{"id":673,"date":"2026-04-15T13:26:43","date_gmt":"2026-04-15T13:26:43","guid":{"rendered":"https:\/\/citations.tools.bio-logic.fr\/?p=673"},"modified":"2026-04-15T13:26:43","modified_gmt":"2026-04-15T13:26:43","slug":"o-h-activation-by-an-unexpected-ferryl-intermediate-during-catalysis-by-2-hydroxyethylphosphonate-dioxygenase","status":"publish","type":"post","link":"https:\/\/citations.tools.bio-logic.fr\/?p=673","title":{"rendered":"O\u2013H Activation by an Unexpected Ferryl Intermediate during Catalysis by 2-Hydroxyethylphosphonate Dioxygenase"},"content":{"rendered":"<h4>DOI:<\/h4>\n<p><a href=\"https:\/\/doi.org\/10.1021\/jacs.6b12147\" target=\"_blank\" rel=\"noopener\">10.1021\/jacs.6b12147<\/a><\/p>\n<h4>Authors:<\/h4>\n<p>Spencer C. Peck, Chen Wang, Laura M. K. Dassama, Bo Zhang, Yisong Guo, Lauren J. Rajakovich, J. Martin Bollinger, Carsten Krebs, Wilfred A. van der Donk<\/p>\n<h4>Abstract:<\/h4>\n<p>Activation of O-H bonds by inorganic metal-oxo complexes has been documented, but no cognate enzymatic process is known. Our mechanistic analysis of 2-hydroxyethylphosphonate dioxygenase (HEPD), which cleaves the C1-C2 bond of its substrate to afford hydroxymethylphosphonate on the biosynthetic pathway to the commercial herbicide phosphinothricin, uncovered an example of such an O-H-bond-cleavage event. Stopped-flow UV-visible absorption and freeze-quench M\u00f6ssbauer experiments identified a transient iron(IV)-oxo (ferryl) complex. Maximal accumulation of the intermediate required both the presence of deuterium in the substrate and, importantly, the use of <sup>2<\/sup>H<sub>2<\/sub>O as solvent. The ferryl complex forms and decays rapidly enough to be on the catalytic pathway. To account for these unanticipated results, a new mechanism that involves activation of an O-H bond by the ferryl complex is proposed. This mechanism accommodates all available data on the HEPD reaction.<\/p>\n","protected":false},"excerpt":{"rendered":"<p>DOI: 10.1021\/jacs.6b12147 Authors: Spencer C. Peck, Chen Wang, Laura M. K. Dassama, Bo Zhang, Yisong Guo, Lauren J. Rajakovich, J. Martin Bollinger, Carsten Krebs, Wilfred A. van der Donk Abstract: Activation of O-H bonds by inorganic metal-oxo complexes has been documented, but no cognate enzymatic process is known. Our mechanistic analysis of 2-hydroxyethylphosphonate dioxygenase (HEPD), [&hellip;]<\/p>\n","protected":false},"author":1,"featured_media":0,"comment_status":"open","ping_status":"open","sticky":false,"template":"","format":"standard","meta":{"footnotes":""},"categories":[5],"tags":[],"class_list":["post-673","post","type-post","status-publish","format-standard","hentry","category-freeze-quench"],"_links":{"self":[{"href":"https:\/\/citations.tools.bio-logic.fr\/index.php?rest_route=\/wp\/v2\/posts\/673","targetHints":{"allow":["GET"]}}],"collection":[{"href":"https:\/\/citations.tools.bio-logic.fr\/index.php?rest_route=\/wp\/v2\/posts"}],"about":[{"href":"https:\/\/citations.tools.bio-logic.fr\/index.php?rest_route=\/wp\/v2\/types\/post"}],"author":[{"embeddable":true,"href":"https:\/\/citations.tools.bio-logic.fr\/index.php?rest_route=\/wp\/v2\/users\/1"}],"replies":[{"embeddable":true,"href":"https:\/\/citations.tools.bio-logic.fr\/index.php?rest_route=%2Fwp%2Fv2%2Fcomments&post=673"}],"version-history":[{"count":0,"href":"https:\/\/citations.tools.bio-logic.fr\/index.php?rest_route=\/wp\/v2\/posts\/673\/revisions"}],"wp:attachment":[{"href":"https:\/\/citations.tools.bio-logic.fr\/index.php?rest_route=%2Fwp%2Fv2%2Fmedia&parent=673"}],"wp:term":[{"taxonomy":"category","embeddable":true,"href":"https:\/\/citations.tools.bio-logic.fr\/index.php?rest_route=%2Fwp%2Fv2%2Fcategories&post=673"},{"taxonomy":"post_tag","embeddable":true,"href":"https:\/\/citations.tools.bio-logic.fr\/index.php?rest_route=%2Fwp%2Fv2%2Ftags&post=673"}],"curies":[{"name":"wp","href":"https:\/\/api.w.org\/{rel}","templated":true}]}}