New Mechanistic Insights: Why Do Plants Produce Isoprene?

[Image: see text] In this article, we argue that the primary role of isoprene is to remove the singlet delta oxygen (O(2)(1)Δ(g)) that forms inside plants by ultraviolet excitation rather than to provide heat protection or scavenge ozone, OH, or other reactive oxygen species (ROS) in the gas phase. By deploying a quantum chemical framework, we address for the first time the exact mode of isoprene reactions with O(2)(1)Δ(g), the most prominent ROS that causes damage to leaves. Initial reactions of isoprene with O(2)(1)Δ(g) comprise its addition at the two terminal carbon atoms. The two primary open-shell adducts that appear in these reactions undergo 1,2-cycloaddition to generate methyl vinyl ketone and methacrolein, the sole products detected from in-house (i.e., inside of plants) oxidation of isoprene. Formation of other products, comprising the peroxy O–O bonds, is kinetically insignificant. Furthermore, these adducts are thermodynamically too unstable to diffuse outside of plants. Oxidation of isoprene with O(2)(1)Δ(g) does not produce new ROS (such as OH or HO(2)), supporting the well-documented role of isoprene as an effective ROS scavenger. Deploying a solvation model reduces the energy requirements for the primary pathways in the range of 10–56 kJ/mol. The present results indicate that plants attach significant value to the in-home protection against O(2)(1)Δ(g) by investing carbon and energy into the formation of isoprene, in spite of the appearance of the cytotoxic methyl vinyl ketone as one of the reaction products. (The same chemical species also form in unrelated gas-phase reactions involving isoprene and other ROS.) This finding explains the primary reason for the appearance of the dynamic biosphere–atmosphere exchange of methyl vinyl ketone.