A 3D printed device covered with Zn/Co-ZIF-derived carbon allows the on-site extraction of fluoroquinolones (FQs) from wastewater, avoiding the sample transportation to the laboratory, and the subsequent elution, separation and determination using an on-line flow system based on sequential injection analysis (SIA) coupled to HPLC-FL. Several parameters that affect the extraction efficiency and desorption were optimized including the sorption phase immobilization technique on the 3D device, extraction time, pH effect, sample volume as well as the type of eluent, eluent volume, and flow rate. Under optimum conditions, detection limits of 3–9 ng L were achieved for norfloxacin, ciprofloxacin, danofloxacin, enrofloxacin and difloxacin. The precision expressed as relative standard deviation (%RSD, n = 3), showed intraday and interday ranges of 1.5–5.3% and 2.8–5.7%, respectively, demonstrating a good precision of the proposed methodology. To assess matrix effects and accuracy of the proposed method in real samples, recovery studies were performed without and with FQs spiked at different concentrations (0.5–10 μg L) to wastewater samples, showing good recoveries in the range of 91–104%. The results allow to confirm the applicability of MOF-derived carbons as adsorbents for on-site extraction, and the satisfactory separation and quantification of FQs by a SIA-HPLC-FL on-line system after their desorption with small eluent volumes.

中文翻译：

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使用涂有 Zn/Co-ZIF 衍生碳的 3D 打印装置进行现场提取，然后使用在线 SIA-HPLC-FL 系统测定废水中的氟喹诺酮类药物

覆盖有 Zn/Co-ZIF 衍生碳的 3D 打印设备可以从废水中现场提取氟喹诺酮类药物 (FQ)，避免将样品运输到实验室，以及随后使用在线流程进行洗脱、分离和测定基于与 HPLC-FL 耦合的顺序注射分析 (SIA) 的系统。对影响萃取效率和解吸的几个参数进行了优化，包括 3D 装置上的吸附相固定技术、萃取时间、pH 效应、样品体积以及洗脱液类型、洗脱液体积和流速。在最佳条件下，诺氟沙星、环丙沙星、达诺沙星、恩诺沙星和二氟沙星的检测限达到 3–9 ng L。以相对标准差（%RSD，n = 3）表示的精度，显示日内和日间范围分别为 1.5-5.3% 和 2.8-5.7%，表明所提出的方法具有良好的精度。为了评估所提出方法在实际样品中的基质效应和准确性，在废水样品中进行了不添加和添加不同浓度（0.5-10 μg/L）FQ 的回收率研究，结果显示回收率良好，在 91-104% 范围内。结果证实了 MOF 衍生碳作为现场萃取吸附剂的适用性，以及在用小体积洗脱液解吸后，通过 SIA-HPLC-FL 在线系统对 FQ 进行令人满意的分离和定量。