High static pressure alters spin trapping rates in solution. Dependence on the structure of nitrone spin traps |
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Authors: | Sueishi Yoshimi Yoshioka Daisuke Yoshioka Chiharu Yamamoto Shunzo Kotake Yashige |
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Institution: | Department of Chemistry, Faculty of Science, Okayama University, 3-1-1 Tsushima Naka, Okayama 700-8530, Japan. ysueishi@cc.okayama-u.ac.jp |
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Abstract: | Using a competitive spin trapping method, relative spin trapping rates were quantified for various short-lived radicals (methyl, ethyl, and phenyl radicals). High static pressure was applied to the competitive spin-trapping system by employing high-pressure electron spin resonance (ESR) equipment. Under high pressure (490 bar), spin trapping rate constants for alkyl and phenyl radicals increased by 10 to 40%, and the increase was dependent on the structure of nitrone spin traps. A maximum increase was obtained when tert-butyl(4-pyridinylmethylene)amine N-oxide (4-POBN) was used as a spin trap. Activation volumes (DeltaDeltaV(double dagger)) for the two spin trapping reactions were calculated to be -17-(-9) cm(3) mol(-1) for the 4-POBN system. |
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