University of São Paulo, São Carlos, Institute of Chemistry of São Carlos, SP, Brazil.
University of São Paulo, São Carlos, Institute of Chemistry of São Carlos, SP, Brazil.
Talanta. 2021 Jan 1;221:121608. doi: 10.1016/j.talanta.2020.121608. Epub 2020 Sep 2.
A novel approach for the online coupling of solid-phase microextraction (SPME) and liquid chromatography (LC) is introduced. An innovative Si@GO@βCD coated needle-sleeve extractant device was developed and then employed in the automated online SPME-LC-UV determination of estrogen-like isoflavones from human urine samples. The extractant SPME device is easily attachable at the endpoint of an analytical syringe needle and operated by a lab-made autosampler. Fully automated online SPME-LC is accomplished by proper autosampler programming to perform the following steps: i) the analytes extraction by direct immersion of the extractant device into the stirred sample, ii) a rinsing step iii) the analytes desorption/enrichment, iv) the online transference of the extract to the LC injection valve. Besides allowing the online SPME hyphenation, this extraction modality efficiently addressed the drawbacks associated with the clogging and dispersion of graphene-based microextraction techniques performed in packed-bed and dispersive formats. The main extraction parameters and the performance of the automated online SPME-LC method developed were carefully studied. The results show a good sensitivity, reliability, and straightforward analytical strategy for the determination of organic compounds in complex samples. The detection limit of the method was 20 μg L for DAI and 10 μg L for GEN, FOR and BIO. The intra-day RSD was below 10% and inter-day RSD was below 13%. The total analysis time was less than 17 min per sample.
介绍了一种将固相微萃取（SPME）与液相色谱（LC）在线偶联的新方法。开发了一种创新的 Si@GO@βCD 涂层针套式萃取剂装置，并将其应用于全自动在线 SPME-LC-UV 测定人尿液中类雌激素异黄酮。萃取剂 SPME 装置可轻松连接在分析注射器针的末端，并由实验室自制自动进样器操作。通过适当的自动进样器编程，可以实现全自动在线 SPME-LC，执行以下步骤：i）通过将萃取器直接浸入搅拌样品中进行分析物萃取，ii）冲洗步骤，iii）分析物解吸/富集，iv）将萃取物在线转移到 LC 进样阀。除了允许在线 SPME 偶联外，这种萃取方式还有效地解决了基于石墨烯的微萃取技术在填充床和分散格式中存在的堵塞和分散问题。仔细研究了主要的萃取参数和所开发的自动在线 SPME-LC 方法的性能。结果表明，该方法具有良好的灵敏度、可靠性和用于复杂样品中有机化合物的直接分析策略。该方法的检测限为 DAI 的 20μg/L 和 GEN、FOR 和 BIO 的 10μg/L。日内 RSD 低于 10%，日间 RSD 低于 13%。每个样品的总分析时间少于 17 分钟。
