Electron paramagnetic resonance clusters

The [NiFe] hydrogenase from D. gigas has been used as a prototype of the [NiFe] hydrogenases. The enzyme is a heterodimer (62 and 26 kDa subunits) and contains four redox active centers one nickel site, one [3Fe-4S], and two [4Fe-4S] clusters, as proven by electron paramagnetic resonance (EPR) and Mosshauer spectroscopic studies (174). The enzyme has been isolated with different isotopic enrichments [6 Ni (I = I), = Ni (I = 0), Fe (I = 0), and Fe (I = )] and studied after reaction with H and D. Isotopic substitutions are valuable tools for spectroscopic assignments and catalytic studies (165, 166, 175). 

The electron paramagnetic resonance spectrum of transition metal ions has been widely used to interpret the state of these ions in systems of catalytic interest. Major emphasis has been placed on supported chromia because of its catalytic importance in low-pressure ethylene polymerization and other commercial reactions. Earlier work on chromia-alumina catalysts has been reviewed by Poole and Maclver 146). On alumina it appears that the chromium is present in three general forms the S phase, which is isolated Cr3+ on the surface or in the lattice the 0 phase, which is clusters of Cr3+ and the y phase, which is isolated Cr5+ on the surface. The S and 0... 

Foumel, A., Gambarelli, S., Guigliarelli, B., More, C., Asso, M., Chouteau, G., Hille, R., and Bertrand, P. 1998. Magnetic interactions between a 4Fe-4S l+ cluster and a flavin mononucleotide radical in the enzyme trimethylamine dehydrogenase a high-field electron paramagnetic resonance study. Journal of Chemical Physics 109 10905-10913. 

The electron paramagnetic resonance experiments on the yttrium ceramics, on the other hand, are ambiguous. In the study by Murrieta et al. [55], the EPR signal of YBa2Cu307 sample was interpreted as a superposition of two different lines attributed to the Cul and Cu2 sites. In some other studies of yttrium ceramics, the EPR signal was not detected or was attributed to an impurity phase [56]. Thus, Ilirther more refined EPR experiments are needed to confirm the location of the unpaired spin in the cluster. 

Electron-nuclear double-resonance studies aconitase, 38 326-328 [4Fe0134S] cluster, 38 355-358 Electron paramagnetic resonance carbon monoxide oxidoreductase, 32 326-328... 

SIMS (61,64,86), microscopy (65), XPS (56), electron microprobe techniques (14,66), electron paramagnetic resonance (EPR) (67) and luminescence experiments (68) have been successfully employed to probe and study V mobility and reactivity on a catalyst surface. TEM, STEM and energy dispersive X-ray emission (EDX) measurements have indicated that V interaction with REY-crystals induced vanadate clusters formation (65). Vanadium was also found capable of reacting with rare-earths outside the zeolite cavities to form LaVQ4... 

Valuable spectroscopic studies on the dithiolene chelated to Mo in various enzymes have been enhanced by the knowledge of the structure from X-ray diffraction. Plagued by interference of prosthetic groups—heme, flavin, iron-sulfur clusters—the majority of information has been gleaned from the DMSO reductase system. The spectroscopic tools of X-ray absorption spectroscopy (XAS), electronic ultraviolet/visible (UV/vis) spectroscopy, resonance Raman (RR), MCD, and various electron paramagnetic resonance techniques [EPR, electron spin echo envelope modulation (ESEEM), and electron nuclear double resonance (ENDOR)] have been particularly effective probes of the metal site. Of these, only MCD and RR have detected features attributable to the dithiolene unit. Selected results from a variety of studies are presented below, chosen because their focus is the Mo-dithiolene unit and organized according to method rather than to enzyme or type of active site. 

Liu A, Graslund A. Electron paramagnetic resonance evidence for a novel interconversion of [3Fe-4S]+ and [4Fe-4S]+ clusters with endogenous iron and sulfide in anaerobic ribonucleotide reductase activase in vitro. J. Biol. Chem. 2000 275 12367-12373. 

M. P. Cifuentes, M. G. Humphrey, J. E. McGrady, P. J. Smith, R. Stranger, K. S. Murray, and B. Moubaraki, High Nuclearity Ruthenium Carbonyl Cluster Chemistry. 5. Local Density Functional, Electronic Spectroscopy, Magnetic Susceptibility, and Electron Paramagnetic Resonance Studies on (Carbido)decaruthenium Carbonil Clusters, J. Am. Chem. Soc. 119,2647-2655 1997. 

---