Discovery of the magnetic behavior of hemoglobin: A beginning of bioinorganic chemistry

Creators: Bren, Kara L.; Eisenberg, Richard; Gray, Harry B.

Abstract

Two articles published by Pauling and Coryell in PNAS nearly 80 years ago described in detail the magnetic properties of oxy- and deoxyhemoglobin, as well as those of closely related compounds containing hemes. Their measurements revealed a large difference in magnetism between oxygenated and deoxygenated forms of the protein and, along with consideration of the observed diamagnetism of the carbonmonoxy derivative, led to an electronic structural formulation of oxyhemoglobin. The key role of hemoglobin as the main oxygen carrier in mammalian blood had been established earlier, and its allosteric behavior had been described in the 1920s. The Pauling–Coryell articles on hemoglobin represent truly seminal contributions to the field of bioinorganic chemistry because they are the first to make connections between active site electronic structure and the function of a metalloprotein.

Additional Information

© 2015 National Academy of Sciences. Edited by Michael A. Marletta, University of California, Berkeley, CA, and approved September 18, 2015 (received for review August 7, 2015). We thank Jay R. Winkler for a critical reading of the manuscript and for several helpful suggestions. Research in biological inorganic chemistry at the California Institute of Technology is supported by the National Institute of Diabetes and Digestive and Kidney Diseases of the National Institutes of Health under Award R01DK019038 (to H.B.G. and J. R. Winkler) and at the University of Rochester is supported by National Science Foundation Award CHE-1409929 (to K.L.B.). Author contributions: K.L.B., R.E., and H.B.G. wrote the paper. The authors declare no conflict of interest. This article is a PNAS Direct Submission. This article is part of the special series of PNAS 100th Anniversary articles to commemorate exceptional research published in PNAS over the last century. See the companion articles, "The magnetic properties and structure of the hemochromogens and related substances" on page 159 in issue 3 of volume 22, and "The magnetic properties and structure of hemoglobin, oxyhemoglobin and carbonmonoxyhemoglobin" on page 210 in issue 4 of volume 22.

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