RESUMO
The role of magnetism in the biological functioning of hemoglobin has been debated since its discovery by Pauling and Coryell in 1936. The hemoglobin molecule contains four heme groups each having a porphyrin layer with a Fe ion at the center. Here, we present combined density-functional theory and quantum Monte Carlo calculations for an effective model of Fe in a heme cluster. In comparison with these calculations, we analyze the experimental data on human adult hemoglobin (HbA) from the magnetic susceptibility, Mössbauer and magnetic circular dichroism (MCD) measurements. In both the deoxygenated (deoxy) and the oxygenated (oxy) cases, we show that local magnetic moments develop in the porphyrin layer with antiferromagnetic coupling to the Fe moment. Our calculations reproduce the magnetic susceptibility measurements on deoxy and oxy-HbA. For deoxy-HbA, we show that the anomalous MCD signal in the UV region is an experimental evidence for the presence of antiferromagnetic Fe-porphyrin correlations. The functional properties of hemoglobin such as the binding of O2, the Bohr effect and the cooperativity are explained based on the magnetic correlations. This analysis suggests that magnetism could be involved in the functioning of hemoglobin.
Assuntos
Heme/metabolismo , Hemeproteínas/fisiologia , Hemoglobinas/metabolismo , Ferro/metabolismo , Oxigênio/metabolismo , Heme/química , Hemoglobinas/química , Humanos , Ferro/química , Fenômenos Magnéticos , Oxigênio/químicaRESUMO
By quantum Monte Carlo simulation of a realistic multiorbital Anderson impurity model, we study the spin-orbit interaction (SOI) of an Fe impurity in Au host metal. We show, for the first time, that the SOI is strongly renormalized by the quantum spin fluctuation. Based on this mechanism, we can explain why the gigantic spin Hall effect in Au with Fe impurities was observed in recent experiments, while it is not visible in the anomalous Hall effect. In addition, we show that the SOI is strongly renormalized by the Coulomb correlation U. Based on this picture, we can explain past discrepancies in the calculated orbital angular momenta for an Fe impurity in an Au host.