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.

Peptide‐Based Optical/Electronic Materials: Assembly and Recent Applications in Biomedicine, Sensing, and Energy Storage

“…Supramolecular self-assembly provides a "bottom-up" processing method for the fabrication of nanoscale or microscale fine structures, which is one of the effective ways to prepare function new materials. [34][35][36] It can constantly self-correct and improve without external interference to make the molecules from chaotic to ordered, the structure from simple to complex, and follow the minimum energy principle until the assembly is completed. [37][38][39] Peptides are particularly attractive building blocks for the construction of supramolecular materials.…”

Self-Assembled Peptide Nanostructures for ECM Biomimicry

“…A similar injectable hydrogel based on Fmoc-FF and Fmoc-RGD was enriched with magnetic nanoparticles in order to increase the mechanical properties of the gel and also to allow for a magnetically targeted cell delivery for tissue regeneration [64]. The Fmoc-based self-assembly strategy allowed to obtain a hydrogel based on Fmoc-F 5 -Phe and a Fmoc-RGD derivative suitable for cell cultures, due to the adhesion properties of RGD combined with antimicrobial properties of Fmoc-F 5 -Phe [65]. Interestingly, fluorescence measurements allowed to establish the cooperative co-assembly of the different peptide sequences.…”

Short Peptide-Based Smart Thixotropic Hydrogels

“…Co-assembly is a special type of self-assembly process where more than one molecule participates in creating supramolecular nanoarchitectures [ 127 , 128 , 129 , 130 ]. In recent years, supramolecular co-assembled gels, i.e., gels made of two or more molecules, have gained enormous attention in supramolecular chemistry and biomedical sciences due to their tunability in physical properties [ 131 , 132 ].…”