Reply to "Comment on 'Reactivity of Ketyl and Acetyl Radicals from Direct Solar Actinic Photolysis of Aqueous Pyruvic Acid'"


The photochemical study of pyruvic acid (PA) in water by Eugene and Guzman (E&G) considered the integration of a body of work in water and ice. The reaction mechanism in these PA photochemistry studies in water and ice not only identified the photoproducts but also integrated knowledge gained by (1) studying the reaction intermediates generated concomitantly to photodecarboxylation at cryogenic temperature, (2) measuring the kinetics of the reaction both in the condensed phase and the evolution of gases at variable temperature, (3) exploring the dynamic nature of the hydration equilibrium at variable temperature in water and ice, (4) determining the dependence of the quantum yield on the initial [PA]0, (5) investigating the effect of variable concentration of radical scavengers such as 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) and dissolved O2, (6) measuring solvent kinetic isotopic effect (KIE) as well as using isotopic labels, and (7) contrasting the optical absorptivity and molecular composition of the mixtures of identifiable aliphatic polyfunctional oligomers obtained during photobleaching and thermochromism cycles.

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Published in The Journal of Physical Chemistry A, v. 121, issue 45, p. 8741-8744.

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Funding Information

M.I.G. thanks research funding from the National Science foundation under NSF CAREER award CHE-1255290. A.J.E. acknowledges support by the NASA Earth and Space Science Fellowship (NESSF) Program.

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The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.jpca.7b08273.