-2790-7361
Colussi, Agustín J.0000-0002-3400-4101
Additional Information:© 2017 American Chemical Society. Received: May 5, 2017; Revised: June 19, 2017; Published: June 21, 2017. We acknowledge Drs. Satoshi Inomata, Akihiro Fushimi, and Kei Sato of NIES and Prof. Yosuke Sakamoto of Kyoto University. This work is partly supported by the research foundation for opto-science and technology, JSPS KAKENHI grant numbers 15H05328 and 15K12188. Author Contributions: S.E. designed and performed research; S.E and A.J.C. analyzed data and wrote the paper.
Funders:
Funding AgencyGrant Number
Japan Society for the Promotion of Science (JSPS)15H05328
Japan Society for the Promotion of Science (JSPS)15K12188
Issue or Number:27
Record Number:CaltechAUTHORS:20170623-131349627
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20170623-131349627
Official Citation:Reactions of Criegee Intermediates with Alcohols at Air–Aqueous Interfaces Shinichi Enami and A. J. Colussi The Journal of Physical Chemistry A 2017 121 (27), 5175-5182 DOI: 10.1021/acs.jpca.7b04272
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:78521
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:24 Jun 2017 03:00
Last Modified:03 Oct 2019 18:09

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