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The kinetic activation parameters controlling the enzymatic reactions and the thermodynamic parameters associated with the process of substrate binding to the enzyme active species have been deduced from the temperature variation of the <jats:italic>k<\/jats:italic><jats:sub>cat<\/jats:sub> and <jats:italic>K<\/jats:italic><jats:sub>M<\/jats:sub> parameters. The activation free energy is dominated by the enthalpic term, the value of which lies in the relatively narrow range of 61\u00b19 kJ\u2009mol<jats:sup>\u22121<\/jats:sup> irrespective of substrate or reaction type (monophenolase or diphenolase). The activation entropies are small and generally negative and contribute no more than 10\u2009% to the activation free energy. The substrate binding parameters are characterized by large and negative enthalpy and entropy contributions, which are typically dictated by polar protein\u2013substrate interactions. The substrate 4\u2010hydroxyphenylpropionic acid exhibits a strikingly anomalous temperature dependence of the enzymatic oxidation rate, with \u0394<jats:italic>H<\/jats:italic><jats:sup>\u2260<\/jats:sup> \u2248150 kJ\u2009mol<jats:sup>\u22121<\/jats:sup> and \u0394<jats:italic>S<\/jats:italic><jats:sup>\u2260<\/jats:sup> \u2248280 J\u2009K<jats:sup>\u22121<\/jats:sup>\u2009mol<jats:sup>\u22121<\/jats:sup>, due to the fact that it can competitively bind to the enzyme through the phenol group, like the other substrates, or the carboxylate group, like carboxylic acid inhibitors. A kinetic model that takes into account the dual substrate\/inhibitor nature of this compound enables rationalization of this anomalous behavior.<\/jats:p>","DOI":"10.1002\/chem.200501097","type":"journal-article","created":{"date-parts":[[2005,12,8]],"date-time":"2005-12-08T05:51:51Z","timestamp":1134021111000},"page":"2504-2514","source":"Crossref","is-referenced-by-count":31,"title":["Mechanistic Insight into the Activity of Tyrosinase from Variable\u2010Temperature Studies in an Aqueous\/Organic Solvent"],"prefix":"10.1002","volume":"12","author":[{"given":"Alessandro","family":"Granata","sequence":"first","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Enrico","family":"Monzani","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Luigi","family":"Bubacco","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Luigi","family":"Casella","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2006,3]]},"reference":[{"key":"e_1_2_7_1_2","doi-asserted-by":"publisher","DOI":"10.1146\/annurev.bi.34.070165.003115"},{"key":"e_1_2_7_2_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0167-4838(01)00237-0"},{"key":"e_1_2_7_3_2","doi-asserted-by":"publisher","DOI":"10.1021\/ar020062p"},{"key":"e_1_2_7_4_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr950046o"},{"key":"e_1_2_7_5_2","doi-asserted-by":"publisher","DOI":"10.1002\/cbic.200300714"},{"key":"e_1_2_7_6_2","doi-asserted-by":"publisher","DOI":"10.1002\/1521-3757(20011217)113:24<4702::AID-ANGE4702>3.0.CO;2-6"},{"key":"e_1_2_7_6_3","doi-asserted-by":"publisher","DOI":"10.1002\/1521-3773(20011217)40:24<4570::AID-ANIE4570>3.0.CO;2-4"},{"key":"e_1_2_7_7_2","doi-asserted-by":"publisher","DOI":"10.1002\/prot.340190405"},{"key":"e_1_2_7_8_2","doi-asserted-by":"publisher","DOI":"10.1006\/jmbi.1998.1647"},{"key":"e_1_2_7_9_2","doi-asserted-by":"publisher","DOI":"10.1038\/4193"},{"key":"e_1_2_7_10_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0014-5793(98)01662-7"},{"key":"e_1_2_7_11_2","doi-asserted-by":"publisher","DOI":"10.1074\/jbc.273.40.25889"},{"key":"e_1_2_7_12_2","doi-asserted-by":"publisher","DOI":"10.1074\/jbc.M010436200"},{"key":"e_1_2_7_13_2","first-page":"183","volume":"33","author":"Gerdemann C.","year":"2000","journal-title":"Acc. 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