Non-oxygen-forming pathways of hydrogen peroxide degradation by bovine liver catalase at low hydrogen peroxide fluxes.
Heme catalases are considered to degrade two molecules of H(2)O(2) to two molecules of H(2)O and one molecule of O(2) employing the catalatic cycle. We here studied the catalytic behaviour of bovine liver catalase at low fluxes of H(2)O(2) (relative to catalase concentration), adjusted by H(2)O(2)-generating systems. At a ratio of a H(2)O(2) flux (given in microM/min(- 1)) to catalase concentration (given in microM) of 10 min(- 1) and above, H(2)O(2) degradation occurred via the catalatic cycle. At lower ratios, however, H(2)O(2) degradation proceeded with increasingly diminished production of O(2). At a ratio of 1 min(- 1), O(2) formation could no longer be observed, although the enzyme still degraded H(2)O(2). These results strongly suggest that at low physiological H(2)O(2) fluxes H(2)O(2) is preferentially metabolised reductively to H(2)O, without release of O(2). The pathways involved in the reductive metabolism of H(2)O(2) are presumably those previously reported as inactivation and reactivation pathways. They start from compound I and are operative at low and high H(2)O(2) fluxes but kinetically outcompete the reaction of compound I with H(2)O(2) at low H(2)O(2) production rates. In the absence of NADPH, the reducing equivalents for the reductive metabolism of H(2)O(2) are most likely provided by the protein moiety of the enzyme. In the presence of NADPH, they are at least in part provided by the coenzyme.
de Groot
Herbert
H
Institut für Physiologische Chemie, Universitätsklinikum, Hufelandstrasse 55, D-45122, Essen, Germany. h.de.groot@uni-essen.de
Auferkamp
Oliver
O
Bramey
Thorsten
T
de Groot
Klaus
K
Kirsch
Michael
M
Korth
Hans-Gert
HG
Petrat
Frank
F
Sustmann
Reiner
R
D000818:Animals; D002374:Catalase / Q000037:antagonists & inhibitors / Q000378:metabolism*; D002384:Catalysis; D002417:Cattle; D006861:Hydrogen Peroxide / Q000737:chemistry* / Q000378:metabolism; D007700:Kinetics; D008099:Liver / Q000201:enzymology*; D009249:NADP / Q000737:chemistry / Q000378:metabolism; D013056:Spectrophotometry, Ultraviolet
D009249:NADP; D006861:Hydrogen Peroxide; D002374:Catalase