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The Role of Packing, Dispersion, Electrostatics, and Solvation in High‐Affinity Complexes of Cucurbit[n]urils with Uncharged Polar Guests

The rationalization of non‐covalent binding trends is both of fundamental interest and provides new design concepts for biomimetic molecular systems. Cucurbit[n]urils (CBn) are known for a long time as the strongest synthetic binders for a wide range of (bio)organic compounds in water. However, thei...

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Autores principales: Grimm, Laura M., Spicher, Sebastian, Tkachenko, Boryslav, Schreiner, Peter R., Grimme, Stefan, Biedermann, Frank
Formato: Online Artículo Texto
Lenguaje:English
Publicado: John Wiley and Sons Inc. 2022
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9401061/
https://www.ncbi.nlm.nih.gov/pubmed/35612260
http://dx.doi.org/10.1002/chem.202200529
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author Grimm, Laura M.
Spicher, Sebastian
Tkachenko, Boryslav
Schreiner, Peter R.
Grimme, Stefan
Biedermann, Frank
author_facet Grimm, Laura M.
Spicher, Sebastian
Tkachenko, Boryslav
Schreiner, Peter R.
Grimme, Stefan
Biedermann, Frank
author_sort Grimm, Laura M.
collection PubMed
description The rationalization of non‐covalent binding trends is both of fundamental interest and provides new design concepts for biomimetic molecular systems. Cucurbit[n]urils (CBn) are known for a long time as the strongest synthetic binders for a wide range of (bio)organic compounds in water. However, their host‐guest binding mechanism remains ambiguous despite their symmetric and simple macrocyclic structure and the wealth of literature reports. We herein report experimental thermodynamic binding parameters (ΔG, ΔH, TΔS) for CB7 and CB8 with a set of hydroxylated adamantanes, di‐, and triamantanes as uncharged, rigid, and spherical/ellipsoidal guests. Binding geometries and binding energy decomposition were obtained from high‐level theory computations. This study reveals that neither London dispersion interactions, nor electronic energies or entropic factors are decisive, selectivity‐controlling factors for CBn complexes. In contrast, peculiar host‐related solvation effects were identified as the major factor for rationalizing the unique behavior and record‐affinity characteristics of cucurbit[n]urils.
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spelling pubmed-94010612022-08-26 The Role of Packing, Dispersion, Electrostatics, and Solvation in High‐Affinity Complexes of Cucurbit[n]urils with Uncharged Polar Guests Grimm, Laura M. Spicher, Sebastian Tkachenko, Boryslav Schreiner, Peter R. Grimme, Stefan Biedermann, Frank Chemistry Research Articles The rationalization of non‐covalent binding trends is both of fundamental interest and provides new design concepts for biomimetic molecular systems. Cucurbit[n]urils (CBn) are known for a long time as the strongest synthetic binders for a wide range of (bio)organic compounds in water. However, their host‐guest binding mechanism remains ambiguous despite their symmetric and simple macrocyclic structure and the wealth of literature reports. We herein report experimental thermodynamic binding parameters (ΔG, ΔH, TΔS) for CB7 and CB8 with a set of hydroxylated adamantanes, di‐, and triamantanes as uncharged, rigid, and spherical/ellipsoidal guests. Binding geometries and binding energy decomposition were obtained from high‐level theory computations. This study reveals that neither London dispersion interactions, nor electronic energies or entropic factors are decisive, selectivity‐controlling factors for CBn complexes. In contrast, peculiar host‐related solvation effects were identified as the major factor for rationalizing the unique behavior and record‐affinity characteristics of cucurbit[n]urils. John Wiley and Sons Inc. 2022-05-25 2022-07-06 /pmc/articles/PMC9401061/ /pubmed/35612260 http://dx.doi.org/10.1002/chem.202200529 Text en © 2022 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH https://creativecommons.org/licenses/by/4.0/This is an open access article under the terms of the http://creativecommons.org/licenses/by/4.0/ (https://creativecommons.org/licenses/by/4.0/) License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.
spellingShingle Research Articles
Grimm, Laura M.
Spicher, Sebastian
Tkachenko, Boryslav
Schreiner, Peter R.
Grimme, Stefan
Biedermann, Frank
The Role of Packing, Dispersion, Electrostatics, and Solvation in High‐Affinity Complexes of Cucurbit[n]urils with Uncharged Polar Guests
title The Role of Packing, Dispersion, Electrostatics, and Solvation in High‐Affinity Complexes of Cucurbit[n]urils with Uncharged Polar Guests
title_full The Role of Packing, Dispersion, Electrostatics, and Solvation in High‐Affinity Complexes of Cucurbit[n]urils with Uncharged Polar Guests
title_fullStr The Role of Packing, Dispersion, Electrostatics, and Solvation in High‐Affinity Complexes of Cucurbit[n]urils with Uncharged Polar Guests
title_full_unstemmed The Role of Packing, Dispersion, Electrostatics, and Solvation in High‐Affinity Complexes of Cucurbit[n]urils with Uncharged Polar Guests
title_short The Role of Packing, Dispersion, Electrostatics, and Solvation in High‐Affinity Complexes of Cucurbit[n]urils with Uncharged Polar Guests
title_sort role of packing, dispersion, electrostatics, and solvation in high‐affinity complexes of cucurbit[n]urils with uncharged polar guests
topic Research Articles
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9401061/
https://www.ncbi.nlm.nih.gov/pubmed/35612260
http://dx.doi.org/10.1002/chem.202200529
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