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dc.contributor.authorWang, Zhandong
dc.contributor.authorPopolan-Vaida, Denisia M.
dc.contributor.authorChen, Bingjie
dc.contributor.authorMoshammer, Kai
dc.contributor.authorMohamed, Samah
dc.contributor.authorWang, Heng
dc.contributor.authorSioud, Salim
dc.contributor.authorRaji, Misjudeen
dc.contributor.authorKohse-Höinghaus, Katharina
dc.contributor.authorHansen, Nils
dc.contributor.authorDagaut, Philippe
dc.contributor.authorLeone, Stephen R.
dc.contributor.authorSarathy, Mani
dc.date.accessioned2017-11-29T11:13:56Z
dc.date.available2017-11-29T11:13:56Z
dc.date.issued2017-11-28
dc.identifier.citationWang Z, Popolan-Vaida DM, Chen B, Moshammer K, Mohamed SY, et al. (2017) Unraveling the structure and chemical mechanisms of highly oxygenated intermediates in oxidation of organic compounds. Proceedings of the National Academy of Sciences: 201707564. Available: http://dx.doi.org/10.1073/pnas.1707564114.
dc.identifier.issn0027-8424
dc.identifier.issn1091-6490
dc.identifier.pmid29183984
dc.identifier.doi10.1073/pnas.1707564114
dc.identifier.urihttp://hdl.handle.net/10754/626247
dc.description.abstractDecades of research on the autooxidation of organic compounds have provided fundamental and practical insights into these processes; however, the structure of many key autooxidation intermediates and the reactions leading to their formation still remain unclear. This work provides additional experimental evidence that highly oxygenated intermediates with one or more hydroperoxy groups are prevalent in the autooxidation of various oxygenated (e.g., alcohol, aldehyde, keto compounds, ether, and ester) and nonoxygenated (e.g., normal alkane, branched alkane, and cycloalkane) organic compounds. These findings improve our understanding of autooxidation reaction mechanisms that are routinely used to predict fuel ignition and oxidative stability of liquid hydrocarbons, while also providing insights relevant to the formation mechanisms of tropospheric aerosol building blocks. The direct observation of highly oxygenated intermediates for the autooxidation of alkanes at 500–600 K builds upon prior observations made in atmospheric conditions for the autooxidation of terpenes and other unsaturated hydrocarbons; it shows that highly oxygenated intermediates are stable at conditions above room temperature. These results further reveal that highly oxygenated intermediates are not only accessible by chemical activation but also by thermal activation. Theoretical calculations on H-atom migration reactions are presented to rationalize the relationship between the organic compound’s molecular structure (n-alkane, branched alkane, and cycloalkane) and its propensity to produce highly oxygenated intermediates via extensive autooxidation of hydroperoxyalkylperoxy radicals. Finally, detailed chemical kinetic simulations demonstrate the influence of these additional reaction pathways on the ignition of practical fuels.
dc.description.sponsorshipThe authors thank Elisabeth Lutanie, Virginia Unkefer, and Ivan Gromicho (Research Publication Services, KAUST) for editorial assistance; Dr. Mikael Ehn and Dr. Matti P. Rissanen (University of Helsinki) and Dr. William H. Green (Massachusetts Institute of Technology) for valuable discussions; and Paul Fugazzi for technical support. This work was supported by King Abdullah University of Science and Technology, Office of Sponsored Research (OSR) under Award OSR-2016-CRG5-3022, and Saudi Aramco under the FUELCOM program (to Z.W., B.C., S.Y.M., H.W., and S.M.S.); Director, Office of Energy Research, Office of Basic Energy Sciences (BES), Chemical Sciences Division of the US Department of Energy (USDOE), Gas Phase Chemical Physics Program, under Contract DE-AC02-05CH11231 (to D.M.P.-V. and S.R.L.); Division of Chemical Sciences, Geosciences and Biosciences, BES/USDOE (N.H. and K.M.); Deutsche Forschungsgemeinschaft Project KO1363/31-1 (to K.K.-H.); European Research Council (ERC) under FP7/2007-2013/ERC Grant 291049-2G-CSafe (to P.D.). Sandia National Laboratories is a multimission laboratory managed and operated by National Technology and Engineering Solutions of Sandia, LLC, a wholly owned subsidiary of Honeywell International, Inc., for the USDOE’s National Nuclear Security Administration under Contract DE-NA0003525. The Advanced Light Source is supported by the Director, Office of BES, of the USDOE under Contract DE-AC02-05CH11231.
dc.publisherProceedings of the National Academy of Sciences
dc.relation.urlhttp://www.pnas.org/content/early/2017/11/27/1707564114
dc.rightsThis open access article is distributed under Creative Commons Attribution-NonCommercial-NoDerivatives License 4.0 (CC BY-NC-ND).
dc.rights.urihttps://creativecommons.org/licenses/by-nc-nd/4.0/
dc.subjectautooxidation
dc.subjectperoxides
dc.subjectignition
dc.subjectsecondary organic aerosol
dc.subjectmass spectrometry
dc.titleUnraveling the structure and chemical mechanisms of highly oxygenated intermediates in oxidation of organic compounds
dc.typeArticle
dc.contributor.departmentClean Combustion Research Center
dc.contributor.departmentAnalytical Core Lab
dc.identifier.journalProceedings of the National Academy of Sciences
dc.eprint.versionPublisher's Version/PDF
dc.contributor.institutionDepartment of Chemistry, University of Central Florida, Orlando, FL 32816-2450
dc.contributor.institutionChemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94720
dc.contributor.institutionDepartment of Physics, University of California, Berkeley, CA 94720
dc.contributor.institutionDepartment of Chemistry, University of California, Berkeley, CA 94720
dc.contributor.institutionPhysikalisch-Technische Bundesanstalt, 38116 Braunschweig, Germany
dc.contributor.institutionCombustion Research Facility, Sandia National Laboratories, Livermore, CA 94551
dc.contributor.institutionDepartment of Chemistry, Bielefeld University, D-33615 Bielefeld, Germany
dc.contributor.institutionCNRS, Institut National des Sciences de l’Ingénierie et des Systèmes, Institut de Combustion, Aérothermique, Réactivité et Environnement, 45071, Orléans, Cedex 2, France
kaust.personWang, Zhandong
kaust.personChen, Bingjie
kaust.personMohamed, Samah
kaust.personWang, Heng
kaust.personSioud, Salim
kaust.personRaji, Misjudeen
kaust.personSarathy, Mani
kaust.grant.numberOSR-2016-CRG5-3022
refterms.dateFOA2018-06-13T19:02:27Z


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This open access article is distributed under Creative Commons Attribution-NonCommercial-NoDerivatives License 4.0 (CC BY-NC-ND).
Except where otherwise noted, this item's license is described as This open access article is distributed under Creative Commons Attribution-NonCommercial-NoDerivatives License 4.0 (CC BY-NC-ND).