School of Pharmaceutical Sciences, Jilin University, Changchun 130021, China.
National Center of Mass Spectrometry in Changchun & Jilin Provincial Key Laboratory of Chinese Medicine Chemistry and Mass Spectrometry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, 130022, China.
Food Funct. 2020 Apr 30;11(4):3719-3729. doi: 10.1039/d0fo00082e.
Citri Exocarpium Rubrum (CER) and Citri Reticulatae Pericarpium (CRP) are used as common functional foods and traditional Chinese medicine (TCM). As different parts of the same fruit, CER and CRP have different effects in clinical applications. However, they are commonly confused due to the similarity of the chemical compounds and a lack of scientific method to distinguish them in the finished product. In this study, an ultra-high performance liquid chromatography-diode array detector (UHPLC-DAD) technique and an ultra-high performance liquid chromatography-quadrupole time-of-flight mass spectrometry (UHPLC-Q-TOF MS) method were employed to generate the characteristic fingerprint under the optimum analytical conditions. Principal component analysis (PCA) and orthogonal partial least squares discrimination analysis (OPLS-DA) were applied to represent different chemical markers for CER and CRP. 44 potential markers including 15 polymethoxylated flavanones (PMFs), 5 flavone-C-glycosides, 6 flavanone-O-glycosides, 3 flavonoid-O-glycosides, 8 organic acids, 5 limonoids and 2 alkaloids were successfully identified by using UNIFI software. The heat map showed that there were significant differences in the CER and CRP samples. Furthermore, 12 potential markers were screened out by characteristic fingerprint and UHPLC-Q-TOF MS methods and were analyzed by quantitative analysis of multicomponents by a single marker (QAMS) method. Finally, a prediction model based on the discovered chemical markers was established for discrimination between CER and CRP. Using these markers can significantly distinguish the unknown processed products of CER and CRP. In conclusion, an effective way to quickly and easily distinguish CER and CRP was successfully established based on the characteristic fingerprint and UHPLC-Q-TOF MS. It could also be a new strategy for analysis of different processed products of the same plant source.
陈皮（CER）和橘红（CRP）作为常见的功能性食品和中药（TCM）被广泛应用。作为同一水果的不同部位，CER 和 CRP 在临床应用中具有不同的作用。然而，由于化学成分的相似性以及缺乏在成品中区分它们的科学方法，它们经常被混淆。在这项研究中，采用超高效液相色谱-二极管阵列检测器（UHPLC-DAD）和超高效液相色谱-四极杆飞行时间质谱（UHPLC-Q-TOF MS）技术，在最佳分析条件下生成特征指纹图谱。主成分分析（PCA）和正交偏最小二乘判别分析（OPLS-DA）用于表示 CER 和 CRP 的不同化学标志物。应用 UNIFI 软件成功鉴定了 44 种潜在标志物，包括 15 种多甲氧基黄酮（PMFs）、5 种黄酮-C-糖苷、6 种黄烷酮-O-糖苷、3 种黄酮-O-糖苷、8 种有机酸、5 种柠檬苦素和 2 种生物碱。热图显示 CER 和 CRP 样品之间存在显著差异。此外，通过特征指纹和 UHPLC-Q-TOF MS 方法筛选出 12 种潜在标志物，并通过单标记定量分析（QAMS）方法进行定量分析。最后，建立了基于发现的化学标志物的区分 CER 和 CRP 的预测模型。使用这些标志物可以显著区分 CER 和 CRP 的未知加工产品。总之，成功建立了基于特征指纹和 UHPLC-Q-TOF MS 快速、简便地区分 CER 和 CRP 的有效方法。这也可能成为分析同一植物源不同加工产品的新策略。
