Magnetic boronate modified molecularly imprinted polymers on magnetite microspheres modified with porous TiO2 (Fe3O4@pTiO2@MIP) with enhanced adsorption capacity for glycoproteins and with wide operational pH range
Magnetic boronate modified molecularly imprinted polymers on magnetite microspheres modified with porous TiO2 (Fe3O4@pTiO2@MIP) with enhanced adsorption capacity for glycoproteins and with wide operational pH range
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多孔 TiO2 改性的磁铁矿微球上的磁性硼酸盐改性分子印迹聚合物 (Fe3O4@pTiO2@MIP)，具有增强的糖蛋白吸附能力和广泛的操作 pH 范围
DOI：
10.1007/s00604-018-3092-z
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发表时间：
2018-12-01
影响因子：
5.7
通讯作者：
Shi, Yan-Ping
中科院分区：
文献类型：
--
作者：
Sun, Xiao-Yu;Ma, Run-Tian;Shi, Yan-Ping
硼酸盐亲和分子印迹聚合物（MIPs）存在吸附容量低、工作pH范围窄等问题。将一种含苯硼酸基的磁性分子印迹聚合物（Fe3O4@pTiO2@MIP）置于多孔TiO 2包覆的Fe 3 O 4（磁铁矿）微球表面。与其二氧化硅类似物（Fe3O4@SiO2@MIP）相比，花状Fe3O4@pTiO 2为模板提供了更多的结合位点。因此，Fe3O4@pTiO2@MIP的吸附能力被强烈增强。Ti（IV）的强吸电子效应使得MIP的硼酸在6.0至9.0的宽pH范围内对糖蛋白具有更好的亲和力。因此，在碱性和酸性条件下，Fe3O4@pTiO2@MIP对糖蛋白的吸附能力均高于Fe3O4@SiO2@MIP。用含30%乙腈的5%乙酸水溶液洗脱Fe3O4@pTiO2@MIPs，MALDI-TOF MS分析，并将该方法应用于加标胎牛血清（FBS）中辣根过氧化物酶（HRP）的选择性提取和定量。方法的线性范围为0.40 ~ 10 μg·mL-1，检出限为0.31 μg·mL-1。在我们看来，这项工作具有广泛的范围，因为它为更广泛地应用基于硼酸酯亲和性的MIP用于分析糖蛋白和相关糖化合物铺平了道路，即使在中等酸性pH值下。磁性硼酸酯修饰的分子印迹聚合物在多孔TiO 2修饰的磁性球上的示意图（Fe3O4@pTiO2@MIP）。在通过MALDI-TOF质谱法定量之前，将其应用于提取加标的碱性胎牛血清（FBS）和酸性尿液样品中的糖蛋白。
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@pTiO2offers 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-1with 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 abstract Schematic 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.