A1 Refereed original research article in a scientific journal
Catenanes from catenanes: quantitative assessment of cooperativity in dynamic combinatorial catenation
Authors: Li JW, Nowak P, Fanlo-Virgos H, Otto S
Publisher: ROYAL SOC CHEMISTRY
Publication year: 2014
Journal: Chemical Science
Journal name in source: CHEMICAL SCIENCE
Journal acronym: CHEM SCI
Volume: 5
Issue: 12
First page : 4968
Last page: 4974
Number of pages: 7
ISSN: 2041-6520
DOI: https://doi.org/10.1039/c4sc01998a
Abstract
A new azobenzene-based dithiol building block was developed which, upon oxidation, forms predominantly a [2]catenane consisting of two interlocked trimers. In the presence of cyclodextrin templates a series of [2] and [3]catenanes was formed instead. We developed a method that enabled estimating the equilibrium constants for catenation in all of these systems. The formation of the [3]catenanes is either cooperative or anticooperative, depending on the nature of the cyclodextrin. Using molecular dynamics simulations, we linked positive and negative cooperativity to, respectively, burying and exposure of hydrophobic surfaces upon catenation. Our results underline the importance of directly quantifying noncovalent interactions within catenanes, as the corresponding pseudo-rotaxane model systems were found to be poor predictors of binding interactions in the actual catenane.
A new azobenzene-based dithiol building block was developed which, upon oxidation, forms predominantly a [2]catenane consisting of two interlocked trimers. In the presence of cyclodextrin templates a series of [2] and [3]catenanes was formed instead. We developed a method that enabled estimating the equilibrium constants for catenation in all of these systems. The formation of the [3]catenanes is either cooperative or anticooperative, depending on the nature of the cyclodextrin. Using molecular dynamics simulations, we linked positive and negative cooperativity to, respectively, burying and exposure of hydrophobic surfaces upon catenation. Our results underline the importance of directly quantifying noncovalent interactions within catenanes, as the corresponding pseudo-rotaxane model systems were found to be poor predictors of binding interactions in the actual catenane.
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