Polypeptide films via N-carboxyanhydride ring-opening polymerization (NCA-ROP): past, present and future

Abstract

The formation of surface-grafted polypeptide films and interfaces via N-carboxyanhydride ring-opening polymerization (NCA-ROP) holds great potential for the facile preparation of next-generation multifunctional and responsive materials with excellent biocompatibility, biodegradability, tunable conformations and chemical functionalities. Therefore, the aim of this feature article is to provide a topical review of developments in the area of polypeptide films derived through NCA-ROP. It is evident that studies reported thus far have only started to unveil the full potential of peptide-based interfaces and materials, and with continued advancements it is anticipated that the strategic combination of NCA-ROP with modern synthetic chemistries will continue to yield versatile platforms for broader applications in the fields of polymer therapeutics, tissue engineering, (bio)nanocoatings, (bio)chemosensors, catalysis and separation technologies.

Responsive hybrid (poly)peptide–polymer conjugates

“…75 ROP has potential for the development of peptide-based stimuli-responsive materials with unique properties such as tunable conformations, chemical functionalities, and 3D nanostructures. In particular, L-glutamic acid NCA has been a widely used monomer in ROP aimed at producing conjugates.…”

Poly(ornithine‐co‐arginine‐co‐glycine‐co‐aspartic Acid): Preparation via NCA Polymerization and its Potential as a Polymeric Tumor‐Penetrating Agent

“…[30] Polypeptides can be synthesized by the ring-opening polymerization (ROP) of N-carboxy anhydrides (NCA) of a-amino acids, which has become the most common technique used for large scale preparation of polypeptides with high molecular weight. [31][32][33][34][35][36][37][38][39] The NCA polymerization is well controlled without detectable side reactions for degree of polymerization close to 100. [40] When ammonium salts with non-nucleophilic tetrafluoroborate anions are used as initiators, multigram scale polyglutamate with defined molecular weight (up to 800 units) and low polydispersity (<1.2) can be synthesized by the ROP of NCAs.…”

“…[41] Many copolypeptides have been reported to be prepared by the NCA polymerization. [42][43][44][45] Especially, as a typical copolypeptide, Glatiramer Acetate (copolymer-1; Cop-1; Copaxone 1 ) has been approved as an effective treatment in relapsing multiple sclerosis (MS). [46] These indicate the great potential of copolypeptide in biomedical applications.…”

Hybrid Nanomaterials by Surface Grafting of Synthetic Polypeptides Using N‐Carboxyanhydride (NCA) Polymerization

“…The synthetic aspects of surface decoration with NCA derived polypeptides has been reviewed recently and will only be highlighted briefly in the following. [25,26] NCAs are readily obtained by the phosgenation reaction of an (protected) amino acid [27][28][29][30] and can be polymerized in a ring-opening polymerization yielding the synthetic polypeptides. [31][32][33][34] Generally, the grafting from approach (growth of the polymer from the surface) requires an initiator being covalently or non-covalently immobilized on the surface, which for NCA polymerization predominantly is a primary amine.…”