UHPLC-UV-Q-Orbitrap HRMS combined with machine learning algorithms reveals the chemical markers of Euodiae Fructus among closely related cultivars
UHPLC-UV-Q-Orbitrap HRMS combined with machine learning algorithms reveals the chemical markers of Euodiae Fructus among closely related cultivars
复制标题
DOI：
10.1016/j.indcrop.2021.113279
复制
发表时间：
2021-04
影响因子：
5.9
通讯作者：
Caihong Li;Yan Zhao;Wenjing Li;Rongrong Xing;Jing Lu;Rongxia Liu
中科院分区：
文献类型：
--
作者：
Caihong Li;Yan Zhao;Wenjing Li;Rongrong Xing;Jing Lu;Rongxia Liu
杜仲（Euodiae Fructus，EF）为芸香科植物Tetradium ruticarpum的果实，遗传背景复杂，分类困难。为了对小花、中花和大花3个近缘品种进行分类并简化鉴定程序，建立了超高效液相色谱-紫外光谱-混合四极杆-轨道阱高分辨质谱（UHPLC-UV-Q-Orbitrap HRMS）与机器学习算法相结合的方法。采用正交偏最小二乘判别分析（OPLS-DA）和随机森林分析（RF）对3个品种的加工品进行分类，并筛选鉴别3个品种的化学标记。根据UHPLC-Q-Orbitrap高分辨质谱仪的化学标记物定量数据，采用极限梯度提升（XGboost）模型确定分类阈值。结果表明，该方法成功区分了3个近缘的EF品种，并筛选出5个化学标记（新绿原酸、（+）-儿茶素、绿原酸、脱氢吴茱萸碱和柠檬苦素）。获得了3个品种的分类依据。新绿原酸含量大于7.52mg/g的样品为小花EF，大于7.52mg/g的样品为中花EF或大花EF。脱氢吴茱萸碱含量大于3.84mg/g的样品为中花EF，大于3.84mg/g的样品为大花EF。总之，本研究为杜仲品种鉴别提供了一种新的策略，以避免误用和可能的副作用。
Euodiae Fructus (EF, the fruit ofTetradium ruticarpum) belongs to the family Rutaceae which has a complex genetic background, making classification a challenge. In order to classify the three closely related cultivars (small flower EF, medium flower EF, and big flower EF) and simplify the identification procedure in the future, an approach integrating ultra-high performance liquid chromatography-ultraviolet spectrum-hybrid quadrupole-Orbitrap high resolution mass spectrometry (UHPLC-UV-Q-Orbitrap HRMS) with machine learning algorithms was developed. Orthogonal partial least squares-discriminant analysis (OPLS-DA) and random forest (RF) were used to assort the processed EF products and select the chemical markers to differentiate among the three EF cultivars, respectively. Then the thresholds of classification were determined using the eXtreme Gradient Boosting (XGboost) model based on the quantitative data of chemical markers by the UHPLC-Q-Orbitrap HRMS. The results demonstrated that the approach successfully discriminated among three closely related cultivars of EF, and five chemical markers (neochlorogenic acid, (+)-catechin, chlorogenic acid, dehydroevodiamine, and limonin) were selected. Thresholds were obtained to classify the three cultivars. If the content of neochlorogenic acid was greater than 7.52 mg/g, the sample belonged to small flower EF, otherwise, it belonged to medium flower EF or big flower EF. Furthermore, if the content of dehydroevodiamine was greater than 3.84 mg/g, the sample was medium flower EF, otherwise, it was big flower EF. In general, this research provides a novel strategy for the discrimination of Euodiae Fructus cultivars to avoid misapplication and possible side effects.