Histidine-Functionalized Diblock Copolymer Nanoparticles Exhibit Enhanced Adsorption onto Planar Stainless Steel

RAFT aqueous emulsion polymerization of isopropylideneglycerol monomethacrylate (IPGMA) is used to prepare a series of PGEO5MA₄₆ -PIPGMA_y nanoparticles, where PGEO5MA is a hydrophilic methacrylic steric stabilizer block bearing pendent cis-diol groups. TEM studies confirm a spherical morphology while dynamic light scattering (DLS) analysis indicated that the z-average particle diameter can be adjusted by varying the target degree of polymerization for the core-forming PIPGMA block. Periodate oxidation is used to convert the cis-diol groups on PGEO5MA₄₆ -PIPGMA₅₀₀ and PGEO5MA₄₆ -PIPGMA₁₀₀₀ nanoparticles into the analogous aldehyde-functionalized nanoparticles, which are then reacted with histidine via reductive amination. In each case, the extent of functionalization is more than 99% as determined by ¹ H NMR spectroscopy. Aqueous electrophoresis studies indicate that such derivatization converts initially neutral nanoparticles into zwitterionic nanoparticles with an isoelectric point at pH 7. DLS studies confirm that such histidine-derivatized nanoparticles remain colloidally stable over a wide pH range. A quartz crystal microbalance is employed at 25°C to assess the adsorption of both the cis-diol- and histidine-functionalized nanoparticles onto planar stainless steel at pH 6. The histidine-bearing nanoparticles adsorb much more strongly than their cis-diol counterparts. For the highest adsorbed amount of 70.5 mg m^-2 , SEM indicates a fractional surface coverage of 0.23 for the adsorbed nanoparticles.