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Role of. pi. -cation radicals in the enzymatic cycles of peroxidases, catalases, and nitrite and sulfite reductases

Conference ·
OSTI ID:5277549
Charge iterative extended Hueckel calculations, and magnetic and optical results on porphyrins, chlorins, and isobacteriochlorins (1) suggest that the catalytic cycles of the enzymes horseradish peroxidase, catalase, Neurospora crassa catalase, and nitrite and sulfite reductases proceed via ..pi..-cation radicals of their prosthetic groups; (2) offer distinguishing features for the optical and magnetic spectra of these radicals, pertinent to their detection as enzymatic intermediates; (3) reconcile the seemingly contradictory optical and NMR data on Compounds I of horseradish peroxidase; and (4) predict that the axial ligation of the heme differs for horseradish peroxidase and catalase.
Research Organization:
Brookhaven National Lab., Upton, NY (USA); Michigan State Univ., East Lansing (USA). Dept. of Chemistry
Sponsoring Organization:
USDOE
DOE Contract Number:
AC02-76CH00016
OSTI ID:
5277549
Report Number(s):
BNL-27860; CONF-800490-1
Country of Publication:
United States
Language:
English