title: Looking for the Origin of Allosteric Cooperativity in Metallopolymers.
abstract: The basic concept of allosteric cooperativity used in biology, chemistry and physics states that any change in the intermolecular host-guest interactions operating in multisite receptors can be assigned to intersite interactions. Using lanthanide metals as guests and linear multi-tridentate linear oligomers of variable lengths and geometries as hosts, this work shows that the quantitative modeling of metal loadings requires the consideration of a novel phenomenon originating from solvation processes. It stepwise modulates the intrinsic affinity of each isolated site in multisite receptors, and this without resorting to allosteric cooperativity. An easy-to-handle additive model predicts a negative power law dependence of the intrinsic affinity on the length of the linear metallopolymer. Applied to lanthanidopolymers, the latter common analysis overestimates cooperativity factors by more than two orders of magnitude.
authors.affiliation: Department of Inorganic, Analytical and Applied Chemistry, University of Geneva, 30 quai E. Ansermet, 1211, Geneva 4, Switzerland.
authors.forename: Lucille
authors.initials: L
authors.lastname: Babel
authors.affiliation: Department of Inorganic, Analytical and Applied Chemistry, University of Geneva, 30 quai E. Ansermet, 1211, Geneva 4, Switzerland.
authors.forename: Thi Nhu Y
authors.initials: TN
authors.lastname: Hoang
authors.affiliation: Laboratory of Crystallography, University of Geneva, 24 quai E. Ansermet, 1211, Geneva 4, Switzerland.
authors.forename: Laure
authors.initials: L
authors.lastname: Guénée
authors.affiliation: Laboratory of Crystallography, University of Geneva, 24 quai E. Ansermet, 1211, Geneva 4, Switzerland.
authors.forename: Céline
authors.initials: C
authors.lastname: Besnard
authors.affiliation: Department Physical Chemistry, University of Geneva, 30 quai E. Ansermet, 1211, Geneva 4, Switzerland.
authors.forename: Tomasz A
authors.initials: TA
authors.lastname: Wesolowski
authors.affiliation: Department Physical Chemistry, University of Geneva, 30 quai E. Ansermet, 1211, Geneva 4, Switzerland.
authors.forename: Marie
authors.initials: M
authors.lastname: Humbert-Droz
authors.affiliation: Department of Inorganic, Analytical and Applied Chemistry, University of Geneva, 30 quai E. Ansermet, 1211, Geneva 4, Switzerland. Claude.Piguet@unige.ch.
authors.forename: Claude
authors.initials: C
authors.lastname: Piguet
keywords: cooperativity; host-guest systems; lanthanides; metallopolymers; solvation