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ABSTRACT: At fixed aerosol acidity, we recently demonstrated that dimers in isoprene epoxydiol-derived secondary organic aerosol (IEPOX-SOA) can heterogeneously react with hydroxyl radical (·OH) at faster rates than monomers. Aerosol acidity influences this aging process by enhancing the formation of oligomers in freshly generated IEPOX-SOA. Therefore, we systematically examined the role of aerosol acidity on kinetics and products resulting from heterogeneous ·OH oxidation of freshly generated IEPOX-SOA. IEPOX reacted with inorganic sulfate aerosol of varying initial pH (0.5, 1.5, and 2.5) in a steady state smog chamber to yield a constant source of freshly generated IEPOX-SOA, which was aged in an oxidation flow reactor for 0−22 equiv days of atmospheric ·OH exposure. Molecular-level chemical analyses revealed that the most acidic sulfate aerosol (pH 0.5) formed the largest oligomeric mass fraction, causing the slowest IEPOX-SOA mass decay with aging. Reactive uptake coefficients of ·OH (γOH) were 0.24 ± 0.06, 0.40 ± 0.05, and 0.49 ± 0.20 for IEPOX-SOA generated at pH 0.5, 1.5, and 2.5, respectively. IEPOXSOA became more liquid-like for pH 1.5 and 2.5, while exhibiting an irregular pattern for pH 0.5 with aging. Using kinetic and physicochemical data derived for a single aerosol pH in atmospheric models could inaccurately predict the fate of the IEPOX-SOA. 

Heterogeneous hydroxyl radical (•OH) oxidation is an important aging process for isoprene epoxydiol-derived secondary organic aerosol (IEPOX-SOA) that alters its chemical composition. It was recently demonstrated that heterogeneous •OH oxidation can age single-component particulate methyltetrol sulfates (MTSs), causing ∼55% of the SOA mass loss. However, our most recent study of freshly generated IEPOX-SOA particulate mixtures suggests that the lifetime of the complete IEPOX-SOA mixture against heterogeneous •OH oxidation can be prolonged through the fragmentation of higher-order oligomers. Published studies suggest that the heterogeneous •OH oxidation of IEPOX SOA could affect the organic atmospheric aerosol budget at varying rates, depending on aerosol chemical composition. However, heterogeneous •OH oxidation kinetics for the full IEPOX-SOA particulate mixture have not been reported. Here, we exposed freshly generated IEPOX-SOA particles to heterogeneous oxidation by •OH under humid conditions (relative humidity ∼57%) for 0−15 atmospheric-equivalent days of aging and derived an effective heterogeneous •OH rate coefficient (kOH) of 2.64 ± 0.4 × 10−13 cm^3 molecules−1 s−1. While ∼44% of particulate organic mass of nonoxidized IEPOX-SOA was consumed over the entire 15 day aging period, only <7% was consumed during the initial 10 aging days. By molecular-level chemical analysis, we determined oligomers were consumed at a faster rate (by a factor of 2−4) than monomers. Analysis of aerosol physicochemical properties shows that IEPOX-SOA has a core−shell morphology, and the shell becomes thinner with •OH oxidation. In summary, this study demonstrates that heterogeneous •OH oxidation of IEPOX-SOA particles is a dynamic process in which aerosol chemical composition and physicochemical properties play important roles. 

Abstract We recently demonstrated that the heterogeneous hydroxyl radical (·OH) oxidation is an important aging process for isoprene epoxydiol-derived secondary organic aerosol (IEPOX-SOA) that alters its chemical composition, and thus, aerosol physicochemical properties. Notably, dimeric species in IEPOX-SOA were found to heterogeneously react with ·OH at a much faster rate than monomers, suggesting that the initial oligomeric content of freshly-generated IEPOX-SOA particles may affect its subsequent atmospheric oxidation. Aerosol acidity could in principle influence this aging process by enhancing the formation of sulfated and non-sulfated oligomers in freshly-generated IEPOX-SOA. Many multifunctional organosulfate (OS) products derived from heterogeneous ·OH oxidation of sulfur-containing IEPOX-SOA have been observed in cloud water residues and ice nucleating particles and could affect the ability of aged IEPOX-SOA particles to act as cloud condensation nuclei. Hence, this study systematically investigated the effect of aerosol acidity on the kinetics and products resulting from heterogeneous ·OH oxidation of IEPOX-SOA particles. Gas-phase IEPOX was reacted with inorganic sulfate particles of varying pH (0.5 to 2.0) in an indoor smog chamber operated under dark, steady-state conditions to form freshly-generated IEPOX-SOA particles. These particles were then aged at a relative humidity of 60% in an oxidation flow reactor (OFR) for 0-15 days of equivalent atmospheric ·OH exposure. Aged IEPOX-SOA particles were sampled by an online aerosol chemical speciation monitor (ACSM) to measure real-time aerosol mass and chemical changes of the SOA particles, and were also collected onto Teflon filters and into PILS vials for molecular-level chemical analyses by hydrophilic liquid interaction chromatography method interfaced to electrospray ionization high-resolution quadrupole time-of-flight mass spectrometry (HILIC/ESI-HR-QTOFMS), ion chromatography, and total OS mass amounts. 

Oxidation of isoprene, the biogenic volatile organic compound with the highest emissions globally, is a large source of secondary organic aerosol (SOA) in the atmosphere. Organosulfates, particularly methyltetrol sulfates, formed from acid-driven reactions of isoprene epoxydiols (IEPOX), a key oxidation product, are important contributors to SOA mass. To date, most studies have focused on organosulfate formation on ammonium sulfate particles at low pH. However, recent work has shown sea spray aerosol (SSA) in the accumulation mode (~100 nm) is often quite acidic (pH ~ 2) and IEPOX-derived organosulfates have been identified in marine environments. Herein, we demonstrate that substantial SOA, including organosulfates, are formed on acidic sodium sulfate particles (pH = 1.3), representative of marine aerosol heterogeneously reacting with H2SO4 to form Na2SO4. For acidic sodium and ammonium sulfate particles, 31 and 28% (±1%), respectively, of inorganic sulfate is incorporated into organosulfate species, even though acidic particles with sodium versus ammonium as the primary cation formed 5% (±0.2) less SOA volume and 45% (±6%) less methyltetrol sulfates, suggesting other organosulfates may form. Even though both exhibited core-shell morphology after IEPOX uptake, physicochemical differences were observed via Raman microspectroscopy, with organosulfates identified in both the core and shell of acidic ammonium sulfate SOA particles, but only in the core for acidic sodium sulfate SOA via Raman microspectroscopy. Our results suggest that isoprene-derived SOA formed on aged SSA is potentially an important, but underappreciated, source of SOA and organosulfates in marine and coastal regions and could modify SOA budgets in these environments. 

This communication describes the synthesis of new bis-oxazoline chiral ligands (SPIROX) derived from the C2-symmetric spirocyclic scaffold (SPIROL). The readily available (R,R,R)-SPIROL (2) previously developed by our group was subjected to a three-step sequence that provided key diacid intermediate (R,R,R)-7 in 75% yield. This intermediate was subsequently coupled with (R)- and (S)-phenylglycinols to provide diastereomeric products, the cyclization of which led to two diastereomeric SPIROX ligands (R,R,R,R,R)-3a and (R,R,R,S,S)-3b in 85% and 79% yield, respectively. The complexation of (R,R,R,R,R)-3a and (R,R,R,S,S)-3b with CuCl and Cu(OTf)2 resulted in active catalysts that promoted the asymmetric reaction of α-diazopropionate and phenol. The resultant O–H insertion product was formed in 88% yield, and with excellent selectivity (97% ee) when ligand (R,R,R,R,R)-3a was used.