PMID: 42447Dec 14, 1979

Influence of steric factors on oxygen binding. I. Studies on 2,4-diisopropyldeuteroheme-myoglobin

Biochimica Et Biophysica Acta
H OgoshiI Tyuma


Sperm whale apomyoglobin was recombined with 2,4-diisopropyldeuterohemin to form 2,4-diisopropyldeuteroheme-myoglobin and its various physico-chemical properties were investigated to get an insight into the structural and functional role of the peripheral vinyl groups. 2,4-Diisopropyldeuteroheme-myoglobin showed a four times lower oxygen affinity at 25 degrees C and larger enthalpy and entropy changes of oxygenation than the corresponding values of native myoglobin. 2,4-Diisopropyldeuteroheme-metmyoglobin shows a pKa value of 9.68 which is higher than those of native metmyoglobin and mesoheme-metmyoglobin. The rate of autooxidation of oxy-form was about seven times larger in 2,4-diisopropyldeuteroheme-myoglobin than in native myoglobin. The electron-donating effect of isopropyl groups does not give straightforward explanation for these anomalous properties of 2,4-diisopropyldeuteroheme-myoglobin. It is proposed that site and stereospecific van der Waals' interaction between the polypeptide side chains and the peripheral 2,4-diisopropyl groups may weaken the interaction between the bound oxygen molecule and the distal His, resulting in the decrease in the stability of oxyform.


May 12, 2006·Chemistry : a European Journal·Mark J BoerakkerNico A J M Sommerdijk


Apr 15, 1975·Annals of the New York Academy of Sciences·W S CaugheyW J Wallace
Mar 1, 1978·Proceedings of the National Academy of Sciences of the United States of America·P W TuckerW S Caughey
Jun 25, 1977·Journal of Molecular Biology·D W Seybert, K Moffat
May 20, 1969·Proceedings of the Royal Society of London. Series B, Containing Papers of a Biological Character·M F Perutz
Jun 6, 1998·Proceedings of the National Academy of Sciences of the United States of America·K UchidaT Osawa
Mar 26, 2005·Proceedings of the National Academy of Sciences of the United States of America·Olafur E SigurjonssonJoel C Glover

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