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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.
Representative terms from entire chapter:
hemoglobins decrease