Physiological and Toxicological Roles of Hydroperoxides

Ullrich, Volker; Schatz, M.; Meisch, F.

doi:10.1007/978-1-4684-5877-0_8

Cited by 2 publications

(1 citation statement)

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“…Organic compounds with hydroxyl (−OH) and hydroperoxyl (−OOH) functional groups are abundant in nature. Alcohols and phenols constitute a considerable fraction of the building blocks in many biological systems and pharmaceutical compounds, and are important components in organic and inorganic synthesis. − Similarly, organic hydroperoxides have drawn appreciable attention because they are strong oxidants and radical reservoirs, and they play important roles in combustion, atmospheric chemistry, and biology. − The protonation state of the oxygen in alcohols, phenols, and hydroperoxides affects their structural and physicochemical properties . The extent of protonation/deprotonation in solution is determined by the acid dissociation constant (p K a ).…”

Section: Introductionmentioning

confidence: 99%

Improved pK_a Prediction of Substituted Alcohols, Phenols, and Hydroperoxides in Aqueous Medium Using Density Functional Theory and a Cluster-Continuum Solvation Model

2017

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Acid dissociation constants (pK's) are key physicochemical properties that are needed to understand the structure and reactivity of molecules in solution. Theoretical pK's have been calculated for a set of 72 organic compounds with -OH and -OOH groups (48 with known experimental pK's). This test set includes 17 aliphatic alcohols, 25 substituted phenols, and 30 hydroperoxides. Calculations in aqueous medium have been carried out with SMD implicit solvation and three hybrid DFT functionals (B3LYP, ωB97XD, and M06-2X) with two basis sets (6-31+G(d,p) and 6-311++G(d,p)). The effect of explicit water molecules on calculated pK's was assessed by including up to three water molecules. pK's calculated with only SMD implicit solvation are found to have average errors greater than 6 pK units. Including one explicit water reduces the error by about 3 pK units, but the error is still far from chemical accuracy. With B3LYP/6-311++G(d,p) and three explicit water molecules in SMD solvation, the mean signed error and standard deviation are only -0.02 ± 0.55; a linear fit with zero intercept has a slope of 1.005 and R = 0.97. Thus, this level of theory can be used to calculate pK's directly without the need for linear correlations or thermodynamic cycles. Estimated pK values are reported for 24 hydroperoxides that have not yet been determined experimentally.

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