Salt-induced Fmoc-tripeptide supramolecular hydrogels: a combined experimental and computational study of the self-assembly

Delving into the mechanism behind the molecular interactions at the atomic level of short-sequence peptides plays a key role in the development of nanomaterials with specific structure–property–function relationships from a bottom-up perspective. Due to their poor water solubility, the self-assembly...

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Autores: Criado González, Miryam, Peñas Núñez, Mario Iván, Barbault, Florent, Müller Sánchez, Alejandro Jesús, Boulmedais, Fouzia, Hernández Velasco, Rebeca
Tipo de recurso: artículo
Fecha de publicación:2024
País:España
Institución:Universidad del País Vasco
Repositorio:Addi. Archivo Digital para la Docencia y la Investigación
OAI Identifier:oai:addi.ehu.eus:10810/68793
Acceso en línea:http://hdl.handle.net/10810/68793
Access Level:acceso abierto
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spelling Salt-induced Fmoc-tripeptide supramolecular hydrogels: a combined experimental and computational study of the self-assemblyCriado González, MiryamPeñas Núñez, Mario IvánBarbault, FlorentMüller Sánchez, Alejandro JesúsBoulmedais, FouziaHernández Velasco, RebecaDelving into the mechanism behind the molecular interactions at the atomic level of short-sequence peptides plays a key role in the development of nanomaterials with specific structure–property–function relationships from a bottom-up perspective. Due to their poor water solubility, the self-assembly of Fmoc-bearing peptides is usually induced by dissolution in an organic solvent, followed by a dilution step in water, pH changes, and/or a heating–cooling process. Herein, we report a straightforward methodology for the gelation of Fmoc-FFpY (F: phenylalanine; Y: tyrosine; and p: PO42−), a negatively charged tripeptide, in NaCl solution. The electrostatic interactions between Fmoc-FFpY and Na+ ions give rise to different nanofibrillar hydrogels with rheological properties and nanofiber sizes modulated by the NaCl concentration in pure aqueous media. Initiated by the electrostatic interactions between the peptide phosphate groups and the Na+ ions, the peptide self-assembly is stabilized thanks to hydrogen bonds between the peptide backbones and the π–π stacking of aromatic Fmoc and phenyl units. The hydrogels showed self-healing and thermo-responsive properties for potential biomedical applications. Molecular dynamics simulations from systems devoid of prior training not only confirm the aggregation of peptides at a critical salt concentration and the different interactions involved, but also corroborate the secondary structure of the hydrogels at the microsecond timescale. It is worth highlighting the remarkable achievement of reproducing the morphological behavior of the hydrogels using atomistic simulations. To our knowledge, this study is the first to report such a correspondence.Financial support from the Spanish Research Council (CSIC) and the French Research Council (CNRS) for the International Emerging Actions 2018 HYDROPRINT project is gratefully acknowledged. The authors also acknowledge the funding from the projects MAT2017-83014-C2-2-P and PID2020-113045GB-C22 by MCIN/AEI/10.13039/501100011033 and the ALBA Synchrotron (Proposal number 2021095380). R. H. is a member of the SUSPLAST+ platform of CSIC. The authors thank Dr Rafael Nuñez from CIB-CSIC for TEM and Cryo-TEM measurements and the technical and human support provided by SGIker (UPV/EHU/ERDF, EU). SAXS experiments were performed at the BL 11 NCD-SWEET beamline at ALBA Synchrotron with the collaboration of ALBA staff. ANR (Agence Nationale de la Recherche) and CGI (Commissariat à l'Investissement d'Avenir) are gratefully acknowledged for their financial support of this work through Labex SEAM (Science and Engineering for Advanced Materials and Devices) ANR 11 LABX 086, and ANR 11 IDEX 05 02. This work benefited from the access to the supercomputing facilities of the GENCI (Grand Equipement National pour le Calcul Informatique) and the access to the ITODYS P3MB facility (Université Paris Cité, CNRS UMR 7086, Paris, France).RSC202420242024info:eu-repo/semantics/articleapplication/pdfhttp://hdl.handle.net/10810/68793reponame:Addi. Archivo Digital para la Docencia y la Investigacióninstname:Universidad del País VascoInglésinfo:eu-repo/grantAgreement/MICIU/MAT2017-83014-C2-2-P/info:eu-repo/grantAgreement/MICINN/PID2020-113045GB-C22/https://pubs.rsc.org/en/content/articlelanding/2024/nr/d4nr00335ginfo:eu-repo/semantics/openAccesshttp://creativecommons.org/licenses/by-nc/3.0/es/This article is licensed under a Creative Commons Attribution-Non Commercial 3.0 Unported Licence.Atribución-NoComercial 3.0 Españaoai:addi.ehu.eus:10810/687932026-06-18T09:23:17Z
dc.title.none.fl_str_mv Salt-induced Fmoc-tripeptide supramolecular hydrogels: a combined experimental and computational study of the self-assembly
title Salt-induced Fmoc-tripeptide supramolecular hydrogels: a combined experimental and computational study of the self-assembly
spellingShingle Salt-induced Fmoc-tripeptide supramolecular hydrogels: a combined experimental and computational study of the self-assembly
Criado González, Miryam
title_short Salt-induced Fmoc-tripeptide supramolecular hydrogels: a combined experimental and computational study of the self-assembly
title_full Salt-induced Fmoc-tripeptide supramolecular hydrogels: a combined experimental and computational study of the self-assembly
title_fullStr Salt-induced Fmoc-tripeptide supramolecular hydrogels: a combined experimental and computational study of the self-assembly
title_full_unstemmed Salt-induced Fmoc-tripeptide supramolecular hydrogels: a combined experimental and computational study of the self-assembly
title_sort Salt-induced Fmoc-tripeptide supramolecular hydrogels: a combined experimental and computational study of the self-assembly
dc.creator.none.fl_str_mv Criado González, Miryam
Peñas Núñez, Mario Iván
Barbault, Florent
Müller Sánchez, Alejandro Jesús
Boulmedais, Fouzia
Hernández Velasco, Rebeca
author Criado González, Miryam
author_facet Criado González, Miryam
Peñas Núñez, Mario Iván
Barbault, Florent
Müller Sánchez, Alejandro Jesús
Boulmedais, Fouzia
Hernández Velasco, Rebeca
author_role author
author2 Peñas Núñez, Mario Iván
Barbault, Florent
Müller Sánchez, Alejandro Jesús
Boulmedais, Fouzia
Hernández Velasco, Rebeca
author2_role author
author
author
author
author
description Delving into the mechanism behind the molecular interactions at the atomic level of short-sequence peptides plays a key role in the development of nanomaterials with specific structure–property–function relationships from a bottom-up perspective. Due to their poor water solubility, the self-assembly of Fmoc-bearing peptides is usually induced by dissolution in an organic solvent, followed by a dilution step in water, pH changes, and/or a heating–cooling process. Herein, we report a straightforward methodology for the gelation of Fmoc-FFpY (F: phenylalanine; Y: tyrosine; and p: PO42−), a negatively charged tripeptide, in NaCl solution. The electrostatic interactions between Fmoc-FFpY and Na+ ions give rise to different nanofibrillar hydrogels with rheological properties and nanofiber sizes modulated by the NaCl concentration in pure aqueous media. Initiated by the electrostatic interactions between the peptide phosphate groups and the Na+ ions, the peptide self-assembly is stabilized thanks to hydrogen bonds between the peptide backbones and the π–π stacking of aromatic Fmoc and phenyl units. The hydrogels showed self-healing and thermo-responsive properties for potential biomedical applications. Molecular dynamics simulations from systems devoid of prior training not only confirm the aggregation of peptides at a critical salt concentration and the different interactions involved, but also corroborate the secondary structure of the hydrogels at the microsecond timescale. It is worth highlighting the remarkable achievement of reproducing the morphological behavior of the hydrogels using atomistic simulations. To our knowledge, this study is the first to report such a correspondence.
publishDate 2024
dc.date.none.fl_str_mv 2024
2024
2024
dc.type.none.fl_str_mv info:eu-repo/semantics/article
format article
dc.identifier.none.fl_str_mv http://hdl.handle.net/10810/68793
url http://hdl.handle.net/10810/68793
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv info:eu-repo/grantAgreement/MICIU/MAT2017-83014-C2-2-P/
info:eu-repo/grantAgreement/MICINN/PID2020-113045GB-C22/
https://pubs.rsc.org/en/content/articlelanding/2024/nr/d4nr00335g
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
http://creativecommons.org/licenses/by-nc/3.0/es/
This article is licensed under a Creative Commons Attribution-Non Commercial 3.0 Unported Licence.
Atribución-NoComercial 3.0 España
eu_rights_str_mv openAccess
rights_invalid_str_mv http://creativecommons.org/licenses/by-nc/3.0/es/
This article is licensed under a Creative Commons Attribution-Non Commercial 3.0 Unported Licence.
Atribución-NoComercial 3.0 España
dc.format.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv RSC
publisher.none.fl_str_mv RSC
dc.source.none.fl_str_mv reponame:Addi. Archivo Digital para la Docencia y la Investigación
instname:Universidad del País Vasco
instname_str Universidad del País Vasco
reponame_str Addi. Archivo Digital para la Docencia y la Investigación
collection Addi. Archivo Digital para la Docencia y la Investigación
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