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Both mechanisms proceed by a multistep sequence and each catalytic cycle begins with the nucleophilic attack by a metal\u2010bound hydroxide on the phosphorus atom of the substrate, leading to the cleavage of the phosphate\u2010ester bond. Four exchange\u2010correlation functionals were used to derive the potential energy profiles in protein environments. Although the enzyme is confirmed to work better as triesterase, as revealed by the barrier heights in the rate\u2010limiting steps of the catalytic processes, its promiscuous ability to hydrolyze also the product of the reaction has been confirmed. The important role played by water molecules and some residues in the outer coordination sphere has been elucidated, while the binuclear Co<jats:sup>II<\/jats:sup> center accomplishes both structural and catalytic functions. To correctly describe the electronic configuration of the d\u2005shell of the metal ions, high\u2010 and low\u2010spin arrangement jointly with the occurrence of antiferromagnetic coupling, have been herein considered.<\/jats:p>","DOI":"10.1002\/chem.201405593","type":"journal-article","created":{"date-parts":[[2015,1,12]],"date-time":"2015-01-12T19:01:05Z","timestamp":1421089265000},"page":"3736-3745","source":"Crossref","is-referenced-by-count":22,"title":["Triesterase and Promiscuous Diesterase Activities of a Di\u2010Co<sup>II<\/sup>\u2010Containing Organophosphate Degrading Enzyme Reaction Mechanisms"],"prefix":"10.1002","volume":"21","author":[{"given":"Marta E.","family":"Alberto","sequence":"first","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Gaspar","family":"Pinto","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Nino","family":"Russo","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Marirosa","family":"Toscano","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2015,1,12]]},"reference":[{"key":"e_1_2_6_1_2","first-page":"63","volume":"9","author":"Ely F.","year":"2007","journal-title":"Curr. 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