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. 2015 Oct 27;112(43):13123-7.
doi: 10.1073/pnas.1515704112.

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

Affiliations

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

Kara L Bren et al. Proc Natl Acad Sci U S A. .

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.

Keywords: bioinorganic; heme; magnetism; metalloproteins; oxygen transport.

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Conflict of interest statement

The authors declare no conflict of interest.

Figures

Fig. 1.
Fig. 1.
The balance used by Coryell and Pauling in 1936 to do the Gouy magnetic susceptibility experiments on oxy- and deoxyhemoglobins, as well as other hemochromogens and hemoglobin derivatives. Image courtesy of J. Barton.
Fig. 2.
Fig. 2.
A view of the oxygen binding sites of oxyhemoglobins (A) and deoxyhemoglobins (B). The view is edge-on with respect to the porphyrin and reveals the subtle structural difference with regard to iron residing in the porphyrin plane in oxyhemoglobin and out of the plane in deoxyhemoglobin, with consequent “doming” of the porphyrin ring. Figure prepared from Protein Data Bank files 1HHO (25) and 4HHB (26) using Pymol (52).

References

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