金柑果实主要次生代谢产物含量及差异分析

Research on the contents and difference of the main secondary metabolites in different kumquat fruits

基于超高效液相色谱串联三重四极杆质谱法(ultra-performance liquid chromatography tandem triple quaternary mass spectrometry,UPLC-QqQ-MS/MS)对6种金柑果实中66种次生代谢产物的含量进行测定,通过统计、聚类分析等方法对6种金柑中类黄酮、酚酸、类柠檬苦素、生物碱和香豆素的含量进行多角度分析比较和差异研究。结果表明,6种金柑果实的类黄酮中黄酮含量最高,黄烷酮次之;宁波罗纹、温州罗浮、融安金弹和长寿金柑的酚酸以芥子酸为主,金豆、金柑杂种则分别以阿魏酸、绿原酸为主;金柑杂种的生物碱以N-甲基酪胺为主,其他5种金柑则以酪胺为主;6种金柑中均检出了滨蒿内酯、欧前胡素、异橙皮内酯、橙皮内酯水合物和橙皮油素;聚类分析结果表明,宁波罗纹和融安金弹的次生代谢模式相近,温州罗浮、长寿金柑、金豆和金柑杂种之间差异较大。该研究是目前测定金柑果实中次生代谢产物的种类最多的研究,研究结果为金柑果实在食品、医药等领域的应用提供数据支持和科学依据。

Sixty-six secondary metabolites in six kumquat fruits were analyzed by a UPLC-QqQ-MS/MS method.Through statistical analysis and cluster analysis,the difference of thirty-one flavonoids,eight phenolic acids,three limonoids,five alkaloids and nineteen coumarins in kumquat fruits were analyzed from multiple perspectives.The results showed that the contents of flavones were the highest among flavonoids in six kumquat fruits,followed by flavanones.The main phenolic acids of Ningbo round kumquat(Fortunella japonica Swingle),Wenzhou nagami kumquat(Fortunella margarita(Lour.)Swingle),Rongan meiwa kumquat(Fortunella crassifolia Swingle)and Changshou kumquat(Fortunella obovata Tanaka)were sinapic acid.Ferulic acid and chlorogenic acid were the main phenolic acids in Jindou kumquat(Fortunella hindsii Swingle)and Jinganzazhong(Fortunella obovata Tanaka),respectively.N-methyltyramine was the main alkaloid in Jinganzazhong,while tyramine was the main alkaloid in the other kumquats.Scoparone,imperatorin,isomeranzin,meranzin hydrate and auraptene were detected in six kumquats.The results of cluster analysis showed that the secondary metabolism patterns of Ningbo round kumquat and Rongan meiwa kumquat were similar,while the difference among Wenzhou nagami kumquat,Changshou kumquat,Jindou kumquat and Jinganzazhong was relatively large.This study is currently the largest study on the number of secondary metabolites detected by the UPLC-QqQ-MS/MS method.The results also provide data support and scientific basis for the application of kumquats in food,medicine and other fields.