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Examples of high-frequency EPR studies in bioinorganic chemistry

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Abstract

Low-temperature EPR spectroscopy with frequencies between 95 and 345 GHz and magnetic fields up to 12 T has been used to study metal sites in proteins or inorganic complexes and free radicals. The high-field EPR method was used to resolve g-value anisotropy by separating it from overlapping hyperfine couplings. The presence of hydrogen bonding interactions to the tyrosyl radical oxygens in ribonucleotide reductases were detected. At 285 GHz the g-value anisotropy from the rhombic type 2 Cu(II) signal in the enzyme laccase has its g-value anisotropy clearly resolved from slightly different overlapping axial species. Simple metal site systems with S>1/2 undergo a zero-field splitting, which can be described by the spin Hamiltonian \(H_{\rm s} = \beta SgB + D\left[ {S_z^{\rm 2} - S\left( {S + {\rm 1}} \right){\rm /3} + \left( {E{\rm /}D} \right)\left( {S_x^{\rm 2} - S_y^{\rm 2} } \right)} \right]\). From high-frequency EPR, the D values that are small compared to the frequency (high-field limit) can be determined directly by measuring the distance of the outermost signal to the center of the spectrum, which corresponds to (2S−1)* ∣D∣. For example, D values of 0.8 and 0.3 cm−1 are observed for S=5/2 Fe(III)-EDTA and transferrin, respectively. When D values are larger compared to the frequency and in the case of half-integer spin systems, they can be obtained from the frequency dependence of the shifts of g eff, as observed for myoglobin in the presence (D=5 cm−1) or absence (D=9.5 cm−1) of fluoride. The 285 and 345 GHz spectra of the Fe(II)-NO-EDTA complex show that it is best described as a S=3/2 system with D=11.5 cm−1, E=0.1 cm−1, and g x =g y =g z =2.0. Finally, the effects of HF-EPR on X-band EPR silent states and weak magnetic interactions are demonstrated.

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Acknowledgements

High-field EPR measurements were carried out in the Grenoble High Magnetic Field Laboratory, CNRS-MPIF, supported by the EU TMR programme under contract no. ERBFMGECT950077 and the "Access to research infrastructure of the improving human potential programme". This work was partly financed by the Norwegian Research Council (K.K.A.), the Norwegian Cancer Society (K.K.A.), the EU TMR programme no. ERBMRFXCT980207 (K.K.A.), and ERBFMBICT 961892 (P.P.S.), NIH grant DK31450 (E.I.S.), and NIH grant GM40392 (E.I.S.), and the Swedish Research Council (A.G.). Prof. John D. Lipscomb (University of Minnesota) is thanked for providing samples for measurements and interesting suggestions. Profs. Patrick Bertrand (CNRS, UPR 9036, Marseille) and Joshua Telser (Roosevelt University, Chicago) are thanked for the use of figures and Høgni Weihe (University of Copenhagen) for the simulation program and Dr. Matthias Kolberg (University of Oslo) for fine suggestions. Prof. Britt-Marie Sjöberg (Stockholm University) is thanked for the use of the E. coli RNR-R2 samples in Fig. 2. Prof. Lawrence Que, Jr is thanked for constructive editing.

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  1. Peter P. Schmidt & Bettina Katterle

    Present address: Max-Planck-Institut für Strahlenchemie/Radiation Chemistry, Stiftstrasse 34–36, 45470 , Mulheim an der Ruhr, Germany

  2. Sang-Kyu Lee

    Present address: Genencor International, 925 Page Mill Road, Palo Alto, CA 94304-1013, USA

Authors and Affiliations

  1. Department of Biochemistry, University of Oslo, Blindern, P.O. Box 1041, 0316, Oslo, Norway

    K. Kristoffer Andersson, Peter P. Schmidt, Bettina Katterle & Kari R. Strand

  2. Department of Chemistry, Stanford University, Stanford, CA 94305-5080, USA

    Amy E. Palmer, Sang-Kyu Lee & Edward I. Solomon

  3. Department of and Biochemistry and Biophysics, Stockholm University, 10691, Stockholm, Sweden

    Astrid Gräslund

  4. High Magnetic Field Laboratory, CNRS/MPI, B.P. 166, 38042, Grenoble, France

    Anne-Laure Barra

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Andersson, K.K., Schmidt, P.P., Katterle, B. et al. Examples of high-frequency EPR studies in bioinorganic chemistry. J Biol Inorg Chem 8, 235–247 (2003). https://doi.org/10.1007/s00775-002-0429-0

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