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Clickable core-shell nanoparticles based on poly(styrene-<i>co-</i>divinylbenzene-<i>co-</i>vinylbenzylazide) have been synthesized via emulsion polymerization. The 38 nm sized particles have been swollen by divinyl benzene (DVB) and 2,2&#8217;-azobis(2-methylpropionitrile) (AIBN) and subsequently processed under high shear rates in a Z-shaped microchannel giving macroporous microclusters (100 &#181;m), through the reactive gelation process. The obtained clusters were post-functionalized by &#8220;click-chemistry&#8222; with propargyl-PEG-NHS-ester and propargylglicidyl ether, yielding epoxide or NHS-ester activated polymer supports for bioconjugation. Macroporous affinity materials for antibody capturing were produced by immobilizing recombinant <i>Staphylococcus aureus</i> protein A on the polymeric support. Coupling chemistry exploiting thiol-epoxide ring-opening reactions with cysteine-containing protein A revealed up to three times higher binding capacities compared to the protein without cysteine. Despite the lower binding capacities compared to commercial affinity phases, the produced polymer&#8211;protein hybrids can serve as stationary phases for immunoglobulin affinity chromatography as the materials revealed superior intra-particle mass transports.