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- W2373394100 abstract "The products of reaction between 2, 2, 6, 6-tetramethyl-4-hydroxypiperidinyl-1-oxy and d, l-cysteine in alkaline buffer solution were identified through column chromatography to be cystine and the corresponding piperidine hydroxylamine. Kinetic study by UV spectrometric method showed the reaction to be second order, with k=0.1～ 1.0 M~(-1)·h~(-1). The reaction has a low activation energy E_a=68.2 kJ·mol~(-1), but a large and negative activation entropy ⊿S~≠=—28 e. u. The rate of the reaction is only influenced to a minor extent by the pH of the medium within the pH range 8.6～11.6. The results indicate that the reaction may proceed through a cyclic transition state, wherein electron transfer takes place between the thiolate anion of cysteine and nitroxide. Pseudo first order kinetic experiments further demonstrated that, with the variation of pH of the medium in the range of 8.6～11.6, the activation enthalpy and activation entropy for the reaction fit the isokinetic relationship, indicating the consistency of the reaction mechanism within the pH range studied.The experiments with TLO and UV spectrometry also showed that the piperidine nitroxide remains stable in alkaline and neutral aqueous solution, but decays in acidic solution." @default.
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- W2373394100 date "1985-01-01" @default.
- W2373394100 modified "2023-09-25" @default.
- W2373394100 title "STUDIES ON NITROXIDES .13. THE MECHANISM OF REACTION BETWEEN 2, 2, 6, 6-TETRAMETHYL-4-HYDROXYPIPERIDINYL-1- OXY AND D, L-CYSTEINE IN ALKALINE BUFFER SOLUTION" @default.
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