Atmospheric heterogeneous stereochemistry

Grace Y. Stokes, Ehow H. Chen, Avram M. Buchbinder, Walter F. Paxton, Alison Keeley, Franz M Geiger

Research output: Contribution to journalArticle

33 Scopus citations

Abstract

While many biogenic and anthropogenic organic constituents in the atmosphere are surface-active and chiral, the role of stereochemistry in heterogeneous oxidation chemistry in the atmosphere has not yet been evaluated. Here, we present nonlinear vibrational surface spectra of fused silica substrates functionalized with quinuclidine diastereomers during exposure to 1011 to 1013 molecules of ozone per cm3 in 1 atm helium to model ozone-limited and ozone-rich tropospheric conditions. Kinetic studies show that diastereomers that orient their reactive C=C double bonds toward the gas phase exhibit heterogeneous ozonolysis rate constants that are 2 times faster than diastereomers that orient their C=C double bonds away from the gas phase. Insofar as our laboratory model studies are representative of real world environments, our studies suggest that the propensity of aerosol particles coated with chiral semivolatile organic compounds to react with ozone may depend on stereochemistry. We expect that the differences in chemical accessibility will lead to the enrichment of one oxidation product stereoisomer over the other. The oxidation products could be gaseous or surface-bound, indicating that kinetic resolution could lead to the stereochemical enrichment of the gas phase or the aerosol, which may have also been important in prebiotic chemistry. Implications of these results for chiral markers that would allow for source appointments of anthropogenic versus biogenic carbon emissions are discussed.

Original languageEnglish (US)
Pages (from-to)13733-13737
Number of pages5
JournalJournal of the American Chemical Society
Volume131
Issue number38
DOIs
StatePublished - Oct 13 2009

ASJC Scopus subject areas

  • Chemistry(all)
  • Catalysis
  • Biochemistry
  • Colloid and Surface Chemistry

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    Stokes, G. Y., Chen, E. H., Buchbinder, A. M., Paxton, W. F., Keeley, A., & Geiger, F. M. (2009). Atmospheric heterogeneous stereochemistry. Journal of the American Chemical Society, 131(38), 13733-13737. https://doi.org/10.1021/ja904206t