Probing the Electronic Structure of the Hemoglobin Active Center in Physiological Solutions

被引：50

作者：

Aziz, Emad F. ^{[1
]}

Ottosson, Niklas ^{[1
,2
]}

Bonhommeau, Sebastien ^{[1
]}

Bergmann, Nora ^{[3
]}

Eberhardt, Wolfgang ^{[1
]}

Chergui, Majed ^{[4
]}

机构：

[1] Helmholtz Zentrum Berlin Mat & Energie, D-12489 Berlin, Germany

[2] Uppsala Univ, Dept Phys & Mat Sci, SE-75121 Uppsala, Sweden

[3] Max Delbruck Ctr Mol Med, D-13125 Berlin, Germany

[4] Ecole Polytech Fed Lausanne, Lab Spect Ultrarapide, Fac Sci Base, ISIC BSP, CH-1015 Lausanne, Switzerland

来源：

PHYSICAL REVIEW LETTERS | 2009年 / 102卷 / 06期

关键词：

X-RAY-ABSORPTION; L-EDGE; IRON; SPECTROSCOPY; COMPLEXES; HEME; MYOGLOBIN; LIGAND; DELOCALIZATION; PARAMETERS;

D O I：

10.1103/PhysRevLett.102.068103

中图分类号：

O4 [物理学];

学科分类号：

0702 ;

摘要：

Soft-x-ray absorption spectroscopy at the L(2,3) edge of the iron center in bovine hemoglobin and hemin under physiological conditions is reported for the first time. Spectra of the same compounds in solid form are presented for comparison. Striking differences in the electronic structure of the metalloporphyrin are observed between the liquid and solid compounds. We unambiguously show that hemoglobin and hemin are in a high-spin ferric state in solution, and that the 2p spin-orbit coupling decreases for hemin compared to the hemoglobin, while this is not the case in solids. The spectra were simulated using ligand field multiplet theory, in good agreement with the experiment, allowing quantification of the amount of charge transfer between the porphyrin and Fe(3+) ion in hemoglobin and in hemin.

引用

页数：4

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