Substrate free radicals are intermediates in ligninase catalysis.

@article{Hammel1986SubstrateFR,
  title={Substrate free radicals are intermediates in ligninase catalysis.},
  author={Kenneth E Hammel and Balaraman Kalyanaraman and Tamara K Kirk},
  journal={Proceedings of the National Academy of Sciences of the United States of America},
  year={1986},
  volume={83 11},
  pages={3708-12}
}
The H2O2-requiring ligninase of the basidiomycete Phanerochaete chrysosporium oxidatively cleaves both lignin and lignin model compounds between C alpha and C beta (C-1 and C-2) of their aliphatic side chains. Previous work has demonstrated a reaction mechanism by which ligninase oxidizes aromatic substrates to their cation radicals, which then undergo side chain cleavage to yield carbon-centered free radicals. These carbon-centered radicals add O2 to give substrate peroxyl radicals that react… CONTINUE READING
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