Abstract Using surface imprinting technique, Cd (II) imprinted polymer surface modified silica monolithic capillary (shortened as Cd(II) imprinted monolithic capillary (Cd(II)-IMC)) was prepared for extraction of Cd (II). Based on it, a method of monolithic capillary microextraction - inductively coupled plasma mass spectrometry was developed for trace analysis of Cd (II) in human serum and urine samples. Taking Mn (II), Cu (II) and Zn (II) as competing ions, the extraction efficiency, distribution ratio and selectivity of the Cd(II)-IMC was investigated. It was found that the relative selectivity coefficients of the prepared Cd(II)-IMC towards Mn (II), Cu (II) and Zn (II) were 3.8, 2.2 and 2.2 respectively. Compared with non-imprinted monolithic capillary, the Cd(II)-IMC presented larger dynamic sorption capacity (6 μg m−1 over 4.2 μg m−1). Under the optimized extraction conditions, the limit of detection for Cd (II) was 3.5 ng L−1, with the relative standard deviation of 4.9% (c = 0.1 μg L−1, n = 7). The enrichment factor was 20-fold. The accuracy of the method was evaluated by measurement of the certified reference material (GBW 07601a, human hair). The proposed method was applied to determine Cd in human serum and urine samples with only consumption of 1 mL samples. The recoveries for the spiked human serum and urine samples were in the range of 86–110%. Compared with other reported methods, the proposed method is featured with easy to remove the template Cd (II), high selectivity, good interference resistance, low sample consumption and easy regeneration. Therefore, this method is suitable for the separation and enrichment of trace Cd (II) in micro-samples with complex matrix.

中文翻译：

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Cd (II) 印迹聚合物改性二氧化硅整体毛细管微萃取结合电感耦合等离子体质谱法测定生物样品中痕量 Cd (II)

摘要 采用表面印迹技术制备了Cd(II)印迹聚合物表面改性二氧化硅整体毛细管(简称Cd(II)印迹整体毛细管(Cd(II)-IMC))用于Cd(II)的提取。在此基础上，开发了一种整体毛细管微萃取-电感耦合等离子体质谱法，用于人血清和尿液样品中的Cd（II）痕量分析。以Mn(II)、Cu(II)和Zn(II)为竞争离子,研究了Cd(II)-IMC的萃取效率、分布比和选择性。发现制备的 Cd(II)-IMC 对 Mn (II)、Cu (II) 和 Zn (II) 的相对选择性系数分别为 3.8、2.2 和 2.2。与非印迹整体毛细管相比，Cd(II)-IMC 具有更大的动态吸附容量（6 μg m-1 超过 4.2 μg m-1）。在优化的提取条件下，Cd (II) 的检测限为 3.5 ng L-1，相对标准偏差为 4.9%（c = 0.1 μg L-1，n = 7）。富集因子是20倍。该方法的准确度通过对有证标准物质（GBW 07601a，人发）的测量来评估。所提出的方法用于测定人血清和尿液样品中的 Cd，仅消耗 1 mL 样品。加标人血清和尿液样品的回收率在 86-110% 的范围内。与其他已报道的方法相比，该方法具有模板Cd(II)易去除、选择性高、抗干扰性好、样品消耗少、易再生等特点。因此，该方法适用于基质复杂的微量样品中痕量Cd(II)的分离富集。