| Title: | "Functionalized Hydroperoxide Formation from the Reaction of Methacrolein-Oxide, an Isoprene-Derived Criegee Intermediate, with Formic Acid: Experiment and Theory" |
| Author(s): | Vansco MF; Zuraski K; Winiberg FAF; Au K; Trongsiriwat N; Walsh PJ; Osborn DL; Percival CJ; Klippenstein SJ; Taatjes CA; Lester MI; Caravan RL; |
| Address: | "Department of Chemistry, University of Pennsylvania, Philadelphia, PA 19104-6323, USA. Argonne National Laboratory, Chemical Sciences and Engineering Division, Lemont, IL 60439, USA. NASA Postdoctoral Program Fellow, NASA Jet Propulsion Laboratory, California Institute of Technology, 4800 Oak Grove Drive, Pasadena, CA 91109, USA. NASA Jet Propulsion Laboratory, California Institute of Technology, 4800 Oak Grove Drive, Pasadena, CA 91109, USA. Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, CA 91125, USA. Combustion Research Facility, Mailstop 9055, Sandia National Laboratories, Livermore, CA 94551, USA. Department of Chemical Engineering, University of California, Davis, CA 95616, USA" |
| DOI: | 10.3390/molecules26103058 |
| ISSN/ISBN: | 1420-3049 (Electronic) 1420-3049 (Linking) |
| Abstract: | "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 degrees 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 m/z 99, consistent with the proposed mechanism and characteristic loss of HO(2) 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" |
| Keywords: | atmospheric chemistry ionization kinetics mass spectrometry oxidation reactions reaction intermediates reaction pathways volatile organic compounds; |
| Notes: | "PubMed-not-MEDLINEVansco, Michael F Zuraski, Kristen Winiberg, Frank A F Au, Kendrew Trongsiriwat, Nisalak Walsh, Patrick J Osborn, David L Percival, Carl J Klippenstein, Stephen J Taatjes, Craig A Lester, Marsha I Caravan, Rebecca L eng DE-FG02-87ER13792/U.S. Department of Energy/ DE-NA0003525/U.S. Department of Energy/ DE-AC02-06CH11357/U.S. Department of Energy/ DE-AC02-05CH11231/U.S. Department of Energy/ Switzerland 2021/06/03 Molecules. 2021 May 20; 26(10):3058. doi: 10.3390/molecules26103058" |
