Unveiling the role of capping groups in naphthalene N-capped dehydrodipeptide hydrogels
Autor(a) principal: | |
---|---|
Data de Publicação: | 2023 |
Outros Autores: | , , , , , , , |
Tipo de documento: | Artigo |
Idioma: | eng |
Título da fonte: | Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) |
Texto Completo: | https://hdl.handle.net/1822/84990 |
Resumo: | Self-assembled peptide-based hydrogels are archetypical nanostructured materials with a plethora of foreseeable applications in nanomedicine and as biomaterials. N-protected di- and tri-peptides are effective minimalist (molecular) hydrogelators. Independent variation of the capping group, peptide sequence and side chain modifications allows a wide chemical space to be explored and hydrogel properties to be tuned. In this work, we report the synthesis of a focused library of dehydrodipeptides N-protected with 1-naphthoyl and 2-naphthylacetyl groups. The 2-naphthylacetyl group was extensively reported for preparation of peptide-based self-assembled hydrogels, whereas the 1-naphthaloyl group was largely overlooked, owing presumably to the lack of a methylene linker between the naphthalene aromatic ring and the peptide backbone. Interestingly, dehydrodipeptides N-capped with the 1-naphthyl moiety afford stronger gels, at lower concentrations, than the 2-naphthylacetyl-capped dehydrodipeptides. Fluorescence and circular dichroism spectroscopy showed that the self-assembly of the dehydrodipeptides is driven by intermolecular aromatic π–π stacking interactions. Molecular dynamics simulations revealed that the 1-naphthoyl group allows higher order aromatic π–π stacking of the peptide molecules than the 2-naphthylacetyl group, together with hydrogen bonding of the peptide scaffold. The nanostructure of the gel networks was studied by TEM and STEM microscopy and was found to correlate well with the elasticity of the gels. This study contributes to understanding the interplay between peptide and capping group structure on the formation of self-assembled low-molecular-weight peptide hydrogels. Moreover, the results presented here add the 1-naphthoyl group to the palette of capping groups available for the preparation of efficacious low-molecular-weight peptide-based hydrogels. |
id |
RCAP_eb73b5bb742752287847197c280843a9 |
---|---|
oai_identifier_str |
oai:repositorium.sdum.uminho.pt:1822/84990 |
network_acronym_str |
RCAP |
network_name_str |
Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) |
repository_id_str |
7160 |
spelling |
Unveiling the role of capping groups in naphthalene N-capped dehydrodipeptide hydrogelsDehydrodipeptide1-naphthyl group2-naphthylacetyl groupSelf-assemblyHydrogelSelf-assembled peptide-based hydrogels are archetypical nanostructured materials with a plethora of foreseeable applications in nanomedicine and as biomaterials. N-protected di- and tri-peptides are effective minimalist (molecular) hydrogelators. Independent variation of the capping group, peptide sequence and side chain modifications allows a wide chemical space to be explored and hydrogel properties to be tuned. In this work, we report the synthesis of a focused library of dehydrodipeptides N-protected with 1-naphthoyl and 2-naphthylacetyl groups. The 2-naphthylacetyl group was extensively reported for preparation of peptide-based self-assembled hydrogels, whereas the 1-naphthaloyl group was largely overlooked, owing presumably to the lack of a methylene linker between the naphthalene aromatic ring and the peptide backbone. Interestingly, dehydrodipeptides N-capped with the 1-naphthyl moiety afford stronger gels, at lower concentrations, than the 2-naphthylacetyl-capped dehydrodipeptides. Fluorescence and circular dichroism spectroscopy showed that the self-assembly of the dehydrodipeptides is driven by intermolecular aromatic π–π stacking interactions. Molecular dynamics simulations revealed that the 1-naphthoyl group allows higher order aromatic π–π stacking of the peptide molecules than the 2-naphthylacetyl group, together with hydrogen bonding of the peptide scaffold. The nanostructure of the gel networks was studied by TEM and STEM microscopy and was found to correlate well with the elasticity of the gels. This study contributes to understanding the interplay between peptide and capping group structure on the formation of self-assembled low-molecular-weight peptide hydrogels. Moreover, the results presented here add the 1-naphthoyl group to the palette of capping groups available for the preparation of efficacious low-molecular-weight peptide-based hydrogels.This work was funded by National Funds through FCT-Portuguese Foundation for Science and Technology under the Project PTDC/QUI-QOR/29015/2017, CQ/UM UID/QUI/00686/2013 and UID/QUI/0686/2016, UID/CTM/50025/2019 and CF-UM-UP (UIDB/04650/2020). The NMR spectrometers are part of the National NMR Network (PTNMR) and are partially supported by Infrastructure Project No 022161 (co-financed by FEDER through COMPETE 2020, POCI and PORL and FCT through PIDDAC).For computing resources: Search-ON2: Revitalization of HPC infrastructure of UMinho, (NORTE-07-0162-FEDER-000086), co-funded by the North Portugal Regional Oper ational Programme (ON.2-O Novo Norte), under the National Strategic Reference Framework (NSRF), through the European Regional Development Fund (ERDF). Norte (ON.2) through the project Matepro—Optimizing Materials and Processes, with reference NORTE-07-0124-FEDER-000037 FEDER COMPETE is also acknowledged. T. Castro thanks the senior position funded by the European Union through the European Regional Development Fund (ERDF) under the Competitiveness Opera tional Program (BioCell-NanoART = Novel Bio-inspired Cellular Nano-architectures, POC-A1.1.4-E 2015 nr. 30/01.09.2016). M. Melle-Franco acknowledges support by the FCT through the programs Ciência 2008, the project IF/00894/2015 and within the Projects Scope: UID/CEC/00319/2013 and UIDB/50011/2020 and UIDP/5 0011/2020 (CICECO-Aveiro Institute of Materials). FCT Investigator Programme through grant IF/00606/2014 to L. Hilliou, is acknowledged. IWH was supported by EPSRC grant EP/L020599/1.info:eu-repo/semantics/publishedVersionMDPIUniversidade do MinhoVilaça, HelenaCarvalho, AndréCastro, Tarsila GabrielCastanheira, Elisabete M. S.Hilliou, L.Hamley, IanMelle-Franco, ManuelFerreira, Paula M. T.Martins, J. A. R.2023-06-062023-06-06T00:00:00Zinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/articleapplication/pdfhttps://hdl.handle.net/1822/84990engVilaça, H.; Carvalho, A.; Castro, T.; Castanheira, E.M.S.; Hilliou, L.; Hamley, I.; Melle-Franco, M.; Ferreira, P.M.T.; Martins, J.A. Unveiling the Role of Capping Groups in Naphthalene N-Capped Dehydrodipeptide Hydrogels. Gels 2023, 9, 464. https://doi.org/10.3390/gels90604642310-286110.3390/gels9060464https://www.mdpi.com/2310-2861/9/6/464info:eu-repo/semantics/openAccessreponame:Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos)instname:Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informaçãoinstacron:RCAAP2024-06-22T01:25:28Zoai:repositorium.sdum.uminho.pt:1822/84990Portal AgregadorONGhttps://www.rcaap.pt/oai/openairemluisa.alvim@gmail.comopendoar:71602024-06-22T01:25:28Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) - Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informaçãofalse |
dc.title.none.fl_str_mv |
Unveiling the role of capping groups in naphthalene N-capped dehydrodipeptide hydrogels |
title |
Unveiling the role of capping groups in naphthalene N-capped dehydrodipeptide hydrogels |
spellingShingle |
Unveiling the role of capping groups in naphthalene N-capped dehydrodipeptide hydrogels Vilaça, Helena Dehydrodipeptide 1-naphthyl group 2-naphthylacetyl group Self-assembly Hydrogel |
title_short |
Unveiling the role of capping groups in naphthalene N-capped dehydrodipeptide hydrogels |
title_full |
Unveiling the role of capping groups in naphthalene N-capped dehydrodipeptide hydrogels |
title_fullStr |
Unveiling the role of capping groups in naphthalene N-capped dehydrodipeptide hydrogels |
title_full_unstemmed |
Unveiling the role of capping groups in naphthalene N-capped dehydrodipeptide hydrogels |
title_sort |
Unveiling the role of capping groups in naphthalene N-capped dehydrodipeptide hydrogels |
author |
Vilaça, Helena |
author_facet |
Vilaça, Helena Carvalho, André Castro, Tarsila Gabriel Castanheira, Elisabete M. S. Hilliou, L. Hamley, Ian Melle-Franco, Manuel Ferreira, Paula M. T. Martins, J. A. R. |
author_role |
author |
author2 |
Carvalho, André Castro, Tarsila Gabriel Castanheira, Elisabete M. S. Hilliou, L. Hamley, Ian Melle-Franco, Manuel Ferreira, Paula M. T. Martins, J. A. R. |
author2_role |
author author author author author author author author |
dc.contributor.none.fl_str_mv |
Universidade do Minho |
dc.contributor.author.fl_str_mv |
Vilaça, Helena Carvalho, André Castro, Tarsila Gabriel Castanheira, Elisabete M. S. Hilliou, L. Hamley, Ian Melle-Franco, Manuel Ferreira, Paula M. T. Martins, J. A. R. |
dc.subject.por.fl_str_mv |
Dehydrodipeptide 1-naphthyl group 2-naphthylacetyl group Self-assembly Hydrogel |
topic |
Dehydrodipeptide 1-naphthyl group 2-naphthylacetyl group Self-assembly Hydrogel |
description |
Self-assembled peptide-based hydrogels are archetypical nanostructured materials with a plethora of foreseeable applications in nanomedicine and as biomaterials. N-protected di- and tri-peptides are effective minimalist (molecular) hydrogelators. Independent variation of the capping group, peptide sequence and side chain modifications allows a wide chemical space to be explored and hydrogel properties to be tuned. In this work, we report the synthesis of a focused library of dehydrodipeptides N-protected with 1-naphthoyl and 2-naphthylacetyl groups. The 2-naphthylacetyl group was extensively reported for preparation of peptide-based self-assembled hydrogels, whereas the 1-naphthaloyl group was largely overlooked, owing presumably to the lack of a methylene linker between the naphthalene aromatic ring and the peptide backbone. Interestingly, dehydrodipeptides N-capped with the 1-naphthyl moiety afford stronger gels, at lower concentrations, than the 2-naphthylacetyl-capped dehydrodipeptides. Fluorescence and circular dichroism spectroscopy showed that the self-assembly of the dehydrodipeptides is driven by intermolecular aromatic π–π stacking interactions. Molecular dynamics simulations revealed that the 1-naphthoyl group allows higher order aromatic π–π stacking of the peptide molecules than the 2-naphthylacetyl group, together with hydrogen bonding of the peptide scaffold. The nanostructure of the gel networks was studied by TEM and STEM microscopy and was found to correlate well with the elasticity of the gels. This study contributes to understanding the interplay between peptide and capping group structure on the formation of self-assembled low-molecular-weight peptide hydrogels. Moreover, the results presented here add the 1-naphthoyl group to the palette of capping groups available for the preparation of efficacious low-molecular-weight peptide-based hydrogels. |
publishDate |
2023 |
dc.date.none.fl_str_mv |
2023-06-06 2023-06-06T00:00:00Z |
dc.type.status.fl_str_mv |
info:eu-repo/semantics/publishedVersion |
dc.type.driver.fl_str_mv |
info:eu-repo/semantics/article |
format |
article |
status_str |
publishedVersion |
dc.identifier.uri.fl_str_mv |
https://hdl.handle.net/1822/84990 |
url |
https://hdl.handle.net/1822/84990 |
dc.language.iso.fl_str_mv |
eng |
language |
eng |
dc.relation.none.fl_str_mv |
Vilaça, H.; Carvalho, A.; Castro, T.; Castanheira, E.M.S.; Hilliou, L.; Hamley, I.; Melle-Franco, M.; Ferreira, P.M.T.; Martins, J.A. Unveiling the Role of Capping Groups in Naphthalene N-Capped Dehydrodipeptide Hydrogels. Gels 2023, 9, 464. https://doi.org/10.3390/gels9060464 2310-2861 10.3390/gels9060464 https://www.mdpi.com/2310-2861/9/6/464 |
dc.rights.driver.fl_str_mv |
info:eu-repo/semantics/openAccess |
eu_rights_str_mv |
openAccess |
dc.format.none.fl_str_mv |
application/pdf |
dc.publisher.none.fl_str_mv |
MDPI |
publisher.none.fl_str_mv |
MDPI |
dc.source.none.fl_str_mv |
reponame:Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) instname:Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informação instacron:RCAAP |
instname_str |
Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informação |
instacron_str |
RCAAP |
institution |
RCAAP |
reponame_str |
Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) |
collection |
Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) |
repository.name.fl_str_mv |
Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) - Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informação |
repository.mail.fl_str_mv |
mluisa.alvim@gmail.com |
_version_ |
1817544766654513152 |