Evaluating Possible Formation Mechanisms of Criegee Intermediates during the Heterogeneous Autoxidation of Squalene.

Organic molecules in the environment oxidatively degrade by a variety of free radical, microbial, and biogeochemical pathways. A significant pathway is heterogeneous autoxidation, in which degradation occurs via a network of carbon and oxygen centered free radicals. Recently, we found evidence for a new heterogeneous autoxidation mechanism of squalene that is initiated by hydroxyl (OH) radical addition to a carbon-carbon double bond and apparently propagated through pathways involving Criegee Intermediates (CI) produced from ß-hydroxy peroxy radicals (ß-OH-RO2•). It remains unclear, however, exactly how CI are formed from ß-OH-RO2•, which could occur by a unimolecular or bimolecular pathway. Combining kinetic models and multiphase OH oxidation measurements of squalene, we evaluate the kinetic viability of three mechanistic scenarios. Scenario 1 assumes that CI are formed by the unimolecular bond scission of ß-OH-RO2•, whereas Scenarios 2 and 3 test bimolecular pathways of ß-OH-RO2• to yield CI. Scenario 1 best replicates the entire experimental data set, which includes effective uptake coefficients vs [OH] as well as the formation kinetics of the major products (i.e., aldehydes and secondary ozonides). Although the unimolecular pathway appears to be kinetically viable, future high-level theory is needed to fully explain the mechanistic relationship between CI and ß-OH-RO2• in the condensed phase.

Catalytic Coupling of Free Radical Oxidation and Electrophilic Chlorine Addition by Phase-Transfer Intermediates in Liquid Aerosols.

While examining the heterogeneous reaction of chlorine atoms with alkenes, in the presence of Cl2, we have observed an unexpectedly large enhancement of reactivity and the predominance of chlorinated reaction products even under high O2 conditions, where Cl atom recycling is expected to be minimal. These observations cannot be explained by known free radical oxidation or cycling mechanisms, but rather we find evidence for the multiphase catalytic coupling of free radical oxidation with electrophilic Cl2 addition. The mechanism entails the production of oxygenated reaction intermediates, which act as gas-liquid phase-transfer catalysts (gl-PTCs) by promoting the accommodation of gas-phase Cl2 by the aerosol, thereby enhancing electrophilic addition. Although the majority of PTCs typically couple chemistry between two immiscible liquid phases (aqueous/organic), there are few examples of PTCs that couple gas-liquid reactions. This work shows how multiphase reaction schemes of aerosols can be reimagined for understanding catalytic reaction mechanisms.

Experimental evidence that halogen bonding catalyzes the heterogeneous chlorination of alkenes in submicron liquid droplets.

A key challenge in predicting the multiphase chemistry of aerosols and droplets is connecting reaction probabilities, observed in an experiment, with the kinetics of individual elementary steps that control the chemistry that occurs across a gas/liquid interface. Here we report evidence that oxygenated molecules accelerate the heterogeneous reaction rate of chlorine gas with an alkene (squalene, Sqe) in submicron droplets. The effective reaction probability for Sqe is sensitive to both the aerosol composition and gas phase environment. In binary aerosol mixtures with 2-decyl-1-tetradecanol, linoleic acid and oleic acid, Sqe reacts 12-23× more rapidly than in a pure aerosol. In contrast, the reactivity of Sqe is diminished by 3× when mixed with an alkane. Additionally, small oxygenated molecules in the gas phase (water, ethanol, acetone, and acetic acid) accelerate (up to 10×) the heterogeneous chlorination rate of Sqe. The overall reaction mechanism is not altered by the presence of these aerosol and gas phase additives, suggesting instead that they act as catalysts. Since the largest rate acceleration occurs in the presence of oxygenated molecules, we conclude that halogen bonding enhances reactivity by slowing the desorption kinetics of Cl2 at the interface, in a way that is analogous to decreasing temperature. These results highlight the importance of relatively weak interactions in controlling the speed of multiphase reactions important for atmospheric and indoor environments.

Efficient Coupling of Reaction Pathways of Criegee Intermediates and Free Radicals in the Heterogeneous Ozonolysis of Alkenes.

In the gas phase, ozonolysis of olefins is known to be a significant source of free radicals. However, for heterogeneous and condensed phase ozone reactions, the importance of reaction pathways that couple Criegee intermediates (CI) with hydroxyl (OH), alkoxy, and peroxy free radicals remains uncertain. Here we report experimental evidence for substantial free radical oxidation during the heterogeneous reaction of O3 with cis-9-tricosene (Tri) aerosol. A kinetic model with three coupled submechanisms that include O3, CI, and free radical reactions is used to explain how the observed Tri reactivity and its product distributions depend upon [O3], [OH], and the presence of CI scavengers. During multiphase ozonolysis, the kinetic model predicts that only ∼30% of the alkene is actually consumed by O3, while the remaining ∼70% is consumed by free radicals that cycle through pathways involving CI. These results reveal the importance of free radical oxidation during heterogeneous ozonolysis, which has been previously difficult to isolate due to the complex coupling of CI and OH reaction pathways.

Evidence that Criegee intermediates drive autoxidation in unsaturated lipids.

Autoxidation is an autocatalytic free-radical chain reaction responsible for the oxidative destruction of organic molecules in biological cells, foods, plastics, petrochemicals, fuels, and the environment. In cellular membranes, lipid autoxidation (peroxidation) is linked with oxidative stress, age-related diseases, and cancers. The established mechanism of autoxidation proceeds via H-atom abstraction through a cyclic network of peroxy-hydroperoxide-mediated free-radical chain reactions. For a series of model unsaturated lipids, we present evidence for an autoxidation mechanism, initiated by hydroxyl radical (OH) addition to C=C bonds and propagated by chain reactions involving Criegee intermediates (CIs). This mechanism leads to unexpectedly rapid autoxidation even in the presence of water, implying that as reactive intermediates, CI could play a much more prominent role in chemistries beyond the atmosphere.