Key Laboratory of Analytical Chemistry for Biology and Medicine (Ministry of Education), Department of Chemistry, Wuhan University, Wuhan 430072, China.
Analyst. 2019 Apr 8;144(8):2736-2745. doi: 10.1039/c8an02057d.
A novel method by hyphenating chip-based array ion-imprinted monolithic microextraction with inductively coupled plasma mass spectrometry (ICP-MS) was proposed for the online analysis of trace Gd in biological samples in this work. The poly(γ-methacryloxypropyltrimethoxysilane@Gd3+-surface ion-imprinted polymer) [poly(γ-MAPS@Gd3+-SIIP)] monolithic capillary was prepared via in situ polymerization on the vinyl-modified surface of poly(γ-MAPS) using Eu3+ as the mimic template. The prepared ion-imprinted monolithic capillary possessed higher selectivity and adsorption capacity to Gd3+ than the non-imprinted monolithic capillary. Eight poly(γ-MAPS@Gd3+-SIIP) monolithic capillaries were embedded in the channels of a microfluidic chip to fabricate a chip-based array microextraction device. Factors affecting the selectivity of the prepared ion-imprinted monolithic capillary including imprinted time and the composition of the prepolymerization solution, and extraction conditions for the fabricated chip-based array ion-imprinted monolithic capillary microextraction platform were optimized. A sample throughput of 18 h-1 was achieved along with a low detection limit of 1.27 ng L-1 for Gd3+. The proposed chip-based array poly(γ-MAPS@Gd3+-SIIP) monolithic microextraction-ICP-MS method was used for the analysis of trace Gd in human urine and serum, and the recovery for spiking experiments was in the range of 88.1-96.7%. The developed integrated analysis platform possesses good interference resistance, high automation, high sensitivity and low consumption of the sample/agent, which makes it very suitable for the analysis of trace elements in complicated biological samples.
本文提出了一种新颖的方法，即将芯片基阵列离子印迹整体微萃取与电感耦合等离子体质谱（ICP-MS）联用，用于在线分析生物样品中的痕量 Gd。通过在聚（γ-甲氧基丙基三甲氧基硅烷@Gd3+-表面离子印迹聚合物）[聚（γ-MAPS@Gd3+-SIIP）]整体毛细管上原位聚合，使用 Eu3+作为模拟模板，在聚（γ-MAPS）的乙烯基改性表面上制备了整体毛细管。制备的离子印迹整体毛细管对 Gd3+具有更高的选择性和吸附容量。将 8 根聚（γ-MAPS@Gd3+-SIIP）整体毛细管嵌入微流控芯片的通道中，制备了芯片基阵列微萃取装置。优化了影响制备的离子印迹整体毛细管选择性的因素，包括印迹时间和预聚合溶液的组成，以及制备的芯片基阵列离子印迹整体毛细管微萃取平台的萃取条件。实现了 18 h-1 的样品通量，并获得了 Gd3+的低检测限为 1.27 ng L-1。该芯片基阵列聚（γ-MAPS@Gd3+-SIIP）整体微萃取-ICP-MS 方法用于分析人尿和血清中的痕量 Gd，加标实验的回收率在 88.1-96.7%之间。所开发的集成分析平台具有良好的抗干扰能力、高自动化程度、高灵敏度和低样品/试剂消耗，非常适合分析复杂生物样品中的微量元素。
