Puigventós Lidia, Navarro Meritxell, Alechaga Élida, Núñez Oscar, Saurina Javier, Hernández-Cassou Santiago, Puignou Lluis
Department of Analytical Chemistry, University of Barcelona, Martí i Franquès 1-11, 08028, Barcelona, Spain.
Anal Bioanal Chem. 2015 Jan;407(2):597-608. doi: 10.1007/s00216-014-8298-2. Epub 2014 Nov 5.
Liquid chromatography-electrospray-tandem mass spectrometry (LC-ESI-MS/MS) was applied to the analysis and authentication of fruit-based products and fruit-based pharmaceutical preparations. A Kinetex C18 reversed-phase column under gradient elution with 0.1 % formic acid aqueous solution and methanol mobile phases was used for the simultaneous determination of 26 polyphenols, allowing an acceptable separation in less than 22 min. Instrumental quality parameters such as limits of detection (LOD, values between 12 and 14 μg/L for 19 of the 26 analyzed polyphenols), linearity (r (2) > 0.991), run-to-run and day-to-day precisions (relative standard deviation (RSD) values lower than 9.9 and 13.5 %, respectively), and accuracy (relative errors lower than 8 %) were established. A simple extraction method, consisting of a sample sonication with acetone/water/hydrochloric acid (70:29.9:0.1 v/v/v) and centrifugation, was proposed. Two calibration procedures, external calibration using standards prepared in water and standard addition, were evaluated for polyphenol quantification in several grape and cranberry fruits and processed fruit products. For a 95 % confidence level, no statistical differences were observed between the two calibration methods (p values between 0.06 and 0.95), denoting that external calibration was suitable enough for the quantitative analysis of polyphenols in fruit-based products. The proposed LC-ESI-MS/MS method was then applied to the analysis of polyphenols in 23 grape-based and cranberry-based natural products and pharmaceutical preparations. Polyphenolic concentration data was then analyzed by principal component analysis (PCA) to extract information of the most significant profile data contributing to authentication of natural extracts according to their fruit of origin.
液相色谱 - 电喷雾串联质谱法（LC - ESI - MS/MS）被应用于水果制品和水果基药物制剂的分析与鉴定。使用Kinetex C18反相柱，以0.1%甲酸水溶液和甲醇为流动相进行梯度洗脱，用于同时测定26种多酚，在不到22分钟内实现了可接受的分离。确定了仪器的质量参数，如检测限（LOD，26种分析多酚中的19种的检测限在12至14μg/L之间）、线性（r(2)＞0.991）、批内和批间精密度（相对标准偏差（RSD）值分别低于9.9%和13.5%）以及准确度（相对误差低于8%）。提出了一种简单的提取方法，包括用丙酮/水/盐酸（70:29.9:0.1 v/v/v）对样品进行超声处理并离心。评估了两种校准程序，即使用水中制备的标准品进行外部校准和标准加入法，用于几种葡萄和蔓越莓果实及加工水果制品中多酚的定量分析。在95%置信水平下，两种校准方法之间未观察到统计学差异（p值在0.06至0.95之间），这表明外部校准足以用于水果制品中多酚的定量分析。然后将所提出的LC - ESI - MS/MS方法应用于23种葡萄基和蔓越莓基天然产物及药物制剂中多酚的分析。然后通过主成分分析（PCA）对多酚浓度数据进行分析，以提取有助于根据天然提取物的原产水果对其进行鉴定的最重要轮廓数据信息。
