Mathai Mammen

Found throughout biology, polyvalent interactions are characterized by the simultaneous binding of multiple ligands on one biological entity to multiple receptors on another (top part of the illustration) and have a number of characteristics that monovalent interactions do not (bottom). In particular, polyvalent interactions can be collectively much stronger than corresponding monovalent interactions, and they can provide the basis for mechanisms of both agonizing and antagonizing biological interactions that are fundamentally different from those available in monovalent systems.

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTNoncovalent Synthesis: Using Physical-Organic Chemistry To Make AggregatesGeorge M. Whitesides, Eric E. Simanek, John P. Mathias, Christopher T. Seto, Donovan Chin, Mathai Mammen, and Dana M. GordonCite this: Acc. Chem. Res. 1995, 28, 1, 37–44Publication Date (Print):January 1, 1995Publication History Published online1 May 2002Published inissue 1 January 1995https://pubs.acs.org/doi/10.1021/ar00049a006https://doi.org/10.1021/ar00049a006research-articleACS PublicationsRequest reuse permissionsArticle Views3607Altmetric-Citations913LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose Get e-Alerts

Überall in der Biologie kommen polyvalente Wechselwirkungen vor. Sie zeichnen sich durch die gleichzeitige Bindung mehrerer Liganden einer biologischen Einheit an mehrere Rezeptoren einer anderen biologischen Einheit aus (oberer Teil der Graphik) und haben eine Reihe von Charakteristika, die monovalenten Wechselwirkungen fehlen (unten). Besonders im Verbund können polyvalente Wechselwirkungen viel stärker sein als entsprechende monovalente Wechselwirkungen, und sie können die Basis für das Verständnis fördernder und hemmender biologischer Wechselwirkungen liefern, die sich grundsätzlich von denen in monovalenten Systemen unterscheiden.

The entropic component of the free energy of assembly for multiparticle hydrogen-bonded aggregates is analyzed using a model based on balls connected by rigid rods or flexible strings. The entropy of assembly, ΔS, is partitioned into translational, rotational, vibrational, and conformational components. While previously reported theoretical treatments of rotational and vibrational entropies for assembly are adequate, treatments of translational entropy in solution and of conformational entropyoften the two largest components of ΔSare not. This paper provides improved estimates and illustrates the methods used to obtain them. First, a model is described for translational entropy of molecules in solution (ΔStrans(sol)); this model provides physically intuitive corrections for values of ΔStrans(sol) that are based on the Sackur−Tetrode equation. This model is combined with one for rotational entropy to estimate the difference in entropy of assembly between a 4-particle aggregate and a 6-particle one. Second, an approximate analysis of a model based on balls connected by rods or strings gives an approximate estimate of the maximum contribution of conformational entropy to the difference in free energy of assembly of flexible and of rigid molecular assemblies. This analysis, although approximate, is easily applied by all types of chemists and biochemists; it serves as a guide to the design of stable molecular aggregates, and the qualitative arguments apply generally to any form of self-assembly.