Microextraction by packed sorbent: Introducing a novel hybrid silica-based chitosan-graphene oxide biosorbent for the evaluation of pesticides and antibiotics in food matrices

IF 5.2 Q1 CHEMISTRY, ANALYTICAL

Advances in Sample Preparation Pub Date : 2024-10-01 DOI:10.1016/j.sampre.2024.100134

Rafael O. Martins, Fernando M. Lanças

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Abstract

This study introduces a novel silica-graphene oxide@chitosan (SiGO@CS) material as a packed biosorbent for microextraction by packed sorbent (MEPS), followed by liquid chromatography-tandem mass spectrometry (LC-MS/MS) analysis of pesticides (atrazine and thiamethoxam) and antibiotics (ceftiofur and sulfonamide) in food samples. The graphene-based aerogel was modified with varying percentages of silica-graphene oxide/chitosan (w/w) and characterized to confirm successful chitosan incorporation. Optimization of the MEPS protocol, using 2^4–1 and 2³ experimental designs, identified draw/eject and washing cycles as the most influential parameters for extraction efficiency. The SiGO@CS biosorbent with 80 % CS/SiGO (w/w) exhibited superior extraction efficiency compared to other ratios and commercial sorbents. The method demonstrated excellent linearity for all analytes (R² > 0.9900), with low limits of detection (LOD) and quantification (LOQ) ranging from 0.020 to 0.045 µg l^-1 and 0.045 to 1.0 µg l^-1 for pesticides, respectively, and 5 to 15 µg l^-1 and 15 to 20 µg l^-1 for antibiotics, respectively. Trueness values were within 82 % to 109 %. The method's green credentials were confirmed using AGREEprep and the Green Analytical Procedure Index (GAPI) approach, highlighting sorbent reusability (over 15 times) and rapid analytical throughput (5 min per sample) with low use of pre-treated sample extract volume (500 µL). The application to local corn, tomato, and milk samples confirmed the detection and quantification of thiamethoxam and atrazine at concentrations above the recommended ingestion per day for one sample of tomato and corn out of the three samples analyzed. Furthermore, using the novel SiGO@CS biosorbent in the MEPS protocol offers a green, high-performance analytical alternative to traditional sorbent phases, with the potential for evaluating trace levels of pesticides and antibiotics in food matrices.

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利用填料吸附剂进行微萃取：采用新型壳聚糖-氧化石墨烯混合硅基生物吸附剂评估食品基质中的农药和抗生素

本研究介绍了一种新型二氧化硅-氧化石墨烯@壳聚糖（SiGO@CS）材料，它是一种填料生物吸附剂，可用于填料吸附剂微萃取（MEPS），然后通过液相色谱-串联质谱（LC-MS/MS）分析食品样品中的农药（阿特拉津和噻虫嗪）和抗生素（头孢噻呋和磺酰胺）。用不同比例的二氧化硅-氧化石墨烯/壳聚糖（重量比）对石墨烯基气凝胶进行了改性，并对其进行了表征，以确认壳聚糖的成功加入。采用 24-1 和 23 实验设计对 MEPS 方案进行了优化，确定抽吸/喷射和洗涤周期是对萃取效率影响最大的参数。与其他比例和商用吸附剂相比，SiGO@CS 生物吸附剂（CS/SiGO（重量比）为 80%）的萃取效率更高。该方法对所有分析物均表现出良好的线性关系（R² > 0.9900），检出限（LOD）和定量限（LOQ）较低，农药的检出限（LOD）和定量限（LOQ）分别为 0.020 至 0.045 µg l-1 和 0.045 至 1.0 µg l-1，抗生素的检出限（LOD）和定量限（LOQ）分别为 5 至 15 µg l-1 和 15 至 20 µg l-1。真实值在 82 % 至 109 % 之间。使用 AGREEprep 和绿色分析程序指数 (GAPI) 方法确认了该方法的绿色证书，突出了吸附剂的可重复使用性（超过 15 次）和快速分析吞吐量（每个样品 5 分钟），且预处理样品提取物用量少（500 µL）。对当地玉米、番茄和牛奶样品的应用证实，在分析的三个样品中，有一个番茄和一个玉米样品的噻虫嗪和阿特拉津的检测和定量浓度超过了建议的每日摄入量。此外，在 MEPS 方案中使用新型 SiGO@CS 生物吸附剂为传统吸附剂相提供了一种绿色、高性能的分析替代品，有望评估食品基质中痕量农药和抗生素的含量。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Advances in Sample Preparation

CiteScore

3.50

自引率

0.00%

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