自1993年以来，孔雀石绿作为一种强效杀菌剂被广泛用于水产养殖业。但随着研究的深入，研究者们发现孔雀石绿对人类具有高毒性、致畸性和致癌性。但由于其价格低廉且用药效果好，违法违规使用的现象屡禁不止，实现水产品及其养殖环境中孔雀石绿的现场快速检测十分必要。在质谱现场检测中，样品前处理方法和电离进样方式是影响检测的效率和灵敏度的重要因素。分子印迹聚合物（Molecular Imprinting Polymer，MIP）是通过在模板分子周围聚合功能性单体，然后将模板分子洗出而制备的高度交联聚合物。MIP有为目标分子设计的特定腔体，能对目标分子表现出高亲和力和特异识别性，在复杂基质的样品前处理中具有独特优势。本文采用多壁碳纳米管为骨架合成了分子印迹聚合物。通过吸附机理研究，多壁碳纳米管分子印迹材料对孔雀石绿表现出了优秀的吸附能力和特异选择性。使用多壁碳纳米管分子印迹材料进行水产养殖水样中孔雀石绿残留的直接质谱检测，采用单晶格设计（SLMD）优化了解吸溶剂配比，整体检测过程可以在3 min内完成，检出限为10 ng/L。然后以磁性纳米颗粒为核心合成了一种磁性分子印迹微球，用于鱼肉基质中微量孔雀石绿的富集。根据磁性分子印迹材料特性进行了检测流程设计，全部检测过程可在20 min内完成，检出限为100 ng/g。磁性吸附材料可以利用磁铁从基质中分离而无需借助离心机，有机溶剂使用量仅为1 mL。为了降低复杂生物组织基质对敞开式离子源质谱检测的背景干扰，提出了一种分子印迹涂层刀片喷雾离子源。在鱼肉基质孔雀石绿残留的检测中，先利用分子印迹涂层对目标物进行快速选择性富集，而后可直接耦合质谱进行检测，在实现与磁性分子印迹材料相同检出限的同时简化了检测操作。本文针对水产基质和养殖水样基质中的孔雀石绿残留，制备了两种以不同材料为支撑的分子印迹聚合物，减少了样品前处理用时，提高了质谱分析灵敏度，使得样品分析更加快速准确。另外，本文把分子印迹技术与涂层刀片-质谱结合起来，在保证灵敏度的基础上简化了检测操作，为现场检测提供了便利。
Since 1993, malachite green has been widely used in aquaculture as a powerful fungicide. But with the deepening of research, researchers found that malachite green is highly toxic, teratogenic and carcinogenic to humans. However, due to its low price and good drug effect, the phenomenon of illegal and illegal use has been repeatedly prohibited. It is necessary to realize the rapid detection of malachite green in aquatic products and their breeding environment.In mass spectrometry field detection, sample preparation methods and ionization injection methods are important factors that affect the efficiency and sensitivity of detection. Molecular Imprinting Polymer (MIP) is a highly cross-linked polymer prepared by polymerizing functional monomers around template molecules and then washing out the template molecules. MIP has a specific cavity designed for the target molecule, showing high affinity and specific recognition to the target molecule, and has unique advantages in sample pretreatment of complex matrices.In this paper, a molecularly imprinted polymer was synthesized using multi-walled carbon nanotubes as the backbone.This material showed excellent adsorption capacity and specific selectivity for malachite green through the study of adsorption mechanism. In the direct mass spectrometric determination of malachite green residues in aquaculture water samples, Single lattice material design (SLMD) was used to optimize the solvent ratio. The overall detection process can be completed in 3 minutes, and the detection limit is 10 ng / L.Then a kind of magnetic molecularly imprinted polymer was synthesized with magnetic nanoparticles as the core, which was used to enrich Malachite Green in fish matrix. According to the characteristics of magnetic molecularly imprinted materials, designed the detection process . The whole detection process can be completed in 20 minutes, and the detection limit is 100 ng/g. Magnetic adsorbents can be separated from the matrix by magnet without centrifuge, and the amount of organic solvent used is 1 ml.A molecularly imprinted coated blade spray ion source was proposed for reducing the background interference of ambient ion source mass spectrometry in complex biological tissue matrix,. In detecting malachite green in fish substrate, molecularly imprinted coating was used to enrich the target substance quickly and selectively. Then the coating blade could be directly coupled with mass spectrometry for detection, which achieved the same detection limit as magnetic molecularly imprinted material and simplified the detection operation.In order to detect malachite green residues in aquatic matrix and aquaculture water matrix by mass spectrometry, this work prepare two kinds of molecularly imprinted polymers supported by different materials . The results show that the proposed method can reduce the sample pretreatment time and improve the sensitivity of mass spectrometry. In addition, the combination of molecular imprinting technology and coated blade mass spectrometry simplifies the detection operation based on ensuring the sensitivity and provides convenience for on-site detection.
