{"id":17763,"date":"2017-03-19T14:10:12","date_gmt":"2017-03-19T14:10:12","guid":{"rendered":"http:\/\/www.ch.imperial.ac.uk\/rzepa\/blog\/?p=17763"},"modified":"2017-03-20T17:05:36","modified_gmt":"2017-03-20T17:05:36","slug":"peroxydisulfate-enables-a-non-enzymatic-krebs-cycle-precursor","status":"publish","type":"post","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=17763","title":{"rendered":"Peroxydisulfate &#8211; &#8220;enables a non-enzymatic Krebs cycle precursor&#8221;"},"content":{"rendered":"<div class=\"kcite-section\" kcite-section-id=\"17763\">\n<p>The Wikipedia entry on <a href=\"https:\/\/en.wikipedia.org\/wiki\/Peroxydisulfate\">peroxydisulfate<\/a> is quite short (as of today). But I suspect this article may change things.<span id=\"cite_ITEM-17763-0\" name=\"citation\"><a href=\"#ITEM-17763-0\">[1]<\/a><\/span>.<\/p>\n<p><a href=\"http:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2017\/03\/peroxydisulfate-page001.svg\"><img decoding=\"async\" class=\"aligncenter size-large wp-image-17765\" src=\"http:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2017\/03\/peroxydisulfate-page001.svg\" alt=\"\" width=\"200\" \/><\/a><\/p>\n<p>A search of the Cambridge structure database reveals around 18 high quality crystal structures containing this species are known, many as metal salts.<\/p>\n<p><img loading=\"lazy\" decoding=\"async\" class=\"aligncenter size-large wp-image-17767\" src=\"http:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2017\/03\/157-1024x364.jpg\" alt=\"\" width=\"450\" height=\"160\" srcset=\"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2017\/03\/157-1024x364.jpg 1024w, https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2017\/03\/157-300x107.jpg 300w, https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2017\/03\/157-768x273.jpg 768w, https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2017\/03\/157.jpg 1852w\" sizes=\"auto, (max-width: 450px) 100vw, 450px\" \/><\/p>\n<p>The article<span id=\"cite_ITEM-17763-0\" name=\"citation\"><a href=\"#ITEM-17763-0\">[1]<\/a><\/span> reports that &#8220;<em>in the presence of sulfate radicals generated from peroxydisulfate<\/em>,<em>\u00a0the (<\/em>Krebs cycle<em>) intermediates underwent 24 interconversion reactions<\/em>&#8221; covering &#8220;<em>the critical topology of the oxidative Krebs cycle, the glyoxylate shunt and the succinic-semialdehyde pathway<\/em>&#8220;. The suggestion therefore is that these crucial metabolic \u00a0reactions may have existed before life itself absorbed them into the <a href=\"https:\/\/en.wikipedia.org\/wiki\/Citric_acid_cycle\">oxidative Krebs cycle<\/a>. The <a href=\"https:\/\/en.wikipedia.org\/wiki\/Nick_Lane\">challenge now<\/a> is to explain how or if the more ancient\u00a0<a href=\"http:\/\/basic-microbiology.blogspot.co.uk\/2011\/11\/reductive-tca-cycle.html\">reductive Krebs cycle<\/a>\u00a0(which <a href=\"http:\/\/www.ch.imperial.ac.uk\/rzepa\/blog\/?p=12395\">fixes carbon dioxide<\/a>) might have arisen prebiotically. More exciting stuff to come I fancy.<\/p>\n<h2>References<\/h2>\n    <ol class=\"kcite-bibliography csl-bib-body\"><li id=\"ITEM-17763-0\">M.A. Keller, D. Kampjut, S.A. Harrison, and M. Ralser, \"Sulfate radicals enable a non-enzymatic Krebs cycle precursor\", <i>Nature Ecology &amp; Evolution<\/i>, vol. 1, 2017. <a href=\"https:\/\/doi.org\/10.1038\/s41559-017-0083\">https:\/\/doi.org\/10.1038\/s41559-017-0083<\/a>\n\n<\/li>\n<\/ol>\n\n<\/div> <!-- kcite-section 17763 -->","protected":false},"excerpt":{"rendered":"<p>The Wikipedia entry on peroxydisulfate is quite short (as of today). But I suspect this article may change things.. A search of the Cambridge structure database reveals around 18 high quality crystal structures containing this species are known, many as metal salts. The article reports that &#8220;in the presence of sulfate radicals generated from peroxydisulfate,\u00a0the [&hellip;]<\/p>\n","protected":false},"author":1,"featured_media":0,"comment_status":"open","ping_status":"open","sticky":false,"template":"","format":"standard","meta":{"jetpack_post_was_ever_published":false,"_jetpack_newsletter_access":"","_jetpack_dont_email_post_to_subs":true,"_jetpack_newsletter_tier_id":0,"_jetpack_memberships_contains_paywalled_content":false,"_jetpack_memberships_contains_paid_content":false,"activitypub_content_warning":"","activitypub_content_visibility":"","activitypub_max_image_attachments":5,"activitypub_interaction_policy_quote":"anyone","activitypub_status":"","footnotes":"","jetpack_publicize_message":"","jetpack_publicize_feature_enabled":true,"jetpack_social_post_already_shared":true,"jetpack_social_options":{"image_generator_settings":{"template":"highway","default_image_id":0,"font":"","enabled":false},"version":2}},"categories":[1745,4],"tags":[2075,2074],"ppma_author":[2661],"class_list":["post-17763","post","type-post","status-publish","format-standard","hentry","category-crystal_structure_mining","category-interesting-chemistry","tag-metal-salts","tag-peroxydisulfate"],"yoast_head":"<!-- This site is optimized with the Yoast SEO plugin v27.5 - https:\/\/yoast.com\/product\/yoast-seo-wordpress\/ -->\n<title>Peroxydisulfate - &quot;enables a non-enzymatic Krebs cycle precursor&quot; - Henry Rzepa&#039;s Blog<\/title>\n<meta name=\"robots\" content=\"index, follow, max-snippet:-1, max-image-preview:large, max-video-preview:-1\" \/>\n<link rel=\"canonical\" href=\"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=17763\" \/>\n<meta property=\"og:locale\" content=\"en_GB\" \/>\n<meta property=\"og:type\" content=\"article\" \/>\n<meta property=\"og:title\" content=\"Peroxydisulfate - &quot;enables a non-enzymatic Krebs cycle precursor&quot; - Henry Rzepa&#039;s Blog\" \/>\n<meta property=\"og:description\" content=\"The Wikipedia entry on peroxydisulfate is quite short (as of today). But I suspect this article may change things.. A search of the Cambridge structure database reveals around 18 high quality crystal structures containing this species are known, many as metal salts. The article reports that &#8220;in the presence of sulfate radicals generated from peroxydisulfate,\u00a0the [&hellip;]\" \/>\n<meta property=\"og:url\" content=\"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=17763\" \/>\n<meta property=\"og:site_name\" content=\"Henry Rzepa&#039;s Blog\" \/>\n<meta property=\"article:published_time\" content=\"2017-03-19T14:10:12+00:00\" \/>\n<meta property=\"article:modified_time\" content=\"2017-03-20T17:05:36+00:00\" \/>\n<meta property=\"og:image\" content=\"http:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2017\/03\/peroxydisulfate-page001.svg\" \/>\n<meta name=\"author\" content=\"Henry Rzepa\" \/>\n<meta name=\"twitter:card\" content=\"summary_large_image\" \/>\n<meta name=\"twitter:label1\" content=\"Written by\" \/>\n\t<meta name=\"twitter:data1\" content=\"Henry Rzepa\" \/>\n\t<meta name=\"twitter:label2\" content=\"Estimated reading time\" \/>\n\t<meta name=\"twitter:data2\" content=\"1 minute\" \/>\n<!-- \/ Yoast SEO plugin. -->","yoast_head_json":{"title":"Peroxydisulfate - \"enables a non-enzymatic Krebs cycle precursor\" - Henry Rzepa&#039;s Blog","robots":{"index":"index","follow":"follow","max-snippet":"max-snippet:-1","max-image-preview":"max-image-preview:large","max-video-preview":"max-video-preview:-1"},"canonical":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=17763","og_locale":"en_GB","og_type":"article","og_title":"Peroxydisulfate - \"enables a non-enzymatic Krebs cycle precursor\" - Henry Rzepa&#039;s Blog","og_description":"The Wikipedia entry on peroxydisulfate is quite short (as of today). 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&#8220;enables a non-enzymatic Krebs cycle precursor&#8221;"}]},{"@type":"WebSite","@id":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/#website","url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/","name":"Henry Rzepa&#039;s Blog","description":"Chemistry with a twist","potentialAction":[{"@type":"SearchAction","target":{"@type":"EntryPoint","urlTemplate":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?s={search_term_string}"},"query-input":{"@type":"PropertyValueSpecification","valueRequired":true,"valueName":"search_term_string"}}],"inLanguage":"en-GB"},{"@type":"Person","@id":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/#\/schema\/person\/2b40f7b9c872a4dc1547e040a11b6281","name":"Henry Rzepa","image":{"@type":"ImageObject","inLanguage":"en-GB","@id":"https:\/\/secure.gravatar.com\/avatar\/897b6740f7f599bca7942cdf7d7914af5988937ae0e3869ab09aebb87f26a731?s=96&d=blank&r=g370be3a7397865e4fd161aefeb0a5a85","url":"https:\/\/secure.gravatar.com\/avatar\/897b6740f7f599bca7942cdf7d7914af5988937ae0e3869ab09aebb87f26a731?s=96&d=blank&r=g","contentUrl":"https:\/\/secure.gravatar.com\/avatar\/897b6740f7f599bca7942cdf7d7914af5988937ae0e3869ab09aebb87f26a731?s=96&d=blank&r=g","caption":"Henry Rzepa"},"description":"Henry Rzepa is Emeritus Professor of Computational Chemistry at Imperial College London.","sameAs":["https:\/\/orcid.org\/0000-0002-8635-8390"],"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?author=1"}]}},"jetpack_publicize_connections":[],"jetpack_featured_media_url":"","jetpack_sharing_enabled":true,"jetpack_shortlink":"https:\/\/wp.me\/pDef7-4Cv","jetpack-related-posts":[{"id":19194,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=19194","url_meta":{"origin":17763,"position":0},"title":"Identification of a simplest hypervalent hydrogen fluoride anion.","author":"Henry Rzepa","date":"December 8, 2017","format":false,"excerpt":"An article with the title shown above in part recently appeared. Given the apparent similarity of HF1- to CH3F1- and CH3F2-, the latter of which I introduced on this blog previously,\u00a0I thought it of interest to apply my analysis to HF1-. The authors conclude that \"the F atom of HF\u2212\u2026","rel":"","context":"In &quot;Hypervalency&quot;","block_context":{"text":"Hypervalency","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?cat=7"},"img":{"alt_text":"","src":"","width":0,"height":0},"classes":[]},{"id":21883,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=21883","url_meta":{"origin":17763,"position":1},"title":"Molecules of the year 2019: Hexagonal planar crystal structures.","author":"Henry Rzepa","date":"January 23, 2020","format":false,"excerpt":"Here is another selection from the Molecules-of-the-Year shortlist published by C&E News, in which hexagonal planar transition metal coordination is identified. This was a mode of metal coordination first mooted more than 100 years ago, but with the first examples only being discovered recently.\u00a0The C&E News example comprises a central\u2026","rel":"","context":"In &quot;crystal_structure_mining&quot;","block_context":{"text":"crystal_structure_mining","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?cat=1745"},"img":{"alt_text":"","src":"https:\/\/i0.wp.com\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2020\/01\/norloy-300x263.jpg?resize=350%2C200&ssl=1","width":350,"height":200},"classes":[]},{"id":17951,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=17951","url_meta":{"origin":17763,"position":2},"title":"Supporting information: chemical graveyard or invaluable resource for chemical structures.","author":"Henry Rzepa","date":"March 31, 2017","format":false,"excerpt":"Nowadays, data supporting\u00a0most publications relating to the synthesis of organic compounds is more likely than not to be found in associated \"supporting information\" rather than the (often page limited) article itself. For example, this article has an SI which is paginated at 907; almost a mini-database in its own right!\u2020\u2026","rel":"","context":"In &quot;Chemical IT&quot;","block_context":{"text":"Chemical IT","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?cat=2"},"img":{"alt_text":"","src":"","width":0,"height":0},"classes":[]},{"id":23187,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=23187","url_meta":{"origin":17763,"position":3},"title":"Dispersion attraction effects on the computed geometry of a leminscular dodecaporphyrin.","author":"Henry Rzepa","date":"January 1, 2021","format":false,"excerpt":"In the previous post, I showed the geometries of three large cyclic porphyrins, as part of an article on exploring the aromaticity of large 4n+2 cyclic rings. One of them had been induced into a \"figure-eight\" or lemniscular conformation, as shown below. Any initial inspection of the geometries of these\u2026","rel":"","context":"In &quot;Interesting chemistry&quot;","block_context":{"text":"Interesting chemistry","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?cat=4"},"img":{"alt_text":"","src":"https:\/\/i0.wp.com\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2020\/12\/c-P12b12_T6f.jpg?resize=350%2C200&ssl=1","width":350,"height":200},"classes":[]},{"id":19339,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=19339","url_meta":{"origin":17763,"position":4},"title":"Multispectral Chiral Imaging with a Metalens.","author":"Henry Rzepa","date":"January 6, 2018","format":false,"excerpt":"The title here is from an article on metalenses which caught my eye. Metalenses are planar and optically thin layers which can be manufactured using a single-step lithographic process. This contrasts with traditional lenses that are not flat and where the optical properties result from very accurately engineered curvatures, which\u2026","rel":"","context":"In &quot;Interesting chemistry&quot;","block_context":{"text":"Interesting chemistry","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?cat=4"},"img":{"alt_text":"","src":"","width":0,"height":0},"classes":[]},{"id":11681,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=11681","url_meta":{"origin":17763,"position":5},"title":"Caesium trifluoride: could it be made?","author":"Henry Rzepa","date":"November 23, 2013","format":false,"excerpt":"Mercury (IV) tetrafluoride attracted much interest when it was reported in 2007 as the first instance of the metal being induced to act as a proper transition element (utilising d-electrons for bonding) rather than a post-transition main group metal (utilising just s-electrons) for which the HgF2 dihalide would be more\u2026","rel":"","context":"In &quot;Hypervalency&quot;","block_context":{"text":"Hypervalency","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?cat=7"},"img":{"alt_text":"Click for 3D","src":"https:\/\/i0.wp.com\/www.ch.imperial.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2013\/11\/CsF31.jpg?resize=350%2C200","width":350,"height":200},"classes":[]}],"jetpack_likes_enabled":false,"authors":[{"term_id":2661,"user_id":1,"is_guest":0,"slug":"admin","display_name":"Henry Rzepa","avatar_url":"https:\/\/secure.gravatar.com\/avatar\/897b6740f7f599bca7942cdf7d7914af5988937ae0e3869ab09aebb87f26a731?s=96&d=blank&r=g","0":null,"1":"","2":"","3":"","4":"","5":"","6":"","7":"","8":""}],"_links":{"self":[{"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=\/wp\/v2\/posts\/17763","targetHints":{"allow":["GET"]}}],"collection":[{"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=\/wp\/v2\/posts"}],"about":[{"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=\/wp\/v2\/types\/post"}],"author":[{"embeddable":true,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=\/wp\/v2\/users\/1"}],"replies":[{"embeddable":true,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Fcomments&post=17763"}],"version-history":[{"count":4,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=\/wp\/v2\/posts\/17763\/revisions"}],"predecessor-version":[{"id":17769,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=\/wp\/v2\/posts\/17763\/revisions\/17769"}],"wp:attachment":[{"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Fmedia&parent=17763"}],"wp:term":[{"taxonomy":"category","embeddable":true,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Fcategories&post=17763"},{"taxonomy":"post_tag","embeddable":true,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Ftags&post=17763"},{"taxonomy":"author","embeddable":true,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Fppma_author&post=17763"}],"curies":[{"name":"wp","href":"https:\/\/api.w.org\/{rel}","templated":true}]}}