聚合物刷型二齿硼酸配体吸附剂的制备及其对尿液中核苷的分离富集性能分析  

Preparation of Polymer Brushes with Diboronic Acid Ligand for Separation and Enrichment of Nucleosides in Human Urine

作　　者：贺茂芳 王欣 张育珍 张博[1] 唐一梅[1] 张剑 HE Mao-Fang;WANG Xin;ZHANG Yu-Zhen;ZHANG Bo;TANG Yi-Mei;ZHANG Jian(College of Pharmacy,Xi'an Medical University,Xi'an 710021,China;College of Pharmacy,Beihua University,Jilin 132013,China)

机构地区：[1]西安医学院药学院,西安710021 [2]北华大学药学院,吉林132013

出　　处：《分析化学》2024年第3期409-418,共10页Chinese Journal of Analytical Chemistry

基　　金：陕西省教育厅自然科学基础研究计划项目(No.23JK0643);陕西高校青年创新团队建设项目(No.2022-85);西安医学院科技创新团队项目(Nos.2021TD03,2021TD07)资助。

摘　　要：为提高硼亲和吸附剂的结合力和吸附容量,以丙烯酰胺为单体,通过原子转移自由基聚合反应在聚多巴胺磁性微球(Fe_(3)O_(4)@pDA)表面接枝富含氨基的聚合物刷,然后键合二齿硼酸配体,获得聚合物刷型二齿硼酸配体吸附剂(Fe_(3)O_(4)@pDA@p-DBA)。利用红外光谱和X-射线光电子能谱对材料进行表征,并研究了材料的吸附性能。结果表明,吸附剂对顺式二羟基化合物具有较高的选择性,并且二齿硼酸配体吸附剂较单齿硼酸配体吸附剂(Fe_(3)O_(4)@pDA@p-BA)具有更高的亲和力和吸附容量,说明二齿硼酸配体对材料的亲和力和吸附容量有促进作用。静态等温吸附和动态吸附研究结果表明,此材料对核苷的吸附符合Freundlich拟合及准二级动力学方程,为多层吸附,其中化学吸附起主导作用。在中性至弱酸性条件下,此材料对顺式二羟基分子仍具有良好的吸附性,有利于生物样品的直接分离富集。当缓冲液pH=6.5时,对于浓度为1.0μg/mL的腺苷、鸟苷、胞苷和尿苷4种核苷混合溶液,最佳吸附剂质量为30.0mg。最佳洗脱条件为0.5mL0.1mol/L甲酸-甲醇(1:1,V/V)混合溶液洗脱2次,每次洗脱5min。将此吸附剂用于尿液中核苷的分离富集,利用高效液相色谱进行检测,检测出尿液中腺苷、鸟苷、胞苷和尿苷的含量分别为8.0、50.4、29.3和35.2ng/mL,加标回收率为87.6%~107.3%,相对标准偏差为2.8%~9.2%,说明本方法的准确度较高,结果可靠。To improve the binding strength and adsorption capacity,a boronate affinity adsorbent was prepared by atom transfer radical polymerization using acrylamide as monomer,and then decorated with a bidentate boronate ligand(DBA)by post-modification.The materials were characterized by infrared spectrum and X-ray photoelectron spectroscopy,and the adsorption properties of the materials were studied.The results showed that the adsorbent had higher selectivity for cis-diols compounds.Meanwhile,the adsorbent modified with DBA had higher affinity adsorption capacity than that modified by single boric acid ligand adsorbent,indicating that the DBA could promote the affinity strength and adsorption capacity of the material.Static isothermal adsorption and dynamic adsorption showed that the adsorption of nucleosides was in accordance with Freundlich fitting and quasi-second-order kinetic equation,so it belonged to multilayer adsorption,and the chemical adsorption played a leading role.Under neutral to weakly acidic conditions,the material still had good adsorption capacity for cis-diols molecules,which was conducive to the direct separation and enrichment of biological samples.When the buffer pH=6.5,the optimal adsorbent mass was 30.0 mg for 1.0μg/mL mixed solution of four nucleosides.The optimal elution was 0.1 mol/L formic acid-methanol(1:1,Ⅴ/Ⅴ).The elution volume was 0.5 mL for twice,and 5 min each time.The material was applied to the separation and enrichment of nucleosides in human urine.The concentration of adenosine,guanosine,cytidine and uridine in urine was detected to be 8.0,50.4,29.3 and 35.2 ng/mL,respectively.The recoveries were 87.6%-107.3%and the relative standard deviations were 2.8%-9.2%,indicating that the method was accurate and reliable.

关 键 词：二齿硼酸配体 线性聚合物刷 亲和力 分离富集 核苷 

分 类 号：TQ424[化学工程]