Functionalized Hydroperoxide Formation from the Reaction of Methacrolein-Oxide, an Isoprene-Derived Criegee Intermediate, with Formic Acid: Experiment and Theory
Methacrolein oxide (MACR-oxide) is a four-carbon, resonance-stabilized Criegee intermediate produced from isoprene ozonolysis, yet its reactivity is not well understood. This study identifies the functionalized hydroperoxide species, 1-hydroperoxy-2-methylallyl formate (HPMAF), generated from the re...
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| Format: | Article |
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MDPI AG
2021-05-01
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/26/10/3058 |
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| author | Michael F. Vansco Kristen Zuraski Frank A. F. Winiberg Kendrew Au Nisalak Trongsiriwat Patrick J. Walsh David L. Osborn Carl J. Percival Stephen J. Klippenstein Craig A. Taatjes Marsha I. Lester Rebecca L. Caravan |
| author_facet | Michael F. Vansco Kristen Zuraski Frank A. F. Winiberg Kendrew Au Nisalak Trongsiriwat Patrick J. Walsh David L. Osborn Carl J. Percival Stephen J. Klippenstein Craig A. Taatjes Marsha I. Lester Rebecca L. Caravan |
| author_sort | Michael F. Vansco |
| collection | DOAJ |
| description | Methacrolein oxide (MACR-oxide) is a four-carbon, resonance-stabilized Criegee intermediate produced from isoprene ozonolysis, yet its reactivity is not well understood. This study identifies the functionalized hydroperoxide species, 1-hydroperoxy-2-methylallyl formate (HPMAF), generated from the reaction of MACR-oxide with formic acid using multiplexed photoionization mass spectrometry (MPIMS, 298 K = 25 °C, 10 torr = 13.3 hPa). Electronic structure calculations indicate the reaction proceeds via an energetically favorable 1,4-addition mechanism. The formation of HPMAF is observed by the rapid appearance of a fragment ion at <i>m</i>/<i>z</i> 99, consistent with the proposed mechanism and characteristic loss of HO<sub>2</sub> upon photoionization of functional hydroperoxides. The identification of HPMAF is confirmed by comparison of the appearance energy of the fragment ion with theoretical predictions of its photoionization threshold. The results are compared to analogous studies on the reaction of formic acid with methyl vinyl ketone oxide (MVK-oxide), the other four-carbon Criegee intermediate in isoprene ozonolysis. |
| first_indexed | 2024-03-10T11:13:12Z |
| format | Article |
| id | doaj.art-5e2f640e42d04a00a54f4cb34d6e410f |
| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-03-10T11:13:12Z |
| publishDate | 2021-05-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Molecules |
| spelling | doaj.art-5e2f640e42d04a00a54f4cb34d6e410f2023-11-21T20:37:41ZengMDPI AGMolecules1420-30492021-05-012610305810.3390/molecules26103058Functionalized Hydroperoxide Formation from the Reaction of Methacrolein-Oxide, an Isoprene-Derived Criegee Intermediate, with Formic Acid: Experiment and TheoryMichael F. Vansco0Kristen Zuraski1Frank A. F. Winiberg2Kendrew Au3Nisalak Trongsiriwat4Patrick J. Walsh5David L. Osborn6Carl J. Percival7Stephen J. Klippenstein8Craig A. Taatjes9Marsha I. Lester10Rebecca L. Caravan11Department of Chemistry, University of Pennsylvania, Philadelphia, PA 19104-6323, USANASA Postdoctoral Program Fellow, NASA Jet Propulsion Laboratory, California Institute of Technology, 4800 Oak Grove Drive, Pasadena, CA 91109, USANASA Jet Propulsion Laboratory, California Institute of Technology, 4800 Oak Grove Drive, Pasadena, CA 91109, USACombustion Research Facility, Mailstop 9055, Sandia National Laboratories, Livermore, CA 94551, USADepartment of Chemistry, University of Pennsylvania, Philadelphia, PA 19104-6323, USADepartment of Chemistry, University of Pennsylvania, Philadelphia, PA 19104-6323, USACombustion Research Facility, Mailstop 9055, Sandia National Laboratories, Livermore, CA 94551, USANASA Jet Propulsion Laboratory, California Institute of Technology, 4800 Oak Grove Drive, Pasadena, CA 91109, USAArgonne National Laboratory, Chemical Sciences and Engineering Division, Lemont, IL 60439, USACombustion Research Facility, Mailstop 9055, Sandia National Laboratories, Livermore, CA 94551, USADepartment of Chemistry, University of Pennsylvania, Philadelphia, PA 19104-6323, USAArgonne National Laboratory, Chemical Sciences and Engineering Division, Lemont, IL 60439, USAMethacrolein oxide (MACR-oxide) is a four-carbon, resonance-stabilized Criegee intermediate produced from isoprene ozonolysis, yet its reactivity is not well understood. This study identifies the functionalized hydroperoxide species, 1-hydroperoxy-2-methylallyl formate (HPMAF), generated from the reaction of MACR-oxide with formic acid using multiplexed photoionization mass spectrometry (MPIMS, 298 K = 25 °C, 10 torr = 13.3 hPa). Electronic structure calculations indicate the reaction proceeds via an energetically favorable 1,4-addition mechanism. The formation of HPMAF is observed by the rapid appearance of a fragment ion at <i>m</i>/<i>z</i> 99, consistent with the proposed mechanism and characteristic loss of HO<sub>2</sub> upon photoionization of functional hydroperoxides. The identification of HPMAF is confirmed by comparison of the appearance energy of the fragment ion with theoretical predictions of its photoionization threshold. The results are compared to analogous studies on the reaction of formic acid with methyl vinyl ketone oxide (MVK-oxide), the other four-carbon Criegee intermediate in isoprene ozonolysis.https://www.mdpi.com/1420-3049/26/10/3058reaction intermediatesoxidation reactionsreaction pathwayskineticsmass spectrometryionization |
| spellingShingle | Michael F. Vansco Kristen Zuraski Frank A. F. Winiberg Kendrew Au Nisalak Trongsiriwat Patrick J. Walsh David L. Osborn Carl J. Percival Stephen J. Klippenstein Craig A. Taatjes Marsha I. Lester Rebecca L. Caravan Functionalized Hydroperoxide Formation from the Reaction of Methacrolein-Oxide, an Isoprene-Derived Criegee Intermediate, with Formic Acid: Experiment and Theory Molecules reaction intermediates oxidation reactions reaction pathways kinetics mass spectrometry ionization |
| title | Functionalized Hydroperoxide Formation from the Reaction of Methacrolein-Oxide, an Isoprene-Derived Criegee Intermediate, with Formic Acid: Experiment and Theory |
| title_full | Functionalized Hydroperoxide Formation from the Reaction of Methacrolein-Oxide, an Isoprene-Derived Criegee Intermediate, with Formic Acid: Experiment and Theory |
| title_fullStr | Functionalized Hydroperoxide Formation from the Reaction of Methacrolein-Oxide, an Isoprene-Derived Criegee Intermediate, with Formic Acid: Experiment and Theory |
| title_full_unstemmed | Functionalized Hydroperoxide Formation from the Reaction of Methacrolein-Oxide, an Isoprene-Derived Criegee Intermediate, with Formic Acid: Experiment and Theory |
| title_short | Functionalized Hydroperoxide Formation from the Reaction of Methacrolein-Oxide, an Isoprene-Derived Criegee Intermediate, with Formic Acid: Experiment and Theory |
| title_sort | functionalized hydroperoxide formation from the reaction of methacrolein oxide an isoprene derived criegee intermediate with formic acid experiment and theory |
| topic | reaction intermediates oxidation reactions reaction pathways kinetics mass spectrometry ionization |
| url | https://www.mdpi.com/1420-3049/26/10/3058 |
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