Head-to-Head Comparison of Ultra-High-Performance Liquid Chromatography with Diode Array Detection versus Quantitative Nuclear Magnetic Resonance for the Quantitative Analysis of the Silymarin Complex in Silybum marianum Fruit Extracts
Head-to-Head Comparison of Ultra-High-Performance Liquid Chromatography with Diode Array Detection versus Quantitative Nuclear Magnetic Resonance for the Quantitative Analysis of the Silymarin Complex in Silybum marianum Fruit Extracts
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DOI：
10.1021/acs.jafc.5b05494
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发表时间：
2016-02-24
影响因子：
6.1
通讯作者：
Stuppner, Hermann
中科院分区：
文献类型：
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作者：
Cheilari, Antigoni;Sturm, Sonja;Stuppner, Hermann
定量核磁共振 (qNMR) 光谱被认为是基于色谱的混合物分析的绝佳替代方案。核磁共振波谱是一种非破坏性方法，仅需要有限的样品制备，并且可以轻松实现自动化。本文对 qNMR 与基于二极管阵列检测的超高效液相色谱 (uHPLC DAD) 进行头对头比较，对水飞蓟素复合物的六种黄酮木脂素同系物（水飞蓟亭、水飞蓟宁、水飞蓟宾 A、水飞蓟宾 B、异水飞蓟宾 A 和异水飞蓟宾 B）进行定量分析。两种检测均显示出相似的性能特征（线性范围、准确度、精密度和定量限），分析时间低于 30 分钟/样品。该测定适用于工业 S. marianum 提取物（AC 样品）和当地从 S. marianum 果实制备的提取物（PL 样品）。通过 Bland-Altman 图（相对方法偏差 AC 样品，-0.1%；2SD 范围，+/- 5.1%；相对方法偏差 PL 样品，-0.3%；2SD 范围，+/- 7.8%）和 Passing-Bablok 回归分析（AC 和 PL 样品的斜率和截距分别与 1.00 和 0.00 没有显着差异；Spearman 等级相关系数， >0.99）确实表明 qNMR 和 uHPLC-DAD 可以互换使用来定量水飞蓟素复合物中的黄酮木脂素。
Quantitative nuclear magnetic resonance (qNMR) spectroscopy is known as an excellent alternative to chromatography-based mixture analysis. NMR spectroscopy is a non-destructive method, needs only limited sample preparation, and can be readily automated. A head-to-head comparison of qNMR to an ultra-high-performance liquid chromatography with diode array detection (uHPLC DAD)-based quantitative analysis of six flavonolignan congeners (silychristin, silydianin, silybin A, silybin B, isosilybin A, and isosilybin B) of the Silybum marianum silymarin complex is presented. Both assays showed similar performance characteristics (linear range, accuracy, precision, and limits of quantitation) with analysis times below 30 min/sample. The assays were applied to industrial S. marianum extracts (AC samples) and to extracts locally prepared from S. marianum fruits (PL samples). An assay comparison by Bland-Altman plots (relative method bias AC samples, -0.1%; 2SD range, +/- 5.1%; relative method bias PL samples, -0.3%; 2SD range, +/- 7.8%) and Passing-Bablok regression analysis (slope and intercept for AC and PL samples not significantly different from 1.00 and 0.00, respectively; Spearman's coefficient of rank correlation, >0.99) did show that qNMR and uHPLC-DAD can be used interchangeably to quantitate flavonolignans in the silymarin complex.