Block Copolypeptides Prepared by N‐Carboxyanhydride Ring‐Opening Polymerization

Abstract

N-Carboxyanhydride ring-opening polymerization (NCA ROP) is a synthetically straightforward methodology to generate homopolypeptides. Extensive control over the polymerization permits the production of highly monodisperse synthetic polypeptides to a targeted molecular weight in the absence of unfavorable side reactions. Sequential NCA ROP permits the creation of block copolypeptides composed of individual polypeptide blocks boasting different functionalities, secondary structures, and desirable chemical properties. Consequently, a plethora of novel materials have been generated that have found wide-range applicability. This review offers an insight into contemporary synthetic approaches toward NCA ROP before highlighting a number of block copolypeptide architectures generated.

Hybrid Block Copolymers Constituted by Peptides and Synthetic Polymers: An Overview of Synthetic Approaches, Supramolecular Behavior and Potential Applications

“…Over the past decade new strategies were developed so as to enable the "living" behavior of NCA's polymerization. The control over the growing polymer chains was achieved using primary amines or ammonium salts, thiol groups and silazanes, by means of the use of transition metal complexes based principally on nickel, cobalt and platinum or using high vacuum techniques [14,15].…”

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

“…NCA polymerization of natural and non-natural amino acids has significantly advanced over the last decade and techniques are available that permit the synthesis of well-defined polypeptide structures with controlled molecular weights, architecture and composition. [2][3][4] Moreover, orthogonal modification chemistries offer synthetic, structural and functional adaptability. [5][6][7] …”

“…[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. The surface initiated NCA polymerization results in the formation of dense, homogeneous polypeptide brushes.…”

Synthesis of Amphiphilic Block Copolypept(o)ides by Bifunctional Initiators: Making PeptoMicelles Redox Sensitive

“…Especially for applications as nano drug delivery system (nanoDDS), block copoly peptides have been broadly investigated. [ 5,[8][9][10] Such block copolypetides are usually synthesized by sequential ring opening polymerization of α-amino acid-N -carboxyanhydrides (NCAs). [ 11 ] But, chemical ligation of homopolymers can also be employed.…”