By J. D. Dunitz
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The State of Copper in Ceruloplasmin. The early room temperature magnetic susceptibility studies of Ehrenberg et al. (58) showed t h a t only about 40~/o of the Cu bound to ceruloplasmin was paramagnetic. Aisen et al. (IS5) have carefully measured the paramagnetic contribution to the magnetic susceptibility of ceruloplasmin over the temperature range 2 - 4 . 2 °K. In this temperature range Curie's law is followed precisely, and the total susceptibility is exactly proportional up to a measuring field strength of 18 kgauss.
It is evident that for the more slowly reacting substrates Vmax/Km-kl obtained from transient studies. The authors point out that the apparent lack of correspondence with the faster reacting substrates is probably due to difficulties in the direct measurement of kl. As might be expected, there is an excellent correlation between kl (obsd) and Km-1, supporting the relatively simple assumptions regarding the rate limiting processes. This correlation may be explained in terms of an enzymatic reaction which does not involve formation of the classical E .
These experiments suggest that NO. may coordinate directly to Type 1 Cu since NO +, necessarily formed upon reduction of the Cu ~+, is known to be a very reactive nitrating agent, and the reversibility or the above reaction suggests that it is probably not released into solution. However, the possibility that the two Type 1 Cu ~'+ are reduced by NO. via an intramolecular route cannot be excluded. If all the assumptions which have been made in the interpretation of the above described perturbation experiments are correct, all Types of Cu are accessible to perturbants; this seems very unlikely.