{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,1,9]],"date-time":"2026-01-09T12:25:18Z","timestamp":1767961518299,"version":"3.49.0"},"reference-count":36,"publisher":"Proceedings of the National Academy of Sciences","issue":"9","content-domain":{"domain":["www.pnas.org"],"crossmark-restriction":true},"short-container-title":["Proc. Natl. Acad. Sci. U.S.A."],"published-print":{"date-parts":[[2006,2,28]]},"abstract":"<jats:p>\n            Cooperativity is a general feature of intermolecular interactions in biomolecular systems, but there are many different facets of the phenomenon that are not well understood. Positive cooperativity stabilizes a system as progressively more interactions are added, and the origin of the beneficial free energy may be entropic or enthalpic in origin. An \u201centhalpic chelate effect\u201d has been proposed to operate through structural tightening that improves all of the functional group interactions in a complex, when it is more strongly bound. Here, we present direct calorimetric evidence that no such enthalpic effects exist in the cooperative assembly of supramolecular ladder complexes composed of metalloporphyrin oligomers coordinated to bipyridine ligands. The enthalpic contributions of the individual coordination interactions are 35 kJ\u00b7mol\n            <jats:sup>\u22121<\/jats:sup>\n            and constant over a range of free energies of self-assembly of \u221235 to \u2212111 kJ\u00b7mol\n            <jats:sup>\u22121<\/jats:sup>\n            . In rigid well defined systems of this type, the enthalpies of individual interactions are additive, and no enthalpic cooperative effects are apparent. The implication is that in more flexible, less well defined systems such as biomolecular assemblies, the enthalpy contributions available from specific functional group interactions are well defined and constant parameters.\n          <\/jats:p>","DOI":"10.1073\/pnas.0508071103","type":"journal-article","created":{"date-parts":[[2006,2,22]],"date-time":"2006-02-22T04:03:47Z","timestamp":1140581027000},"page":"3034-3038","update-policy":"https:\/\/doi.org\/10.1073\/pnas.cm10313","source":"Crossref","is-referenced-by-count":65,"title":["Cooperativity in the self-assembly of porphyrin ladders"],"prefix":"10.1073","volume":"103","author":[{"given":"Amaya","family":"Camara-Campos","sequence":"first","affiliation":[{"name":"Centre for Chemical Biology, Krebs Institute for Biomolecular Science, Department of Chemistry, University of Sheffield, Sheffield S3 7HF, United Kingdom"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Christopher 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