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Pulse-radiolysis studies on 4-pyridinemethanol and 4-pyridinecarboxaldehyde in aqueous solutions: dimer radical anion formation in the case of 4-pyridinecarboxaldehyde

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Reactions of eaq, H atom and OH radicals with 4-pyridinemethanol (4-PM) and 4-pyridinecarboxaldehyde (4-PCA) have been studied at various pH values using the pulse radiolysis technique. Reaction of eaq with 4-PM and 4-PCA leads to the formation of pyridinyl and ketyl radicals of 4-PM and 4-PCA, respectively. Ketyl radicals formed from 4-PCA react with the parent molecule to give a dimeric radical species. At pH 7, the equilibrium constant for the dimer formation was determined to be 13 500 M-1. At pH 13 also dimer radical formation was observed. Reaction of eaq with 4-PM was found to give highly reducing pyridinyl radicals. Reaction of OH radicals with 4-PM gives a mixture of species, viz., OH adducts and radicals formed by H-atom abstraction from the –CH2OH moiety. Radicals formed by H-atom abstraction reaction from 4-PM were found to be reducing in nature. O˙– radicals were found to react with 4-PM exclusively by H-abstraction pathway.


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