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  • 1985-1989  (4)
  • 1950-1954
  • 1988  (4)
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  • 1985-1989  (4)
  • 1950-1954
Year
  • 1
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 89 (1988), S. 732-740 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The hyperfine coupling parameters of Fe(II) in the FeS4 unit of the complex anion [Fe(SC6H5)4]2− have been determined from an analysis of Mössbauer spectra of a monocrystal in the temperature range of 1.5 to 20 K and in magnetic fields of 0 to 6.7 T. Dynamic spin fluctuation effects have been included in the analysis by a stochastic model with spin–lattice relaxation. Anisotropy in the relaxation matrix element was of moderate significance and apparent only at low fields. The use of a monocrystal allows more precise determination of hyperfine parameters, because it avoids the averaging procedures which are inherent in studies on polycrystalline material. The set of parameters is essentially identical with that reported for reduced rubredoxin and indicates that the electronic ground state of [Fe(SC6H5)4]2−, predominantly of [3z2−r2] character, simulates very well the ground state of the protein FeS core.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Springer
    European biophysics journal 16 (1988), S. 219-229 
    ISSN: 1432-1017
    Keywords: Relaxation kinetics ; ultrasound absorption ; temperature jump ; proton transfer ; vitamin B 6
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Physics
    Notes: Abstract UV-visible and 13C NMR measurements described in the literature and our 31P NMR measurements support the following mechanism of proton transfer reactions in aqueous solutions of pyridoxamine phosphate: Only the tautomeric equilibrium between neutral form, A N, and zwitterion, A Z, which is analogous to the tautomeric equilibrium of 3-hydroxypyridine in aqueous solution, is important, and that equilibrium does not change upon the dissociation of the second phosphate proton. With these simplifying assumption, we have simulated the relaxation spectrum of the proton transfer reactions of pyridoxamine phosphate in water using parameters from analogous reactions and compared it with our ultrasound and temperature jump measurements. We have found that the relaxation process measured by the temperature jump experiment is mainly caused by the overall reaction A N=A Z (or A N - =A Z - ) and the ultrasound absorption at the isoelectric point between pK2 and pK3 is mainly caused by the overall reaction $$A^{\text{ + }} + {\text{x}} A_N^ - + \left( {1 - {\text{x}}} \right)A_Z^ - = {\text{y}}A_N + \left( {2 - {\text{y}}} \right)A_Z , 0 \leqq {\text{x}} \leqq {\text{1,}} {\text{0}} \leqq {\text{y}} \leqq 2$$ .
    Type of Medium: Electronic Resource
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  • 3
    ISSN: 1572-9540
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Abstract The electronic structure of Fe(II) substituting Zn in Horse Liver Alcohol Dehydrogenase was investigated by Mössbauer spectroscopy at various temperatures and applied magnetic fields and by spin Hamiltonian analysis of the results. The novelty we found, is an unusually weak spin coupling of Fe(II) with a diradical (S=1). From ESR results and biochemical findings we conclude, that the corresponding chemical species is triplet oxygen (O2). Oxidation experiments, followed by Mössbauer spectroscopy, show that the spin-coupled species is an outer-sphere Fe(II)… O2 complex occuring as an intermediate of the dioxygen activation reaction, catalysed by Fe(II). A second Fe(II)−O2 complex could be detected, which corresponds to an inner-sphere complex with O2 directly bound to iron. The spin hamiltonian parameters in the coupled system describing the electronic properties of iron are presented. The results are compared with those of iron in other nonheme iron proteins.
    Type of Medium: Electronic Resource
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  • 4
    ISSN: 1572-9540
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Abstract We have used temperature dependent magnetic susceptibility, Mössbauer and EXAFS measurements to study the high spin (HS) — low spin (LS) conversion in Fe(II) (bptn) (NCS)2, and we have combined consistently the information obtained from the different methods.
    Type of Medium: Electronic Resource
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