Hierarchical self-assembly of aromatic peptide conjugates into supramolecular polymers: it takes two to tango.

Sébastien Ulrich,Maëva Coste,Esteban Suárez-Picado

doi:10.1039/d1sc05589e

Abstract

Supramolecular polymers are self-assembled materials displaying adaptive and responsive “life-like” behaviour which are often made of aromatic compounds capable of engaging in π–π interactions to form larger assemblies. Major advances have been made recently in controlling their mode of self-assembly, from thermodynamically-controlled isodesmic to kinetically-controlled living polymerization. Dynamic covalent chemistry has been recently implemented to generate dynamic covalent polymers which can be seen as dynamic analogues of biomacromolecules. On the other hand, peptides are readily-available and structurally-rich building blocks that can lead to secondary structures or specific functions. In this context, the past decade has seen intense research activity in studying the behaviour of aromatic-peptide conjugates through supramolecular and/or dynamic covalent chemistries. Herein, we review those impressive key achievements showcasing how aromatic- and peptide-based self-assemblies can be combined using dynamic covalent and/or supramolecular chemistry, and what it brings in terms of the structure, self-assembly pathways, and function of supramolecular and dynamic covalent polymers.

Highlights

Strong degree of biomimicry for accessing supramolecular biomaterials that resemble some of the biopolymers found in the cytoskeleton like actin microfilaments,[15] and are currently considered of strong potential toward functional smart polymers.[16]
There, the presence of amino acids imparts molecular recognition properties to the system. These building blocks undergo a stepgrowth polycondensation with a complementary synthetic bisaldehyde 3, through both acylhydrazone and oxime ligations, that lead to Dynamic covalent polymers (DCPs)
These “proteoids” form according to a nucleationelongation polymerization[47] and have degree of polymerization reaching 60 and Mw ≈ 42 kDa using a tryptophan-derived amino acid building block, while much shorter DCPs are formed when using a tyrosine-derived building blocks, thereby pointing out the role of the hydrophobic effect that is imparted by the aromatic amino acid side-group in the polymerization process

Summary

Introduction

Strong degree of biomimicry for accessing supramolecular biomaterials that resemble some of the biopolymers found in the cytoskeleton like actin microfilaments,[15] and are currently considered of strong potential toward functional smart polymers.[16]. In this review we will summarize the achievements that have been reported in the last decade when inserting peptides into both supramolecular and dynamic covalent polymers, either for endowing them with specific structures and/or functions, or for impacting their complex self-assembly pathways

What are dynamic covalent polymers?

Functional DCPs by peptide insertion

Peptide-enforced folded DCPs

What are supramolecular polymers?

Effect of aromatics on peptide self-assembly

Effect of peptides on the supramoleculaDrOpIo

Multi-component precision polymers

Transient supramolecular polymers

Conclusions

Findings

Perspectives