scholarly journals E.p.r.-spectroscopic studies on the molybdenum–iron site of nitrogenase from Clostridium pasteurianum

1989 ◽  
Vol 262 (1) ◽  
pp. 349-352 ◽  
Author(s):  
G N George ◽  
R E Bare ◽  
H Y Jin ◽  
E I Stiefel ◽  
R C Prince

The e.p.r. spectroscopy of the nitrogenase molybdenum-iron protein from Clostridium pasteurianum was re-investigated. The sharpness of the delta Ms = +/- 3 g′z peak from the +/- 3/2 Kramer's doublet enables the observation and quantification of incompletely resolved hyperfine splittings from the stable magnetic nuclei 95Mo and 57Fe in samples enriched in these isotopes. No couplings to 1H or 17O could be discerned by examination of spectra from samples exchanged into 2H2O and H2(17)O respectively. Simulation of the spectrum from 95Mo-enriched samples yields a hyperfine coupling of 2.9 MHz, and indicates that the earlier electron-nuclear-double-resonance-derived estimate of 8.1 +/- 0.2 MHz is substantially in error.

1986 ◽  
Vol 237 (2) ◽  
pp. 609-612 ◽  
Author(s):  
G J Baker ◽  
P F Knowles ◽  
K B Pandeya ◽  
J B Rayner

Electron nuclear double-resonance (‘ENDOR’) spectroscopic studies on pig plasma amine oxidase have been carried out at 15 K. Deuterium-exchange studies show the presence of two sets of exchangeable protons, probably from two water molecules; from the magnitude of their hyperfine couplings, one is assigned to be equatorially, and the other axially, co-ordinated. Only one 14N hyperfine coupling is observed, suggesting that the bonding of all amino acid (histidine) or organic cofactor ligands is similar. Upon addition of azide, a further hyperfine coupling to nitrogen is observed which is smaller than that observed for the native enzyme; the hyperfine couplings to the remaining nitrogens are slightly altered.


Endor measurements on a type 1b diamond with paramagnetic nitrogen centres were made at 4.2, 77 and 300 °K by means of a 35000 Mc/s spectrometer. The axially symmetric nitrogen hyperfine coupling and quadrupole coupling parameters at 4.2 °K are A iso. , = 92.228 ± 0.001, A aniso. = 10.903 ± 0.002, P = – 3.974 ± 0.001 Mc/s. A small change of hyperfine coupling with temperature was observed.


1999 ◽  
Vol 77 (3) ◽  
pp. 1712-1720 ◽  
Author(s):  
Milagros Medina ◽  
Anabel Lostao ◽  
Javier Sancho ◽  
Carlos Gómez-Moreno ◽  
Richard Cammack ◽  
...  

1988 ◽  
Vol 66 (9) ◽  
pp. 2395-2402 ◽  
Author(s):  
D. Larry Haire ◽  
Uwe M. Oehler ◽  
H. Duane Goldman ◽  
Robert L. Dudley ◽  
Edward G. Janzen

We report the first 1H and 14N electron nuclear double resonance (ENDOR) spectra of oxygen-centered radical adducts (i.e., derived from the addition of tert-butoxyl radicals) of 5,5-dimethyl-1-pyrroline-N-oxide (DMPO) as well as the related cyclic nitrones: 4-phenyl-5,5-dimethyl-1-pyrroline-N-oxide (4-Ph-DMPO) and 3,3,5,5-tetramethyl-1-pyrroline-N-oxide (M4PO). Features of the electron paramagnetic resonance (EPR) and ENDOR spectra of these cyclic (pyrrolidine) aminoxyl (nitroxide) species along with some deuterated analogues in liquid toluene solutions are highlighted. For instance, we found several long-range γ-H hyperfine splittings (HFS's) detectable by ENDOR that provide unique spectral signatures for these radical adducts. Conformational assignments of the pyrrolidine aminoxyl structures based upon the EPR and ENDOR findings are also discussed. Signs of the various hyperfine splittings (i.e., aN, [Formula: see text]) investigated by cross-relaxation intensity sequence patterns (CRISP) in the ENDOR spectra are also presented.


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