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Two of the monofunctional catalases belong to Clade 1, 17 to Clade 2, and 33 to Clade 3. The full list includes complete enzymes, subunits, substrate complexes, and catalytic intermediates."},{"key":"ref43\/cit43","doi-asserted-by":"crossref","first-page":"423","DOI":"10.1002\/prot.10284","volume":"50","author":"Carpena X.","year":"2003","journal-title":"Proteins: Struct., Funct., Genet."},{"key":"ref44\/cit44","doi-asserted-by":"crossref","first-page":"11","DOI":"10.1021\/bi061519w","volume":"46","author":"Hara I.","year":"2007","journal-title":"Biochemistry"},{"key":"ref45\/cit45","doi-asserted-by":"crossref","first-page":"270","DOI":"10.1002\/prot.1092","volume":"44","author":"Melik-Adamyan W. R.","year":"2001","journal-title":"Proteins: Struct., Funct., Genet."},{"key":"ref46\/cit46","doi-asserted-by":"crossref","first-page":"971","DOI":"10.1016\/j.jmb.2004.07.027","volume":"342","author":"Diaz A.","year":"2004","journal-title":"J. Mol. 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A feature similar to the chain of water molecules (W197, W21, W224, W171) on the proximal side of the heme of HEC shown in Figure3was also found in all of the other catalases except BLC (see Table S1 and Figure S5 in theSupporting Information). Thus, in BLC, the water may simply have escaped detection. Therefore, we suggest that this catalase should be reanalyzed."},{"key":"ref57\/cit57","doi-asserted-by":"crossref","first-page":"127","DOI":"10.1016\/j.bbabio.2005.01.004","volume":"1707","author":"Svistunenko D. A.","year":"2005","journal-title":"Biochim. Biophys. Acta"},{"key":"ref58\/cit58","doi-asserted-by":"crossref","first-page":"12852","DOI":"10.1021\/ja9628361","volume":"118","author":"Ivancich A.","year":"1996","journal-title":"J. Am. Chem. 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Scand."},{"key":"ref73\/cit73","doi-asserted-by":"crossref","first-page":"947","DOI":"10.1016\/S0021-9258(19)51207-8","volume":"180","author":"Chance B.","year":"1949","journal-title":"J. Biol. Chem."},{"key":"ref74\/cit74","doi-asserted-by":"crossref","first-page":"1183","DOI":"10.1021\/bi062266+","volume":"46","author":"Jakopitsch C.","year":"2007","journal-title":"Biochemistry"},{"key":"ref75\/cit75","unstructured":"It should be noted that in earlier calculations of possible electron-tunneling pathways,(12, 14, 15)the THR\u2212PRO couple adjacent to NADPH (THR149\u2212PRO150 in BLC) in fact was located as the first relay, from which one of two favorable electron paths to the heme vinyl involves the serine residue (e.g., SER216 in BLC)."},{"key":"ref76\/cit76","doi-asserted-by":"crossref","first-page":"9551","DOI":"10.1021\/ic061019r","volume":"45","author":"de Visser S. P.","year":"2006","journal-title":"Inorg. Chem."},{"key":"ref77\/cit77","doi-asserted-by":"crossref","first-page":"323","DOI":"10.1016\/S0166-1280(03)00309-9","volume":"632","author":"Barea G.","year":"2003","journal-title":"THEOCHEM"},{"key":"ref78\/cit78","unstructured":"There is in fact an ambiguity with respect to the use of the notation Cpd II\u2032 (as opposed to Cpd I\u2032) for our proposed intermediate HO\u2212por\u2022FeIV\u2550O. In terms of unpaired electrons (of which it has three, i.e., two electrons missing from the resting state), it is in fact closer to Cpd I, but in terms of geometry and spin density at the Fe\u2550O center, it much more resembles Cpd II (as shown by a comparison of the data in Figure4and Figure S8 in theSupporting Information). It should be noted that a similar ambiguity exists in designating porFeIV\u2550O\/protein\u2022, the product of one-electron reduction of Cpd I by the surrounding protein, as Cpd I* (see theIntroduction)."},{"key":"ref79\/cit79","unstructured":"If the reasonable assumption that \u0394G\u2248 \u0394Eis made, these data correspond to values ranging from 7 \u00d7 10\u22124to 3.3 for the equilibrium constantKeq."},{"key":"ref80\/cit80","unstructured":"When the C3\u2212O4H bonds in2and6were fixed at 1.47 \u00c5 in the optimizations, the corresponding hypothetical reduced intermediates2(H\u2212)and6(H\u2212)(see Figure S10 in theSupporting Information) were computed to be stabilized by 4.1 and 24.7 kcal mol\u22121with respect to2and6, respectively, i.e., their energies were 41.3 and 32.8 kcal mol\u22121greater than those of products5and4. Since structures2(H\u2212)and6(H\u2212)in turn would represent the initial products of nucleophilic OH\u2212 addition to complex5and ferricatalase4, respectively, it is evident that such an addition is highly unlikely to occur."},{"key":"ref81\/cit81","unstructured":"Kirsch, M., Auferkamp, O., Meier, A.C., Korth, H.G., Sustmann, R., and de Groot, H.Universit\u00e4t Duisburg-Essen. Unpublished results, 2007."},{"key":"ref82\/cit82","unstructured":"With the C3\u2212O4H bond fixed at 1.47 \u00c5, the energy of2(e\u2212), the one-electron reduction product of2, was estimated to be ~40 kcal mol\u22121higher than that of9(see Figure S10 in theSupporting Information). The system utilized the extra electron for reduction of the porphyrin radical to the corresponding anion rather than for reduction of the FeIVcenter."},{"key":"ref83\/cit83","doi-asserted-by":"crossref","first-page":"463","DOI":"10.1038\/417463a","volume":"417","author":"Berglund G. 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