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Fe 2+
OH
OH
O
HO
FAD
HO
O
OH
HO
O
OH
OH
Fe 3+
Cellobiose
FADH ￿
Fe 2+
Cellobionolactone
FADH 2
OH
OH
Fe 3+
O
O
HO
HO
O
HO
O
OH
OH
Fig. 7. Catalytic cycle of cellobiose dehydrogenase. FAD oxidizes cellobiose to
cellobionolactone which undergoes spontaneous hydrolysis to produce cellobionic
acid. FADH 2 is further reoxidized by two monoelectronic transfers to the heme part.
The cleavage of heme induces a drastic decrease of CDH activity ( Sigoillot et al.,
2002 ). Reduced heme iron may reduce dioxygen or participate in Fenton reaction.
acceptors such as dioxygen, quinones, phenoxyradicals ( Kremer and Wood,
1992; Mason et al., 2002; Samejima and Eriksson, 1992 ), or a subsequent
one-electron transfer to the heme domain by intramolecular electron transfer
( Igarashi et al., 2002 ). The heme part is also involved in electron transfer to a
wide variety of substrates acting as electron acceptors including quinones
( Henriksson et al., 2000a; Westermark and Eriksson, 1975 ), metal ions and
organic dyes. When CDHs are reduced, the enzymes can react with dioxygen
to produce hydrogen peroxide in situ ( Pricelius et al., 2009 ).
Although most lignocellulolytic fungi produce CDHs, their biological func-
tion is still unclear, but these enzymes participate to a diversity of reactions.
These enzymes are involved in cellulose ( Bao and Renganathan, 1992 )and
lignin ( Dumonceaux et al., 2001 ) degradation, in the inhibition of phenol
radical repolymerization ( Ander et al., 1990; Henriksson et al., 1993 ), in the
enhancement of MnP turn over ( Roy and Archibald, 1994 ) and in the produc-
tion of hydroxyl radicals by a Fenton-type reaction, which is one of the most
often cited CDH-driven reactions. The heme part of CDH may carry out a
Fenton-type reaction with H 2 O 2 and generate hydroxyl radicals by iron reduc-
tion. This hydroxyl radical-generating mechanism might be a key component
of lignocellulose breakdown ( Henriksson et al., 1995, 2000a ). The effect of
CDH on a non-phenolic lignin model has been studied by Henriksson et al.
(2000b) . The results indicated that CDH can affect lignins in three ways, the
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