Emerging bioinspired polymers: glycopolypeptides

Abstract

This article highlights the very recent advances in glycopolypeptide synthesis via NCA polymerization and first studies on stimuli-responsive solution behavior and self-assembling structures. Yet glycopolypeptides are almost exclusively considered as smart biofunctional materials for use in biomedical applications, for instance in targeted drug delivery, but also have high potential for usage as structural materials to fabricate bioinspired hierarchical structures.

Glycosylated Star Polypeptides from NCA Polymerization: Selective Binding as a Function of Degree of Branching and Glycosylation

“…Preparation of glycopeptides from NCA‐derived polypeptides has been described in a number of recent reports either by the post‐modification of amino acid side chains or polymerization of glycosylated NCA monomers . Extensive progress on the latter synthetic pathway has recently been reported by the Deming group generating well‐defined glycopolymers .…”

“…[8][9][10][11][12] Preparation of glycopeptides from NCA-derived polypeptides has been described in a number of recent reports either by the post-modification of amino acid side chains or polymerization of glycosylated NCA monomers. [12][13][14] Extensive progress on the latter synthetic pathway has recently been reported by the Deming group generating well-defined glycopolymers. [15,16] Alternatively, postmodification of polypeptide amino acid side chains with carbohydrates has been explored, in particular with the advent of highly efficient and selective coupling reactions, for example, ''click'' chemistry including thiol-ene, [17,18] thiol-yne, [19,20] and azide-alkyne, [11,[21][22][23][24][25] which means sugars may be readily adapted to include alkyne, azide, thiol, and alkene functionalities to permit coupling to the corresponding compatible polypeptide side chains.…”

Scaffold and scaffold‐free self‐assembled systems in regenerative medicine

“…From a physicochemical point of view, these naturally occurring extrinsic signals can be readily recapitulated artificially by incorporating responsive sequences into natural and synthetic structures. Numerous stimuli-responsive self-assembled peptides (Maude et al, 2012), polysaccharides (Alvarez-Lorenzo et al, 2013), glycopolypeptides (Krannig and Schlaad, 2014) and synthetic polymers (He et al, 2008) have been explored over the years, enabling materialisation of more tunable implantable devices, revolutionising that way modern biomedicine. Of significant importance are recent developments in the field of multi-domain responsive (e.g., chemical, physical or biological responsiveness) materials (Zhuang et al, 2013) that by careful selection of the individual building blocks, controlled is offered over dimensionality, viscoelastic properties, cargo delivery capacity, sensitivity to local stimuli (e.g., proteolytic degradation) (Galler et al, 2010) and even programmable transformation capacity (Estephan et al, 2013).…”

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

“…[2][3][4] Moreover, orthogonal modification chemistries offer synthetic, structural and functional adaptability. [5][6][7] …”