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Face‐Fusion of Icosahedral Boron Hydride Increases Affinity to γ‐Cyclodextrin: closo,closo‐[B(21)H(18)](−) as an Anion with Very Low Free Energy of Dehydration

The supramolecular recognition of closo,closo‐[B(21)H(18)](−) by cyclodextrins (CDs) has been studied in aqueous solution by isothermal titration calorimetry and nuclear magnetic resonance spectroscopy. These solution studies follow up on previous mass‐spectrometric measurements and computations, wh...

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Autores principales: Assaf, Khaleel I., Holub, Josef, Bernhardt, Eduard, Oliva‐Enrich, Josep M., Fernández Pérez, M. Isabel, Canle, Moisés, Santaballa, J. Arturo, Fanfrlík, Jindřich, Hnyk, Drahomír, Nau, Werner M.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: John Wiley and Sons Inc. 2020
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7318346/
https://www.ncbi.nlm.nih.gov/pubmed/32163219
http://dx.doi.org/10.1002/cphc.201901225
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author Assaf, Khaleel I.
Holub, Josef
Bernhardt, Eduard
Oliva‐Enrich, Josep M.
Fernández Pérez, M. Isabel
Canle, Moisés
Santaballa, J. Arturo
Fanfrlík, Jindřich
Hnyk, Drahomír
Nau, Werner M.
author_facet Assaf, Khaleel I.
Holub, Josef
Bernhardt, Eduard
Oliva‐Enrich, Josep M.
Fernández Pérez, M. Isabel
Canle, Moisés
Santaballa, J. Arturo
Fanfrlík, Jindřich
Hnyk, Drahomír
Nau, Werner M.
author_sort Assaf, Khaleel I.
collection PubMed
description The supramolecular recognition of closo,closo‐[B(21)H(18)](−) by cyclodextrins (CDs) has been studied in aqueous solution by isothermal titration calorimetry and nuclear magnetic resonance spectroscopy. These solution studies follow up on previous mass‐spectrometric measurements and computations, which indicated the formation and stability of CD ⋅ B(21)H(18) (−) complexes in the gas phase. The thermodynamic signature of solution‐phase binding is exceptional, the association constant for the γ‐CD complex with B(21)H(18) (−) reaches 1.8×10(6) M(−1), which is on the same order of magnitude as the so far highest observed value for the complex between γ‐CD and a metallacarborane. The nature of the intermolecular interaction is also examined by quantum‐mechanical computational protocols. These suggest that the desolvation penalty, which is particularly low for the B(21)H(18) (−) anion, is the decisive factor for its high binding strength. The results further suggest that the elliptical macropolyhedral boron hydride is another example of a CD binder, whose extraordinary binding affinity is driven by the chaotropic effect, which describes the intrinsic affinity of large polarizable and weakly solvated chaotropic anions to hydrophobic cavities and surfaces in aqueous solution.
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spelling pubmed-73183462020-06-29 Face‐Fusion of Icosahedral Boron Hydride Increases Affinity to γ‐Cyclodextrin: closo,closo‐[B(21)H(18)](−) as an Anion with Very Low Free Energy of Dehydration Assaf, Khaleel I. Holub, Josef Bernhardt, Eduard Oliva‐Enrich, Josep M. Fernández Pérez, M. Isabel Canle, Moisés Santaballa, J. Arturo Fanfrlík, Jindřich Hnyk, Drahomír Nau, Werner M. Chemphyschem Communications The supramolecular recognition of closo,closo‐[B(21)H(18)](−) by cyclodextrins (CDs) has been studied in aqueous solution by isothermal titration calorimetry and nuclear magnetic resonance spectroscopy. These solution studies follow up on previous mass‐spectrometric measurements and computations, which indicated the formation and stability of CD ⋅ B(21)H(18) (−) complexes in the gas phase. The thermodynamic signature of solution‐phase binding is exceptional, the association constant for the γ‐CD complex with B(21)H(18) (−) reaches 1.8×10(6) M(−1), which is on the same order of magnitude as the so far highest observed value for the complex between γ‐CD and a metallacarborane. The nature of the intermolecular interaction is also examined by quantum‐mechanical computational protocols. These suggest that the desolvation penalty, which is particularly low for the B(21)H(18) (−) anion, is the decisive factor for its high binding strength. The results further suggest that the elliptical macropolyhedral boron hydride is another example of a CD binder, whose extraordinary binding affinity is driven by the chaotropic effect, which describes the intrinsic affinity of large polarizable and weakly solvated chaotropic anions to hydrophobic cavities and surfaces in aqueous solution. John Wiley and Sons Inc. 2020-04-07 2020-05-18 /pmc/articles/PMC7318346/ /pubmed/32163219 http://dx.doi.org/10.1002/cphc.201901225 Text en © 2020 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the http://creativecommons.org/licenses/by/4.0/ License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.
spellingShingle Communications
Assaf, Khaleel I.
Holub, Josef
Bernhardt, Eduard
Oliva‐Enrich, Josep M.
Fernández Pérez, M. Isabel
Canle, Moisés
Santaballa, J. Arturo
Fanfrlík, Jindřich
Hnyk, Drahomír
Nau, Werner M.
Face‐Fusion of Icosahedral Boron Hydride Increases Affinity to γ‐Cyclodextrin: closo,closo‐[B(21)H(18)](−) as an Anion with Very Low Free Energy of Dehydration
title Face‐Fusion of Icosahedral Boron Hydride Increases Affinity to γ‐Cyclodextrin: closo,closo‐[B(21)H(18)](−) as an Anion with Very Low Free Energy of Dehydration
title_full Face‐Fusion of Icosahedral Boron Hydride Increases Affinity to γ‐Cyclodextrin: closo,closo‐[B(21)H(18)](−) as an Anion with Very Low Free Energy of Dehydration
title_fullStr Face‐Fusion of Icosahedral Boron Hydride Increases Affinity to γ‐Cyclodextrin: closo,closo‐[B(21)H(18)](−) as an Anion with Very Low Free Energy of Dehydration
title_full_unstemmed Face‐Fusion of Icosahedral Boron Hydride Increases Affinity to γ‐Cyclodextrin: closo,closo‐[B(21)H(18)](−) as an Anion with Very Low Free Energy of Dehydration
title_short Face‐Fusion of Icosahedral Boron Hydride Increases Affinity to γ‐Cyclodextrin: closo,closo‐[B(21)H(18)](−) as an Anion with Very Low Free Energy of Dehydration
title_sort face‐fusion of icosahedral boron hydride increases affinity to γ‐cyclodextrin: closo,closo‐[b(21)h(18)](−) as an anion with very low free energy of dehydration
topic Communications
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7318346/
https://www.ncbi.nlm.nih.gov/pubmed/32163219
http://dx.doi.org/10.1002/cphc.201901225
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