Enhanced binding of methyl alkylammonium cations through preorganization of a water-soluble calix[4]pyrrole

We describe the synthesis of two tetra-α aryl-extended calix[4]pyrroles (C[4]Ps) 4a–b bearing four terminal carboxylic groups in their meso-propyl chains defining the lower rims. The synthesized C[4]Ps became soluble (1–3 mM) in water at pD = 10. We probed the interaction of 4a towards tetra-methyla...

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Detalles Bibliográficos
Autores: Valencia, Esteban, Ballester, Pablo
Tipo de recurso: artículo
Estado:Versión aceptada para publicación
Fecha de publicación:2024
País:España
Institución: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:2072/537733
Acceso en línea:http://hdl.handle.net/2072/537733
https://doi.org/10.1039/D4OB00843J
Access Level:acceso abierto
Palabra clave:Química
54 - Química
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spelling Enhanced binding of methyl alkylammonium cations through preorganization of a water-soluble calix[4]pyrroleValencia, EstebanBallester, PabloQuímica54 - QuímicaWe describe the synthesis of two tetra-α aryl-extended calix[4]pyrroles (C[4]Ps) 4a–b bearing four terminal carboxylic groups in their meso-propyl chains defining the lower rims. The synthesized C[4]Ps became soluble (1–3 mM) in water at pD = 10. We probed the interaction of 4a towards tetra-methylammonium (G1) chloride in water using 1H NMR spectroscopy. The C[4]P 4a includes G1 in the shallow aromatic cavity defined by the pyrrole rings in cone conformation forming a 1 : 1 complex G1⊂4a. Pyridine-N-oxide (PNO) binding in the larger polar aromatic cavity of 4a results in the quantitative self-assembly of the supramolecular receptor PNO@4a featuring the pyrrole rings preorganized in cone conformation. The PNO@4a receptor displays improved binding properties towards G1 than the parent C[4]P 4a. We thermodynamically characterized (1H NMR titrations and ITC experiments) the 1 : 1 complexes of PNO@4a with a series of tetra-alkylammonium salts, including biologically relevant examples. The PNO@4a supramolecular receptor displays significant affinity (log K = 3–4) but lacks selectivity in water binding of methyl trialkyl ammonium cations. Cation–π and coulombic interactions are the main intermolecular forces stabilizing the complexes. We also performed DFT calculations to gain some insights into the complexes’ structures.Royal Society of Chemistry2024info:eu-repo/semantics/articleinfo:eu-repo/semantics/acceptedVersion8 p.application/pdfhttp://hdl.handle.net/2072/537733https://doi.org/10.1039/D4OB00843JRECERCAT (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)InglésMinisterio de Ciencia e Innovación/Agencia Estatal de Investigación (MICIN/AEI/10.13039/501100011033; PID2020-114020GB-I00; CEX2019-000925-SCERCA Programme/Generalitat de CatalunyaAGAUR (2021SGR00851)ICIQ FoundationE.V. thanks MICIN for a predoctoral fellowship (PRE2021-098708) and the financial support from Ajuntament de la Canonja (La Canonja Green Educational and Scientific ProjectCC-BYinfo:eu-repo/semantics/openAccessoai:recercat.cat:2072/5377332026-05-29T05:05:01Z
dc.title.none.fl_str_mv Enhanced binding of methyl alkylammonium cations through preorganization of a water-soluble calix[4]pyrrole
title Enhanced binding of methyl alkylammonium cations through preorganization of a water-soluble calix[4]pyrrole
spellingShingle Enhanced binding of methyl alkylammonium cations through preorganization of a water-soluble calix[4]pyrrole
Valencia, Esteban
Química
54 - Química
title_short Enhanced binding of methyl alkylammonium cations through preorganization of a water-soluble calix[4]pyrrole
title_full Enhanced binding of methyl alkylammonium cations through preorganization of a water-soluble calix[4]pyrrole
title_fullStr Enhanced binding of methyl alkylammonium cations through preorganization of a water-soluble calix[4]pyrrole
title_full_unstemmed Enhanced binding of methyl alkylammonium cations through preorganization of a water-soluble calix[4]pyrrole
title_sort Enhanced binding of methyl alkylammonium cations through preorganization of a water-soluble calix[4]pyrrole
dc.creator.none.fl_str_mv Valencia, Esteban
Ballester, Pablo
author Valencia, Esteban
author_facet Valencia, Esteban
Ballester, Pablo
author_role author
author2 Ballester, Pablo
author2_role author
dc.subject.none.fl_str_mv Química
54 - Química
topic Química
54 - Química
description We describe the synthesis of two tetra-α aryl-extended calix[4]pyrroles (C[4]Ps) 4a–b bearing four terminal carboxylic groups in their meso-propyl chains defining the lower rims. The synthesized C[4]Ps became soluble (1–3 mM) in water at pD = 10. We probed the interaction of 4a towards tetra-methylammonium (G1) chloride in water using 1H NMR spectroscopy. The C[4]P 4a includes G1 in the shallow aromatic cavity defined by the pyrrole rings in cone conformation forming a 1 : 1 complex G1⊂4a. Pyridine-N-oxide (PNO) binding in the larger polar aromatic cavity of 4a results in the quantitative self-assembly of the supramolecular receptor PNO@4a featuring the pyrrole rings preorganized in cone conformation. The PNO@4a receptor displays improved binding properties towards G1 than the parent C[4]P 4a. We thermodynamically characterized (1H NMR titrations and ITC experiments) the 1 : 1 complexes of PNO@4a with a series of tetra-alkylammonium salts, including biologically relevant examples. The PNO@4a supramolecular receptor displays significant affinity (log K = 3–4) but lacks selectivity in water binding of methyl trialkyl ammonium cations. Cation–π and coulombic interactions are the main intermolecular forces stabilizing the complexes. We also performed DFT calculations to gain some insights into the complexes’ structures.
publishDate 2024
dc.date.none.fl_str_mv 2024
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/2072/537733
https://doi.org/10.1039/D4OB00843J
url http://hdl.handle.net/2072/537733
https://doi.org/10.1039/D4OB00843J
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv Ministerio de Ciencia e Innovación/Agencia Estatal de Investigación (MICIN/AEI/10.13039/501100011033; PID2020-114020GB-I00; CEX2019-000925-S
CERCA Programme/Generalitat de Catalunya
AGAUR (2021SGR00851)
ICIQ Foundation
E.V. thanks MICIN for a predoctoral fellowship (PRE2021-098708) and the financial support from Ajuntament de la Canonja (La Canonja Green Educational and Scientific Project
dc.rights.none.fl_str_mv CC-BY
info:eu-repo/semantics/openAccess
rights_invalid_str_mv CC-BY
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv 8 p.
application/pdf
dc.publisher.none.fl_str_mv Royal Society of Chemistry
publisher.none.fl_str_mv Royal Society of Chemistry
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
repository.name.fl_str_mv
repository.mail.fl_str_mv
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score 15,811543

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