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The peroxide detected at the ring electrode could arise either from direct release of peroxide during the catalytic cycle or from release and rapid disproportionation of superoxide (42, The hydrolytic autoxidation of heme oxygen complexes in aqueous solution is a well-documented phenomenon (39, 43, This process is known to be catalyzed by protons, and preliminary results indicate that the selectivity of all of our catalysts can be markedly improved by raising the pH (to the range of 8 to 12, Furthermore, our prior work with CcO models on edge-plane graphite provided evidence that superoxide is a substantial source of PROS 30
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The peroxide detected at the ring electrode could arise either from direct release of peroxide during the catalytic cycle or from release and rapid disproportionation of superoxide (42). The hydrolytic autoxidation of heme oxygen complexes in aqueous solution is a well-documented phenomenon (39, 43). This process is known to be catalyzed by protons, and preliminary results indicate that the selectivity of all of our catalysts can be markedly improved by raising the pH (to the range of 8 to 12). Furthermore, our prior work with CcO models on edge-plane graphite provided evidence that superoxide is a substantial source of PROS (30).
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We dedicate this scientific contribution to the memory of the late H. Taube. We thank J. I. Brauman, T. D. P. Stack, C. C. Cummins, R. Boulatov, and P. H. Dinolfo for helpful discussions. N.K.D, R.A.D, and W.E. acknowledge a Stanford graduate fellowship, a Lavoisier fellowship, and a Dreyfus undergraduate fellowship, respectively. This material has its basis in work supported by the NIH under grant GM-17880-35
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We dedicate this scientific contribution to the memory of the late H. Taube. We thank J. I. Brauman, T. D. P. Stack, C. C. Cummins, R. Boulatov, and P. H. Dinolfo for helpful discussions. N.K.D., R.A.D., and W.E. acknowledge a Stanford graduate fellowship, a Lavoisier fellowship, and a Dreyfus undergraduate fellowship, respectively. This material has its basis in work supported by the NIH under grant GM-17880-35.
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