期刊名称：Proceedings of the National Academy of Sciences
印刷版ISSN：0027-8424
电子版ISSN：1091-6490
出版年度：1973
卷号：70
期号：7
页码：2020-2024
DOI：10.1073/pnas.70.7.2020
语种：English
出版社：The National Academy of Sciences of the United States of America
摘要：Conditions are described under which the catalytic Brdi[c]ka currents observed in ammoniacal buffer solutions containing cobalt(III) hexammine chloride or cobalt(II) and very little bovine-serum albumin (0.1-0.2 {micro}M) are purely kinetically controlled. Under these conditions the kinetic current at pH 9.3-10.3 exhibits a sharp maximum followed by a decrease of the current to a well-defined minimum. The maximum and minimum are eliminated in the presence of 5 mM or more concentrated calcium chloride when a short plateau occurs at the potential of the maximum followed by a well-defined second wave. Both currents are kinetically controlled. When the albumin concentration is 2 {micro}M or greater, the kinetic currents approach diffusion control, the rate of diffusion of cobalt(III) or (II) being close to rate determining. Under these conditions the currents become proportional to the cobalt(III) or (II) concentration in the concentration range between 25 and 200 {micro}M.
