Chemical characterization of α‐pinene secondary organic aerosol constituents using gas chromatography, liquid chromatography, and paper spray‐based mass spectrometry techniques

Abstract

The use of HPLC/TOF and paper spray ionization methods to identify previously unobserved α-pinene-derived products helps lower the uncertainty in α-pinene oxidation chemistry and provides new platforms that can be used to identify and quantify important atmospheric compounds that relate to air quality in a complex sample matrix, such as ambient aerosol particles. Additionally, the use of paper spray ionization for direct filter analysis is a fast, relatively inexpensive sample preparation technique that can be used to reduce sample manipulation from solvent-induced reactions. Copyright © 2016 John Wiley & Sons, Ltd.

Technical note: Preparation and purification of atmospherically relevant <i>α</i>-hydroxynitrate esters of monoterpenes

“…Nitrate ester (22) was isolated as a clear, colorless oil: IR (ATR) cm −1 3353 (bd w, alcoholic OH), 2917 (w), 1614 (vs, NO 2 ), 1293 (s, NO 2 ), 868 (m, NO 2 ); 1 H NMR (400 MHz, chloroform-d) δ 5.32 (ddd, J = 9.9, 3.5, 2.1 Hz, 1 H), 4.12 (ddd, J = 10.6, 4.6, 1.9 Hz, 1 H), 2.68-2.49 (m, 2 H), 1.88 (t, J = 4.8 Hz, 1 H), 1.43 (dd, J = 14.1, 3.7 Hz, 1 H), 1.24 (dd, J = 13.8, 4.8 Hz, 1 H), 1.11 (s, 3 H), 0.97 (s, 3 H), 0.94 (s, 3 H) ppm. Spectral data are consistent with literature reports (Rindelaub et al, 2016b). 3.3, 0.9 Hz, 1 H), 2.37 (ddd, J = 13.8, 7.1, 2.5 Hz, 1 H), 1.81 (d, J = 4.3 Hz, 1 H), 1.60-1.51 (m, 3 H), 1.32 (dt, J = 13.8, 4.0 Hz, 1 H), 1.23 (s, 3 H), 1.22 (s, 3 H), 0.89 (s, 3 H); 13 C NMR (101 MHz, chloroform-d) δ 94.…”

“…Previous reports have described the opening of epoxides and aziridines using bismuth nitrate in acetonitrile (Das et al, 2007). Others report optimal conditions in dichloromethane (Rindelaub et al, 2016b), or 1,4-dioxane with undesired side reactions in acetonitrile (Pinto et al, 2007). Thus, we began our investigations into the nitration of trans-carene oxide (3) using bismuth nitrate in various solvents (Fig.…”

“…To the best of our knowledge there is only one study of the hydrolysis of an isolated terpene-derived hydroxynitrate (2 in Fig. 1) (Rindelaub et al, 2016a).…”

“…With these molecules in hand, the atmospheric chemistry community could directly study the ON reactivity, such as hydrolysis, and deconvolute the structure-reactivity relationships. Additionally, novel method development would be enabled and validated (Rindelaub et al, 2016b). For example, Nozière and co-authors called attention to "the lack of NMR spectra libraries for atmospheric markers" as a barrier to utilizing nuclear magnetic resonance (NMR) spectroscopy in atmospheric science.…”

“…1). Two main methods appear to have been attempted, treating an epoxide with either fuming nitric acid (Rollins et al, 2010) or bismuth nitrate (Rindelaub et al, 2016b;Romonosky et al, 2015). The utility of the former is limited by the extreme hazards involved with mixing fuming nitric acid with organic materials (Parker, 1995;Univ.…”