pH-responsive self-assembly of amyloid fibrils for dual hydrolase-oxidase reactions

There is an increasing interest in synthetic systems that can execute bioinspired chemical reactions without requiring the complex structures that characterize enzymes in their components. The hierarchical self-assembly of peptides provides a means to create catalytic microenvironments. Ideally, as...

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Detalles Bibliográficos
Autores: Díaz-Caballero, Marta|||0000-0001-9032-9819, Navarro, Susanna|||0000-0001-8160-9536, Nuez-Martínez, Miquel, Peccati, Francesca|||0000-0002-7813-8216, Rodríguez-Santiago, Luis|||0000-0003-4983-4228, Sodupe, Mariona|||0000-0003-0276-0524, Teixidor, Francesc|||0000-0002-3010-2417, Ventura, Salvador|||0000-0002-9652-6351
Tipo de recurso: artículo
Fecha de publicación:2021
País:España
Institución:Universitat Autònoma de Barcelona
Repositorio:Dipòsit Digital de Documents de la UAB
Idioma:inglés
OAI Identifier:oai:ddd.uab.cat:277745
Acceso en línea:https://ddd.uab.cat/record/277745
https://dx.doi.org/urn:doi:10.1021/acscatal.0c03093
Access Level:acceso abierto
Palabra clave:Amyloid fibrils
Artificial enzymes
Hydrogels
Ph-responsive materials
Self-assembly
Short peptides
Descripción
Sumario:There is an increasing interest in synthetic systems that can execute bioinspired chemical reactions without requiring the complex structures that characterize enzymes in their components. The hierarchical self-assembly of peptides provides a means to create catalytic microenvironments. Ideally, as it occurs in enzymes, the catalytic activity of peptide nanostructures should be reversibly regulated. In a typical enzyme mimetic design, the peptide's self-assembling and catalytic activities are segregated into different regions of the sequence. Here, we aimed to design minimal peptides in which the self-assembly and function were all encoded in the same amino acids. Moreover, we wanted to endow the resulting one-component nanomaterial with divergent, chemically unrelated, catalytic activities, a property not observed in natural enzymes. We show that short peptides consisting only of histidine and tyrosine residues, arranged in a binary pattern, form biocompatible amyloid-like fibrils and hydrogels combining hydrolytic and electrocatalytic activities. The nanofibers' mesoscopic properties are controlled by pH, the transition between assembled active β-sheet fibrils, and disassembled inactive random coil species occurring in a physiologically relevant pH range. The structure of one of such amyloid-like fibrils, as derived from molecular dynamic simulations, provides insights on how they attain this combination of structural and catalytic properties.