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Wetting the lock and key enthalpically favours polyelectrolyte binding

By using a combination of readily accessible experimental and computational experiments in water, we explored the factors governing the association between polyanionic dyn[4]arene and a series of α,ω-alkyldiammonium ions of increasing chain length. We found that the lock-and-key concept based on the...

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Detalles Bibliográficos
Autores principales: Jeamet, Emeric, Septavaux, Jean, Héloin, Alexandre, Donnier-Maréchal, Marion, Dumartin, Melissa, Ourri, Benjamin, Mandal, Pradeep, Huc, Ivan, Bignon, Emmanuelle, Dumont, Elise, Morell, Christophe, Francoia, Jean-Patrick, Perret, Florent, Vial, Laurent, Leclaire, Julien
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Royal Society of Chemistry 2018
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6335637/
https://www.ncbi.nlm.nih.gov/pubmed/30746081
http://dx.doi.org/10.1039/c8sc02966k
Descripción
Sumario:By using a combination of readily accessible experimental and computational experiments in water, we explored the factors governing the association between polyanionic dyn[4]arene and a series of α,ω-alkyldiammonium ions of increasing chain length. We found that the lock-and-key concept based on the best match between the apolar and polar regions of the molecular partners failed to explain the observed selectivities. Instead, the dissection of the energetic and structural contributions demonstrated that the binding events were actually guided by two crucial solvent-related phenomena as the chain length of the guest increases: the expected decrease of the enthalpic cost of guest desolvation and the unexpected increase of the favourable enthalpy of complex solvation. By bringing to light the decisive enthalpic impact of complex solvation during the binding of polyelectrolytes by inclusion, this study may provide a missing piece to a puzzle that one day could display the global picture of molecular recognition in water.