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OCR for page 225
226 PART III. ABNORMAL HEMOGLOBINS decrease under the same condition of hydrolysis. No increase is observed after ]5 minutes. There is very little DNP-valine after 15 minutes of hydrolysis, but thereafter it increases with continued hydrolysis more rapidly than DNP- valine is released from DNP-valyl-leucine. Because we know the rate at which DNP-valine is released from DNP-valyl-leucine, we can calculate the amount that must be coming from the other two chains that do not release DNP-valyl-leucine. When we do this, we find that the first order reaction rate constant is something like 0.70 hr.-i, whereas the constant for DNP- valyl-leucine itself is 0.143 hr.-~. The DNP-valine from the two chains other than those that release DNP-valyl-leucine is coming off more slowly. By cal- culation we find that in 22 hours of hydrolysis there still should remain ap- proximately 20 per cent of the two resistant chains unhydrolyzed. Since there are two chains, this is equivalent to 0.4 of an N-terminal group. Our previous value was 3.6 and the addition of 0.4 comes out so perfectly to 4.0 as to be almost unrealistic. There are a good many implications in these results that I don't have time to discuss. They certainly show, however, that there are two kinds of chains in the molecule. This work is described in an article scheduled for publication.) REFEREN CE 1. Rhinesmith, H. S., Schroeder, W. A., and Pauling, I.: N-terminal amino acid residues of normal adult human hemoglobin: A quantitative study of certain aspects of Sanger's dinitrophenyl (DNP) method, J. Am. Chem. Soc. 79: 609 615, 1957.