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高效液相色谱结合二阶数据建模用于测定秘鲁乳香中四种黄酮醇的固液和液液微萃取方法的开发、优化及比较

Development, optimization and comparison of solid-liquid and liquid-liquid microextraction for the determination of four flavonols in Schinus molle L. using high-performance liquid chromatography coupled with second-order data modeling.

作者信息

Aschemacher Nicolás A, Siano Álvaro S, Teglia Carla M, Goicoechea Héctor C

机构信息

Laboratorio de Péptidos Bioactivos (LPB), Departamento de Química Orgánica. Facultad de Bioquímica y Ciencias Biológicas, Universidad Nacional del Litoral, Ciudad Universitaria, 3000, Santa Fe, Argentina.

Consejo Nacional de Investigaciones Científicas y Técnicas (CONICET), Godoy Cruz, 2290 CP C1425FQB, Buenos Aires, Argentina.

出版信息

Anal Bioanal Chem. 2025 Mar;417(7):1381-1392. doi: 10.1007/s00216-024-05700-3. Epub 2024 Dec 17.

DOI:10.1007/s00216-024-05700-3
PMID:39681698
Abstract

Flavonoids are particularly interesting because they have a broad spectrum of biological effects, including antioxidant and free radical scavenging activities. In this work, solid-liquid microextraction and dispersive liquid-liquid microextraction enhanced by ultrasound were developed and compared with the conventional method (Soxhlet extraction) to optimize the extraction of four flavonoids: rutin, quercitrin, quercetin, and myricetin in samples of Schinus molle (Aguaribay). During the development of the analytical method, different chemometric tools were used to optimize the microextraction procedure. In addition, an analytical method based on high-performance liquid chromatography with diode array detector (HPLC-DAD) and second order calibration using multivariate curve resolution-alternating least square (MCR-ALS) is presented to quantify the flavonoids with limits of quantification between 0.011 and 0.082 µg mL. Finally, solid-liquid microextraction using 4.00 mL water/ethanol (54.3:45.7%), 14 s vortex, and 45 min was selected as the most suitable method due to its high recovery rate and environmental friendliness (with a greenness score of 0.78). After the optimization step, the concentrations found in the plant samples were 1825.3, 632.6, 110.2, and 18.9 µg g for rutin, quercitrin, quercetin, and myricetin, respectively. The present work is the first achievement of simultaneously determining these four analytes with exceptional sensitivity, demonstrating lower LOQs compared to previous reports.

摘要

黄酮类化合物特别有趣,因为它们具有广泛的生物效应,包括抗氧化和自由基清除活性。在这项工作中,开发了超声增强的固液微萃取和分散液液微萃取,并与传统方法(索氏提取)进行比较,以优化对秘鲁乳香(阿瓜里贝)样品中四种黄酮类化合物:芦丁、槲皮苷、槲皮素和杨梅素的提取。在分析方法的开发过程中,使用了不同的化学计量工具来优化微萃取程序。此外,还提出了一种基于高效液相色谱-二极管阵列检测器(HPLC-DAD)和使用多元曲线分辨交替最小二乘法(MCR-ALS)的二阶校准的分析方法,用于定量黄酮类化合物,定量限在0.011至0.082μg/mL之间。最后,由于其高回收率和环境友好性(绿色度评分为0.78),选择使用4.00 mL水/乙醇(54.3:45.7%)、14 s涡旋和45 min的固液微萃取作为最合适的方法。在优化步骤之后,植物样品中芦丁、槲皮苷、槲皮素和杨梅素的浓度分别为1825.3、632.6、110.2和18.9μg/g。本工作首次实现了以极高的灵敏度同时测定这四种分析物,与先前的报告相比,检测限更低。

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