Synthesis and Application of Glycopolymers

Abstract

Multimeric representations of carbohydrates play a pivotal role in many biological processes. Polymer chemists aim at copying these biologically active biopolymers by the design of glycopolymers, synthetic polymers with pendant sugars. This article is focused on the synthetic methods as well as applications of these macromolecules. Since the first description of glycopolymers in the late 1950s, a myriad of glycopolymer structures have been reported. The first glycopolymer was prepared via free radical polymerization, but soon other techniques including ionic chain polymerization, ring‐opening polymerization, and ring‐opening methatesis polymerization followed. The arrival of living radical polymerization techniques caused a surge in publications on glycopolymers. Although most polymerization techniques have been employed to create glycopolymers, atom‐transfer radical polymerization and reversible addition‐fragmentation chain transfer (RAFT) polymerization dominate the literature. Architectures reported range from simple homopolymers to block copolymers, endfunctional glycopolymers, and stars and gels. Immobilization of initiators or RAFT agents led to bioactive surfaces. In recent years, the focus has shifted from the pure interest in the synthesis to the investigation of the biological activity of these glycopolymers. While the direct synthesis using glycomonomers dominated the literature for years, recent times saw the increased use of postmodification procedures. Reactive polymers were conjugated with sugars using an array of reactions including click chemistry and various reactions based on thiol‐ or amino sugars. This article gives a brief historical account on the synthesis of glycopolymers and outline briefly the different techniques—direct synthesis and postmodification—to design glycopolymers. The main focus will be, however, the advancements in applications of glycopolymers since around 2010, which contributed to the existing knowledge on how the structure of the glycopolymer affects the binding with lectin.

Modulation of Macrophages M1/M2 Polarization Using Carbohydrate-Functionalized Polymeric Nanoparticles

“…Glycopolymers can be prepared either by post-polymerization modification, which consists in the functionalization of a preformed polymeric backbone, or in the polymerization of glycosylated monomers [ 51 , 52 ] that can be performed by several synthetic routes that provide controllable architectures, stereochemistry, and molecular weights, such as free radical polymerization (ring-opening polymerization (ROP)), ionic polymerization, controlled radical polymerization (nitroxide-mediated polymerization (NMP), atom transfer radical polymerization (ATRP), reversible addition fragmentation chain transfer (RAFT), and enzyme-mediated polymerization [ 51 , 53 , 54 , 55 ]. Here, we will focus on the post-functionalization of polymeric nanoparticles with carbohydrates, as it allows the attachment of pendant carbohydrate moieties ( Figure 3 ), making it ideal for targeted delivery.…”

Enzymatic synthesis and structural characterization of methacryloyl‐D‐fructose‐ and methacryloyl‐D‐glucose‐based monomers and poly(methacryloyl‐D‐fructose)‐based hydrogels

“…In the polymer field, these renewable raw materials have been widely used in recent years and many studies have been performed to produce a wide range of monomers and polymers based on carbohydrates . Polymers with carbohydrates moieties, named glycopolymers, have been prepared using two main routes: synthesis of carbohydrate‐based monomers, followed by their polymerization, and functionalization of polymers with carbohydrates . Glycopolymers based on carbohydrate methacrylate were first reported by Haworth and co‐workers, who prepared crosslinked and hard polymers from sorbitol and mannitol (meth)acrylates …”

“…2,3 Polymers with carbohydrates moieties, named glycopolymers, have been prepared using two main routes: synthesis of carbohydrate-based monomers, followed by their polymerization, and functionalization of polymers with carbohydrates. [4][5][6][7] Glycopolymers based on carbohydrate methacrylate were first reported by Haworth and co-workers, who prepared crosslinked and hard polymers from sorbitol and mannitol (meth)acrylates. 8 Carbohydrate (meth)acrylate-based polymers combine an apolar backbone with polar carbohydrate moieties, which endow polymers with water solubility without backbone degradation.…”

Thermoresponsive Glycopolymers Based on Enzymatically Synthesized Oligo-β-Mannosyl Ethyl Methacrylates and N-Isopropylacrylamide

“…FRP is the most common type of polymerization in the industry, accounting for around 40–45% of all industrial polymers due to its simplicity and tolerance to impurities which reduces costs. Several studies have demonstrated that glycopolymers synthesized via FRP possess adequate affinity to biological targets, although they are polydisperse. , A brief summary of potential applications of glycopolymers synthesized with FRP has been reported by Babiuch and Stenzel . We expect that in the future, the use of FRP will increase the viability of these applications at large scale.…”

“… 1 , 23 A brief summary of potential applications of glycopolymers synthesized with FRP has been reported by Babiuch and Stenzel. 24 We expect that in the future, the use of FRP will increase the viability of these applications at large scale. We anticipate that the introduction of a biobased molecule with mannose moieties would lead to a certain degree of affinity for lectins, viruses, and/or toxins, and that such interactions can be tuned for specific applications.…”