{"id":6821,"date":"2024-06-20T12:57:00","date_gmt":"2024-06-20T11:57:00","guid":{"rendered":"https:\/\/lewin.ch.pw.edu.pl\/?p=6821"},"modified":"2025-01-25T19:23:46","modified_gmt":"2025-01-25T18:23:46","slug":"calcium-peroxides-paper-awarded-jacs-cover","status":"publish","type":"post","link":"https:\/\/lewin.ch.pw.edu.pl\/?p=6821","title":{"rendered":"Calcium peroxides paper awarded JACS cover"},"content":{"rendered":"<div>J. Am. Chem. Soc., <b>2024<\/b>, <i>146<\/i>, 18938\u201318947.<\/div>\n<p>&nbsp;<\/p>\n<h1>Fresh Impetus in the Chemistry of Calcium Peroxides<\/h1>\n<p><strong>Arkadiusz Kornowicz, Tomasz Pietrzak, Krzesimir Korona, Micha\u0142 Terlecki, Iwona Justyniak, Adam Kubas,* Janusz Lewi\u0144ski*<\/strong><\/p>\n<p><img decoding=\"async\" src=\"wp-content\/uploads\/2025\/01\/images_large_ja4c00906_0007.jpeg\" style=\"width:500px;\"><\/p>\n<p><b>Abstract:<\/b> Redox-inactive metal ions are essential in modulating the reactivity of various oxygen-containing metal complexes and metalloenzymes, including photosystem II (PSII). The heart of this unique membrane\u2013protein complex comprises the Mn<sub>4<\/sub>CaO<sub>5<\/sub> cluster, in which the Ca<sup>2+<\/sup> ion acts as a critical cofactor in the splitting of water in PSII. However, there is still a lack of studies involving Ca-based reactive oxygen species (ROS) systems, and the exact nature of the interaction between the Ca<sup>2+<\/sup> center and ROS in PSII still generates intense debate. Here, harnessing a novel Ca-TEMPO complex supported by the \u03b2-diketiminate ligand to control the activation of O<sub>2<\/sub>, we report the isolation and structural characterization of hitherto elusive Ca peroxides, a homometallic Ca hydroperoxide and a heterometallic Ca\/K peroxide. Our studies indicate that the presence of K<sup>+<\/sup> cations is a key factor controlling the outcome of the oxygenation reaction of the model Ca-TEMPO complex. Combining experimental observations with computational investigations, we also propose a mechanistic rationalization for the reaction outcomes. The designed approach demonstrates metal-TEMPO complexes as a versatile platform for O<sub>2<\/sub> activation and advances the understanding of Ca\/ROS systems.<\/p>\n<p><a href=\"https:\/\/pubs.acs.org\/doi\/10.1021\/jacs.4c00906\" target=\"_blank\">Read the paper on the publisher\u2019s website.<\/a><\/p>\n<p><img decoding=\"async\" src=\"wp-content\/uploads\/2025\/01\/jacsat.2024.146.issue-28.xlargecover-2.jpg\" style=\"width:98%;\"><\/p>\n","protected":false},"excerpt":{"rendered":"<p>J. Am. Chem. Soc., 2024, 146, 18938\u201318947. &nbsp; Fresh Impetus in the Chemistry of Calcium Peroxides Arkadiusz Kornowicz, Tomasz Pietrzak, Krzesimir Korona, Micha\u0142 Terlecki, Iwona Justyniak, Adam Kubas,* Janusz Lewi\u0144ski* Abstract: Redox-inactive metal ions are essential in modulating the reactivity of various oxygen-containing metal complexes and metalloenzymes, including photosystem II (PSII). The heart of this [&hellip;]<\/p>\n","protected":false},"author":2,"featured_media":6824,"comment_status":"closed","ping_status":"closed","sticky":false,"template":"","format":"standard","meta":{"inline_featured_image":false,"footnotes":""},"categories":[19],"tags":[],"class_list":["post-6821","post","type-post","status-publish","format-standard","has-post-thumbnail","hentry","category-paper"],"_links":{"self":[{"href":"https:\/\/lewin.ch.pw.edu.pl\/index.php?rest_route=\/wp\/v2\/posts\/6821","targetHints":{"allow":["GET"]}}],"collection":[{"href":"https:\/\/lewin.ch.pw.edu.pl\/index.php?rest_route=\/wp\/v2\/posts"}],"about":[{"href":"https:\/\/lewin.ch.pw.edu.pl\/index.php?rest_route=\/wp\/v2\/types\/post"}],"author":[{"embeddable":true,"href":"https:\/\/lewin.ch.pw.edu.pl\/index.php?rest_route=\/wp\/v2\/users\/2"}],"replies":[{"embeddable":true,"href":"https:\/\/lewin.ch.pw.edu.pl\/index.php?rest_route=%2Fwp%2Fv2%2Fcomments&post=6821"}],"version-history":[{"count":9,"href":"https:\/\/lewin.ch.pw.edu.pl\/index.php?rest_route=\/wp\/v2\/posts\/6821\/revisions"}],"predecessor-version":[{"id":6836,"href":"https:\/\/lewin.ch.pw.edu.pl\/index.php?rest_route=\/wp\/v2\/posts\/6821\/revisions\/6836"}],"wp:featuredmedia":[{"embeddable":true,"href":"https:\/\/lewin.ch.pw.edu.pl\/index.php?rest_route=\/wp\/v2\/media\/6824"}],"wp:attachment":[{"href":"https:\/\/lewin.ch.pw.edu.pl\/index.php?rest_route=%2Fwp%2Fv2%2Fmedia&parent=6821"}],"wp:term":[{"taxonomy":"category","embeddable":true,"href":"https:\/\/lewin.ch.pw.edu.pl\/index.php?rest_route=%2Fwp%2Fv2%2Fcategories&post=6821"},{"taxonomy":"post_tag","embeddable":true,"href":"https:\/\/lewin.ch.pw.edu.pl\/index.php?rest_route=%2Fwp%2Fv2%2Ftags&post=6821"}],"curies":[{"name":"wp","href":"https:\/\/api.w.org\/{rel}","templated":true}]}}