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Abstract: Boronate-affinity based molecularly imprinted polymers (MIPs) are beset by the unsatisfied adsorption capacity and narrow working pH ranges. A magnetic molecularly imprinted polymer containing phenylboronic acid groups was placed on the surface of Fe3O4 (magnetite) microspheres coated with porous TiO2 (Fe3O4@pTiO2@MIP). In contrast to its silica analog (Fe3O4@SiO2@MIP), the flowerlike Fe3O4@pTiO2 offers more binding sites for templates. Thus, the adsorption capacity of the Fe3O4@pTiO2@MIP is strongly enhanced. The strong electron-withdrawing effects of Ti(IV) enable the boronic acid of the MIP to have better affinity for glycoproteins at a wide pH range from 6.0 to 9.0. Consequently, the Fe3O4@pTiO2@MIP exhibits higher adsorption for glycoproteins than Fe3O4@SiO2@MIP in both basic and acidic medium. The Fe3O4@pTiO2@MIPs were eluted with 5% acetic acid aqueous solution containing 30% acetonitrile, and the eluate was analyzed by MALDI-TOF MS. The method was applied to the selective extraction and quantitation of horseradish peroxidase (HRP) in spiked fetal bovine serum (FBS). The linear range is 0.40-10 μg mL-1 with the limit of detection of 0.31 μg mL-1. In our perception, this work has a wide scope in that is paves the way to a more widespread application of boronate affinity based MIPs for analysis of glycoproteins and related glyco compounds even at moderately acidic pH values
Template and target information: glycoprotein, protein
Author keywords: magnetic separation, boronate-affinity, Moderate acidic conditions, Horseradish peroxidase, MALDI-TOF MS