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Surface Functionalization by Stimuli-Sensitive Microgels for Effective Enzyme Uptake and Rational Design of Biosensor Setups

2018, Sigolaeva, Larisa V., Pergushov, Dmitry V., Oelmann, Marina, Schwarz, Simona, Brugnoni, Monia, Kurochkin, Ilya N., Plamper, Felix A., Fery, Andreas, Richtering, Walter

We highlight microgel/enzyme thin films that were deposited onto solid interfaces via two sequential steps, the adsorption of temperature- and pH-sensitive microgels, followed by their complexation with the enzyme choline oxidase, ChO. Two kinds of functional (ionic) microgels were compared in this work in regard to their adsorptive behavior and interaction with ChO, that is, poly(N-isopropylacrylamide-co-N-(3-aminopropyl)methacrylamide), P(NIPAM-co-APMA), bearing primary amino groups, and poly(N-isopropylacrylamide-co-N-[3-(dimethylamino) propyl]methacrylamide), P(NIPAM-co-DMAPMA), bearing tertiary amino groups. The stimuli-sensitive properties of the microgels in the solution were characterized by potentiometric titration, dynamic light scattering (DLS), and laser microelectrophoresis. The peculiarities of the adsorptive behavior of both the microgels and the specific character of their interaction with ChO were revealed by a combination of surface characterization techniques. The surface charge was characterized by electrokinetic analysis (EKA) for the initial graphite surface and the same one after the subsequent deposition of the microgels and the enzyme under different adsorption regimes. The masses of wet microgel and microgel/enzyme films were determined by quartz crystal microbalance with dissipation monitoring (QCM-D) upon the subsequent deposition of the components under the same adsorption conditions, on a surface of gold-coated quartz crystals. Finally, the enzymatic responses of the microgel/enzyme films deposited on graphite electrodes to choline were tested amperometrically. The presence of functional primary amino groups in the P(NIPAM-co-APMA) microgel enables a covalent enzyme-to-microgel coupling via glutar aldehyde cross-linking, thereby resulting in a considerable improvement of the biosensor operational stability.

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Selective Grafting of Polyamines to Polyether Ether Ketone Surface during Molding and Its Use for Chemical Plating

2018, Nagel, Jürgen, Zimmermann, Philipp, Schwarz, Simona, Schlenstedt, Kornelia

We present a new approach of surface functionalization of polyether ether ketone (PEEK) that is carried out during the molding step. Thin films of polymers with different functional groups were applied to the surface of a mold and brought in close contact with a PEEK melt during injection molding. The surfaces of the produced parts were characterized after solidification. Only those PEEK surfaces that were in contact with polymers bearing primary amino groups exhibited a wettability for water. Obviously, the thin polymer film was grafted to the surface by a chemical reaction initiated by the high melt temperature. The formation of azomethine bonds between PEEK and the polyamine by coupling to the ketone groups was proposed. The other amino groups in the molecule were still in function after the molding process. They adsorbed different anionic molecules and anionic charged nanoparticles from aqueous solutions. The surfaces could be chemically plated by copper and nickel with high adhesion.