Abstract
The active centers of chymopapains A and B (jointly designated EC 3.4.22.6) and papaya (Carica papaya L.) peptidase A were investigated by using 2,2''-dipyridyl disulfide and 5,5''-dithiobis-(2-nitrobenzoic acid) as thiol-specific reactivity probes. Whereas the first active-center pKa values for chymopapain B and papaya peptidase A are less than 5, as is the case for papain (EC 3.4.22.2) and ficin (EC 3.4.22.3), that for chymopapain A is about 6.8. The reason why the reactions of thiols of pKa approximately 6.5 with 2.2''-dipyridyl disulfide are essentially pH-independent in the pH range around the thiol pKa is delineated. The value of the Bronsted coefficient (.beta.nuc.) for the reactions of thiolate ions with the 2,2''-dipyridyl disulfide monocation appears to be smaller than its value for the corresponding reactions with the neutral disulfide.

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