Industrial & Engineering Chemistry Research, Vol.50, No.22, 12358-12365, 2011
Temperature-Swing Adsorption of Proteins in Water Using Cationic Copolymer-Grafted Silica Particles
We have prepared silica particles grafted with-poly(N-isopropylacrylamide) (PNIPA) copolymers as adsorbent for the temperature swing adsorption of bovine serum albumin (BSA), in Water, where vinylbenzyl trimethylammonium chloride (VBTA); 2-(dimethylamino)ethyl methacrylate (DMAEMA), or N,N-dimethylacrylamide (DMAA) was employed as a comonomer. The surface potentials of PNIPA-grafted and P(NIPA-co-DMAA)-grafted silica particles in water at 298 and 313 K were negative, while those of P(NIPA-co-VBTA)-grafted silica particle were positive, because VBTA is a quaternary ammonium salt and positively charged in aqueous solutions. As for the P(NIPA-co-DMAEMA)-grafted silica particle, the surface potential changed from positive to near zero with increasing temperature from 298 K to 313 K. This may be because the coil-to-globule transition of grafted copolymers leads to the dehydration and deprotonation of DMAEMA group, which is a tertiary amine and can be positively charged only in the aqueous phase. Although PNIPA-grafted and P(NIPA-co-DMAA)grafted silica particles failed to adsorb BSA, P(NIPA-co-VBTA)-grafted and P(NIPA-co-DMAEMA)-grafted silica particles adsorbed BSA, indicating that BSA, is adsorbed by the electrostatic attraction between the negatively charged BSA and the positively charged copolymers on the silica surface. Moreover, P(NIPA-co-VBTA)-grafted and P(NIPA-co-DMAEMA)-grafted silica particles repeatedly adsorbed BSA at 298K and desorbed some of the preadsorbed BSA at 313 K via the temperature swing Operation. This BSA desorption may result from the decrease in the number of the positively charged groups accessible to BSA due the Coil-to-globule transition of the grafted copolymers increasing temperature.