Chiral pH-sensitive cyclobutane beta-amino acid-based cationic amphiphiles

Chiral cis/trans diastereomeric cationic amphiphiles have been synthesized and studied. They are based on beta-amino acids and contain C-12- and C-16-alkyl chains, respectively, as hydrophobic tails while the polar head consists of an ammonium cation linked to a cyclobutane ring. Their physicochemic...

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Autores: Pi i Boleda, Bernat|||0000-0003-1050-6788, Bouzas, Mireia, Gaztelumendi, Nerea|||0000-0002-3837-2956, Illa, Ona|||0000-0001-7390-4893, Nogués, Carme|||0000-0002-6361-8559, Branchadell, Vicenç|||0000-0003-3480-1669, Pons, Ramon|||0000-0003-4273-9084, Ortuño Mingarro, Rosa María|||0000-0001-7635-7354
Tipo de recurso: artículo
Fecha de publicación:2020
País:España
Institución:Universitat Autònoma de Barcelona
Repositorio:Dipòsit Digital de Documents de la UAB
Idioma:inglés
OAI Identifier:oai:ddd.uab.cat:274089
Acceso en línea:https://ddd.uab.cat/record/274089
https://dx.doi.org/urn:doi:10.1016/j.molliq.2019.111856
Access Level:acceso abierto
Palabra clave:Density-Functional Theory
Cis/Trans Stereochemistry
Gemini Surfactants
Aggregation
Transfection
Transition
Titration
Micelles
Bromide
Systems
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spelling Chiral pH-sensitive cyclobutane beta-amino acid-based cationic amphiphilesPossible candidates for use in gene therapyPi i Boleda, Bernat|||0000-0003-1050-6788Bouzas, MireiaGaztelumendi, Nerea|||0000-0002-3837-2956Illa, Ona|||0000-0001-7390-4893Nogués, Carme|||0000-0002-6361-8559Branchadell, Vicenç|||0000-0003-3480-1669Pons, Ramon|||0000-0003-4273-9084Ortuño Mingarro, Rosa María|||0000-0001-7635-7354Density-Functional TheoryCis/Trans StereochemistryGemini SurfactantsAggregationTransfectionTransitionTitrationMicellesBromideSystemsChiral cis/trans diastereomeric cationic amphiphiles have been synthesized and studied. They are based on beta-amino acids and contain C-12- and C-16-alkyl chains, respectively, as hydrophobic tails while the polar head consists of an ammonium cation linked to a cyclobutane ring. Their physicochemical properties, such as the cmc (critical micellar concentration), the pK(a), the ratio of cationic versus non-ionic species, and the surface tension are strongly dependent on the pH of the medium. At the same time the aggregation state influences on the apparent pK(a) values of the aggregates, with release of protons at the cmc whose values, as well as those of the adsorption effectiveness, account for their efficient surfactant behavior. A tail-length effect is manifest because surfactant cmc of compounds with a C-16-alkyl chain are smaller than the C-12-ones, although not as small as expected. On the other hand, while for C-12-surfactants the role of the stereochemistry on the physicochemical parameters is patent, it is not very clear for C-16-surfactants. The stereochemistry also determines the predominant mode of self-assembly since the trend for cis-isomers is to form micelles or vesicles while trans-isomers preferably form fibers. CD spectroscopy confirmed the aggregation through the formation of intermolecular hydrogen bonds between the amide groups of the monomers. An alternative method to determine the cmc of these surfactants is provided by considering the relationship of the CD lambda(max) with concentration, although it is restricted to those surfactants in which the chromophore is located in a chiral environment. Furthermore, the non- toxicity of the surfactants has been verified by the MTT assay. This characteristic, jointly with the efficiency and the good properties shown, the fact that the cationic species are present in a high concentration at physiological pH, as well as the weak acid behavior of the aggregates, confirm these amphiphiles as promising candidates to be used as non-viral vectors for gene therapy applications. 22020-01-0120202020-01-01Articlehttp://purl.org/coar/resource_type/c_6501AMhttp://purl.org/coar/version/c_ab4af688f83e57aainfo:eu-repo/semantics/articleapplication/pdfhttps://ddd.uab.cat/record/274089https://dx.doi.org/urn:doi:10.1016/j.molliq.2019.111856reponame: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 document està subjecte a una llicència d'ús Creative Commons. Es permet la reproducció total o parcial, la distribució, i la comunicació pública de l'obra, sempre que no sigui amb finalitats comercials, i sempre que es reconegui l'autoria de l'obra original. No es permet la creació d'obres derivades.https://creativecommons.org/licenses/by-nc-nd/4.0/info:eu-repo/semantics/openAccessoai:ddd.uab.cat:2740892026-06-06T12:50:31Z
dc.title.none.fl_str_mv Chiral pH-sensitive cyclobutane beta-amino acid-based cationic amphiphiles
Possible candidates for use in gene therapy
title Chiral pH-sensitive cyclobutane beta-amino acid-based cationic amphiphiles
spellingShingle Chiral pH-sensitive cyclobutane beta-amino acid-based cationic amphiphiles
Pi i Boleda, Bernat|||0000-0003-1050-6788
Density-Functional Theory
Cis/Trans Stereochemistry
Gemini Surfactants
Aggregation
Transfection
Transition
Titration
Micelles
Bromide
Systems
title_short Chiral pH-sensitive cyclobutane beta-amino acid-based cationic amphiphiles
title_full Chiral pH-sensitive cyclobutane beta-amino acid-based cationic amphiphiles
title_fullStr Chiral pH-sensitive cyclobutane beta-amino acid-based cationic amphiphiles
title_full_unstemmed Chiral pH-sensitive cyclobutane beta-amino acid-based cationic amphiphiles
title_sort Chiral pH-sensitive cyclobutane beta-amino acid-based cationic amphiphiles
dc.creator.none.fl_str_mv Pi i Boleda, Bernat|||0000-0003-1050-6788
Bouzas, Mireia
Gaztelumendi, Nerea|||0000-0002-3837-2956
Illa, Ona|||0000-0001-7390-4893
Nogués, Carme|||0000-0002-6361-8559
Branchadell, Vicenç|||0000-0003-3480-1669
Pons, Ramon|||0000-0003-4273-9084
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
Bouzas, Mireia
Gaztelumendi, Nerea|||0000-0002-3837-2956
Illa, Ona|||0000-0001-7390-4893
Nogués, Carme|||0000-0002-6361-8559
Branchadell, Vicenç|||0000-0003-3480-1669
Pons, Ramon|||0000-0003-4273-9084
Ortuño Mingarro, Rosa María|||0000-0001-7635-7354
author_role author
author2 Bouzas, Mireia
Gaztelumendi, Nerea|||0000-0002-3837-2956
Illa, Ona|||0000-0001-7390-4893
Nogués, Carme|||0000-0002-6361-8559
Branchadell, Vicenç|||0000-0003-3480-1669
Pons, Ramon|||0000-0003-4273-9084
Ortuño Mingarro, Rosa María|||0000-0001-7635-7354
author2_role author
author
author
author
author
author
author
dc.subject.none.fl_str_mv Density-Functional Theory
Cis/Trans Stereochemistry
Gemini Surfactants
Aggregation
Transfection
Transition
Titration
Micelles
Bromide
Systems
topic Density-Functional Theory
Cis/Trans Stereochemistry
Gemini Surfactants
Aggregation
Transfection
Transition
Titration
Micelles
Bromide
Systems
description Chiral cis/trans diastereomeric cationic amphiphiles have been synthesized and studied. They are based on beta-amino acids and contain C-12- and C-16-alkyl chains, respectively, as hydrophobic tails while the polar head consists of an ammonium cation linked to a cyclobutane ring. Their physicochemical properties, such as the cmc (critical micellar concentration), the pK(a), the ratio of cationic versus non-ionic species, and the surface tension are strongly dependent on the pH of the medium. At the same time the aggregation state influences on the apparent pK(a) values of the aggregates, with release of protons at the cmc whose values, as well as those of the adsorption effectiveness, account for their efficient surfactant behavior. A tail-length effect is manifest because surfactant cmc of compounds with a C-16-alkyl chain are smaller than the C-12-ones, although not as small as expected. On the other hand, while for C-12-surfactants the role of the stereochemistry on the physicochemical parameters is patent, it is not very clear for C-16-surfactants. The stereochemistry also determines the predominant mode of self-assembly since the trend for cis-isomers is to form micelles or vesicles while trans-isomers preferably form fibers. CD spectroscopy confirmed the aggregation through the formation of intermolecular hydrogen bonds between the amide groups of the monomers. An alternative method to determine the cmc of these surfactants is provided by considering the relationship of the CD lambda(max) with concentration, although it is restricted to those surfactants in which the chromophore is located in a chiral environment. Furthermore, the non- toxicity of the surfactants has been verified by the MTT assay. This characteristic, jointly with the efficiency and the good properties shown, the fact that the cationic species are present in a high concentration at physiological pH, as well as the weak acid behavior of the aggregates, confirm these amphiphiles as promising candidates to be used as non-viral vectors for gene therapy applications.
publishDate 2020
dc.date.none.fl_str_mv 2
2020-01-01
2020
2020-01-01
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/274089
https://dx.doi.org/urn:doi:10.1016/j.molliq.2019.111856
url https://ddd.uab.cat/record/274089
https://dx.doi.org/urn:doi:10.1016/j.molliq.2019.111856
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://creativecommons.org/licenses/by-nc-nd/4.0/
dc.rights.openaire.fl_str_mv info:eu-repo/semantics/openAccess
rights_invalid_str_mv open access
http://purl.org/coar/access_right/c_abf2
https://creativecommons.org/licenses/by-nc-nd/4.0/
eu_rights_str_mv openAccess
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dc.source.none.fl_str_mv reponame:Dipòsit Digital de Documents de la UAB
instname:Universitat Autònoma de Barcelona
instname_str Universitat Autònoma de Barcelona
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