Surface-Attached Poly(oxanorbornene) Hydrogels with Antimicrobial and Protein-Repellent Moieties: The Quest for Simultaneous Dual Activity.

By copolymerizing an amphiphilic oxanorbornene monomer bearing N- tert-butyloxycarbonyl (Boc) protected cationic groups with an oxanorbornene-functionalized poly(ethylene glycol) (PEG) macromonomer, bifunctional comb copolymers were obtained. Varying the comonomer ratios led to copolymers with PEG contents between 5⁻25 mol %. These polymers were simultaneously surface-immobilized on benzophenone-bearing substrates and cross-linked with pentaerythritoltetrakis(3-mercaptopropionate). They were then immersed into HCl to remove the Boc groups. The thus obtained surface-attached polymer hydrogels (called SMAMP*--PEG) were simultaneously antimicrobial and protein-repellent. Physical characterization data showed that the substrates used were homogeneously covered with the SMAMP*--PEG polymer, and that the PEG moieties tended to segregate to the polymer⁻air interface. Thus, with increasing PEG content, the interface became increasingly hydrophilic and protein-repellent, as demonstrated by a protein adhesion assay. With 25 mol % PEG, near-quantitative protein-adhesion was observed. The antimicrobial activity of the SMAMP*--PEG polymers originates from the electrostatic interaction of the cationic groups with the negatively charged cell envelope of the bacteria. However, the SMAMP*--PEG surfaces were only fully active against , while their activity against was already compromised by as little as 5 mol % (18.8 mass %) PEG. The long PEG chains seem to prevent the close interaction of bacteria with the surface, and also might reduce the surface charge density.