Cyclobutane scaffold in bolaamphiphiles
Cationic bolaamphiphiles have been synthesized starting from meso cis- or chiral trans-1,2-difunctionalized cyclobutane derivatives. They include cis/trans pairs of diastereoisomers, of N- or C-centered bisamides. The goal of this work was to investigate the influence of stereochemistry and regioche...
| Autores: | , , , , , , |
|---|---|
| Formato: | artículo |
| Fecha de publicación: | 2018 |
| País: | España |
| Recursos: | Universitat Autònoma de Barcelona |
| Repositorio: | Dipòsit Digital de Documents de la UAB |
| Idioma: | inglés |
| OAI Identifier: | oai:ddd.uab.cat:274087 |
| Acesso em linha: | https://ddd.uab.cat/record/274087 https://dx.doi.org/urn:doi:10.1021/acs.langmuir.8b01462 |
| Access Level: | acceso abierto |
| Palavra-chave: | Surfactant SAXS Cyclobutane Bolaamphiphile Aggregation Diastereoisomerism Regiochemistry |
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Cyclobutane scaffold in bolaamphiphilesEffect of diastereoisomerism and regiochemistry on their surface activity aggregate structurePi i Boleda, Bernat|||0000-0003-1050-6788Sorrenti, AlessandroSans, MartaIlla, Ona|||0000-0001-7390-4893Pons, Ramon|||0000-0003-4273-9084Branchadell, Vicenç|||0000-0003-3480-1669Ortuño Mingarro, Rosa María|||0000-0001-7635-7354SurfactantSAXSCyclobutaneBolaamphiphileAggregationDiastereoisomerismRegiochemistryCationic bolaamphiphiles have been synthesized starting from meso cis- or chiral trans-1,2-difunctionalized cyclobutane derivatives. They include cis/trans pairs of diastereoisomers, of N- or C-centered bisamides. The goal of this work was to investigate the influence of stereochemistry and regiochemistry on their abilities as surfactants and self-assembly. Very large differences in surface coverage (2-fold), critical micellar concentration (cmc, up to 2 orders of magnitude), and aggregate structure (from lamellae to fibers) for the four molecules are remarkable due to regio- and stereochemistry differences. Computational calculations were carried out to rationalize the experimental findings and a new methodology has been developed to calculate the structure of these bolaamphiphiles at the surface. Although the four surfactants adopt a wicket-like conformation, for N-centered trans, the distance between polar heads is much larger than that for the other three molecules, as suggested by calculations. We have shown that the interplay between the regiochemistry and stereoisomerism, enhanced by rigidity of the cyclobutane ring, affects different physicochemical properties quite differently. That is, the cmc value is mainly governed by stereochemistry, with regiochemistry only modulating this value. On the other hand, regiochemistry definitely governs the morphology of the supramolecular aggregates (i.e., long fibers versus plates or spherical assemblies), with stereochemistry finely modulating their structural parameters. All these results must help in the rational design of new bolaamphiphiles with predictable properties and useful potential applications. 22018-01-0120182018-01-01Articlehttp://purl.org/coar/resource_type/c_6501AMhttp://purl.org/coar/version/c_ab4af688f83e57aainfo:eu-repo/semantics/articleapplication/pdfhttps://ddd.uab.cat/record/274087https://dx.doi.org/urn:doi:10.1021/acs.langmuir.8b01462reponame:Dipòsit Digital de Documents de la UABinstname:Universitat Autònoma de BarcelonaInglésengAgencia Estatal de Investigación https://doi.org/10.13039/501100011033 CTQ2016-77978-RAgencia Estatal de Investigación https://doi.org/10.13039/501100011033 CTQ2017-88948-Popen accesshttp://purl.org/coar/access_right/c_abf2Aquest material està protegit per drets d'autor i/o drets afins. Podeu utilitzar aquest material en funció del que permet la legislació de drets d'autor i drets afins d'aplicació al vostre cas. Per a d'altres usos heu d'obtenir permís del(s) titular(s) de drets.https://rightsstatements.org/vocab/InC/1.0/info:eu-repo/semantics/openAccessoai:ddd.uab.cat:2740872026-06-06T12:50:31Z |
| dc.title.none.fl_str_mv |
Cyclobutane scaffold in bolaamphiphiles Effect of diastereoisomerism and regiochemistry on their surface activity aggregate structure |
| title |
Cyclobutane scaffold in bolaamphiphiles |
| spellingShingle |
Cyclobutane scaffold in bolaamphiphiles Pi i Boleda, Bernat|||0000-0003-1050-6788 Surfactant SAXS Cyclobutane Bolaamphiphile Aggregation Diastereoisomerism Regiochemistry |
| title_short |
Cyclobutane scaffold in bolaamphiphiles |
| title_full |
Cyclobutane scaffold in bolaamphiphiles |
| title_fullStr |
Cyclobutane scaffold in bolaamphiphiles |
| title_full_unstemmed |
Cyclobutane scaffold in bolaamphiphiles |
| title_sort |
Cyclobutane scaffold in bolaamphiphiles |
| dc.creator.none.fl_str_mv |
Pi i Boleda, Bernat|||0000-0003-1050-6788 Sorrenti, Alessandro Sans, Marta Illa, Ona|||0000-0001-7390-4893 Pons, Ramon|||0000-0003-4273-9084 Branchadell, Vicenç|||0000-0003-3480-1669 Ortuño Mingarro, Rosa María|||0000-0001-7635-7354 |
| author |
Pi i Boleda, Bernat|||0000-0003-1050-6788 |
| author_facet |
Pi i Boleda, Bernat|||0000-0003-1050-6788 Sorrenti, Alessandro Sans, Marta Illa, Ona|||0000-0001-7390-4893 Pons, Ramon|||0000-0003-4273-9084 Branchadell, Vicenç|||0000-0003-3480-1669 Ortuño Mingarro, Rosa María|||0000-0001-7635-7354 |
| author_role |
author |
| author2 |
Sorrenti, Alessandro Sans, Marta Illa, Ona|||0000-0001-7390-4893 Pons, Ramon|||0000-0003-4273-9084 Branchadell, Vicenç|||0000-0003-3480-1669 Ortuño Mingarro, Rosa María|||0000-0001-7635-7354 |
| author2_role |
author author author author author author |
| dc.subject.none.fl_str_mv |
Surfactant SAXS Cyclobutane Bolaamphiphile Aggregation Diastereoisomerism Regiochemistry |
| topic |
Surfactant SAXS Cyclobutane Bolaamphiphile Aggregation Diastereoisomerism Regiochemistry |
| description |
Cationic bolaamphiphiles have been synthesized starting from meso cis- or chiral trans-1,2-difunctionalized cyclobutane derivatives. They include cis/trans pairs of diastereoisomers, of N- or C-centered bisamides. The goal of this work was to investigate the influence of stereochemistry and regiochemistry on their abilities as surfactants and self-assembly. Very large differences in surface coverage (2-fold), critical micellar concentration (cmc, up to 2 orders of magnitude), and aggregate structure (from lamellae to fibers) for the four molecules are remarkable due to regio- and stereochemistry differences. Computational calculations were carried out to rationalize the experimental findings and a new methodology has been developed to calculate the structure of these bolaamphiphiles at the surface. Although the four surfactants adopt a wicket-like conformation, for N-centered trans, the distance between polar heads is much larger than that for the other three molecules, as suggested by calculations. We have shown that the interplay between the regiochemistry and stereoisomerism, enhanced by rigidity of the cyclobutane ring, affects different physicochemical properties quite differently. That is, the cmc value is mainly governed by stereochemistry, with regiochemistry only modulating this value. On the other hand, regiochemistry definitely governs the morphology of the supramolecular aggregates (i.e., long fibers versus plates or spherical assemblies), with stereochemistry finely modulating their structural parameters. All these results must help in the rational design of new bolaamphiphiles with predictable properties and useful potential applications. |
| publishDate |
2018 |
| dc.date.none.fl_str_mv |
2 2018-01-01 2018 2018-01-01 |
| dc.type.none.fl_str_mv |
Article http://purl.org/coar/resource_type/c_6501 AM http://purl.org/coar/version/c_ab4af688f83e57aa |
| dc.type.openaire.fl_str_mv |
info:eu-repo/semantics/article |
| format |
article |
| dc.identifier.none.fl_str_mv |
https://ddd.uab.cat/record/274087 https://dx.doi.org/urn:doi:10.1021/acs.langmuir.8b01462 |
| url |
https://ddd.uab.cat/record/274087 https://dx.doi.org/urn:doi:10.1021/acs.langmuir.8b01462 |
| dc.language.none.fl_str_mv |
Inglés eng |
| language_invalid_str_mv |
Inglés |
| language |
eng |
| dc.relation.none.fl_str_mv |
Agencia Estatal de Investigación https://doi.org/10.13039/501100011033 CTQ2016-77978-R Agencia Estatal de Investigación https://doi.org/10.13039/501100011033 CTQ2017-88948-P |
| dc.rights.none.fl_str_mv |
open access http://purl.org/coar/access_right/c_abf2 https://rightsstatements.org/vocab/InC/1.0/ |
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info:eu-repo/semantics/openAccess |
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open access http://purl.org/coar/access_right/c_abf2 https://rightsstatements.org/vocab/InC/1.0/ |
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openAccess |
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application/pdf |
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reponame:Dipòsit Digital de Documents de la UAB instname:Universitat Autònoma de Barcelona |
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Universitat Autònoma de Barcelona |
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Dipòsit Digital de Documents de la UAB |
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Dipòsit Digital de Documents de la UAB |
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