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Reactivity of Monoterpene Criegee Intermediates at Gas-Liquid Interfaces

Qiu, Junting and Ishizuka, Shinnosuke and Tonokura, Kenichi and Colussi, Agustín J. and Enami, Shinichi (2018) Reactivity of Monoterpene Criegee Intermediates at Gas-Liquid Interfaces. Journal of Physical Chemistry A, 122 (39). pp. 7910-7917. ISSN 1089-5639. doi:10.1021/acs.jpca.8b06914.

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Biogenic monoterpenes are major sources of Criegee intermediates (CIs) in the troposphere. Recent studies underscored the importance of their heterogeneous chemistry. The study of monoterpene CI reactions on liquid surfaces, however, is challenging due to the lack of suitable probes. Here, we report the first mass spectrometric detection of the intermediates and products, which include labile hydroperoxides, from reactions of CIs of representative monoterpenes (α-terpinene, γ-terpinene, terpinolene, D-limonene, α-pinene) with water, cis-pinonic acid (CPA) and octanoic acid (OA) on the surface of liquid microjets. Significantly, the relative yields of α-hydroxy-hydroperoxides production from CIs hydration at the gas–liquid interface—α-terpinene (1.00) ≫ D-limonene (0.18) > γ-terpinene (0.11) ∼ terpinolene (0.10) ≫ α-pinene (0.01)—do not track the rate constants of their gas-phase ozonolyses. Notably, in contrast with the inertness of the other CIs, the CIs derived from α-terpinene ozonolysis readily react with CPA and OA to produce C_(20) and C_(18) ester hydroperoxides, respectively. Present results reveal hitherto unknown structural effects on the reactivities of CIs at aqueous interfaces.

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URLURL TypeDescription Information
Ishizuka, Shinnosuke0000-0002-5915-3576
Tonokura, Kenichi0000-0003-1910-8508
Colussi, Agustín J.0000-0002-3400-4101
Enami, Shinichi0000-0002-2790-7361
Additional Information:© 2018 American Chemical Society. 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: July 18, 2018; Revised: August 22, 2018; Published: September 5, 2018. S.E. is grateful to the JSPS KAKENHI Grant No. 15H05328. A.J.C. acknowledges funding from the National Science Foundation under Grant AGS-1744353. Author Contributions: S.E. designed the research; J.Q. performed experiments; S.E. contributed new reagents/analytic tools; J.Q., S.I., K.T., A.J.C., and S.E. analyzed data and wrote the paper. The authors declare no competing financial interest.
Funding AgencyGrant Number
Japan Society for the Promotion of Science (JSPS)15H05328
Issue or Number:39
Record Number:CaltechAUTHORS:20180905-094849047
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Official Citation:Reactivity of Monoterpene Criegee Intermediates at Gas–Liquid Interfaces. Junting Qiu, Shinnosuke Ishizuka, Kenichi Tonokura, Agustín J. Colussi, and Shinichi Enami. The Journal of Physical Chemistry A 2018 122 (39), 7910-7917 DOI: 10.1021/acs.jpca.8b06914
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:89380
Deposited By: Tony Diaz
Deposited On:05 Sep 2018 20:47
Last Modified:16 Nov 2021 00:34

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