量研学術機関リポジトリ「QST-Repository」は、国立研究開発法人 量子科学技術研究開発機構に所属する職員等が生み出した学術成果(学会誌発表論文、学会発表、研究開発報告書、特許等)を集積しインターネット上で広く公開するサービスです。 Welcome to QST-Repository where we accumulates and discloses the academic research results(Journal Publications, Conference presentation, Research and Development Report, Patent, etc.) of the members of National Institutes for Quantum Science and Technology.
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A large kinetic isotope effect in the reaction of ascorbic acid with 2-phenyl-4,4,5,5-tetramethylimidazoline-1-oxyl 3-oxide (PTIO˙) in aqueous buffer solutions
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A large kinetic isotope effect (KIE, k(H)/k(D)) of 12.8 was observed for the hydrogen-transfer reaction from ascorbic acid to 2-phenyl-4,4,5,5-tetramethylimidazoline-1-oxyl 3-oxide (PTIO center dot) in a phosphate buffer solution (0.05 M, pH/pD 7.0) at 298 K. The isotopic difference in the activation energies (6.8 kJ mol(-1)) determined from the temperature dependence of the KIE suggests that quantum mechanical tunneling may partly play a role in the reaction, although the isotopic ratio of the Arrhenius prefactor (A(H)/A(D) = 0.86) is within the semiclassical limits.