FigureĀ 2.
(a) Free copper reactions based on [44] (b) Cu-LPMO reactions based on [31,48]. Pathway I: O2 binds to the Cu(I)-active site of the Enzyme (E). In the presence of a polysaccharide substrate (S), O2 reduction leads to substrate hydroxylation. In the absence of a polysaccharide, O2 reduction produces H2O2. Pathway II: H2O2 generated in situ can react with the Cu(I)-active site. When the polysaccharide is bound, substrate oxidation occurs. Small-molecule reductants or enzymes, such as cellobiose dehydrogenase, can provide the necessary reducing equivalents.
Simplified reaction schemes for free copper and Cu-LPMO.

(a) Free copper reactions based on [44] (b) Cu-LPMO reactions based on [31,48]. Pathway I: O2 binds to the Cu(I)-active site of the Enzyme (E). In the presence of a polysaccharide substrate (S), O2 reduction leads to substrate hydroxylation. In the absence of a polysaccharide, O2 reduction produces H2O2. Pathway II: H2O2 generated in situ can react with the Cu(I)-active site. When the polysaccharide is bound, substrate oxidation occurs. Small-molecule reductants or enzymes, such as cellobiose dehydrogenase, can provide the necessary reducing equivalents.

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