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Journal of the American Society of Brewing Chemists
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Journal of the American Society of Brewing Chemists
J Agr Food Chem, 1991
Page 1. 1732 J. Agdc. Food Chem. 1001, 39, 1732-1734 Efficient One-Step Preparation of the Beer A... more Page 1. 1732 J. Agdc. Food Chem. 1001, 39, 1732-1734 Efficient One-Step Preparation of the Beer Additive Tetrahydroiso a-Acids Bruce A. Hay' and John W. Homiski Central Research Division, Pfizer Inc., Groton, Connecticut 06340 ...
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](Journal of the American Chemical Society, 1986
Cyclic voltammetry (Figure 1) was used to further probe the electrocatalytic system. Without diox... more Cyclic voltammetry (Figure 1) was used to further probe the electrocatalytic system. Without dioxygen, all solutions have voltammograms typical of a one-electron reversible Mn(III/II) couple (Figure 1, curve 1, Eo =-0.27 V). With dioxygen, the Mn(TPP)CI reduction and oxidation peak currentsg are increased (Figure 1, curve 2), consistent with partial oxygen binding and a net two-electron reversible reduction to a Mn(II1) superoxo complex! Voltammetry of a similar solution containing porphyrin and benzoic anhydride (Figure 1, curve 3) gives, upon dioxygen addition, greatly enhanced reduction currents (Figure 1, curves 4 and 5)'O that, after normalization with respect to (scan rate)'/', have characteristic catalytic wave shapes and scan-rate dependencies. In Scheme I, the postulated high-valent manganese oxo-porphyrin should" be easily reduced (Scheme I, dashed arrow) at the potentials of the catalytic waves. In an electrolysis with olefin present, such a reduction occurs in competition with epoxidation, perhaps accounting for the less than 100% faradaic efficiencies. This kinetic competition should be amenable to further study by electrochemical methods. This paper shows that electrochemistry provides a powerful new format within which to study model cytochrome P-450 systems. Judicious choice of electrode material and applied potential allows one to discriminate against undesired reaction pathways and background processes. We anticipate that the available electrochemical methodology will permit detailed study of the kinetics and mechanism of this and similar systems.
Journal of the American Society of Brewing Chemists
RefDoc Bienvenue - Welcome. Refdoc est un service / is powered by. ...
Journal of the American Society of Brewing Chemists
J Agr Food Chem, 1991
Page 1. 1732 J. Agdc. Food Chem. 1001, 39, 1732-1734 Efficient One-Step Preparation of the Beer A... more Page 1. 1732 J. Agdc. Food Chem. 1001, 39, 1732-1734 Efficient One-Step Preparation of the Beer Additive Tetrahydroiso a-Acids Bruce A. Hay' and John W. Homiski Central Research Division, Pfizer Inc., Groton, Connecticut 06340 ...
Journal of the American Chemical Society, 1986
Cyclic voltammetry (Figure 1) was used to further probe the electrocatalytic system. Without diox... more Cyclic voltammetry (Figure 1) was used to further probe the electrocatalytic system. Without dioxygen, all solutions have voltammograms typical of a one-electron reversible Mn(III/II) couple (Figure 1, curve 1, Eo =-0.27 V). With dioxygen, the Mn(TPP)CI reduction and oxidation peak currentsg are increased (Figure 1, curve 2), consistent with partial oxygen binding and a net two-electron reversible reduction to a Mn(II1) superoxo complex! Voltammetry of a similar solution containing porphyrin and benzoic anhydride (Figure 1, curve 3) gives, upon dioxygen addition, greatly enhanced reduction currents (Figure 1, curves 4 and 5)'O that, after normalization with respect to (scan rate)'/', have characteristic catalytic wave shapes and scan-rate dependencies. In Scheme I, the postulated high-valent manganese oxo-porphyrin should" be easily reduced (Scheme I, dashed arrow) at the potentials of the catalytic waves. In an electrolysis with olefin present, such a reduction occurs in competition with epoxidation, perhaps accounting for the less than 100% faradaic efficiencies. This kinetic competition should be amenable to further study by electrochemical methods. This paper shows that electrochemistry provides a powerful new format within which to study model cytochrome P-450 systems. Judicious choice of electrode material and applied potential allows one to discriminate against undesired reaction pathways and background processes. We anticipate that the available electrochemical methodology will permit detailed study of the kinetics and mechanism of this and similar systems.