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. Author manuscript; available in PMC: 2019 Nov 28.
Published in final edited form as: Chem Rev. 2018 Oct 29;118(22):10840–11022. doi: 10.1021/acs.chemrev.8b00074

Figure 142.

Figure 142.

Copper- and proton-dependent reaction pathways of CuBMb beginning with met-CuBMb (bottom, left). In the presence of CuII, oxy-CuBMb decays and self-oxidizes to yield verdoheme (HO-type heme degradation chemistry, top pathway and spectra). If there are protons available in the active site (provided by H2O2), the product is ferryl-heme (“peroxide shunt” mechanism known for P450s, HCOs), suggesting that proton shuttling to the active site and H-bonding residues are important for directing the mechanism toward O–O cleavage rather than ROS release. Adapted with permission from ref 832. Copyright 2008 Verlag Helvetica Chimica Acta AG.