Self-assembly pathways in a triphenylalanine peptide capped with aromatic groups

Peptide derivatives and, most specifically, their self-assembled supramolecular structures are being considered in the design of novel biofunctional materials. Although the self-assembly of triphenylalanine homopeptides has been found to be more versatile than that of homopeptides containing an even...

Descripción completa

Detalles Bibliográficos
Autores: Pérez Madrigal, Maria del Mar|||0000-0002-2498-8485, Gil, Ana M., Casanovas Salas, Jordi|||0000-0002-4914-9194, Jimenez Sanz, Ana Isabel, Macor, Lorena Paola, Alemán Llansó, Carlos|||0000-0003-4462-6075
Tipo de recurso: artículo
Fecha de publicación:2022
País:España
Institución:Universitat Politècnica de Catalunya (UPC)
Repositorio:UPCommons. Portal del coneixement obert de la UPC
Idioma:inglés
OAI Identifier:oai:upcommons.upc.edu:2117/370264
Acceso en línea:https://hdl.handle.net/2117/370264
https://dx.doi.org/10.1016/j.colsurfb.2022.112522
Access Level:acceso abierto
Palabra clave:Supramolecular chemistry
Biomedical materials
Aromatic interactions
Beta-sheet
Phenylalanine homopeptides
Triphenylalanine
Hierarchical structures
Supramolecular structures
Química supramolecular
Materials biomèdics
Àrees temàtiques de la UPC::Enginyeria biomèdica::Biomaterials
Àrees temàtiques de la UPC::Enginyeria química
Descripción
Sumario:Peptide derivatives and, most specifically, their self-assembled supramolecular structures are being considered in the design of novel biofunctional materials. Although the self-assembly of triphenylalanine homopeptides has been found to be more versatile than that of homopeptides containing an even number of residues (i.e. diphenylalanine and tetraphenylalanine), only uncapped triphenylalanine (FFF) and a highly aromatic analog blocked at both the N- and C-termini with fluorenyl-containing groups (Fmoc-FFF-OFm), have been deeply studied before. In this work, we have examined the self-assembly of a triphenylalanine derivative bearing 9-fluorenylmethyloxycarbonyl and benzyl ester end-capping groups at the N- and C-termini, respectively (Fmoc-FFF-OBzl). The antiparallel arrangement clearly dominates in ß-sheets formed by Fmoc-FFF-OBzl, whereas the parallel and antiparallel dispositions are almost isoenergetic in Fmoc-FFF-OFm ß-sheets and the parallel one is slightly favored for FFF. The effects of both the peptide concentration and the medium on the self-assembly process have been examined considering Fmoc-FFF-OBzl solutions in a wide variety of solvent:co-solvent mixtures. In addition, Fmoc-FFF-OBzl supramolecular structures have been compared to those obtained for FFF and Fmoc-FFF-OFm under identical experimental conditions. The strength of p-p stacking interactions involving the end-capping groups plays a crucial role in the nucleation and growth of supramolecular structures, which determines the resulting morphology. Finally, the influence of a non-invasive external stimulus, ultrasounds, on the nucleation and growth of supramolecular structures has been examined. Overall, FFF-based peptides provide a wide range of supramolecular structures that can be of interest in the biotechnological field.