无梗五加根化学成分的UPLC-MS/MS分析及与细柱五加、刺五加的比较

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目的:分析无梗五加、细柱五加和刺五加根中的化学成分并将三者进行比较。方法:运用UPLC-MS/MS对无梗五加、细柱五加和刺五加根中的化学成分进行一级和二级质谱分析,通过与对照品色谱峰的保留时间以及一级、二级质谱图比对鉴定其中的已知成分,并根据一级二级质谱信息推测未知成分的化学结构。色谱-质谱条件:采用Acquity UPLCTMBEH C1 8色谱柱(1.7μm,100 mm×2.1 mm),以乙腈(A)-2 mmol·L-1醋酸铵水(B)为流动相,梯度洗脱(0~15 min,8%A→25%A;15~30 min,25%A→55%A;30~40 min,55%A→80%A),流速0.15 mL·min-1;质谱离子源为电喷雾离子化(ESI)源,正、负离子检测。结果:从3种五加属植物根中共鉴定了13个化合物,包括奎宁酸类成分如1,3-二咖啡酰奎宁酸、3,4-二咖啡酰奎宁酸、3,5-二咖啡酰奎宁酸;酚苷类成分如紫丁香苷;木脂素类成分如松脂醇二葡萄糖苷、无梗五加苷B、无梗五加苷D、芝麻脂素、细辛脂素、洒维宁、台湾脂素C、台湾脂素E、赛菊宁黄脂。同时推测了15个化合物,包括奎宁酸类成分如一咖啡酰奎宁酸、对香豆酰奎宁酸、阿魏酰奎宁酸;酚苷类成分如紫丁香树脂酚二葡萄糖苷、松柏苷、松柏醛葡萄糖苷、芥子醛葡萄糖苷;木脂素类成分如紫丁香苷A、紫丁香苷B、Simplexoside、Pluviatolide、3-(3,4-二甲氧基苄基)-2(3,4-亚甲基二氧苄基)丁内酯;黄酮类成分如安妥苷;香豆素类成分如刺五加苷B2、异嗪皮啶。将3种五加根中的化学成分进行比较,无梗五加根与细柱五加根成分比较相近,刺五加根中含有在无梗五加根和细柱五加根中未检测到的多种酚苷类成分如紫丁香树脂酚二葡萄糖苷、松柏苷、紫丁香苷、松柏醛葡萄糖苷、芥子醛葡萄糖苷。结论:无梗五加根和细柱五加根中的化学成分组成比较相似,从化学成分的角度验证了《中华本草》中对“五加皮”的来源记载,即“五加皮”为细柱五加和无梗五加植物的根皮;二者化学成分与刺五加差别较大,在药用过程中应进行区分。 OBJECTIVE: To analyze the chemical constituents in Sessica pentaphyllae, Schizocarpia capillaries and Acanthopanax senticosus roots and to compare them. Methods: The chemical constituents in Radix Astragali, Radix Aconitum and Acanthopanax Senticosus were analyzed by UPLC-MS / MS. The chemical constituents were analyzed by first order and second order MS, Level mass spectrometry to identify the known components among them, and infer the chemical structure of unknown components according to the information of the first-level and second-level mass spectrometry. Chromatography-Mass Spectrometry Conditions: The mobile phase was eluted with a gradient of 0 on an Acquity UPLC TMBEH C1 8 column (1.7 μm, 100 mm × 2.1 mm) with acetonitrile (A) -2 mmol·L -1 ammonium acetate in water 15 min to 30 min, 25% A to 55% A, 30 to 40 min, 55% A to 80% A) at a flow rate of 0.15 mL · min -1; Electrospray ionization (ESI) source, positive and negative ion detection. Results: Thirteen compounds were identified from three genus five genus plants, including quinine acids such as 1,3-dicaffeoylquinic acid, 3,4-dicaffeoylquinic acid, 3,5- Dicaffeoylquinic acid; phenolic glycosides such as syringoside; lignan components such as pinoresinol diglucoside, sesame plus glycoside B, sesame plus glycosides D, sesamin, asarone , Sprinkle Weining, Taiwan fat C, Taiwan fat E, Saiju Ning yellow fat. At the same time, 15 compounds were speculated to be included, including quinine acids such as caffeoylquinic acid, p-coumaroylquinic acid and feruloylquinic acid, and phenolic compounds such as linalool phenolic diglucoside, coniferin, Aldoglucoside, sinapyl glucoside; lignan components such as syringin A, syringin B, Simplexoside, Pluviatolide, 3- (3,4- dimethoxybenzyl) -2 (3,4- Methylenedioxybenzyl) butyrolactone; flavonoids such as Etidronate; coumarins such as Acanthopanax B2, Isozine. The chemical composition of three kinds of five-plus roots were compared, the five-rooted and five-rooted stems were similar in composition, and the root of Acanthopanax sect. A variety of phenolic compounds such as lilac resin phenol diglucoside, coniferin, syringin, cypress glucoside, sinapyl glucoside. Conclusion: The composition of chemical constituents in the stems of Radix Aconiti Kusnezoffii and Radix Scutellariae is relatively similar, and the source of “Radix Cacaoe” in “Zhonghua Materia Medica” is verified from the aspect of chemical composition, that is, Skin "for the fine column five plus and sessile five plus plant root bark; chemical composition and Acanthopanax difference is larger, in the medical process should be distinguished.
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