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- W1988452425 abstract "Lipoamide anion radicals (LS-2·) produced by the reaction of ·OH with dihydrolipoamide, L(SH)2, or ·CO-2 with lipoamide (LS2) at pH 9 have an absorption (λmax= 400 nm, ϵmax = 7750 M−1cm−1) similar to the anion radical formed from lipoate ions by the same reactants in previous studies, and they decay at similar rates. The yields G(LS2) and G(L(SH)2) in λ-radiolyses show that the radicals disproportionate. As with lipoate, the absorbance of the protonated form LS2H is less intense and slightly blue shifted. At pH 7 the latter reacts with formate ion. This causes a chain LS2H + HCO-2→L(SH)2 + ·CO-2 sequence which leads to G(SH)≃ 45 and precludes the use of formate radicals as stoichiometric reductants of lipoamide at pH ⩽ 7. The alcohol radicals formed by ·OH attack on ethanol, isopropanol and ter-butanol also produced transients with λmax near 400 nm on reaction with LS2. However, the absorbances were weaker and the yields of G(SH) demonstrated that LS-2· was not the only species present. The alcohol radicals evidently react rapidly to form adducts with LS2, which then decay by electron transfer to LS2, opening of the disulphide ring or other subsidiary reactions. Based on this study, quantitative (i.e. g ⋍ 6/100 eV) formation of lipoamide radicals at pH ≃ 6 is best accomplished by abstraction of H atoms from L(SH)2 or by a combination of e-aq and ethanol radicals reacting with LS2." @default.
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- W1988452425 date "1984-01-01" @default.
- W1988452425 modified "2023-09-24" @default.
- W1988452425 title "Formation of lipoamide anion radicals by hydroxyl, formate and alcohol radicals at pH 6–9" @default.
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- W1988452425 doi "https://doi.org/10.1016/0146-5724(84)90116-x" @default.
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