Use of quantum-chemical descriptors to analyse reaction rate constants between organic chemicals and superoxide/hydroperoxyl (O2•−/HO2•)
OPEN ACCESS
Loading...
Author / Producer
Date
2018
Publication Type
Journal Article
ETH Bibliography
yes
Citations
Altmetric
OPEN ACCESS
Data
Abstract
The reaction between superoxide (O2•−) and organic chemicals is of interest in many scientific disciplines including biology and synthetic chemistry, as well as for the evaluation of chemical fate in the environment. Due to limited data and lack of congeneric modelling, the involvement of superoxide in many complex processes cannot be adequately evaluated. In this study, we developed new quantitative structure–property relationship (QSPR) models for the prediction of the aqueous-phase rate constant for the reaction between superoxide and a wide variety of organic chemicals reacting via one-electron oxidation, reduction and hydrogen-transfer. It is shown that the relative importance of these pathways is related to frontier molecular orbital (FMO) interaction and to pH. The class-specific QSPRs developed have good statistics (0.84 ≤ R2 ≤ 0.92). For non-congeneric chemicals it is demonstrated that the reactivity toward superoxide can be described by applying explicit descriptions for competition kinetics and speciation. Therefore, the relationships developed in this study are useful as a starting point to evaluate more complex molecules having, for example, multiple reactive functional groups, labile H bonds, or delocalised cationic charges. However, additional kinetic data and more rigorous computation are needed to evaluate such molecules.
Permanent link
Publication status
published
External links
Editor
Book title
Journal / series
Volume
52 (10)
Pages / Article No.
1118 - 1131
Publisher
Taylor & Francis
Event
Edition / version
Methods
Software
Geographic location
Date collected
Date created
Subject
Superoxide; hydroperoxyl; radicals; antioxidants; reaction rate constants; quantitative structure-property relationship; organic chemicals; frontier molecular orbital; kinetics