Probing the Reactivity of Singlet Oxygen with Cyclic Monoterpenes

Nassim Zeinali, Ibukun Oluwoye, Mohammednoor K. Altarawneh, Mansour H. Almatarneh, Bogdan Z. Dlugogorski

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    Abstract

    Monoterpenes represent a class of hydrocarbons consisting of two isoprene units. Like many other terpenes, monoterpenes emerge mainly from vegetation, indicating their significance in both atmospheric chemistry and pharmaceutical and food industries. The atmospheric recycling of monoterpenes constitutes a major source of secondary organic aerosols. Therefore, this contribution focuses on the mechanism and kinetics of atmospheric oxidation of five dominant monoterpenes (i.e., limonene, α-pinene, β-pinene, sabinene, and camphene) by singlet oxygen. The reactions are initiated via the ene-type addition of singlet oxygen (O2 1δg) to the electron-rich double bond, progressing favorably through the concerted reaction mechanisms. The physical analyses of the frontier molecular orbitals agree well with the thermodynamic properties of the selected reagents, and the computed reaction rate parameters. The reactivity of monoterpenes with O2 1δg follows the order of α-pinene > sabinene > limonene > β-pinene > camphene, i.e., α-pinene and camphene retain the highest and lowest reactivity toward singlet oxygen, with rate expressions of k(T) (M-1 s-1) = 1.13 × 108 exp(-48(kJ)/RT(K)) and 6.93 × 108 exp(-139(kJ)/RT(K)), respectively. The effect of solvent on the primary reaction pathways triggers a slight reduction in energy, ranging between 12 and 34 kJ/mol.

    Original languageEnglish
    Pages (from-to)14040-14048
    Number of pages9
    JournalACS Omega
    Volume4
    Issue number9
    DOIs
    Publication statusPublished - 14 Aug 2019

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    Zeinali, N., Oluwoye, I., Altarawneh, M. K., Almatarneh, M. H., & Dlugogorski, B. Z. (2019). Probing the Reactivity of Singlet Oxygen with Cyclic Monoterpenes. ACS Omega, 4(9), 14040-14048. https://doi.org/10.1021/acsomega.9b01825