ArticleProceedings of the National Academy of Sciences of the United States of America2006
Cooperativity in the self-assembly of porphyrin ladders.
Article in Proceedings of the National Academy of Sciences of the United States of America, 2006. The graph could read no effect estimate from its abstract, so it casts no vote on the map. Cited by 9 papers.
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Who cites it
9 citing papers in PubMed, 66 citations in OpenAlex.
- Assembly and Functionality of 2D Protein Arrays.Advanced science (Weinheim, Baden-Wurttemberg, Germany) · 2025Review
- Duplex-forming oligocarbamates with tunable nonbonding sites.Chemical science · 2024Article
- Simplicity in the Design, Operation, and Applications of Mechanically Interlocked Molecular Machines.ACS central science · 2020Review
- Thermodynamic insights into the entropically driven self-assembly of amphiphilic dyes in water.Chemical science · 2019Article
- Multivalence cooperativity leading to "all-or-nothing" assembly: the case of nucleation-growth in supramolecular polymers.Chemical science · 2016Article
- Analysis of cooperativity by isothermal titration calorimetry.International journal of molecular sciences · 2009Review
- Molecular recognition and self-assembly special feature: Supramolecular polymer formed by reversible self-assembly of tetrakisporphyrin.Proceedings of the National Academy of Sciences of the United States of America · 2009Article
- Protein allostery, signal transmission and dynamics: a classification scheme of allosteric mechanisms.Molecular bioSystems · 2009Review
- Allostery: absence of a change in shape does not imply that allostery is not at play.Journal of molecular biology · 2008Review
Corrections and comments
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Authors and funding
3 authors at 2 institutions in 2 countries.
Funding
No grant is acknowledged in the PubMed record.
Abstract
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 "enthalpic chelate effect" 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.mol(-1) and constant over a range of free energies of self-assembly of -35 to -111 kJ.mol(-1). 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.
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