Journal
JOURNAL OF MOLECULAR STRUCTURE
Volume 928, Issue 1-3, Pages 46-53Publisher
ELSEVIER SCIENCE BV
DOI: 10.1016/j.molstruc.2009.03.010
Keywords
Embelin; Semiquinone radical; Pulse radiolysis; Density functional theory
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Embelin, 2,5-dihydroxy-3-undecyl-1,4-benzoquinone, has two intra-molecular hydrogen bonds between the quinone and hydroquinone groups present on the same ring. Therefore, it is expected to produce semiquinone radical in the oxidation as well reduction reactions. To investigate this aspect, kinetics and mechanism of reduction reactions of embelin have been studied using nanosecond electron pulse radiolysis technique and compared with the oxidation process. Two distinct transients observed in the reduction (lambda(max)=450 nm) and the oxidation (lambda(max)=410 nm) processes with various free radicals have been characterized and assigned to two different embelin semiquinone radicals on the basis of pulse radiolysis studies. The structures of these transients have been further ascertained using density functional theory with B3LYP functional and 6-31+G(d,p) basis set. Reduction reaction of embelin has been found to produce delocalized semiquinone anion radical. On the other hand, oxidation of embelin is expected to produce several transient species. However, the calculations suggest that oxidation of hydroquinone group is the first step, which is followed by transformation into carbon-centered radical. (C) 2009 Elsevier B.V. All rights reserved.
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