Facile Synthesis of Catechol-Containing Polyacrylamide Copolymers: Synergistic Effects of Amine, Amide and Catechol Residues in Mussel-Inspired Adhesives.

The straightforward synthesis of polyamide-derived statistical copolymers with catechol, amine, amide and hydroxy residues via free radical polymerization is presented. In particular, catechol, amine and amide residues are present in natural mussel foot proteins, enabling strong underwater adhesion due to synergistic effects where cationic residues displace hydration and ion layers, followed by strong short-rang hydrogen bonding between the catechol or primary amides and SiO2 surfaces. The present study is aimed at investigating whether such synergistic effects also exist for statistical copolymer systems that lack the sequence-defined positioning of functional groups in mussel foot proteins. A series of copolymers is established and the adsorption in saline solutions on SiO2 is determined by quartz crystal microbalance measurements and ellipsometry. These studies confirm a synergy between cationic amine groups with catechol units and primary amide groups via an increased adsorptivity and increased polymer layer thicknesses. Therefore, the free radical polymerization of catechol, amine and amide monomers as shown here may lead to simplified mussel-inspired adhesives that can be prepared with the readily scalable methods required for large-scale applications.

Specific Binding of Ligand-Functionalized Thermoresponsive Microgels: Effect of Architecture, Ligand Density, and Hydrophobicity.

The biomolecular interaction of ligand-presenting switchable microgels is studied with respect to the polymer type, composition, and structure of the microgels. Monodisperse microgels are prepared through precipitation polymerization of N-isopropylacrylamide (PNIPAM microgels) or oligo(ethylene glycol methacrylamide)s (POEGMA microgels) in the presence of crosslinkers or in their absence (self-crosslinked). Functionalization with mannose or biotin as model ligands and affinity measurements upon heating/cooling are conducted to obtain mechanistic insights into how the microgel phase transition affects the specific interactions. In particular, we are interested in adjusting the crosslinking, swelling degree, and ligand density of mannose-functionalized microgels to reversibly catch and release mannose binding Escherichia coli by setting the temperature below or above the microgels' volume phase transition temperature (VPTT). The increased mannose density for collapsed microgels above the VPTT results in stronger E. coli binding. Detachment of E. coli by reswelling the microgels below the VPTT is achieved only for self-crosslinked microgels showing a stronger decrease in ligand density compared to microgels with dedicated crosslinkers. Owing to a reduced mannose density in the shell of POEGMA microgels, their E. coli binding was lower compared to PNIPAM microgels, as supported by ultraresolution microscopy. Importantly, an inverse temperature-controlled binding of microgels decorated with hydrophilic mannose and hydrophobic biotin ligands is observed. This indicates that hydrophobic ligands are inaccessible in the collapsed hydrophobic network above the VPTT, whereas hydrophilic mannose units are then enriched at the microgel-water interface and thus are more accessible.

Lectin and E. coli Binding to Carbohydrate-Functionalized Oligo(ethylene glycol)-Based Microgels: Effect of Elastic Modulus, Crosslinker and Carbohydrate Density.

The synthesis of carbohydrate-functionalized biocompatible poly(oligo(ethylene glycol) methacrylate microgels and the analysis of the specific binding to concanavalin A (ConA) and Escherichia coli (E. coli) is shown. By using different crosslinkers, the microgels' size, density and elastic modulus were varied. Given similar mannose (Man) functionalization degrees, the softer microgels show increased ConA uptake, possibly due to increased ConA diffusion in the less dense microgel network. Furthermore, although the microgels did not form clusters with E. coli in solution, surfaces coated with mannose-functionalized microgels are shown to bind the bacteria whereas galactose (Gal) and unfunctionalized microgels show no binding. While ConA binding depends on the overall microgels' density and Man functionalization degree, E. coli binding to microgels' surfaces appears to be largely unresponsive to changes of these parameters, indicating a rather promiscuous surface recognition and sufficiently strong anchoring to few surface-exposed Man units. Overall, these results indicate that carbohydrate-functionalized biocompatible oligo(ethylene glycol)-based microgels are able to immobilize carbohydrate binding pathogens specifically and that the binding of free lectins can be controlled by the network density.