基于亲水性表面分子印迹限进磁性核壳微球的各种复杂基质中超痕量内分泌干扰物轮廓谱分析的研究

Residues of endocrine disrupting chemicals (EDCs) show serious hazards to human health, and have become an important issue in the fields of environment and food. Sample pretreatment technique is the bottleneck of the analysis of EDCs in complex matrices. In order to overcome shortcomings of the existing sample pretreatment methods, such as poor specificity, low sensitivity, poor anti-matrix interference, the project is intended to choose typical synthetic steroid hormone and alkylphenols among EDCs as target pollutants, screen particular EDCs as template molecules that contain typical three-dimensional structure and functional group sites, prepare a new kind of adsorption material named hydrophilic surface molecular imprinted restricted-access magnetic core-shell microspheres by surface molecular imprinting method with homemade Fe3O4/SiO2 nanospheres as "seeds". The obtained microspheres exhibit merits of strong magnetic response, high molecular recognition in aqueous medium, high adsorption capacity, and good restricted-access of biological macromolecules. Under external magnetic field, the microspheres can fast targeted enrich the ultra-trace template molecules and its structural analogues from crude sample solution with complex matrices. Combined with the proposed comprehensive identification strategy of EDCs on the basis of LC/GC-MS, a new hyphenated technique of molecular imprinting recognition-magnetic separation-LC/GC-MS is established for comprehensive analysis of ultra-trace EDCs in various complex matrices. On the basis of the analysis of a large number of real samples, the preliminary profile of EDCs types-distribution-content in different environmental, food and biological samples will be depicted, providing reference data for early warning and control of the related pollutants.

内分泌干扰物残留严重危害人类健康，是环境和食品领域亟待解决的重要命题。样品处理是复杂基质EDCs分析的瓶颈。为了克服现有方法选择性差、灵敏度低、抗基体干扰差的缺点，本项目拟以典型合成甾体激素类和烷基酚类为目标污染物，筛选具有特征立体结构和官能团位点的EDCs为模板分子，以自制Fe3O4/SiO2纳米微球为种子，采用表面分子印迹法制备出磁响应强、高水相分子识别、高吸附容量和排阻生物大分子的亲水性表面分子印迹限进磁性核壳微球。该微球以外加磁场为驱动力，主动从基质复杂的样品粗制液中靶向富集出超痕量模板分子及其结构相似物；构建全面的EDCs LC/GC-MS鉴定策略；建立一套广泛适用于各种复杂基质中超痕量EDCs全面分析的分子印迹识别-磁分离-LC/GC-MS联用新技术。在大量样本分析的基础上，初步勾勒出不同环境、食品和生物样品中EDCs种类-分布-含量轮廓谱，为相关污染物预警和治理提供参考数据。

环境内分泌干扰物残留对人类健康危害严重，成为环境和食品领域亟待解决的重要命题。样品前处理是复杂基质中环境内分泌干扰物残留分析的瓶颈。为了克服现有方法选择性差、灵敏度低、抗基体干扰差的缺点，本课题拟以提高现有环境内分泌干扰物分析方法的特异性、灵敏度和抗基质干扰能力为目标，发展可广泛适用于环境、食品、生物等复杂基质中环境内分泌干扰物分析的新方法和新技术。制备了C18功能化的磁性材料（C18-Fe3O4@SiO2），构建了可用于生物基质样品中五种抗抑郁药的MSPME样品前处理方法；制备了C18/NH2-混合功能化磁性介孔纳米粒子(C18/NH2-Fe3O4@SiO2)，并用于肉类样品处理方法QuEChERS法的改进，构建了肉类样品中11种雌激素及其类似物的样品处理方法；制备了BSA限进C18/Ph混合功能化的磁性二氧化硅微球材料，开发了针对市售水产品中五种药物残留的样品前处理方法；提出了一条CBZ磁性分子印迹聚合物快速合成路线，构建了基于MMIP的鱼、沉积物和水样的样品前处理方法。此外还开发了基于极性增强相（PEP）的薄膜固相萃取（PEP-PAN@PSF）小棒的微型化固相萃取装置，构建了可满足不同环境样品基质的9种环境激素类药物和47种环境抗精神疾病药物的样品前处理方法。研究还采用3种衍生化试剂对含羰基或含羟基的环境内分泌干扰素进行衍生化，大大提升了分析物在质谱检测中的灵敏度；研究了不同结构类型的衍生化产物在质谱中的裂解规律并进行推导和归纳，构建了一套可用于该类成分全面表征的分析方法。大量实际样品分析结果初步勾勒出了环境内分泌干扰物在食品和不同环境样品中的残留现状，为相关污染物的预警和治理提供了丰富的参考数据。