Xing Shige, He Muyi, Liu Tong, Yong Wei, Zhang Feng
Institute of Food Safety, Chinese Academy of Inspection and Quarantine, Beijing 100176, China.
Se Pu. 2021 May;39(5):455-462. doi: 10.3724/SP.J.1123.2020.07004.
Monitoring of trace heavy metal pollutants released during industrial and agricultural processes is essential because of their widespread distribution in the environment and health hazards. Several techniques, including inductively coupled plasma-mass spectrometry (ICP-MS), inductively coupled plasma-optical emission spectrometry (ICP-OES), electrothermal atomic absorption (ETAAS), and flame atomic absorption spectrometry (FAAS), have been proposed for the determination of heavy metals in serum, plasma, whole blood, and food. All these techniques have earned robust recognition in the field of trace heavy metals and have many advantages such as multi-elemental analysis capability, large dynamic linear range, low detection limits, and high productivity. Nevertheless, most of the recommended techniques require digestion of the sample and extraction with an organic solvent for isolation of the metal ion from the sample solution prior to analysis. Despite improvements in the performance of modern analytical instruments, the direct determination of heavy metal ions in real samples is difficult because of their low concentration levels and matrix interference. Thus, extraction and clean-up steps are required for pre-concentration of the analyte, so that detection and elimination of the interfering matrix component are possible. Solid-phase extraction (SPE) is one of the popular metal ion pretreatment methods. The advantages of SPE include easy cartridge/column regeneration, high analytical frequency, and high preconcentration factors for sorbents with high adsorption capacities. On the other hand, when the analytes are extracted from a complex matrix such as serum and meat samples, large amounts of proteins from the samples can be retained on the sorbent surface, obstructing the binding sites on the sorbent and leading to poor precision and accuracy. The key to metal ion detection is the development of new SPE materials with high efficiency and enrichment factors as well as an effective pretreatment technology. Nanomaterials such as restricted-access carbon nanotubes, nanoadsorbents, nanoparticle carriers, and magnetic nanoparticles have shown great promise in advancing biomedical and environmental analysis because of the unique properties originating from their ultrafine dimensions. Nanomaterials can provide large specific surface areas and tunable functional groups to facilitate metal ion absorption. They could also possess superior optical properties and allow for high sensitivity in simple fluorescent or colorimetric detection methods. Owing to their excellent mechanical and chemical stability, polymer materials have been of great interest as adsorbents for the SPE of metal ions from solution. Moreover, a designed polymeric material can show triple functionality such as physical adsorption, chelate formation, and ion exchange for the target metal ions. A dual-functional nanomaterial-DNAzyme platform can simultaneously allow for the sensitive detection and effective removal of heavy metal ions in water. Thus, this platform can serve as a simple, cost-effective tool for rapid and accurate metal quantification in the determination of human metal exposure and inspection of environmental contamination. Furthermore, the new photocaged chelator can uncage and release the combined metal ions into an aqueous solution that is free of the other components of the matrix. In this manner, we can develop diagnostic tests for metal ions that are often difficult to detect using other methods. In this paper, the characteristics of new SPE materials, including nanomaterials, polymer materials, and functional materials as well as advances in their applications to the preparation of complex samples are summarized, and the direction for future development is proposed.
监测工农业生产过程中释放的痕量重金属污染物至关重要,因为它们在环境中广泛分布且危害健康。已提出多种技术用于测定血清、血浆、全血和食物中的重金属,包括电感耦合等离子体质谱法(ICP-MS)、电感耦合等离子体发射光谱法(ICP-OES)、电热原子吸收法(ETAAS)和火焰原子吸收光谱法(FAAS)。所有这些技术在痕量重金属领域都获得了广泛认可,具有多元素分析能力、大动态线性范围、低检测限和高生产率等诸多优点。然而,大多数推荐技术在分析前需要对样品进行消解并用有机溶剂萃取,以从样品溶液中分离出金属离子。尽管现代分析仪器的性能有所改进,但由于实际样品中重金属离子浓度低且存在基体干扰,直接测定仍很困难。因此,需要进行萃取和净化步骤以预富集分析物,从而实现干扰基体成分的检测和消除。固相萃取(SPE)是常用的金属离子预处理方法之一。SPE的优点包括柱/管再生容易、分析频率高以及对具有高吸附容量的吸附剂有高预富集因子。另一方面,当从血清和肉类样品等复杂基体中萃取分析物时,样品中的大量蛋白质会保留在吸附剂表面,阻塞吸附剂上的结合位点,导致精密度和准确度较差。金属离子检测的关键在于开发具有高效率和富集因子的新型SPE材料以及有效的预处理技术。受限进入碳纳米管、纳米吸附剂、纳米颗粒载体和磁性纳米颗粒等纳米材料,因其超细尺寸所具有的独特性能,在推进生物医学和环境分析方面显示出巨大潜力。纳米材料可以提供大的比表面积和可调节的官能团以促进金属离子吸附。它们还可能具有优异的光学性能,并允许在简单的荧光或比色检测方法中实现高灵敏度。由于其优异的机械和化学稳定性,聚合物材料作为从溶液中固相萃取金属离子的吸附剂备受关注。此外,设计的聚合物材料对目标金属离子可表现出物理吸附、螯合形成和离子交换等三重功能。双功能纳米材料 - DNAzyme平台可同时实现水中重金属离子的灵敏检测和有效去除。因此,该平台可作为一种简单、经济高效的工具,用于在测定人体金属暴露和检查环境污染时快速准确地进行金属定量。此外,新型光笼式螯合剂可解除束缚并将结合的金属离子释放到不含基体其他成分的水溶液中。通过这种方式,我们可以开发针对其他方法难以检测的金属离子的诊断测试。本文总结了新型SPE材料(包括纳米材料、聚合物材料和功能材料)的特性及其在复杂样品制备中的应用进展,并提出了未来的发展方向。