Molecular Co-Assembly of Two Building Blocks Harnesses Both their Attributes into a Functional Supramolecular Hydrogel

Abstract

Engineering ordered nanostructures through molecular self-assembly of simple building blocks constitutes the essence of modern nanotechnology to develop functional supramolecular biomaterials. However, the lack of adequate chemical and functional diversity often hinders the utilization of unimolecular self-assemblies for practical applications. Co-assembly of two different building blocks can essentially harness both of their attributes and produce nanostructured macro-scale objects with improved physical properties and desired functional complexity. Herein, the authors report the co-operative co-assembly of a modified amino acid, fluorenylmethoxycarbonyl-pentafluoro-phenylalanine (Fmoc-F₅ -Phe), and a peptide, Fmoc-Lys(Fmoc)-Arg-Gly-Asp [Fmoc-K(Fmoc)-RGD] into a functional supramolecular hydrogel. A change in the morphology and fluorescence emission, as well as improvement of the mechanical properties in the mixed hydrogels compared to the pristine hydrogels, demonstrate the signature of co-operative co-assembly mechanism. Intriguingly, this approach harnesses the advantages of both components in a synergistic way, resulting in a single homogeneous biomaterial possessing the antimicrobial property of Fmoc-F₅ -Phe and the biocompatibility and cell adhesive characteristics of Fmoc-K(Fmoc)-RGD. This work exemplifies the importance of the co-assembly process in nanotechnology and lays the foundation for future developments in supramolecular chemistry by harnessing the advantages of diverse functional building blocks into a mechanically stable functional biomaterial.

Keywords: amino acid; antibacterial property; biocompatibility; co-assembly; hydrogel; peptide.