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Cucurbit[n]urils (CB[n]) are among the most promising host molecules for direct biocompatible Xe encapsulation. Building on earlier observations that alkali cations influence the binding of Xe to CB[n], this study provides a comprehensive experimental and computational analysis of how the ratio of Na+ to K+ in the solution governs Xe uptake by CB[6] and CB[5]. Using one- and two-dimensional 129Xe NMR together with quantum-mechanical modeling, we elucidate the molecular mechanism by which alkali cations modulate cage Xe uptake. Our calculations reveal that Na+ can adopt a near-central position inside CB[6], directly competing with Xe for the hydrophobic core, thereby suppressing encapsulation. In contrast, K+ remains confined to peripheral portal sites, leaving the central cavity accessible, and enabling Xe to displace the cation and stabilize inside the cage. Elevated temperatures and cage\u2013cage competition further amplify these effects. By combining experimental and theoretical results, we thus provide the first detailed mechanistic explanation of Na+\/K+ competition in Xe-CB[n] systems, and establish clear design principles to optimize Xe hosts for future in vivo applications.<\/jats:p>","DOI":"10.1021\/jacs.6c09510","type":"journal-article","created":{"date-parts":[[2026,8,19]],"date-time":"2026-08-19T12:02:23Z","timestamp":1787140943000},"page":"36900-36911","source":"Crossref","is-referenced-by-count":1,"title":["Sodium\u2013Potassium\nCompetition Controls Xenon\nUptake in Cucurbiturils"],"prefix":"10.1021","volume":"148","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-4526-841X","authenticated-orcid":true,"given":"Katarzyna","family":"Dziubin\u0301ska-Ku\u0308hn","sequence":"first","affiliation":[{"name":"Maastricht University , , Paul-Henri Spaaklaan 1 , ,","place":["Maastricht, The Netherlands, 6229 EN"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-9661-3087","authenticated-orcid":true,"given":"Guzel","family":"Musabirova","sequence":"additional","affiliation":[{"name":"Leipzig University , , Linne\u0301stra\u00dfe 3 , ,","place":["Leipzig, Germany, 04103"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Sophie","family":"Effertz","sequence":"additional","affiliation":[{"name":"Leipzig University , , Linne\u0301stra\u00dfe 3 , ,","place":["Leipzig, Germany, 04103"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-8404-2421","authenticated-orcid":true,"given":"Luca","family":"Gerhards","sequence":"additional","affiliation":[{"name":"Carl von Ossietzky Universita\u0308t Oldenburg , , Carl-von-Ossietzky Str. 9-11 , ,","place":["Oldenburg, Germany, 26129"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-7800-7443","authenticated-orcid":true,"given":"Jo\u0308rg","family":"Matysik","sequence":"additional","affiliation":[{"name":"Leipzig University , , Linne\u0301stra\u00dfe 3 , ,","place":["Leipzig, Germany, 04103"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-8626-145X","authenticated-orcid":true,"given":"Ilia A.","family":"Solov\u2019yov","sequence":"additional","affiliation":[{"name":"Carl von Ossietzky Universita\u0308t Oldenburg , , Carl-von-Ossietzky Str. 9-11 , ,","place":["Oldenburg, Germany, 26129"]},{"name":"Carl von Ossietzky Universita\u0308t Oldenburg , , ,","place":["Oldenburg, Germany, 26111"]},{"name":"Carl von Ossietzky Universita\u0308t Oldenburg , , Ammerla\u0308nder Heerstr. 114-118 , ,","place":["Oldenburg, Germany, 26129"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-5167-0851","authenticated-orcid":true,"given":"Renaud B.","family":"Jolivet","sequence":"additional","affiliation":[{"name":"Maastricht University , , Paul-Henri Spaaklaan 1 , ,","place":["Maastricht, The Netherlands, 6229 EN"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2026,8,19]]},"reference":[{"key":"2026090312085436700_cit1","doi-asserted-by":"publisher","first-page":"199","DOI":"10.1038\/370199a0","article-title":"Biological\nmagnetic resonance imaging\nusing laser-polarized 129Xe","volume":"370","author":"Albert","year":"1994","journal-title":"Nature"},{"key":"2026090312085436700_cit2","doi-asserted-by":"publisher","first-page":"809","DOI":"10.1002\/mrm.1910370602","article-title":"MR imaging and spectroscopy using hyperpolarized 129Xe gas: Preliminary human results","volume":"37","author":"Mugler","year":"1997","journal-title":"Magn. 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Eur J."},{"key":"2026090312085436700_cit26","doi-asserted-by":"crossref","unstructured":"Lu, H.; Li, J.\n          The\nSolubility of Cucurbit[5]uril\nin Pure Water and Hydrochloric Acid at Different Temperature and Some\nRelative Thermodynamic Functions. In  Proceedings\nof the 5th International Conference on Information Engineering for\nMechanics and Materials; Atlantis Press, 2015.","DOI":"10.2991\/icimm-15.2015.50"},{"key":"2026090312085436700_cit27","doi-asserted-by":"publisher","first-page":"804","DOI":"10.1039\/b008623l","article-title":"NMR study of the reversible complexation of xenon by\ncucurbituril","volume":"2","author":"El Haouaj","year":"2001","journal-title":"J. Chem. 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Chem."},{"key":"2026090312085436700_cit31","doi-asserted-by":"publisher","first-page":"6083","DOI":"10.1039\/C2DT32180G","article-title":"DFT study\nof caesium ion complexation by cucurbit[n]urils (n = 5\u20137)","volume":"42","author":"Pichierri","year":"2013","journal-title":"Dalton Trans."},{"key":"2026090312085436700_cit32","doi-asserted-by":"publisher","first-page":"9224","DOI":"10.1021\/acs.jpca.8b08031","article-title":"Barriers for Extrusion\nof a Guest from the Interior\nBinding Cavity of a Host: Gas Phase Experimental and Computational\nResults for Ion-Capped Decamethylcucurbit[5]uril Complexes","volume":"122","author":"Hickenlooper","year":"2018","journal-title":"J. Phys. Chem. 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