{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,3]],"date-time":"2026-09-03T22:30:18Z","timestamp":1788474618978,"version":"build-2803163510"},"reference-count":93,"publisher":"MDPI AG","issue":"2","license":[{"start":{"date-parts":[[2023,1,28]],"date-time":"2023-01-28T00:00:00Z","timestamp":1674864000000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"name":"Spanish Ministerio de Ciencia e Innovaci\u00f3n","award":["PID2021-127898OB-I00"],"award-info":[{"award-number":["PID2021-127898OB-I00"]}]},{"name":"Spanish Ministerio de Ciencia e Innovaci\u00f3n","award":["GPC ED431B 2020\/52"],"award-info":[{"award-number":["GPC ED431B 2020\/52"]}]},{"name":"Spanish Ministerio de Ciencia e Innovaci\u00f3n","award":["GRC ED431C 2019\/24"],"award-info":[{"award-number":["GRC ED431C 2019\/24"]}]},{"DOI":"10.13039\/501100010801","name":"regional government Xunta de Galicia","doi-asserted-by":"publisher","award":["PID2021-127898OB-I00"],"award-info":[{"award-number":["PID2021-127898OB-I00"]}],"id":[{"id":"10.13039\/501100010801","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100010801","name":"regional government Xunta de Galicia","doi-asserted-by":"publisher","award":["GPC ED431B 2020\/52"],"award-info":[{"award-number":["GPC ED431B 2020\/52"]}],"id":[{"id":"10.13039\/501100010801","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100010801","name":"regional government Xunta de Galicia","doi-asserted-by":"publisher","award":["GRC ED431C 2019\/24"],"award-info":[{"award-number":["GRC ED431C 2019\/24"]}],"id":[{"id":"10.13039\/501100010801","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Antioxidants"],"abstract":"<jats:p>Electronic structure calculations using the density-functional theory (DFT) have been performed to analyse the effect of water molecules and protonation on the heme group of peroxidases in different redox (ferric, ferrous, compounds I and II) and spin states. Shared geometries, spectroscopic properties at the Soret region, and the thermodynamics of peroxidases are discussed. B3LYP and M06-2X density functionals with different basis sets were employed on a common molecular model of the active site (Fe-centred porphine and proximal imidazole). Computed Gibbs free energies indicate that the corresponding aquo complexes are not thermodynamically stable, supporting the five-coordinate Fe(III) centre in native ferric peroxidases, with a water molecule located at a non-bonding distance. Protonation of the ferryl oxygen of compound II is discussed in terms of thermodynamics, Fe\u2013O bond distances, and redox properties. It is demonstrated that this protonation is necessary to account for the experimental data, and computed Gibbs free energies reveal pKa values of compound II about 8.5\u20139.0. Computation indicates that the general oxidative properties of peroxidase intermediates, as well as their reactivity towards water and protons and Soret bands, are mainly controlled by the iron porphyrin and its proximal histidine ligand.<\/jats:p>","DOI":"10.3390\/antiox12020303","type":"journal-article","created":{"date-parts":[[2023,1,30]],"date-time":"2023-01-30T05:57:23Z","timestamp":1675058243000},"page":"303","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":5,"title":["Common Reactivity and Properties of Heme Peroxidases: A DFT Study of Their Origin"],"prefix":"10.3390","volume":"12","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-7963-9119","authenticated-orcid":false,"given":"Daniel R.","family":"Ramos","sequence":"first","affiliation":[{"name":"Chemical Reactivity & Photoreactivity Group (React!), Department of Chemistry, CICA & Faculty of Sciences, Universidade da Coru\u00f1a, Campus da Zapateira, E-15071 A Coru\u00f1a, Spain"},{"name":"Departamento de Qu\u00edmica F\u00edsica, Universidade de Vigo, Campus Universitario Lagoas-Marcosende, E-36310 Vigo, Spain"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-1199-2469","authenticated-orcid":false,"given":"Paul G.","family":"Furtm\u00fcller","sequence":"additional","affiliation":[{"name":"Institute of Biochemistry, Department of Chemistry, University of Natural Resources and Life Sciences, Muthgasse 18, A-1190 Vienna, Austria"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-7133-3430","authenticated-orcid":false,"given":"Christian","family":"Obinger","sequence":"additional","affiliation":[{"name":"Institute of Biochemistry, Department of Chemistry, University of Natural Resources and Life Sciences, Muthgasse 18, A-1190 Vienna, Austria"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"\u00c1ngeles","family":"Pe\u00f1a-Gallego","sequence":"additional","affiliation":[{"name":"Departamento de Qu\u00edmica F\u00edsica, Universidade de Vigo, Campus Universitario Lagoas-Marcosende, E-36310 Vigo, Spain"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Ignacio","family":"P\u00e9rez-Juste","sequence":"additional","affiliation":[{"name":"Departamento de Qu\u00edmica F\u00edsica, Universidade de Vigo, Campus Universitario Lagoas-Marcosende, E-36310 Vigo, Spain"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"J. Arturo","family":"Santaballa","sequence":"additional","affiliation":[{"name":"Chemical Reactivity & Photoreactivity Group (React!), Department of Chemistry, CICA & Faculty of Sciences, Universidade da Coru\u00f1a, Campus da Zapateira, E-15071 A Coru\u00f1a, Spain"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"1968","published-online":{"date-parts":[[2023,1,28]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","unstructured":"Ortiz de Montellano, P.R. (1986). Cytochrome P-450: Structure, Mechanism, and Biochemistry, Plenum Press.","DOI":"10.1007\/978-1-4757-9939-2"},{"key":"ref_2","unstructured":"Everse, J., Everse, K.E., and Grisham, M.B. (1991). Peroxidases in Chemistry and Biology, CRC Press."},{"key":"ref_3","doi-asserted-by":"crossref","first-page":"108","DOI":"10.1016\/j.abb.2014.12.025","article-title":"Independent evolution of four heme peroxidase superfamilies","volume":"574","author":"Hofbauer","year":"2015","journal-title":"Arch. Biochem. 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