Self-Assembled Multi- and Single-Chain Glyconanoparticles and Their Lectin Recognition

Abstract

In this work, we describe the physicochemical characterization of amphiphilic glycopolymers synthesized via copper(0)-mediated reversible-deactivation radical polymerization (Cu-RDRP). Depending on the chemical composition of the polymer, these glycopolymers are able to form multi-chain or single-chain polymeric nanoparticles. The folding of these polymers is first of all driven by the amphiphilicity of the glycopolymers and furthermore by the supramolecular formation of helical supramolecular stacks of benzene-1,3,5-tricarboxamides (BTAs) stabilized by threefold hydrogen bonding. The obtained polymeric nanoparticles were subsequently evaluated for their lectin-binding affinity toward a series of mannose- and galactose-binding lectins via surface plasmon resonance. We found that addition of 2-ethylhexyl acrylate to the polymer composition results in compact particles, which translates to a reduction in binding affinity, whereas with the addition of BTAs, the relation between the nature of the particle and the binding ability system becomes more unpredictable.

Controlling Amphiphilic Polymer Folding beyond the Primary Structure with Protein-Mimetic Di(Phenylalanine)

“…Despite this need for higher-order structure, there are few examples of synthetic polymer assemblies that demonstrate these motifs in an aqueous environment . Within the single-chain nanoparticle (SCNP) literature, protein-mimetic collapse dictating the global morphology has been generated with hydrogen-bonding using a pendent benzene-1,3,5-tricarboxamide (BTA) moiety, − hydrophobic collapse using alkyl chains, − host–guest interactions, metal–ligand interactions, and covalent cross-links. , As secondary structure is driven by backbone hydrogen bonding in proteins, it is challenging to mimic this local rigidity with an amide-lacking polymer backbone. Helices can be introduced with the BTA-pendent methacrylate monomer that is incorporated into a random amphiphilic copolymer through ruthenium-catalyzed living radical polymerization. , However, the synthetic versatility of the polymerizable BTA methacrylate is not currently available for β-sheet-like structures, which have only been introduced into aqueous assemblies through incorporation of a peptide block into the polymer backbone.…”

Hierarchy of Complex Glycomacromolecules: From Controlled Topologies to Biomedical Applications

“…Glyconanoparticles can also be prepared from a single-chain polymer, through exclusive intramolecular cross-linking of polymer chain, as investigated in several studies. − Single-chain polymer nanoparticles can be used as noninvasive drug-delivery system, taking advantage of their small sizes, specific molecular recognition, and increased lectin binding in comparison to their linear precursors . In this regard, Becer et al investigated how the chemical composition of the polymer plays a role in the formation of multichain rather than single-chain polymeric nanoparticles . In this study, three distinct sets of glycopolymers were prepared by using Cu-RDRP.…”

From poly(vinylimidazole) to cationic glycopolymers and glyco-particles: effective antibacterial agents with enhanced biocompatibility and selectivity

“…It should be noted that ATRP in an aqueous system is often challenging, mainly due to the side reactions of catalysts and terminal halogen groups, which will lead to uncontrolled polymerizations. Although there have been emerging works, 26 it still shows deficiencies in the largescale production of glycopolymers. Alternatively, saccharides with pendant functional groups can be grafted to polymer chains via "Click Chemistry", for example, thio-ene, 27 Diels-Alder, 28,29 thio-epoxy, 30 copper-mediated azide alkyne cycloaddition (CuAAC) reactions, etc.…”