Citation: ZHANG Jun-Cai, CHENG You-Ning, WEI Yin-Mao. Preparation of Boron Affinity Magnetic Adsorbent with High Adsorption Capacity and Its Application in Extraction of Cis-Diol Biomolecules. Chinese Journal of Analytical Chemistry, 2018, 46(9): 1464-1471. doi: 10.11895/j.issn.0253-3820.181369 [复制]
Preparation of Boron Affinity Magnetic Adsorbent with High Adsorption Capacity and Its Application in Extraction of Cis-Diol Biomolecules
硼亲和吸附法是分离富集邻羟基物质的重要方法。为提高吸附剂的吸附容量，本研究采用聚乙烯亚胺修饰磁性纳米粒子，增加粒子表面引发剂的密度，再通过表面引发原子转移自由基聚合法（SI-ATRP）将3-丙烯酰基苯硼酸原位聚合在纳米粒子表面，制备了一种高密度聚合物分子刷型的硼酸亲和磁性纳米粒子吸附剂。采用磁性分散固相萃取法对非邻羟基和邻羟基物质的混合液进行富集，发现此吸附剂对邻羟基小分子和生物大分子具有良好的吸附特异性；采用吸附等温线法测定了吸附剂的吸附容量，发现此吸附剂对邻苯二酚、腺苷和卵清蛋白的吸附容量分别为（151±32）μmol/g、（123±18）μmol/g和1.5 μmol/g，远高于传统吸附剂的吸附容量。采用所制备的硼酸亲和磁性纳米粒子对尿液中4种核苷和蛋清中的糖蛋白进行萃取，结果表明，此吸附剂能够有效去除生物样品中的干扰物，且对核苷具有较高的萃取回收率（83.8%-108.7%，RSD < 15%），对糖蛋白有特异性富集作用，说明此吸附剂在生物样品的选择性富集中具有良好应用潜能。
Boronate affinity is an important method to extract selectively cis-diol biomolecules. In this work, a novel polymeric brush-type magnetic adsorbent with high density of boronate was successfully prepared. Specifically, polyethyleneimine was firstly employed to supply a large quantity of initiator sites on the surface of the magnetic nanoparticales, and then 3-acrylamidophenylboronic acid (AAPBA) monomer was grafted from the surface of magnetic nanoparticales using surface-initiated atom transfer radical polymerization (SI-ATRP). The mixture of cis-diol and non-cis-diol compounds was extracted by magnetic dispersion solid-phase extraction method, and it was found that the obtained adsorbent showed good selectivity to cis-diol small molecules and biomacromolecules. In addition, the binding capacity was measured by the adsorption isotherm method to be (151±32) mmol/g for catechol, (123±18) mmol/g for adenosine and 1.5 μmol/g for ovalbumin, respectively, which was far higher than those reported in the references. Finally the prepared nanoparticles were employed to extract four nucleosides in urine and glycoproteins in egg white, respectively. The results showed that the nanoparticles could effectively remove some potential interference in biological samples. In addition, the developed method exhibited good recovery for four nucleosides (83.8%-108.7%, RSD < 15%) and excellent selectivity for glycoprotein. The adsorbents had potential in selective enrichment of cis-diol compounds from real biological samples.