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Tunable, biodegradable grafting-from glycopolypeptide bottlebrush polymers

ABSTRACT: The cellular glycocalyx and extracellular matrix are rich in glycoproteins and proteoglycans that play essential physical and biochemical roles in all life. Synthetic mimics of these natural bottlebrush polymers have wide applications in biomedicine, yet preparation has been challenged by their high grafting and glycosylation densities. Using one-pot dual-catalysis polymerization of glycan-bearing α-amino acid N-carboxyanhydrides, we report grafting-from glycopolypeptide brushes. The materials are chemically and conformationally tunable where backbone and sidechain lengths were precisely altered, grafting density modulated up to 100%, and glycan density and identity tuned by monomer feed ratios. The glycobrushes are composed entirely of sugars and amino acids, are non-toxic to cells, and are degradable by natural proteases. Inspired by native lipid-anchored proteoglycans, cholesterol-modified glycobrushes were displayed on the surface of live human cells. Our materials overcome long-standing challenges in glycobrush polymer synthesis and offer new opportunities to examine glycan presentation and multivalency from chemically defined scaffolds. Synthetic mimics of glycoproteins and proteoglycans have wide applications in biomedicine, yet preparation has been challenged by their high grafting and glycosylation densities. Here the authors show one-pot dual-catalysis polymerization of glycan-bearing α-amino acid N-carboxyanhydrides to form glycopolypeptide brushes.

SUBMITTER: Clauss Z

PROVIDER: S-EPMC8578664 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Project description:In this work, we compare three routes to prepare antifouling coatings that consist of poly(l-lysine)-poly(N-(2-hydroxypropyl)methacrylamide) bottlebrushes. The poly(l-lysine) (PLL) backbone is self-assembled onto the surface by charged-based interactions between the lysine groups and the negatively charged silicon oxide surface, whereas the poly(N-(2-hydroxypropyl)methacrylamide) [poly(HPMA)] side chains, grown by reversible addition-fragmentation chain-transfer (RAFT) polymerization, provide antifouling properties to the surface. First, the PLL-poly(HPMA) coatings are synthesized in a bottom-up fashion through a grafting-from approach. In this route, the PLL is self-assembled onto a surface, after which a polymerization agent is immobilized, and finally HPMA is polymerized from the surface. In the second explored route, the PLL is modified in solution by a RAFT agent to create a macroinitiator. After self-assembly of this macroinitiator onto the surface, poly(HPMA) is polymerized from the surface by RAFT. In the third and last route, the whole PLL-poly(HPMA) bottlebrush is initially synthesized in solution. To this end, HPMA is polymerized from the macroinitiator in solution and the PLL-poly(HPMA) bottlebrush is then self-assembled onto the surface in just one step (grafting-to approach). Additionally, in this third route, we also design and synthesize a bottlebrush polymer with a PLL backbone and poly(HPMA) side chains, with the latter containing 5% carboxybetaine (CB) monomers that eventually allow for additional (bio)functionalization in solution or after surface immobilization. These three routes are evaluated in terms of ease of synthesis, scalability, ease of characterization, and a preliminary investigation of their antifouling performance. All three coating procedures result in coatings that show antifouling properties in single-protein antifouling tests. This method thus presents a new, simple, versatile, and highly scalable approach for the manufacturing of PLL-based bottlebrush coatings that can be synthesized partly or completely on the surface or in solution, depending on the desired production process and/or application.

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Tunable, biodegradable grafting-from glycopolypeptide bottlebrush polymers

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