Electron paramagnetic resonance , metal centers

The possibility that there might be long-range electron transfer between redox-active centers in enzymes was first suspected by biochemists working on the mechanism of action of metalloenzymes such as xanthine oxidase which contain more than one metal-based redox center. In these enzymes electron transfer frequently proceeds rapidly but early spectroscopic measurements, notably those by electron paramagnetic resonance, failed to provide any indication that these centers were close to one another. 

Electron nuclear double resonance (ENDOR) and electron spin-echo envelope modulation (ESEEM) are two of a variety of pulsed EPR techniques that are used to study paramagnetic metal centers in metalloenzymes. The techniques are discussed in Chapter 4 of reference la and will not be discussed in any detail here. The techniques can define electron-nuclear hyperfine interactions too small to be resolved within the natural width of the EPR line. For instance, as a paramagnetic transition metal center in a metalloprotein interacts with magnetic nuclei such as H, H, P, or these... 

Seventeen-electron species have also been found to form complexes with noble gases. For example, the two paramagnetic radicals RrMn(00)5 and [KrFe(00)5]+ have been detected by EPR spectroscopy by Morton, Perutz, and co-workers following the y-radiolysis of HMn(00)5 and Fe(00)5 in laypton matrices at 77 and 20 K, respectively (37). Evidence for the interaction of Kr with the unpaired electron on the metal center came from the observation of hyperfine couphng with a single Kr nucleus in the EPR spectra of these species. As an example, the EPR spectrum obtained from y-radiolysis of HMn(CO)5 in a matrix of krypton enriched to 42% in the isotope Kr (I = ) is shown in Fig. 5. The spectrum shows the resonances of the Mn(CO)5 radical with characteristic decets of satellites due to hyperfine interaction between the unpaired spin on Mn and a Kr nucleus. 

Electrons and holes that are generated in particulate semiconductors are localized at different defect sites on the surface and in the lattice of the particles. Electron paramagnetic resonance (EPR) results have shown that electrons are trapped as two reduced metal centers—Ti(III) sites—eoordinated either [38, 39] 1) with anatase lattice oxygen atoms only, or 2) with OH or H2O the holes are trapped as oxygen-centered radicals covalently linked to surface titanium atoms [40] (Figure 7). This is summarized by Eqs. (7)-(9). 

The electron-donor centers on metal oxides can be measured by adsorbing certain organic molecules on the surface of the oxide. The transfer of an electron from the donor site of the oxide to the adsorbed molecule creates a paramagnetic ion detectable using electron paramagnetic resonance (EPR) spectroscopy. Che et al. (1972) studied the adsorption of tetracya-noethylene (TCNE) on MgO that had been pretreated between 100 and 800°C. Using EPR methods they identified the presence of adsorbed TCNE radical anion. As the pretreatment temperature increased from 100 to 800°C, the concentration of the radical anion passed through two maxima, one at 200°C and the other at 700°C. The electron-donor centers were found to be associated with OH and O ions with a low coordination number. 

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