Quantification of the Hydrophobic Effect Using Water-Soluble Super Aryl-Extended Calix[4]pyrroles

We describe the syntheses of the tetra-α isomers of three unprecedented super aryl-extended calix[4]pyrroles (SAE-C[4]Ps) functionalized with either eight carboxylic acids, eight pyridinium or eight 1-methyl-1H-imidazolium ions. The functional groups are located at the terminal positions of the four...

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Detalhes bibliográficos
Autores: Escobar, Luis, Ballester, Pablo
Formato: artículo
Estado:Versión aceptada para publicación
Fecha de publicación:2019
País:España
Recursos:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
Repositorio:Recercat. Dipósit de la Recerca de Catalunya
OAI Identifier:oai:recercat.cat:2072/357523
Acesso em linha:http://hdl.handle.net/2072/357523
https://doi.org/10.1039/C9QO00171A
Access Level:acceso abierto
Palavra-chave:54
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spelling Quantification of the Hydrophobic Effect Using Water-Soluble Super Aryl-Extended Calix[4]pyrrolesEscobar, LuisBallester, Pablo54We describe the syntheses of the tetra-α isomers of three unprecedented super aryl-extended calix[4]pyrroles (SAE-C[4]Ps) functionalized with either eight carboxylic acids, eight pyridinium or eight 1-methyl-1H-imidazolium ions. The functional groups are located at the terminal positions of the four meso-aryl (upper rim) and four meso-alkyl (lower rim) substituents. The synthesized SAE-C[4]Ps are soluble in neutral or basic water solutions at mM concentrations. The cavity of the receptors is suitable for the inclusion of sizeable polar guests. We report the results of the binding studies of a series of pyridyl N-oxides, having a non-polar para-substituent, with the SAE-C[4]P receptors in water using 1H NMR spectroscopy titrations and isothermal titration calorimetry (ITC) experiments. The receptors formed thermodynamically and kinetically stable 1:1 inclusion complexes with the N-oxide derivatives, featuring binding constant values larger than 105 M-1. We demonstrate the existence of linear relationships between the free energies of binding of the inclusion complexes and the surface area of the non-polar substituent of the guests. The slopes of the linear regressions provide quantitative values for the hydrophobic effect (33-38 cal·mol-1·Å-2) in the binding of non-polar residues. The energy values derived for the hydrophobic effect using these simple host-guest systems are in line with those reported from studies of site-directed mutagenesis of protein residues and the transfer of solutes from non-polar solvents to water2019info:eu-repo/semantics/articleinfo:eu-repo/semantics/acceptedVersion1738 p.application/mswordhttp://hdl.handle.net/2072/357523https://doi.org/10.1039/C9QO00171ARECERCAT (Dipòsit de la Recerca de Catalunya)reponame:Recercat. Dipósit de la Recerca de Catalunyainstname:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)InglésL'accés als continguts d'aquest document queda condicionat a l'acceptació de les condicions d'ús establertes per la següent llicència Creative Commons:http://creativecommons.org/licenses/by-nc-nd/4.0/info:eu-repo/semantics/openAccessoai:recercat.cat:2072/3575232026-05-29T05:05:01Z
dc.title.none.fl_str_mv Quantification of the Hydrophobic Effect Using Water-Soluble Super Aryl-Extended Calix[4]pyrroles
title Quantification of the Hydrophobic Effect Using Water-Soluble Super Aryl-Extended Calix[4]pyrroles
spellingShingle Quantification of the Hydrophobic Effect Using Water-Soluble Super Aryl-Extended Calix[4]pyrroles
Escobar, Luis
54
title_short Quantification of the Hydrophobic Effect Using Water-Soluble Super Aryl-Extended Calix[4]pyrroles
title_full Quantification of the Hydrophobic Effect Using Water-Soluble Super Aryl-Extended Calix[4]pyrroles
title_fullStr Quantification of the Hydrophobic Effect Using Water-Soluble Super Aryl-Extended Calix[4]pyrroles
title_full_unstemmed Quantification of the Hydrophobic Effect Using Water-Soluble Super Aryl-Extended Calix[4]pyrroles
title_sort Quantification of the Hydrophobic Effect Using Water-Soluble Super Aryl-Extended Calix[4]pyrroles
dc.creator.none.fl_str_mv Escobar, Luis
Ballester, Pablo
author Escobar, Luis
author_facet Escobar, Luis
Ballester, Pablo
author_role author
author2 Ballester, Pablo
author2_role author
dc.subject.none.fl_str_mv 54
topic 54
description We describe the syntheses of the tetra-α isomers of three unprecedented super aryl-extended calix[4]pyrroles (SAE-C[4]Ps) functionalized with either eight carboxylic acids, eight pyridinium or eight 1-methyl-1H-imidazolium ions. The functional groups are located at the terminal positions of the four meso-aryl (upper rim) and four meso-alkyl (lower rim) substituents. The synthesized SAE-C[4]Ps are soluble in neutral or basic water solutions at mM concentrations. The cavity of the receptors is suitable for the inclusion of sizeable polar guests. We report the results of the binding studies of a series of pyridyl N-oxides, having a non-polar para-substituent, with the SAE-C[4]P receptors in water using 1H NMR spectroscopy titrations and isothermal titration calorimetry (ITC) experiments. The receptors formed thermodynamically and kinetically stable 1:1 inclusion complexes with the N-oxide derivatives, featuring binding constant values larger than 105 M-1. We demonstrate the existence of linear relationships between the free energies of binding of the inclusion complexes and the surface area of the non-polar substituent of the guests. The slopes of the linear regressions provide quantitative values for the hydrophobic effect (33-38 cal·mol-1·Å-2) in the binding of non-polar residues. The energy values derived for the hydrophobic effect using these simple host-guest systems are in line with those reported from studies of site-directed mutagenesis of protein residues and the transfer of solutes from non-polar solvents to water
publishDate 2019
dc.date.none.fl_str_mv 2019
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/acceptedVersion
format article
status_str acceptedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/2072/357523
https://doi.org/10.1039/C9QO00171A
url http://hdl.handle.net/2072/357523
https://doi.org/10.1039/C9QO00171A
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv 1738 p.
application/msword
dc.source.none.fl_str_mv RECERCAT (Dipòsit de la Recerca de Catalunya)
reponame:Recercat. Dipósit de la Recerca de Catalunya
instname:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
instname_str Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
reponame_str Recercat. Dipósit de la Recerca de Catalunya
collection Recercat. Dipósit de la Recerca de Catalunya
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repository.mail.fl_str_mv
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