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• W2236707312 abstract "It is pointed out that the measurement of the static magnetic susceptibilities over a wide temperature range will be able to the detailed information about the electronic structure of the paramagnetic heme derivatives. On the basis of the data given by the electron paramagnetic resonance experiment, formulas for the temperature dependence of the effective magnetic moment (ne,rr) of the ferrihemoglobin fluoride and the ferrihemoglobin azide are derived; further the temperature dependence of nett of the ferrohemoglobin is studied theoretically and it is shown from the observed value of nett at room temperature that the non-cubic ligand field is weaker in the case of ferrohemoglobin compared with the ~ase of ferrihemoglobin azide. The structure of molecules in biological substances, particularly of proteins, can be studied by means of chemical, optical, electrical and rheological experiments, but in the case of paramagnetic molecules such as hemoglobin magnetic properties can be utilized as important sources of information. In this line we have two methods-the electron paramagnetic resonance (EPR) and the measurement of static paramagnetic susceptibilities. The EPR method, when it can be applied at all, is capable of giving fairly detailed information concerning the behavior of magnetic electrons in the molecule, particularly concerning wave-function and ligand fields to which 3d electrons in heme iron are subjected; the measurement of principal g values in ferrihemoglobin azide by Gibson and Ingram/> and the determination of orbital energies of 3d electrons from analysis of these g-values by Griffith> are fruitful examples of such studies. The study of static magnetic susceptibilities is regarded very often as inferior to EPR in the accuracy and the varieties of information obtainable from experiments. The former method has, however, merits which are not always shared by EPR. One of the merits is its wide applicability to various cases. For example in the case of hemes with reduced iron (Fe++) the number of unpaired electrons is even, so that the degeneracy is completely lifted as long as the symmetry of the ligand field is not particularly high. In such * On leave of absence from the University of Tokyo. Present address: Department of Physics. Faculty of Science, The University of Tokyo. Theoretical Study on the Effective Magnetic Moments of Some Hemeproteins 5 cases the method of EPR is not usually applicable. Even in the case of odd number of electrons, EPR is difficult to apply in the presence of large magnetic anisotropy unless a single crystal of reasonable size can be produced and the spin-lattice relaxation time is sufficiently long. Contrary to this, the measurement of the susceptibility can be carried out even in the case of even number of electrons as well as for samples not in the state of single crystals. In this sense the measurement of the susceptibility is not always superseded by EPR, but these two methods are complementary to each other. The study of the behavior of the susceptibility at low temperatures is expected to provide valuable information, although practically all measurements have been hitherto made at room temperatures. In this paper the author will show, on some examples, how one can predict the temperature dependence of the static susceptibility, based on the results of EPR experiments carried out on the same molecule or closely related molecules. The discussion in the following is based on the so-called ligand field theory. In its most naive form the ligand field theory was introduced as a model in which electrons on the central metallic ion (Fe) are subjected to inhomogeneous electrostatic field due to the ligands, but it is now generally known that the formalism of the theory remains true even when there is a partial covalency in the bonds between Fe and the ligands. Particularly when the five d orbitals are classified into two groups, de(d11.z, dza:, dx11) and dr(dz2, dx2_112), dr itself is non-magnetic, so that the precise forms of dr orbitals do not matter so much. This is fortunate because dr orbitals may participate in forming a bonds with the ligands and are often much deformed from their atomic d shape. de orbitals may also form weak covalent rc bonds with ligands, but these rc bonds are usually weak, and this phenomenon can be taken into account in the theory by reducing the magnitude of the spin-orbit interaction parameter a. The results of measurement of paramagnetic susceptibility . are usually represented by Curie's formula" @default.
• W2236707312 created "2016-06-24" @default.
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• W2236707312 date "1961-07-01" @default.
• W2236707312 modified "2023-09-23" @default.
• W2236707312 title "Theoretical study on the effective magnetic moments of some hemeproteins." @default.
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