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EPR measurements of weak exchange interactions coupling unpaired spins in model compounds

  • R. Calvo
Article

Abstract

I review electron paramagnetic resonance (EPR) measurements performed to evaluate very weak exchange interactions (defined as ℋex(i, j) = −J ij S i S j , with 10−3 cm−1<|J ij|<1 cm−1) between unpaired spins, transmitted through long and weak chemical pathways typical of protein structures. They are performed in appropriate model compounds, mainly copper derivatives of amino acids and peptides, making use of the phenomenon of exchange narrowing and collapse of the resonances. I describe the theoretical basis and the implementations of the method to different situations, including selected experimental values of the exchange couplingsJ between metal centers, and briefly discuss correlations betweenJ and the structure of the paths. Results obtained in relatively simple EPR experiments performed at room temperature in single-crystal samples are compared with those obtained from thermodynamic magnetic measurements having higher experimental difficulties. The experimental information allows describing the role of molecular segments typical of biomolecules (H bonds, aromatic ring stacking, cation-π contacts, etc.) in the transmission of the exchange interaction. The values ofJ obtained in some model compounds are compared with those obtained in proteins to conclude that the magnitudes of the exchange interactions are useful to characterize long and weak biologically relevant chemical pathways. One observes that these exchange couplings are weakly dependent on the nature of the unpaired spins and strongly dependent on the chemical pathway. Thus, measurements of exchange couplings in model compounds may provide useful information about biological function, particularly about electron transfer in proteins.

Keywords

Electron Paramagnetic Resonance Exchange Interaction Electron Paramagnetic Resonance Spectrum Electron Paramagnetic Resonance Measurement Chemical Pathway 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.

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Copyright information

© Springer 2007

Authors and Affiliations

  • R. Calvo
    • 1
    • 2
  1. 1.Departamento de Fisica, Facultad de Bioquímica y Ciencias BiológicasUniversidad Nacional del LitoralSanta FeArgentina
  2. 2.Instituto de Desarollo Technológico para la Industria Quimica, Consejo Nacional de Investigaciones Científicas y TécnicasUniversidad Nacional del LitoralSanta FeArgentina

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