沙棘油含有丰富的不饱和脂肪酸、生育酚、β-类胡萝卜素和甾醇类等物质，具有良好的药理学及传统功效。故沙棘油因其营养丰富、市场价值高等原因，导致掺假售假现象日益严重。沙棘油掺假售假不仅侵犯消费者的合法权益，食用掺假沙棘油也会危害消费者的身心健康，现已报道的针对沙棘油真伪鉴别的技术有两种，但均无法实现沙棘油及其掺假油中详细组分表征，目前有关于超高效液相色谱-四极杆飞行时间质谱（Ultra-performance Liquid Chromatography Coupled with Quadrupole Time-of-flight Mass Spectrometry，UPLC-QTOF-MS）对于沙棘油真实属性研究还未有报道。UPLC-QTOF-MS具有高通量、高灵敏度等优点，可以实现食用油中大量微量化合物检测，对食用油真伪鉴别具有重要意义。因此本研究采用基于UPLC-QTOF-MS的脂质组学方法和非靶标代谢组学方法，结合主成分分析（Principal Component Analysis，PCA）及正交偏最小二乘法（Orthogonal Partial Least Squares Discrimination Analysis，OPLS-DA）等化学计量学方法，对沙棘油的真伪进行鉴别，并对沙棘油及其对照油（葵花籽油、菜籽油及大豆油）中所含有的特征化合物进行推测鉴定，以此发掘各食用油之间差异，实现沙棘油与对照油有效鉴别，并进一步对所得图谱进行验证。研究内容与主要结果如下：

1. 沙棘油UPLC-QTOF-MS脂质组学真伪鉴别研究

采用基于UPLC-QTOF-MS的脂质组学方法对食用油样品中甘油酯进行检测，检测得甘油二酯（DAG）及甘油三酯（TAG）共92种，其中，甘油二酯为16种，甘油三酯为76种，沙棘油中存在而其对照油中不存在的甘油酯主要有：DAG32:1、TAG36:0、TAG38:0、TAG40:0、TAG42:1、TAG42:3、TAG44:5、TAG44:6、TAG46:0、TAG46:1、TAG58:6、TAG60:6和TAG60:6。根据所测甘油酯，建立模型对沙棘油及对照油聚类区分度进行表征及预测，实现沙棘油与葵花籽油、菜籽油、大豆油及其不同种类掺假油之间的真伪鉴别。结果表明，PCA、OPLS-DA图谱具有良好的区分度及解释能力，各食用油之间单独成簇，聚类区分明显，可基本实现不同种类食用油之间的有效区分；应用聚类分析利用不同颜色对沙棘油及对照油中的92甘油酯分布和相对含量进行对比，并通过层次聚类分析热图对各食用油中甘油酯相对含量进行直观反应，以此实现沙棘油及对照油的明显区分；利用观测值对比预测值的预测图对沙棘油及对照油的掺假比例进行预测，所得预测模型具有良好的线性关系，预测能力强，能够根据生成点的位置及所测数据，实现各梯度掺假沙棘油有效鉴别，为解决实际掺假浓度检测提供支持。

1. 沙棘油UPLC-QTOF-MS非靶标代谢组学真伪鉴别研究

采用基于UPLC-QTOF-MS的非靶标代谢组学方法对食用油进行检测，结合PCA及OPLS-DA法对沙棘油及其对照油进行聚类区分，并利用MarkerView软件及SIMCA软件对食用油中的特征离子进行筛选，根据设定条件，将所得特征化合物化学方程式、一级及二级离子图谱对比线上数据库、MS-FINDER软件及文献，推测其特征化合物名称，并对食用油鉴别进行进一步验证。结果表明，基于UPLC-QTOF-MS的非靶标代谢组学方法能够实现沙棘油、葵花籽油、菜籽油及大豆油的有效区分鉴别，所建化学计量学模型可靠，OPLS-DA模型聚类区分度良好，具有良好的解释及预测能力，同种类食用油聚类及不同种类食用油区分状况明显，可对沙棘油及其对照油进行有效鉴别，通过特征化合物丰度分析可以鉴别1%沙棘油的掺假，因此基于UPLC-QTOF-MS的非靶标代谢组学技术可以作为鉴别沙棘油及其掺假油的有效手段之一，为后期应用基于UPLC-QTOF-MS的非靶标代谢组学结合化学计量学分析技术对沙棘油及其掺假食用油进行真伪鉴别研究提供经验和参考。本研究对沙棘油及其对照油中非挥发性特征代谢化合物进行推测，共推测出20种特征化合物，包括有机酸、醇类等，其中沙棘油10种，葵花籽油4种，菜籽油5种，大豆油1种。不同种类食用油中所含有的特征化合物具有较大差异，部分特征化合物仅存在与沙棘油中，例如松油醇、党参炔醇、蓖麻油醇、熊果酸/齐墩果酸等。特征化合物能够从小分子物质对4种食用油进行区分，并能探求掺假油的种类。并对图谱起到了进一步验证的效果，因此，此方法与模型鉴别相互验证，互为补充，可以作为沙棘油及其对照油的真实性鉴定的有效手段，实现对未知沙棘油样品真实性的准确判别。可为沙棘油真伪鉴别提供坚实理论和科学依据，为后期应用此方法验证沙棘油及其掺假食用油提供一定经验和参考。

Sea buckthorn oil is rich in unsaturated fatty acids, tocopherol, β-carotenoids and sterols and so on, and it has good pharmacological and traditional effects. Therefore, due to its rich nutrition and high market value and many other reasons, sea buckthorn oil adulterated very seriously. The adulteration of sea buckthorn oil not only infringe upon the legitimate rights and interests of consumers, but also harm the health body and mind of consumers. There are only two kinds of authenticity identification technology has been reported to identified sea buckthorn oil, and both of them cannot to achieve its characterization of sea buckthorn oil and its adulterated oil in the detailed components. So far the study about the technology of UPLC-QTOF-MS (Ultra-Performance Liquid Chromatography Coupled with Quadrupole Time-of-Flight Mass Spectrometry, UPLC-QTOF-MS) to distinguish the true nature of the sea buckthorn oil has not reported. The UPLC-QTOF-MS has the advantages of high throughput, high sensitivity, and can be used to detect a large number of trace compounds in edible oils, which has a great significance for the identification of the authenticity of edible oils. Therefore, in this study, we used the methods of lipidomics and metabolomics based on UPLC-QTOF-MS, and combined with PCA (Principal Component Analysis, PCA) and OPLS-DA (Orthogonal Partial Least Squares Discrimination Analysis, OPLS-DA) of chemometrics methods to identify the authenticity of sea buckthorn oil, and to use this methods to speculate the compounds which contained in the sea buckthorn oil and its adulterated oil (sunflower seed oil, rapeseed oil and soybean oil), and to explore the differences among various edible oils to further distinguish sea buckthorn oil and oil adulteration, and further to authenticate the map. The research contents and main results are as follows:

1. Research on identification of UPLC-QTOF-MS lipidomics of sea buckthorn oil

The research based on UPLC-QTOF-MS lipidomics to test the glyceride in edible oil samples, can clearly distinguish the sea buckthorn oil and its adulterated oil. A total of 92 species of diacylglycerols (DAG) and triacylglycerols (TAG) has been detected, among them, 16 species are diacylglycerols, 76 species are triacylglycerols. The glycerides mainly in sea buckthorn but not exist in adulterated oil are: DAG32:1、TAG36:0、TAG38:0、TAG40:0、TAG42:1、TAG42:3、TAG44:5、TAG44:6、TAG46:0、TAG46:1、TAG58:6、TAG60:6 and TAG60:6. According to the measured glyceride, the model was established to characterize and predict the clustering differentiation of sea buckthorn oil and its adulterated oil. The authenticity identification of sea buckthorn oil, sunflower seed oil, rapeseed oil, soybean oil and different kinds of adulterated oil was realized. The results showed that the models of PCA and OPLS-DA had a good degree of differentiation and explain ability, and the clustering differentiation among edible oils was obvious. The various edible oils were separated in clusters. It can basically realize the effective distinction between different kinds of edible oil. The application of clustering analysis was used to compared the distribution and relative content of 92 glycerides in sea buckthorn oil and its adulterated oil by different colors, and the hierarchical clustering algorithm heatmap was used to compared the relative content of glyceride in edible oil straightly. The identification of sea buckthorn oil and its adulterated oil was predicted by using the prediction chart of observed value and predicted value, and the prediction proved that the method to detect sea buckthorn oil and its adulterated oil has good linear relationship and strong prediction ability, which can achieve the effective identification of each gradient of sea buckthorn oil and its adulterated oil rely on the production point and the measure data. It can provides support for solving the actual detection of adulteration concentration.

2. Research on identification of UPLC-QTOF-MS non-target metabolomics of sea buckthorn oil

We used UPLC-QTOF-MS non-targeted metabolomics to detected the edible oils, and coupled with the methods of PCA and OPLC-DA to conducted the cluster differentiation of sea buckthorn oil and its adulterated oil. The MarkerView (Ver1.3.1 AB Sciex company) software and the SIMCA (Ver15 MKS Data Analytics Solutions (the original Umetrics)) software were used to filtrate the characteristic ions. According to the conditions, we compared the chemical equation of compound, primary and secondary ion chromatogram with the online databases, MS-FINDER software and literature comparison to speculate the name of characteristic compounds, and to identify the verification of edible oil furtherly. The experimental data showed that the method which based on non-targeted metabolomics of UPLC-QTOF-MS can effectively distinguish the differentiation of sea buckthorn oil, sunflower seed oil, rapeseed oil and soybean oil. The chemical metrology model is reliable. OPLS-DA model clustering degree of differentiation is good, and it has the good explanation and prediction ability. The clustering of same kind of edible oil and the distinguish situation of different kinds of edible oil is clearly, it can effectively identify among the sea buckthorn oil and its adulteration oil. Through the analysis of characteristics of compound abundance, the 1% adulterated sea buckthorn oil can be identified, therefore on the basis of UPLC-QTOF-MS of non-target metabolomics technology can be used as the one of the effective means to identified the sea buckthorn oil and its adulteration oil. It can provide experience and reference for the application of non-target metabolomics and chemometrics analysis technology based on UPLC-QTOF-MS for the authenticity identification of sea buckthorn oil and its adulterated edible oils. In this research, the non-volatile characteristic metabolic compounds of sea buckthorn oil and its adulterated oil were speculated. Through this way 20 characteristic compounds have been detected, which include organic acids and alcohols. 10 of characteristic compounds are sea buckthorn oil, 4 of characteristic compounds are sunflower seed oil, 5 of characteristic compounds are rapeseed oil and 1 of characteristic compounds is soybean oil. Different kinds of edible oils have different characteristic compounds. Some characteristic compounds are only existing in sea buckthorn oil, such as Sclareol, Lobetyol, Ricinoleyl alcohol, Ursonic acid/Oleanonic acid and so on. Characteristic compounds can be used to distinguish 4 kinds of oil from the level of small molecules, explore the types of adulterated oil and to verify the map furtherly. Therefore, this method and model identification are mutually verified and complementary, which can be used as a good way to identify the authenticity of sea buckthorn oil and its adulterated oil and accurately determined the authenticity of unknown sea buckthorn oil samples. This way can provide solid identification theory and scientific basis for the identify of sea buckthorn oil, and provide certain experience and reference for the late application through this method to verify the sea buckthorn oil and adulterated edible oil.

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