An Offset Patterned Cross-ß Structure in Assemblies of C 3 -Symmetric Peptide Amphiphiles.
Por:
Zagorodko O, Melnyk T, Nebot VJ, Dankers PYW and Vicent MJ
Publicada:
1 feb 2024
Ahead of Print:
15 nov 2023
Resumen:
Developing peptide-based materials with controlled morphology is a critical theme of soft matter research. Herein, we report the formation of a novel, patterned cross-ß structure formed by self-assembled C 3 -symmetric peptide amphiphiles based on diphenylalanine and benzene-1,3,5-tricarboxamide (BTA). The cross-ß motif is an abundant structural element in amyloid fibrils and aggregates of fibril-forming peptides, including diphenylalanine. The incorporation of topological constraints on one edge of the diphenylalanine fragment limits the number of ß-strands in ß-sheets and leads to the creation of an unconventional offset-patterned cross-ß structure consisting of short 3×2 parallel ß-sheets stabilized by phenylalanine zippers. In the reported assembly, two patterned cross-ß structures bind parallel arrays of BTA stacks in a superstructure within a single-molecule-thick nanoribbon. In addition to a threefold network of hydrogen bonds in the BTA stack, each molecule becomes simultaneously bound by hydrogen bonds from three ß-sheets and four phenylalanine zippers. The diffuse layer of alkyl chains with terminal polar groups prevents the nanoribbons from merging and stabilizes cross-ß-structure in water. Our results provide a simple approach to the incorporation of novel patterned cross-ß motifs into supramolecular superstructures and shed light on the general mechanism of ß-sheet formation in C 3 -symmetric peptide amphiphiles.
Filiaciones:
:
Polymer Therapeutics Lab, Centro de Investigación Príncipe Felipe, C/d'Eduardo Primo Yúfera, 3, 46012, Valencia, Spain
Institute for Complex Molecular Systems (ICMS), Eindhoven University of Technology, P. O. Box 513, 5600 MB, Eindhoven, The Netherlands
Melnyk T:
Polymer Therapeutics Lab, Centro de Investigación Príncipe Felipe, C/d'Eduardo Primo Yúfera, 3, 46012, Valencia, Spain
Centro de Investigación, Biomédica en Red en Oncología (CIBERONC), Av. Monforte de Lemos, 3-5, 28029, Madrid, Spain
Nebot VJ:
Polymer Therapeutics Lab, Centro de Investigación Príncipe Felipe, C/d'Eduardo Primo Yúfera, 3, 46012, Valencia, Spain
Curapath, Av. Benjamín Franklin, 19, 46980, Paterna, Valencia, Spain
Dankers PYW:
Institute for Complex Molecular Systems (ICMS), Eindhoven University of Technology, P. O. Box 513, 5600 MB, Eindhoven, The Netherlands
:
Polymer Therapeutics Lab, Centro de Investigación Príncipe Felipe, C/d'Eduardo Primo Yúfera, 3, 46012, Valencia, Spain
Centro de Investigación, Biomédica en Red en Oncología (CIBERONC), Av. Monforte de Lemos, 3-5, 28029, Madrid, Spain
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