{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,4,1]],"date-time":"2026-04-01T03:10:16Z","timestamp":1775013016812,"version":"3.50.1"},"reference-count":34,"publisher":"MDPI AG","issue":"11","license":[{"start":{"date-parts":[[2020,6,8]],"date-time":"2020-06-08T00:00:00Z","timestamp":1591574400000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"DOI":"10.13039\/501100001809","name":"National Natural Science Foundation of China","doi-asserted-by":"publisher","award":["21673239"],"award-info":[{"award-number":["21673239"]}],"id":[{"id":"10.13039\/501100001809","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100001809","name":"National Natural Science Foundation of China","doi-asserted-by":"publisher","award":["21501179"],"award-info":[{"award-number":["21501179"]}],"id":[{"id":"10.13039\/501100001809","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100001809","name":"National Natural Science Foundation of China","doi-asserted-by":"publisher","award":["21531008"],"award-info":[{"award-number":["21531008"]}],"id":[{"id":"10.13039\/501100001809","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100003392","name":"Natural Science Foundation of Fujian Province","doi-asserted-by":"publisher","award":["2017J06008"],"award-info":[{"award-number":["2017J06008"]}],"id":[{"id":"10.13039\/501100003392","id-type":"DOI","asserted-by":"publisher"}]},{"name":"Strategic Priority Research Program of the Chinese Academy of Sciences","award":["Grant XDB20000000"],"award-info":[{"award-number":["Grant XDB20000000"]}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Molecules"],"abstract":"<jats:p>The cooperative binding behavior of a face-directed octahedral metal-organic supercontainer featuring one endo cavity and six exo cavities was thoroughly examined in chloroform solution through ultraviolet-visible (UV-Vis) titration technique using two representative drug molecules as the guests. The titration curves and their nonlinear fit to Hill equation strongly suggest the efficient encapsulation of the guest molecules by the synthetic host, which exhibit interesting cooperative and stepwise binding behavior. Based on the control experiments using tetranuclear complex as a reference, it is clear that two equivalents of the guest molecules are initially encapsulated inside the endo cavity, followed by the trapping of six additional equivalents of the drug molecules through six exo cavities (1 eq. per exo cavity), and the remaining guests are entrapped by the external pockets. The results provide an in-depth understanding of the cooperative binding behavior of metal-organic supercontainers, which opens up new opportunities for designing synthetic receptors for truly biomimetic functional applications.<\/jats:p>","DOI":"10.3390\/molecules25112656","type":"journal-article","created":{"date-parts":[[2020,6,9]],"date-time":"2020-06-09T08:49:11Z","timestamp":1591692551000},"page":"2656","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":14,"title":["Cooperative Binding and Stepwise Encapsulation of Drug Molecules by Sulfonylcalixarene-Based Metal-Organic Supercontainers"],"prefix":"10.3390","volume":"25","author":[{"given":"Tian-Pu","family":"Sheng","sequence":"first","affiliation":[{"name":"State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, Fujian, China"},{"name":"University of Chinese Academy of Sciences, Beijing 100049, China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Xin-Xia","family":"Fan","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, Fujian, China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Guo-Zong","family":"Zheng","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, Fujian, China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Feng-Rong","family":"Dai","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, Fujian, China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Zhong-Ning","family":"Chen","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, Fujian, China"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"1968","published-online":{"date-parts":[[2020,6,8]]},"reference":[{"key":"ref_1","unstructured":"Fersht, A. (1999). Structure and Mechanism in Protein Science, W. H. Freeman and Company."},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"435","DOI":"10.1038\/nchembio0808-435","article-title":"Cooperativity and biological complexity","volume":"4","author":"Whitty","year":"2008","journal-title":"Nat. Chem. Biol."},{"key":"ref_3","doi-asserted-by":"crossref","first-page":"458","DOI":"10.1038\/nchembio.102","article-title":"Cooperativity in macromolecular assembly","volume":"4","author":"Williamson","year":"2008","journal-title":"Nat. Chem. Biol."},{"key":"ref_4","doi-asserted-by":"crossref","unstructured":"Stephan, D.W., and Erker, G. (2015). Frustrated Lewis Pair Chemistry: Development and Perspectives. Angew. Chem. Int. Ed., 6400\u20136441.","DOI":"10.1002\/anie.201409800"},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"1762","DOI":"10.1002\/anie.201004201","article-title":"Allosteric, Chelate, and Interannular Cooperativity: A Mise au Point","volume":"50","author":"Ercolani","year":"2011","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"7488","DOI":"10.1002\/anie.200902490","article-title":"What is Cooperativity?","volume":"48","author":"Hunter","year":"2009","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_7","doi-asserted-by":"crossref","first-page":"1295","DOI":"10.1110\/ps.03259908","article-title":"Allostery and cooperativity revisited","volume":"17","author":"Cui","year":"2008","journal-title":"Protein Sci. A Publ. Protein Soc."},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"723","DOI":"10.1021\/ar040223k","article-title":"Multivalency and cooperativity in supramolecular chemistry","volume":"38","author":"Badjic","year":"2005","journal-title":"Acc. Chem. Res."},{"key":"ref_9","doi-asserted-by":"crossref","first-page":"4755","DOI":"10.1002\/anie.200460398","article-title":"Allosterically driven multicomponent assembly","volume":"43","author":"Thordarson","year":"2004","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"10340","DOI":"10.1021\/ja503506a","article-title":"A multi-state, allosterically-regulated molecular receptor with switchable selectivity","volume":"136","author":"Lifschitz","year":"2014","journal-title":"J. Am. Chem. Soc."},{"key":"ref_11","doi-asserted-by":"crossref","first-page":"14004","DOI":"10.1021\/ja1063789","article-title":"A Coordination Cage with an Adaptable Cavity Size","volume":"132","author":"Mirtschin","year":"2010","journal-title":"J. Am. Chem. Soc."},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"3374","DOI":"10.1002\/chem.201203751","article-title":"Size-selective encapsulation of hydrophobic guests by self-assembled M4L6 cobalt and nickel cages","volume":"19","author":"Ronson","year":"2013","journal-title":"Chem. Eur. J."},{"key":"ref_13","doi-asserted-by":"crossref","first-page":"35","DOI":"10.1007\/128_2011_272","article-title":"Drug Delivery by Water-Soluble Organometallic Cages","volume":"319","author":"Therrien","year":"2012","journal-title":"Top. Curr. Chem."},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"14394","DOI":"10.1039\/C5DT01526J","article-title":"Structure modeling, synthesis and X-ray diffraction determination of an extra-large calixarene-based coordination cage and its application in drug delivery","volume":"44","author":"Du","year":"2015","journal-title":"Dalton Trans."},{"key":"ref_15","doi-asserted-by":"crossref","first-page":"106","DOI":"10.1016\/j.ccr.2016.07.007","article-title":"Supramolecular nanoreactors for catalysis","volume":"324","author":"Deraedt","year":"2016","journal-title":"Coord. Chem. Rev."},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"251","DOI":"10.1126\/science.1124985","article-title":"Diels-alder in aqueous molecular hosts: Unusual regioselectivity and efficient catalysis","volume":"312","author":"Yoshizawa","year":"2006","journal-title":"Science"},{"key":"ref_17","doi-asserted-by":"crossref","first-page":"5291","DOI":"10.1021\/cr050565j","article-title":"Thiacalixarenes","volume":"106","author":"Morohashi","year":"2006","journal-title":"Chem. Rev."},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"8002","DOI":"10.1021\/ja300095j","article-title":"Modular Assembly of Metal\u2013Organic Supercontainers Incorporating Sulfonylcalixarenes","volume":"134","author":"Dai","year":"2012","journal-title":"J. Am. Chem. Soc."},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"10965","DOI":"10.1002\/anie.201406733","article-title":"pH-Modulated Molecular Assemblies and Surface Properties of Metal\u2013Organic Supercontainers at the Air\u2013Water Interface","volume":"53","author":"Netzer","year":"2014","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_20","doi-asserted-by":"crossref","first-page":"7480","DOI":"10.1021\/ja502839b","article-title":"Synthetic Supercontainers Exhibit Distinct Solution versus Solid State Guest-Binding Behavior","volume":"136","author":"Dai","year":"2014","journal-title":"J. Am. Chem. Soc."},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"5385","DOI":"10.1039\/C3CC47420H","article-title":"Modulating guest binding in sulfonylcalixarene-based metal-organic supercontainers","volume":"50","author":"Dai","year":"2014","journal-title":"Chem. Commun."},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"243","DOI":"10.1039\/C5QI00212E","article-title":"Designing structurally tunable and functionally versatile synthetic supercontainers","volume":"3","author":"Dai","year":"2016","journal-title":"Inorg. Chem. Front."},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"6580","DOI":"10.1002\/chem.201705210","article-title":"Sensitive and Specific Guest Recognition through Pyridinium-Modification in Spindle-Like Coordination Containers","volume":"24","author":"Bhuvaneswari","year":"2018","journal-title":"Chem. A Eur. J."},{"key":"ref_24","doi-asserted-by":"crossref","first-page":"23559","DOI":"10.1039\/C7TA05797K","article-title":"Pyridinium functionalized coordination containers as highly efficient electrocatalysts for sustainable oxygen evolution","volume":"5","author":"Bhuvaneswari","year":"2017","journal-title":"J. Mater. Chem. A"},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"61","DOI":"10.1016\/j.inoche.2017.03.005","article-title":"Engineering solid-state porosity of synthetic supercontainers via modification of exo-cavities","volume":"78","author":"Cheng","year":"2017","journal-title":"Inorg. Chem. Commun."},{"key":"ref_26","doi-asserted-by":"crossref","first-page":"61","DOI":"10.1016\/j.ccr.2014.06.011","article-title":"Thiacalixarene-based nanoscale polyhedral coordination cages","volume":"276","author":"Bi","year":"2014","journal-title":"Coord. Chem. Rev."},{"key":"ref_27","doi-asserted-by":"crossref","first-page":"1585","DOI":"10.1002\/anie.201106732","article-title":"Calixarene-Based Nanoscale Coordination Cages","volume":"51","author":"Liu","year":"2012","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_28","doi-asserted-by":"crossref","first-page":"2321","DOI":"10.1039\/c2sc20264f","article-title":"Truncated octahedral coordination cage incorporating six tetranuclear-metal building blocks and twelve linear edges","volume":"3","author":"Xiong","year":"2012","journal-title":"Chem. Sci."},{"key":"ref_29","doi-asserted-by":"crossref","first-page":"16236","DOI":"10.1021\/jacs.6b11218","article-title":"Ultrafine Pt Nanoclusters Confined in a Calixarene-Based {Ni24} Coordination Cage for High-Efficient Hydrogen Evolution Reaction","volume":"138","author":"Wang","year":"2016","journal-title":"J. Am. Chem. Soc."},{"key":"ref_30","doi-asserted-by":"crossref","first-page":"1765","DOI":"10.1002\/ejic.200501086","article-title":"Highly symmetrical tetranuclear cluster complexes supported by p-tert-butylsulfonylcalix[4]arene as a cluster-forming ligand","volume":"9","author":"Kajiwara","year":"2006","journal-title":"Eur. J. Inorg. Chem."},{"key":"ref_31","doi-asserted-by":"crossref","unstructured":"Schalley, C.A. (2012). Analytical Methods in Supramolecular Chemistry, Wiley.","DOI":"10.1002\/9783527644131"},{"key":"ref_32","doi-asserted-by":"crossref","unstructured":"Bisswanger, H. (2008). Enzyme Kinetics: Principles and Methods, Wiley. [2nd ed.].","DOI":"10.1002\/9783527622023"},{"key":"ref_33","first-page":"iv","article-title":"The possible effects of the aggregation of the molecules of h\u00e6moglobin on its dissociation curves","volume":"40","author":"Hill","year":"1910","journal-title":"J. Physiol."},{"key":"ref_34","doi-asserted-by":"crossref","first-page":"829","DOI":"10.1021\/ed1000125","article-title":"Measuring Binding Affinity of Protein-Ligand Interaction Using Spectrophotometry: Binding of Neutral Red to Riboflavin-Binding Protein","volume":"87","author":"Chenprakhon","year":"2010","journal-title":"J. Chem. Educ."}],"container-title":["Molecules"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/1420-3049\/25\/11\/2656\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,11]],"date-time":"2025-10-11T09:36:35Z","timestamp":1760175395000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/1420-3049\/25\/11\/2656"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2020,6,8]]},"references-count":34,"journal-issue":{"issue":"11","published-online":{"date-parts":[[2020,6]]}},"alternative-id":["molecules25112656"],"URL":"https:\/\/doi.org\/10.3390\/molecules25112656","relation":{},"ISSN":["1420-3049"],"issn-type":[{"value":"1420-3049","type":"electronic"}],"subject":[],"published":{"date-parts":[[2020,6,8]]}}}