Exploiting Minimalistic Backbone Engineered γ-Phenylalanine for the Formation of Supramolecular Co-Polymer

Rajkumar Misra, Yiming Tang, Yujie Chen, Priyadarshi Chakraborty, Francesca Netti, Thangavel Vijayakanth, Linda J.W. Shimon, Guanghong Wei*, Lihi Adler-Abramovich*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

2 Scopus citations

Abstract

Ordered supramolecular hydrogels assembled by modified aromatic amino acids often exhibit low mechanical rigidity. Aiming to stabilize the hydrogel and understand the impact of conformational freedom and hydrophobicity on the self-assembly process, two building blocks based on 9-fluorenyl-methoxycarbonyl-phenylalanine (Fmoc-Phe) gelator which contain two extra methylene units in the backbone, generating Fmoc-γPhe and Fmoc-(3-hydroxy)-γPhe are designed. Fmoc-γPhe spontaneously assembled in aqueous media forming a hydrogel with exceptional mechanical and thermal stability. Moreover, Fmoc-(3-hydroxy)-γPhe, with an extra backbone hydroxyl group decreasing its hydrophobicity while maintaining some molecular flexibility, self-assembled into a transient fibrillar hydrogel, that later formed microcrystalline aggregates through a phase transition. Molecular dynamics simulations and single crystal X-ray analyses reveal the mechanism underlying the two residues' distinct self-assembly behaviors. Finally, Fmoc-γPhe and Fmoc-(3-OH)-γPhe co-assembly to form a supramolecular hydrogel with notable mechanical properties are demonstrated. It has been believed that the understanding of the structure-assembly relationship will enable the design of new functional amino acid-based hydrogels.

Original languageEnglish
Article number2200223
JournalMacromolecular Rapid Communications
Volume43
Issue number19
DOIs
StatePublished - Oct 2022

Funding

FundersFunder number
European Research Council
Department of Science and Technology, Ministry of Science and Technology, IndiaDST/INSPIRE/04/2020/002499
Ministry of Science, Technology and Space
National Natural Science Foundation of China12074079
Israel Science Foundation1732/17
Horizon 2020948102
National Key Research and Development Program of China2016YFA0501702

    Keywords

    • X-ray structures
    • co-assembly
    • gamma amino acids
    • hydrogels
    • molecular dynamics simulation

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