Superstructured Biomaterials Formed by Exchange Dynamics and Host–Guest Interactions in Supramolecular Polymers

Abstract

Dynamic and reversible assembly of molecules is ubiquitous in the hierarchical superstructures of living systems and plays a key role in cellular functions. Recent work from the laboratory reported on the reversible formation of such superstructures in systems of peptide amphiphiles conjugated to oligonucleotides and electrostatically complimentary peptide sequences. Here, a supramolecular system is reported upon where exchange dynamics and host-guest interactions between -cyclodextrin and adamantane on peptide amphiphiles lead to superstructure formation. Superstructure formation with bundled nanoribbons generates a mechanically robust hydrogel with a highly porous architecture that can be 3D printed. Functionalization of the porous superstructured material with a biological signal results in a matrix with significant in vitro bioactivity toward neurons that could be used as a supramolecular model to design novel biomaterials.

Bottom‐Up versus Top‐Down Strategies for Morphology Control in Polymer‐Based Biomedical Materials

“…[47] Recent work from the Stupp laboratory has demonstrated the ability to tune the molecular exchange of PA molecules in assemblies to drive the spontaneous assembly of hierarchical superstructures for dynamic material properties. [48][49][50] In fact, it has been demonstrated by both coarse-grained simulation and through recent experimentation that as long as the strength of noncovalent interactions among monomers in the PA self-assembly is low enough to allow monomers to escape from their original assemblies (dynamic molecular exchange), then there is potential for the formation of hierarchical superstructures. [49] In a study by Edelbrock et al, PA molecules were designed to contain β-cyclodextrin and adamantyl moieties on the surface of PA nanoribbon assemblies that could form noncovalent hostguest inclusion complexes between molecules.…”

“…This superstructure was driven by the formation of host-guest inclusion complexes, and more importantly, the ability for these molecules to escape their original assemblies and enrich in the superstructure bundles (Figure 3A-C). [48] When the intermolecular cohesive energy of the PA molecules was increased, through the addition of hydrophobic amino acids that favor Neurons demonstrated the greatest infiltration when the bioactive BDNF mimetic peptide sequence was combined with the increased porosity resulting from the superstructure self-assembly. Reproduced under the terms and conditions of the Creative Commons Attribution license 4.0.…”

“…Reproduced under the terms and conditions of the Creative Commons Attribution license 4.0. [48] Copyright 2021, The Authors, published by Wiley-VCH.…”

Self‐Stabilized Supramolecular Assemblies Constructed from PEGylated Dendritic Peptide Conjugate for Augmenting Tumor Retention and Therapy

“…Supramolecular peptides can be used to create a myriad of well‐organized structures with advanced functions, and they have great potential in biomedicine. [ 1 ] By tailoring the sequences and external stimuli, peptide can be self‐assembled into micelles, vesicles, spheres, fibers, and tubes driven by supramolecular chemistry, and these assemblies have shown promising applications in drug delivery, gene transfection, biophotonic imaging, tissue engineering, regenerative medicine, and immunology. [ 2 ] However, there are two major challenges of applying supramolecular peptides in clinical practice.…”

Globular Aggregates Stemming from the Self-Assembly of an Amphiphilic N-Annulated Perylene Bisimide in Aqueous Media

“…At the same time, and thanks to the versatility provided by organic synthesis, a large number of examples of supramolecular structures with different morphology and able to exert a variety functions have been reported. Thus, the self-assembly of oligopeptides or amphiphilic benzenetricarboxmides (BTAs) allows the achievement of fibrillar aggregates that can be utilized in biomedical applications [8][9][10], and self-assembled capsules have been reported to act as nanoreactors [9]. Kinetically controlled aggregation processes in aqueous media have been also described for organometallic complexes [11][12][13] or for well-known dyes such as BODIPY [14,15] that yield different species, evolving with time to afford new aggregates with different functions.…”