Synthetic polypeptides from the ring-opening polymerization of N-carboxyanhydrides (NCAs) are one of the most important biomaterials. The unique features of these synthetic polypeptides, including their chemical diversity of side chains and their ability to form secondary structures, enable their broad applications in the field of gene delivery, drug delivery, bio-imaging, tissue engineering, and antimicrobials. In this review article, we summarize the recent advances in the design of polypeptide-based supramolecular structures, including complexes with nucleic acids, micelles, vesicles, hybrid nanoparticles, and hydrogels. We also highlight the progress in the chemical design of functional polypeptides, which plays a crucial role to manipulate their assembly behaviours and optimize their biomedical performances. Finally, we conclude the review by discussing the future opportunities in this field, including further studies on the secondary structures and cost-effective synthesis of polypeptide materials.

Synthetic polypeptides: from polymer design to supramolecular assembly and biomedical application

Self-assembled peptide nanostructures have been increasingly exploited as functional materials for applications in biomedicine and energy. The emergent properties of these nanomaterials determine the applications for which they can be exploited. It has recently been appreciated that nanomaterials composed of multicomponent coassembled peptides often display unique emergent properties that have the potential to dramatically expand the functional utility of peptide-based materials. This review presents recent efforts in the development of multicomponent peptide assemblies. The discussion includes multicomponent assemblies derived from short low molecular weight peptides, peptide amphiphiles, coiled coil peptides, collagen, and β-sheet peptides. The design, structure, emergent properties, and applications for these multicomponent assemblies are presented in order to illustrate the potential of these formulations as sophisticated next-generation bio-inspired materials.

/pdf/multicomponent-peptide-assemblies-1mxig4zs64.pdf

Multicomponent peptide assemblies

Supramolecular synthesis is a powerful strategy for assembling complex molecules, but to do this by targeted design is challenging. This is because multicomponent assembly reactions have the potential to form a wide variety of products. High-throughput screening can explore a broad synthetic space, but this is inefficient and inelegant when applied blindly. Here we fuse computation with robotic synthesis to create a hybrid discovery workflow for discovering new organic cage molecules, and by extension, other supramolecular systems. A total of 78 precursor combinations were investigated by computation and experiment, leading to 33 cages that were formed cleanly in one-pot syntheses. Comparison of calculations with experimental outcomes across this broad library shows that computation has the power to focus experiments, for example by identifying linkers that are less likely to be reliable for cage formation. Screening also led to the unplanned discovery of a new cage topology-doubly bridged, triply interlocked cage catenanes.

/pdf/high-throughput-discovery-of-organic-cages-and-catenanes-4di8nkb9k6.pdf

High-throughput discovery of organic cages and catenanes using computational screening fused with robotic synthesis

Secondary structures of synthetic polypeptide polymers

Polypeptides have attracted considerable attention in recent decades due to their inherent biodegradability and tunable cytocompatibility. Macromolecular design in conjunction with rational monomer composition can direct architecture, self-assembly and chemical behavior, ultimately guiding the choice of appropriate application within the biomedical field. This review focuses on the applications of polypeptides alongside the synthetic advances in the ring opening polymerization of α-amino acid N-carboxyanhydrides achieved in the past five years. Key architectures obtained through NCA ROP or in combination with other polymerization methods are reviewed, as these play an important role in the wide range of applications towards which polypeptides have been applied.

Ring opening polymerization of α-amino acids: advances in synthesis, architecture and applications of polypeptides and their hybrids.

https://www.rsc.org/suppdata/c5/cc/c5cc06905j/c5cc06905j1.pdf

Primary ammonium/tertiary amine-mediated controlled ring opening polymerisation of amino acid N-carboxyanhydrides.

Helical structures are ubiquitous in biological materials and often serve a structural purpose. Bioinspired helical materials can be challenging to synthesize and rarely reach the degree of hierarc...

Self-Assembly of α-Helical Polypeptides into Microscopic and Enantiomorphic Spirals

https://publishup.uni-potsdam.de/opus4-ubp/files/10228/pmnr301_online.pdf

Fibrillar gels via the self-assembly of poly(L-glutamate)-based statistical copolymers

https://pure.mpg.de/pubman/item/item_2465432_10/component/file_3153694/Accepted%20Manuscript.pdf

Controlled ring-opening polymerization of α-amino acid N-carboxyanhydrides in the presence of tertiary amines

Polyetheretherketone (PEEK) is a semicrystalline thermoplastic with excellent mechanical and chemical resistance properties that are retained to high temperatures. For these reasons, it is classified as a high performance thermoplastic. The first reinforced PEEK product was an impregnated continuous carbon fibre pre-preg tape called APC-2, but since then there have been many others. Most of the applications using PEEK involve joining it to itself or to another material; for instance, in the automotive or aerospace industries, lightweight structures need to be joined to metallic surfaces. However, the challenging processability of PEEK due to its high melting point (343°C) and high melt viscosity remains a limitation for its extensive use. This characteristic makes the processing of it time and energy consuming. Even so, interest in this thermoplastic is currently growing, driven by the constant search for lightweight and recyclable materials. Solutions to overcome these process limitations are investigate...

Charlotte D. Vacogne

Papers

Primary ammonium/tertiary amine-mediated controlled ring opening polymerisation of amino acid N-carboxyanhydrides.

Self-Assembly of α-Helical Polypeptides into Microscopic and Enantiomorphic Spirals

Fibrillar gels via the self-assembly of poly(L-glutamate)-based statistical copolymers

Controlled ring-opening polymerization of α-amino acid N-carboxyanhydrides in the presence of tertiary amines

Joining of high performance carbon fibre/PEEK composites