Supramolecular Chemistry Controlled by Conformational Space during Structure Direction of Nanoporous Materials: Self-Assembly of Ephedrine and Pseudoephedrine

In an attempt to produce chiral solids, where chirality arises from an asymmetric ordering of the spatial distribution of dopants, we have studied the supramolecular aggregation of π–π-type interactions between aromatic rings of two closely related diastereoisomers, (1R,2S)-ephedrine and (1S,2S)-pse...

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Detalhes bibliográficos
Autores: Bernardo-Maestro, Beatriz, López-Arbeloa, Fernando, Pérez-Pariente, Joaquín, Gómez-Hortigüela Sainz, Luis
Tipo de documento: artigo
Estado:Versión aceptada para publicación
Data de publicação:2015
País:España
Recursos:Consejo Superior de Investigaciones Científicas (CSIC)
Repositório:DIGITAL.CSIC. Repositorio Institucional del CSIC
OAI Identifier:oai:digital.csic.es:10261/162409
Acesso em linha:http://hdl.handle.net/10261/162409
Access Level:Acceso aberto
Palavra-chave:Zeolite
Ephedrine
Supramolecular
Self-assembly
Chirality
Conformation
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spelling Supramolecular Chemistry Controlled by Conformational Space during Structure Direction of Nanoporous Materials: Self-Assembly of Ephedrine and PseudoephedrineBernardo-Maestro, BeatrizLópez-Arbeloa, FernandoPérez-Pariente, JoaquínGómez-Hortigüela Sainz, LuisZeoliteEphedrineSupramolecularSelf-assemblyChiralityConformationIn an attempt to produce chiral solids, where chirality arises from an asymmetric ordering of the spatial distribution of dopants, we have studied the supramolecular aggregation of π–π-type interactions between aromatic rings of two closely related diastereoisomers, (1R,2S)-ephedrine and (1S,2S)-pseudoephedrine, during structure direction of the microporous AFI large-pore aluminophosphate framework. Despite their very similar molecular structures, differing only in the stereochemistry of the hydroxyl substituent, fluorescence spectroscopy clearly shows completely different aggregation behaviors of the two isomers, with ephedrine displaying a much stronger aggregation trend than pseudoephedrine in aqueous solution; interestingly, this supramolecular behavior is reproduced when the molecules are occluded within the AFI framework during crystallization. A molecular mechanics study of the conformational behavior of the two chiral flexible molecules, both in a vacuum and in aqueous solution, revealed that the lower trend of pseudoephedrine to form supramolecular aggregates is caused by the occurrence of a particular conformation with a folded molecular structure. This conformation, which is stable for pseudoephedrine but not for ephedrine, provokes steric hindrance that prevents the approaching of a neighboring molecule to form an aggregate, hence providing an explanation for the experimental observations. Our work represents the first example in which the conformational space of a molecule determines its supramolecular aggregation behavior during structure direction and could play a role in molecular-recognition phenomena in host–guest systems.The research leading to these results received funding from the Spanish Ministry of Economy and Innovation MINECO (MAT2012-31127). L.G.-H. and B.B.-M. acknowledge the Spanish Ministry of Economy and Competitivity for Ramón y Cajal (RYC-2012-11794) and predoctoral (BES-2013-064605) contracts, respectively.Peer reviewedAmerican Chemical SocietyMinisterio de Economía y Competitividad (España)Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]201820182015info:eu-repo/semantics/articlehttp://purl.org/coar/resource_type/c_6501Postprintinfo:eu-repo/semantics/acceptedVersionhttp://hdl.handle.net/10261/162409reponame:DIGITAL.CSIC. Repositorio Institucional del CSICinstname:Consejo Superior de Investigaciones Científicas (CSIC)Ingléshttp://dx.doi.org/10.1021/acs.jpcc.5b10016Síinfo:eu-repo/semantics/openAccessoai:digital.csic.es:10261/1624092026-05-22T06:33:51Z
dc.title.none.fl_str_mv Supramolecular Chemistry Controlled by Conformational Space during Structure Direction of Nanoporous Materials: Self-Assembly of Ephedrine and Pseudoephedrine
title Supramolecular Chemistry Controlled by Conformational Space during Structure Direction of Nanoporous Materials: Self-Assembly of Ephedrine and Pseudoephedrine
spellingShingle Supramolecular Chemistry Controlled by Conformational Space during Structure Direction of Nanoporous Materials: Self-Assembly of Ephedrine and Pseudoephedrine
Bernardo-Maestro, Beatriz
Zeolite
Ephedrine
Supramolecular
Self-assembly
Chirality
Conformation
title_short Supramolecular Chemistry Controlled by Conformational Space during Structure Direction of Nanoporous Materials: Self-Assembly of Ephedrine and Pseudoephedrine
title_full Supramolecular Chemistry Controlled by Conformational Space during Structure Direction of Nanoporous Materials: Self-Assembly of Ephedrine and Pseudoephedrine
title_fullStr Supramolecular Chemistry Controlled by Conformational Space during Structure Direction of Nanoporous Materials: Self-Assembly of Ephedrine and Pseudoephedrine
title_full_unstemmed Supramolecular Chemistry Controlled by Conformational Space during Structure Direction of Nanoporous Materials: Self-Assembly of Ephedrine and Pseudoephedrine
title_sort Supramolecular Chemistry Controlled by Conformational Space during Structure Direction of Nanoporous Materials: Self-Assembly of Ephedrine and Pseudoephedrine
dc.creator.none.fl_str_mv Bernardo-Maestro, Beatriz
López-Arbeloa, Fernando
Pérez-Pariente, Joaquín
Gómez-Hortigüela Sainz, Luis
author Bernardo-Maestro, Beatriz
author_facet Bernardo-Maestro, Beatriz
López-Arbeloa, Fernando
Pérez-Pariente, Joaquín
Gómez-Hortigüela Sainz, Luis
author_role author
author2 López-Arbeloa, Fernando
Pérez-Pariente, Joaquín
Gómez-Hortigüela Sainz, Luis
author2_role author
author
author
dc.contributor.none.fl_str_mv Ministerio de Economía y Competitividad (España)
Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]
dc.subject.none.fl_str_mv Zeolite
Ephedrine
Supramolecular
Self-assembly
Chirality
Conformation
topic Zeolite
Ephedrine
Supramolecular
Self-assembly
Chirality
Conformation
description In an attempt to produce chiral solids, where chirality arises from an asymmetric ordering of the spatial distribution of dopants, we have studied the supramolecular aggregation of π–π-type interactions between aromatic rings of two closely related diastereoisomers, (1R,2S)-ephedrine and (1S,2S)-pseudoephedrine, during structure direction of the microporous AFI large-pore aluminophosphate framework. Despite their very similar molecular structures, differing only in the stereochemistry of the hydroxyl substituent, fluorescence spectroscopy clearly shows completely different aggregation behaviors of the two isomers, with ephedrine displaying a much stronger aggregation trend than pseudoephedrine in aqueous solution; interestingly, this supramolecular behavior is reproduced when the molecules are occluded within the AFI framework during crystallization. A molecular mechanics study of the conformational behavior of the two chiral flexible molecules, both in a vacuum and in aqueous solution, revealed that the lower trend of pseudoephedrine to form supramolecular aggregates is caused by the occurrence of a particular conformation with a folded molecular structure. This conformation, which is stable for pseudoephedrine but not for ephedrine, provokes steric hindrance that prevents the approaching of a neighboring molecule to form an aggregate, hence providing an explanation for the experimental observations. Our work represents the first example in which the conformational space of a molecule determines its supramolecular aggregation behavior during structure direction and could play a role in molecular-recognition phenomena in host–guest systems.
publishDate 2015
dc.date.none.fl_str_mv 2015
2018
2018
dc.type.none.fl_str_mv info:eu-repo/semantics/article
http://purl.org/coar/resource_type/c_6501
Postprint
info:eu-repo/semantics/acceptedVersion
format article
status_str acceptedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/10261/162409
url http://hdl.handle.net/10261/162409
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv http://dx.doi.org/10.1021/acs.jpcc.5b10016
Sí
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
dc.publisher.none.fl_str_mv American Chemical Society
publisher.none.fl_str_mv American Chemical Society
dc.source.none.fl_str_mv reponame:DIGITAL.CSIC. Repositorio Institucional del CSIC
instname:Consejo Superior de Investigaciones Científicas (CSIC)
instname_str Consejo Superior de Investigaciones Científicas (CSIC)
reponame_str DIGITAL.CSIC. Repositorio Institucional del CSIC
collection DIGITAL.CSIC. Repositorio Institucional del CSIC
repository.name.fl_str_mv
repository.mail.fl_str_mv
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score 15,811543

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