Chen Xinwei, Tian Weijun
College of Environmental Science and Engineering, Ocean University of China, Qingdao 266000, China; Qingdao Engineering Vocational College, Qingdao 266000, China.
College of Environmental Science and Engineering, Ocean University of China, Qingdao 266000, China; Laoshan Laboratory, Qingdao 266234, China; Key Laboratory of Marine Environment and Ecology, Ministry of Education, Qingdao 266100, China.
J Chromatogr A. 2025 Jan 25;1741:465611. doi: 10.1016/j.chroma.2024.465611. Epub 2024 Dec 19.
The concentration of chlorpyrifos (CPF) in aqueous samples was determined using a novel molecularly imprinted dispersive solid-phase extraction (MISPE) approach that was presented in this research. Using a non-covalent molecular imprinting technique, a biochar (BC)-functionalized molecularly imprinted polymers (MIPs) (BC-MIPs) was created. These MIPs were used in dispersive solid-phase extraction (DSPE) in conjunction with high-performance liquid chromatography with photodiode array detection (HPLC-PDA) to detect CPF in aqueous samples with high sensitivity. Using methacrylic acid (MAA) as the monomer and ethylene glycol dimethacrylate (EGDMA) as the cross-linker, BC-MIPs were created using CPF as a template. By using the suggested dispersive solid-phase extraction (DSPE) approach, the efficiency of the synthesized BC-MIPs granules was evaluated. Analytical performance of the devised DSPE-HPLC-PDA technique was assessed under optimal settings. The optimized parameters included extraction time, aqueous sample pH, desorption time and desorption reagents. Compared with the traditional method, the established method has better selective adsorption capacity, reusability and sensitivity for CPF. The suggested method presented that limit of detection and limit of quantification were 1.0 ng/mL and 4.0 ng/mL, along with excellent linear range (4.0-1500 ng/mL) with coefficients of determination (R=0.9982). The established method was successfully used to determination CPF in aqueous samples from the Baisha River in Qingdao, with the advantages of accuracy (recoveries: 81.2 %-103.6 %, RSDs≤9.2 %), speed (CPF-BC-MIPs-DSPE time: 75 min; HPLC-PDA time: 12 min), selectivity (imprinting factor: 4.24), and economy (50 mg of adsorbent synthesized using cheap straw and 1 mL of solvents), which partially conform to the current advanced principle of "3S+2A" in analytical chemistry. The BC-MIPs granules shown potential for CPF preconcentration in complicated samples and were effective carriers for the selective adsorption of CPF.
采用本研究提出的新型分子印迹分散固相萃取（MISPE）方法测定水样中毒死蜱（CPF）的浓度。利用非共价分子印迹技术，制备了生物炭（BC）功能化的分子印迹聚合物（MIPs）（BC-MIPs）。这些MIPs与高效液相色谱-光电二极管阵列检测（HPLC-PDA）联用，用于分散固相萃取（DSPE），以高灵敏度检测水样中的CPF。以甲基丙烯酸（MAA）为单体，乙二醇二甲基丙烯酸酯（EGDMA）为交联剂，以CPF为模板制备了BC-MIPs。通过所建议的分散固相萃取（DSPE）方法，评估了合成的BC-MIPs颗粒的效率。在最佳条件下评估了所设计的DSPE-HPLC-PDA技术的分析性能。优化参数包括萃取时间、水样pH值、解吸时间和解吸试剂。与传统方法相比，所建立的方法对CPF具有更好的选择性吸附能力、可重复使用性和灵敏度。所建议的方法表明，检测限和定量限分别为1.0 ng/mL和4.0 ng/mL，线性范围良好（4.0 - 1500 ng/mL），决定系数（R = 0.9982）。所建立的方法成功用于测定青岛白沙河水样中的CPF，具有准确性（回收率：81.2 % - 103.6 %，相对标准偏差≤9.2 %）、速度快（CPF-BC-MIPs-DSPE时间：75分钟；HPLC-PDA时间：12分钟）、选择性好（印迹因子：4.24）和经济性好（使用廉价秸秆合成50 mg吸附剂和1 mL溶剂）等优点，部分符合当前分析化学中“3S + 2A”的先进原则。BC-MIPs颗粒在复杂样品中对CPF预富集显示出潜力，是选择性吸附CPF的有效载体。
