{"id":28233,"date":"2025-01-25T08:34:07","date_gmt":"2025-01-25T08:34:07","guid":{"rendered":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=28233"},"modified":"2025-01-27T13:28:02","modified_gmt":"2025-01-27T13:28:02","slug":"molecules-of-the-year-2024-molecular-shuttle-in-a-box","status":"publish","type":"post","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=28233","title":{"rendered":"Molecules of the Year 2024: Molecular shuttle in a box."},"content":{"rendered":"
\n

This is another in the C&E News list of candidates for the Molecule of the Year, Molecular shuttle in a box<\/em> [1]<\/a><\/span><\/p>\n

    \n
  1. Mirror-image cyclodextrin [2]<\/a><\/span><\/li>\n
  2. Molecular shuttle in a box<\/strong> [1]<\/a><\/span><\/li>\n
  3. Rule-bending strained alkene [3]<\/a><\/span><\/li>\n
  4. First soluble promethium complex [4]<\/a><\/span><\/li>\n
  5. Single-electron carbon-carbon bond [5]<\/a><\/span><\/li>\n
  6. Hot MOF for capturing carbon[6]<\/a><\/span><\/li>\n<\/ol>\n

    The molecule shown below inside the cavity is coronene. A free energy barrier of ~13 kcal\/mol was determined using NMR peak coalescence temperatures, and inferred to correspond to the energy required to move the coronene from one end of the cavity to the other. Here I perform a simple reality check on this result using \u03c9B97XD\/Def2-SVP DFT calculations.[7]<\/a><\/span>,[8]<\/a><\/span>,[9]<\/a><\/span>. This functional includes a second generation dispersion correction, which is the primary effect controlling the position of the coronene inside the cavity.<\/p>\n

    Firstly, the fully optimised geometry of the complex.<\/p>\n

    \"\"<\/p>\n

    A spacefill representation shows the coronene is a perfect fit inside the cavity!<\/p>\n

    \"\"<\/p>\n

    An NCI analysis (non-covalent-interaction) shows the NCI region around the coronene providing the dispersion stabilisation of the complex. The red regions by the way are related to the Ir, which has very different NCI cut-offs compared to\u00a0C,N,O and shows up as an artefact.<\/p>\n

    \"\"<\/p>\n

    The barrier is induced by steric interactions between the coronene and the t-butyl groups attached to the edge of the cavitand, shown with a red arrow in the spacefill representation below.<\/p>\n

    \"\" \"\"<\/p>\n

    Here is the crunch, the calculated \u03c9B97XD\/Def2-SVP barrier is \u0394G\u2021<\/sup> 5.7 kcal\/mol, significantly less than the value of ~13 kcal\/mol measured for this dynamic process. But wait, another intermediate was located, shown below, now only 3.8 kcal\/mol above the structure shown above.\u00a0So the energy potential inside the cavity is more complex than just two minima and one transition state!<\/p>\n

    \"\"<\/p>\n

    What are we to make of the disparity between the measured NMR barrier for the shuttle to move from one end of the cavitand to the other and the calculated value? Well, the barrier is likely to mostly arise from dispersion interactions, thus making this molecule a very sensitive test of how accurately the dispersion interactions are being calculated. It is known that the \u03c9B97XD method does rather over-estimate these, and perhaps this is resulting in a barrier which is considerably too low? So this makes this molecule a useful test of potentially more-accurate dispersion corrected methods! The\u00a0B3LYP+GD3+BJ method for this barrier is 6.6 kcal\/mol [10]<\/a><\/span>,[11]<\/a><\/span>. When new dispersion methods become available, I might add these as well to see if a trend develops.<\/p>\n

    References<\/h2>\n
    1. S. Ib\u00e1\u00f1ez, P. Salv\u00e0, L.N. Dawe, and E. Peris, \"Guest\u2010Shuttling in a Nanosized Metallobox\", Angewandte Chemie International Edition<\/i>, vol. 63, 2024. https:\/\/doi.org\/10.1002\/anie.202318829<\/a>\n\n<\/li>\n
    2. Y. Wu, S. Aslani, H. Han, C. Tang, G. Wu, X. Li, H. Wu, C.L. Stern, Q. Guo, Y. Qiu, A.X. Chen, Y. Jiao, R. Zhang, A.H.G. David, D.W. Armstrong, and J. Fraser Stoddart, \"Mirror-image cyclodextrins\", Nature Synthesis<\/i>, vol. 3, pp. 698-706, 2024. https:\/\/doi.org\/10.1038\/s44160-024-00495-8<\/a>\n\n<\/li>\n
    3. L. McDermott, Z.G. Walters, S.A. French, A.M. Clark, J. Ding, A.V. Kelleghan, K.N. Houk, and N.K. Garg, \"A solution to the anti-Bredt olefin synthesis problem\", Science<\/i>, vol. 386, 2024. https:\/\/doi.org\/10.1126\/science.adq3519<\/a>\n\n<\/li>\n
    4. D.M. Driscoll, F.D. White, S. Pramanik, J.D. Einkauf, B. Ravel, D. Bykov, S. Roy, R.T. Mayes, L.H. Delmau, S.K. Cary, T. Dyke, A. Miller, M. Silveira, S.M. VanCleve, S.M. Davern, S. Jansone-Popova, I. Popovs, and A.S. Ivanov, \"Observation of a promethium complex in solution\", Nature<\/i>, vol. 629, pp. 819-823, 2024. https:\/\/doi.org\/10.1038\/s41586-024-07267-6<\/a>\n\n<\/li>\n
    5. T. Shimajiri, S. Kawaguchi, T. Suzuki, and Y. Ishigaki, \"Direct evidence for a carbon\u2013carbon one-electron \u03c3-bond\", Nature<\/i>, vol. 634, pp. 347-351, 2024. https:\/\/doi.org\/10.1038\/s41586-024-07965-1<\/a>\n\n<\/li>\n
    6. R.C. Rohde, K.M. Carsch, M.N. Dods, H.Z.H. Jiang, A.R. McIsaac, R.A. Klein, H. Kwon, S.L. Karstens, Y. Wang, A.J. Huang, J.W. Taylor, Y. Yabuuchi, N.V. Tkachenko, K.R. Meihaus, H. Furukawa, D.R. Yahne, K.E. Engler, K.C. Bustillo, A.M. Minor, J.A. Reimer, M. Head-Gordon, C.M. Brown, and J.R. Long, \"High-temperature carbon dioxide capture in a porous material with terminal zinc hydride sites\", Science<\/i>, vol. 386, pp. 814-819, 2024. https:\/\/doi.org\/10.1126\/science.adk5697<\/a>\n\n<\/li>\n
    7. H. Rzepa, \"Molecular shuttle, wB97XD\/Def2-svp, G = -8172.276752\", 2025. https:\/\/doi.org\/10.5281\/zenodo.14746877<\/a>\n\n<\/li>\n
    8. H. Rzepa, \"Molecular shuttle, wB97XD\/def2-svp TS half way point, E = -8175.3727 G = -8172.267664 DG = 5.7\", 2025. https:\/\/doi.org\/10.5281\/zenodo.14746910<\/a>\n\n<\/li>\n
    9. H. Rzepa, \"Molecular shuttle, wB97XD\/def2-svp TS half way point, (calcfc) optimisation G =-8172.270606 DG = 3.8\", 2025. https:\/\/doi.org\/10.5281\/zenodo.14746936<\/a>\n\n<\/li>\n
    10. H. Rzepa, \"Molecular shuttle, B3LYP+GD3+BJ\/Def2-svp, G = -8175.526700\", 2025. https:\/\/doi.org\/10.5281\/zenodo.14748031<\/a>\n\n<\/li>\n
    11. H. Rzepa, \"Molecular shuttle, B3LYP+GD3+BJ\/def2-svp TS half way point, -8175.516132 DG = 6.6\", 2025. https:\/\/doi.org\/10.5281\/zenodo.14748035<\/a>\n\n<\/li>\n<\/ol>\n\n<\/div> ","protected":false},"excerpt":{"rendered":"

      This is another in the C&E News list of candidates for the Molecule of the Year, Molecular shuttle in a box Mirror-image cyclodextrin Molecular shuttle in a box Rule-bending strained alkene First soluble promethium complex Single-electron carbon-carbon bond Hot MOF for capturing carbon The molecule shown below inside the cavity is coronene. A free energy […]<\/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":false,"_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":[4],"tags":[],"ppma_author":[2661],"class_list":["post-28233","post","type-post","status-publish","format-standard","hentry","category-interesting-chemistry"],"yoast_head":"\nMolecules of the Year 2024: Molecular shuttle in a box. - Henry Rzepa'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=28233\" \/>\n<meta property=\"og:locale\" content=\"en_GB\" \/>\n<meta property=\"og:type\" content=\"article\" \/>\n<meta property=\"og:title\" content=\"Molecules of the Year 2024: Molecular shuttle in a box. - Henry Rzepa's Blog\" \/>\n<meta property=\"og:description\" content=\"This is another in the C&E News list of candidates for the Molecule of the Year, Molecular shuttle in a box Mirror-image cyclodextrin Molecular shuttle in a box Rule-bending strained alkene First soluble promethium complex Single-electron carbon-carbon bond Hot MOF for capturing carbon The molecule shown below inside the cavity is coronene. A free energy […]\" \/>\n<meta property=\"og:url\" content=\"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=28233\" \/>\n<meta property=\"og:site_name\" content=\"Henry Rzepa's Blog\" \/>\n<meta property=\"article:published_time\" content=\"2025-01-25T08:34:07+00:00\" \/>\n<meta property=\"article:modified_time\" content=\"2025-01-27T13:28:02+00:00\" \/>\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=\"4 minutes\" \/>\n<!-- \/ Yoast SEO plugin. -->","yoast_head_json":{"title":"Molecules of the Year 2024: Molecular shuttle in a box. - Henry Rzepa'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=28233","og_locale":"en_GB","og_type":"article","og_title":"Molecules of the Year 2024: Molecular shuttle in a box. - Henry Rzepa's Blog","og_description":"This is another in the C&E News list of candidates for the Molecule of the Year, Molecular shuttle in a box Mirror-image cyclodextrin Molecular shuttle in a box Rule-bending strained alkene First soluble promethium complex Single-electron carbon-carbon bond Hot MOF for capturing carbon The molecule shown below inside the cavity is coronene. A free energy […]","og_url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=28233","og_site_name":"Henry Rzepa's Blog","article_published_time":"2025-01-25T08:34:07+00:00","article_modified_time":"2025-01-27T13:28:02+00:00","author":"Henry Rzepa","twitter_card":"summary_large_image","twitter_misc":{"Written by":"Henry Rzepa","Estimated reading time":"4 minutes"},"schema":{"@context":"https:\/\/schema.org","@graph":[{"@type":"Article","@id":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=28233#article","isPartOf":{"@id":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=28233"},"author":{"name":"Henry Rzepa","@id":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/#\/schema\/person\/2b40f7b9c872a4dc1547e040a11b6281"},"headline":"Molecules of the Year 2024: Molecular shuttle in a box.","datePublished":"2025-01-25T08:34:07+00:00","dateModified":"2025-01-27T13:28:02+00:00","mainEntityOfPage":{"@id":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=28233"},"wordCount":473,"commentCount":0,"image":{"@id":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=28233#primaryimage"},"thumbnailUrl":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2025\/01\/shuttle-complex.jpg","articleSection":["Interesting chemistry"],"inLanguage":"en-GB","potentialAction":[{"@type":"CommentAction","name":"Comment","target":["https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=28233#respond"]}]},{"@type":"WebPage","@id":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=28233","url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=28233","name":"Molecules of the Year 2024: Molecular shuttle in a box. - Henry Rzepa's Blog","isPartOf":{"@id":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/#website"},"primaryImageOfPage":{"@id":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=28233#primaryimage"},"image":{"@id":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=28233#primaryimage"},"thumbnailUrl":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2025\/01\/shuttle-complex.jpg","datePublished":"2025-01-25T08:34:07+00:00","dateModified":"2025-01-27T13:28:02+00:00","author":{"@id":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/#\/schema\/person\/2b40f7b9c872a4dc1547e040a11b6281"},"breadcrumb":{"@id":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=28233#breadcrumb"},"inLanguage":"en-GB","potentialAction":[{"@type":"ReadAction","target":["https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=28233"]}]},{"@type":"ImageObject","inLanguage":"en-GB","@id":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=28233#primaryimage","url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2025\/01\/shuttle-complex.jpg","contentUrl":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2025\/01\/shuttle-complex.jpg","width":1766,"height":907},{"@type":"BreadcrumbList","@id":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=28233#breadcrumb","itemListElement":[{"@type":"ListItem","position":1,"name":"Home","item":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog"},{"@type":"ListItem","position":2,"name":"Molecules of the Year 2024: Molecular shuttle in a box."}]},{"@type":"WebSite","@id":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/#website","url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/","name":"Henry Rzepa'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\/pDef7-7ln","jetpack-related-posts":[{"id":28187,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=28187","url_meta":{"origin":28233,"position":0},"title":"Molecules of the Year 2024: A crystal structure perspective on anti-Bredt olefins.","author":"Henry Rzepa","date":"January 8, 2025","format":false,"excerpt":"Each year C&E News publishes a list of candidates for the Molecule of the Year. For 2024 the list is (in order of votes cast for each) Mirror-image cyclodextrin Molecular shuttle in a box Rule-bending strained alkene First soluble promethium complex Single-electron carbon-carbon bond Hot MOF for capturing carbon I\u2026","rel":"","context":"In "Interesting chemistry"","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":26646,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=26646","url_meta":{"origin":28233,"position":1},"title":"Macrocyclic peptide antibiotics – now Zosurabalpin – then antibacterial agents based on cyclic D,L-\u03b1-peptide architectures.","author":"Henry Rzepa","date":"January 8, 2024","format":false,"excerpt":"Zosurabalbin,, is receiving a great deal of attention as a new class of antibiotic which can target infections for which\u00a0current treatment options are inadequate. It is a\u00a0cyclic peptide and seeing this triggered memory of an earlier such species reported way back in 1995,. This octa-peptide (YIJDIE, DOI: 10.5517\/cc58gxs) was presumed\u2026","rel":"","context":"Similar post","block_context":{"text":"Similar post","link":""},"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":28233,"position":2},"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 "crystal_structure_mining"","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":26601,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=26601","url_meta":{"origin":28233,"position":3},"title":"Molecules of the year: 2023","author":"Henry Rzepa","date":"December 28, 2023","format":false,"excerpt":"The Science education unit at the ACS publication C&EN publishes its list of molecules of the year (as selected by the editors and voted upon by the readers) in December. Here are some observations about three of this year's batch. Diberyllocene with its unusual Be-Be bond has already beeen covered\u2026","rel":"","context":"Similar post","block_context":{"text":"Similar post","link":""},"img":{"alt_text":"","src":"https:\/\/i0.wp.com\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2023\/12\/CF.gif?resize=350%2C200&ssl=1","width":350,"height":200},"classes":[]},{"id":2828,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=2828","url_meta":{"origin":28233,"position":4},"title":"Can a cyclobutadiene and carbon dioxide co-exist in a calixarene cavity?","author":"Henry Rzepa","date":"November 19, 2010","format":false,"excerpt":"On 8th August this year, I posted on a fascinating article that had just appeared in Science in which the crystal structure was reported of two small molecules,\u00a01,3-dimethyl cyclobutadiene\u00a0and\u00a0carbon dioxide, entrapped together inside a calixarene cavity. Other journals (e.g.\u00a0Nature Chemistry ran the article as a research highlight (where the purpose\u2026","rel":"","context":"In "Interesting chemistry"","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\/2010\/11\/cbd.jpg?resize=350%2C200","width":350,"height":200},"classes":[]},{"id":10733,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=10733","url_meta":{"origin":28233,"position":5},"title":"Is dicarbon (C2) a molecule of chemical interest?","author":"Henry Rzepa","date":"July 3, 2013","format":false,"excerpt":"C2\u00a0(dicarbon) is certainly interesting from a theoretical point of view. Whether or not it can be described as having a quadruple bond has induced much passionate discussion,,,. Its occurrence in space and in flames is also well-known. But does it have what might be called a conventional chemistry? Other highly\u2026","rel":"","context":"In "Interesting chemistry"","block_context":{"text":"Interesting chemistry","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?cat=4"},"img":{"alt_text":"Click for 3D","src":"https:\/\/i0.wp.com\/www.ch.imperial.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2013\/07\/LaOsC1.jpeg?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\/28233","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=28233"}],"version-history":[{"count":25,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=\/wp\/v2\/posts\/28233\/revisions"}],"predecessor-version":[{"id":28277,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=\/wp\/v2\/posts\/28233\/revisions\/28277"}],"wp:attachment":[{"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Fmedia&parent=28233"}],"wp:term":[{"taxonomy":"category","embeddable":true,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Fcategories&post=28233"},{"taxonomy":"post_tag","embeddable":true,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Ftags&post=28233"},{"taxonomy":"author","embeddable":true,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Fppma_author&post=28233"}],"curies":[{"name":"wp","href":"https:\/\/api.w.org\/{rel}","templated":true}]}}