RT Journal Article
T1 2D Assemblies Based on a Tetraphenylethylene D,L-Cyclic Peptide Scaffold
A1 Bayón Fernández, Alfonso
A1 Torrón Celada, Alba
A1 Méndez Ardoy, Alejandro
A1 Coste, Maëva
A1 Delgado Gestoso, David
A1 Ulrich, Sébastien
A1 Granja Guillán, Juan Ramón
A1 Montenegro García, Javier
AB Two dimensional (2D) materials and aggregation-induced emission (AIE) fluorophores have recently gained attention due to their unique properties and application potential. However, the combination of AIE probes into 2D self-assembled systems under nanometric control remains elusive due to the sensitivity of supramolecular assemblies to subtle changes in the monomer structure. Herein, we present a new scaffold based on four nanotube-forming cyclic peptide (CP) units attached to a tetraphenylethene (TPE) core whose pH-dependent self-assembly results in light-emitting 2D nanosheets. An oxime bond connection was exploited to synthesize a discrete library of tetrakis-(cyclopeptide) tetraphenylethene monomers that self-assemble into 2D macrotubular nanoarrays under the suitable external stimulus. This new tetrameric CP motif tolerates a broad range of molecular modifications, both on the peptide backbone and TPE core, without compromising the integrity of the 2D self-assembly. We also discovered that adjusting the molecular structure of the TPE aromatic core enabled precise height control of the supramolecular nanosheets. The alignment of the histidine residues within neighboring CPs allowed the application of 2D nanoarchitectures as enzyme mimics with esterase activity. The excellent tolerance to molecular diversity in both the external CP moiety and the internal aromatic AIE core, invites the design of new functional 2D supramolecular materials.
PB Wiley and Gesellschaft Deutscher Chemiker
YR 2025
FD 2025-11-10
LK https://hdl.handle.net/10347/46538
UL https://hdl.handle.net/10347/46538
LA eng
NO A.Bayón-Fernández, A.Torrón-Celada, A.Méndez-Ardoy, M.Coste, D.Delgado-Gestoso, S.Ulrich, J.Montenegro, & J. R.Granja (2025). Angewandte Chemie International Edition, 64, e14543. https://doi.org/10.1002/anie.202514543
NO This work was supported by the Spanish Agencia Estatalde Investigación (AEI) (PID2022-142440NB-I00, PID2023-152181OB-I00), and by the Xunta de Galicia (ED431C2021/21, ED431C 2024–03, ED431C 2025/15, the Oportunius Program (GAIN), the Centro de investigación do Sistemauniversitario de Galicia accreditation 2024–2027, ED431G2023/03), and the European Union (European RegionalDevelopment Fund - ERDF). We also thank the ORFEO-CINCA network and Mineco (RED2022-134287-T). A. B.-F.and A. T.-C. thank Xunta de Galicia for their predoc-toral contracts (ED481A-2019/085 and ED481A-2023–083).A. M.-A. supported the Ministry of Science and Innova-tion/State Research Agency (RYC2021-034263-I) and theEuropean Union “NextGenerationEU/Recovery, Transfor-mation and Resilience Plan” (10.13039/501100011033). M.C.and S.U. thank the ANR for the funding of the SelfBioMatproject (ANR-17-CE07-0042-01). We acknowledge Jose M.Valpuesta, Noelia Zamarreño and M. Teresa Bueno forassistance in sample preparation and data acquisition atthe CryoEM Facility CNB-CSIC, supported by the “SeveroOchoa” Programme for Centres of Excellence in R&D(CEX2023-001386-S).
DS Minerva
RD 20 may 2026