AbstractBoronate-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. Graphical abstractSchematic presentation of the magnetic boronate modified molecularly imprinted polymer on magnetic spheres modified with porous TiO2 (Fe3O4@pTiO2@MIP). It was applied to extract glycoprotein in spiked both basic fetal bovine serum (FBS) and acidic urine samples prior to quantitation by MALDI-TOF mass spectrometry.

中文翻译：

---

磁性硼酸盐修饰的分子印迹聚合物在用多孔 TiO2 (Fe3O4@pTiO2@MIP) 修饰的磁铁矿微球上具有增强的糖蛋白吸附能力和宽操作 pH 范围

摘要 基于硼酸盐亲和性的分子印迹聚合物 (MIP) 受到吸附容量不满意和工作 pH 范围窄的困扰。将含有苯基硼酸基团的磁性分子印迹聚合物置于涂有多孔 TiO2 (Fe3O4@pTiO2@MIP) 的 Fe3O4（磁铁矿）微球表面。与其二氧化硅类似物 (Fe3O4@SiO2@MIP) 相比，花朵状的 Fe3O4@pTiO2 为模板提供了更多的结合位点。因此，Fe3O4@pTiO2@MIP 的吸附能力大大增强。Ti(IV) 的强吸电子作用使 MIP 的硼酸在 6.0 到 9.0 的宽 pH 范围内对糖蛋白具有更好的亲和力。因此，在碱性和酸性介质中，Fe3O4@pTiO2@MIP 对糖蛋白的吸附比 Fe3O4@SiO2@MIP 更高。Fe3O4@pTiO2@MIPs用含30%乙腈的5%醋酸水溶液洗脱，洗脱液用MALDI-TOF MS分析。该方法用于选择性提取和定量加标胎牛血清 (FBS) 中辣根过氧化物酶 (HRP)。线性范围为 0.40–10 μg·mL-1，检测限为 0.31 μg·mL-1。在我们看来，这项工作具有广泛的范围，为更广泛地应用基于硼酸盐亲和力的 MIP 分析糖蛋白和相关糖化合物铺平了道路，即使在中等酸性的 pH 值下也是如此。图解摘要：在用多孔 TiO2 (Fe3O4@pTiO2@MIP) 改性的磁性球体上的磁性硼酸盐改性分子印迹聚合物的示意图。