水中激素与抗生素污染的现场快速固相微萃取研究

This project aims at the on-site rapid sample preparation of hormone and antibiotic pollution in environmental water. Based on the preliminary research foundation of rapid array capillary in-tube solid-phase microextraction (ACIT-SPME), focusing on the two key scientific problems including high selectivity of solid phase microextraction and high reliability of on-site sample preparation and quantification of environmental water, the on-site rapid solid phase microextraction of hormone and antibiotic contamination in water will be carried out as follows: (1) To improve the extraction selectivity of hormones and antibiotics, composite extraction phase materials, namely, ultra-thin microporous cross-linking coating/macroporous polar polymer extraction phase, will be developed. Large extraction capacity and high mass transfer rate could be retained while the adhesion of particles and macromolecule/sol in water was blocked and the competitive adsorption of common weak polar organic pollutants was inhibited. (2) To comprehensively improve the quantification reliability of the on-site ACIT-SPME procedure, study of preparation of ACIT-SPME devices with high repeatability, calibration of extraction parameters, and optimization of storage and transportation conditions of extraction devices will be carried out. (3) To perform the validation test in laboratory with natural water and domestic water as model water samples and strive for cooperation with environmental monitoring institution to carry out preliminary application demonstration with water samples from the typical Yangtze River Delta. This project will provide an efficient and feasible technical scheme for monitoring the contamination of hormones and antibiotics in water, and provide reference for complex sample preparation, material preparation, extraction device design, environmental monitoring, etc.

本项目以水中激素与抗生素污染的现场快速样品前处理为目的，基于集束毛细管快速固相微萃取（ACIT-SPME）前期基础，聚焦环境水体固相微萃取的高选择性、现场制样定量的高可靠性两个关键科学问题，开展水中激素与抗生素污染的现场快速固相微萃取研究：（1）发展复合萃取材料——超薄微孔交联涂层/大孔极性聚合物萃取相，在保留大萃取容量、高传质速率的同时，阻隔水中的颗粒和大分子/溶胶的粘附，抑制弱极性有机分子竞争吸附，提高萃取的选择性；（2）研制高重复ACIT-SPME器件，校正萃取参数，优化贮存运输条件，综合提高现场ACIT-SPME样品制备的定量可靠性；（3）选取自然水体、生活用水，在实验室内完成验证测试，并争取与环境监测单位合作，选取长三角典型流域，开展初步应用示范。本项目将为水中激素、抗生素污染监测提供一种高效可行的技术方案，并为复杂样品前处理、材料制备、器件设计、环境监测等方面提供技术借鉴。

本研究计划拟基于“集束毛细管固相微萃取技术”开展水中激素和抗生素污染物的现场快速固相微萃取研究。实际研究过程中，对研究内容进行了一些调整，采用了更为简便的方法实现水中激素和抗生素污染物的现场快速固相微萃取。在2020-2022三年期间，项目负责人带领研究团队逐步实现了复合萃取相的制备和水中激素和抗生素的快速固相微萃取：探索制备了多种不同形式的聚酰亚胺（PI）萃取相，包括PI纳米片微球、磁性PI纳米片微球、串状磁性PI纳米片材料、多孔PI电纺丝、多孔PI薄膜等；开发了聚苯并咪唑（PBI）为新型固相微萃取的萃取相；基于磁性PI纳米片复合材料，建立了环境水和尿液中的雌激素的分析检测方法，1 min内即可达到萃取平衡；基于多孔PI电纺丝SPE，建立了环境水、鸡蛋和牛奶中的氟喹诺酮类抗生素的分析测试方法，多孔PI电纺丝微纤维比常规电纺丝纳米纤维直径粗、比表面积大，作为SPE填料阻力小、萃取速度快、萃取容量大。我们的科研工作为激素和抗生素污染的监测提供了新的思路和策略。在项目执行期间，发表了学术论文5篇，均为SCI收录；申请国家发明专利2项；培养了硕士研究生2名。