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  1. This review highlights examples of synthetic organic chemistry used in the context of studying terpene-derived oxidation products in the atmosphere, with a focus on species produced from biogenic isoprene, pinene and caryophyllene.

     
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    Free, publicly-accessible full text available April 26, 2024
  2. Abstract. Highly oxygenated organic molecules (HOMs) from α-pinene ozonolysis have been shown to be significant contributors to secondary organic aerosol (SOA), yet our mechanistic understanding of how the peroxy-radical-driven autoxidation leads to their formation in this system is still limited. The involved isomerisation reactions such as H-atom abstractions followed by O2 additions can take place on sub-second timescales in short-lived intermediates, making the process challenging to study. Similarly, while the end-products and sometimes radical intermediates can be observed using mass spectrometry, their structures remain elusive. Therefore, we propose a method utilising selective deuterations for unveiling the mechanisms of autoxidation, where the HOM products can be used to infer which C atoms have taken part in the isomerisation reactions. This relies on the fact that if a C−D bond is broken due to an abstraction by a peroxy group forming a −OOD hydroperoxide, the D atom will become labile and able to be exchanged with a hydrogen atom in water vapour (H2O), effectively leading to loss of the D atom from the molecule. In this study, we test the applicability of this method using three differently deuterated versions of α-pinene with the newly developed chemical ionisation Orbitrap (CI-Orbitrap) mass spectrometer to inspect the oxidation products. The high mass-resolving power of the Orbitrap is critical, as it allows the unambiguous separation of molecules with a D atom (mD=2.0141) from those with two H atoms (mH2=2.0157). We found that the method worked well, and we could deduce that two of the three tested compounds had lost D atoms during oxidation, suggesting that those deuterated positions were actively involved in the autoxidation process. Surprisingly, the deuterations were not observed to decrease HOM molar yields, as would have been expected due to kinetic isotope effects. This may be an indication that the relevant H (or D) abstractions were fast enough that no competing pathways were of relevance despite slower abstraction rates of the D atom. We show that selective deuteration can be a very useful method for studying autoxidation on a molecular level and likely is not limited to the system of α-pinene ozonolysis tested here.

     
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  3. Interfacial reactions drive all elemental cycling on Earth and play pivotal roles in human activities such as agriculture, water purification, energy production and storage, environmental contaminant remediation, and nuclear waste repository management. The onset of the 21st century marked the beginning of a more detailed understanding of mineral aqueous interfaces enabled by advances in techniques that use tunable high-flux focused ultrafast laser and X-ray sources to provide near-atomic measurement resolution, as well as by nano-fabrication approaches that enable transmission electron microscopy in a liquid cell. This leap into atomic- and nm-scale measurements has uncovered scale-dependent phenomena whose reaction thermodynamics, kinetics, and pathways deviate from previous observations made on larger systems. A second key advance is new experimental evidence for what scientists hypothesized but could not test previously: Namely, interfacial chemical reactions are frequently driven by “anomalies” or “non-idealities”, such as defects, nanoconfinement, and other non-typical chemical structures. Third, progress in computational chemistry have yielded new insights that allow a move beyond simple schematics leading to a molecular model of these complex interfaces. In combination with surface-sensitive measurements, we have gained knowledge of the interfacial structure and dynamics, including the underlying solid surface and the immediately adjacent water and aqueous ions, enabling a better definition of what constitutes the oxide- and silicate-water interfaces. This critical review discusses how science progresses from understanding ideal solid-water interfaces to more realistic systems, focusing on accomplishments in the last 20 years and identifying challenges and future opportunities for the community to address. We anticipate that the next 20 years will focus on understanding and predicting dynamic transient and reactive structures over greater spatial and temporal ranges, as well as systems of greater structural and chemical complexity. Closer collaborations of theoretical and experimental experts across disciplines will continue to be critical to achieving this great aspiration. 
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    Free, publicly-accessible full text available May 24, 2024