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Published July 13, 2017 | Supplemental Material + Accepted Version
Journal Article Open

Reactions of Criegee Intermediates with Alcohols at Air-Aqueous Interfaces


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.

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.

Attached Files

Accepted Version - acs_2Ejpca_2E7b04272.pdf

Supplemental Material - jp7b04272_si_001.pdf


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