UHPLC-Q-TOF-MS/MS分析青钱柳嫩叶渗漉提取液化学成分

马博稷; 肖岩; 陈祖德; 舒任庚; 李冰涛; 姜丽; 徐国良; 张启云

doi:10.13386/j.issn1002-0306.2022070294

UHPLC-Q-TOF-MS/MS分析青钱柳嫩叶渗漉提取液化学成分

doi: 10.13386/j.issn1002-0306.2022070294

马博稷^1,,
肖岩¹,
陈祖德¹,
舒任庚²,
李冰涛^{1, 3},
姜丽^{1, 3, 4},
徐国良^{1, 3, 4, ,},
张启云^{1, 3, ,}

1.
江西中医药大学中医基础理论分化发展研究中心，江西南昌 330004
2.
江西中医药大学药学院，江西南昌 330004
3.
江西省中医病因生物学重点实验室，江西南昌 330004
4.
江西省中药药理学重点实验室，江西南昌 330004

基金项目: 国家自然科学基金项目（82060826）；江西省教育厅科学技术研究项目（GJJ190645）；江西中医药大学博士启动基金（2018WBZR008）；江西中医药大学校级科技创新团队发展计划（CXTD22015）。

详细信息

作者简介:
马博稷（1997−），女，硕士研究生，研究方向：中药药效物质基础研究，E-mail：Maboji02@163.com

通讯作者:
徐国良（1966−），男，博士，教授，研究方向：中药药理研究，E-mail：xuguoliang6606@126.com

张启云（1982−），女，博士，副教授，研究方向：中药药效物质基础和中药复方代谢组学研究，E-mail：zhangqiyun0923@163.com

中图分类号: O657.63
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出版历程
- 收稿日期: 2022-08-01
- 网络出版日期: 2023-05-22
- 刊出日期: 2023-07-01

Analysis of Chemical Constituents in Percolate the Extract of Cyclocarya paliurus Tender Leaves by UHPLC-Q-TOF-MS/MS

Boji MA^1
,,
Yan XIAO¹,
Zude CHEN¹,
Rengeng SHU²,
Bingtao LI^{1, 3},
Li JIANG^{1, 3, 4},
Guoliang XU^{1, 3, 4
, ,},
Qiyun ZHANG^{1, 3
, ,}

1.
Research Center for Differentiation and Development of Traditional Chinese Medicine (TCM) Basic Theory, Jiangxi University of Chinese Medicine, Nanchang 330004, China
2.
School of Pharmacy, Jiangxi University of Chinese Medicine, Nanchang 330004, China
3.
Jiangxi Provincial Key Laboratory of TCM Etiopathogenisis, Nanchang 330004, China
4.
Key Laboratory of Pharmacology of Traditional Chinese Medicine in Jiangxi, Nanchang 330004, China

摘要

摘要: 为分析青钱柳嫩叶的化学成分，本研究采取高效液相色谱-四级杆飞行时间串联质谱法（UHPLC-Q-TOF-MS/MS）对青钱柳嫩叶渗漉提取液的化学成分进行快速定性分析。在正、负离子模式下全扫描和对母离子电子轰击，根据各化合物的精确分子量及元素组成、主要碎片信息、保留时间以及结合青钱柳相关文献和数据库检索，从青钱柳中共鉴定出94种化合物，包括29种黄酮类、16种三萜类、25种有机酸类、24种其他类化合物。分析结果显示，青钱柳渗漉提取液中含有黄酮、有机酸、三萜、香豆素、氨基酸类等多种化合物，且苹果酸、橙皮素、松脂素、6, 7-二羟基香豆素、6-甲基香豆素、5,7-二甲氧基香豆素为首次在青钱柳中发现，本研究结果可为进一步明确青钱柳药效物质基础奠定了基础，为开发青钱柳相关产品提供了理论依据。
- 青钱柳嫩叶 /
- 渗漉 /
- 化学成分 /
- 高效液相色谱-四级杆飞行时间串联质谱法（UHPLC-Q-TOF-MS/MS）
Abstract: To analyze the chemical components of the tender leaves of Cyclocarya paliurus, a rapid qualitative analysis of the chemical components of the percolation extracts of the tender leaves of Cyclocarya paliurus was carried out by ultrahigh-performance liquid chromatography coupled with quadrupole-time-of-flight tandem mass spectrometry (UHPLC-Q-TOF-MS/MS). Mass spectrum data were collected in the positive and negative ion modes, and MassHunter qualitative analysis software was used, according to the retention time and mass spectrum information of each compound, combined with existing literature and mass spectrum databases, the compounds were analyzed for the fragmentation rule, 94 compounds were identified from Cyclocarya paliurus, including 29 flavonoids, 16 triterpenes, 25 organic acids, 24 other compounds. The analysis results showed that the percolation extract of Cyclocarya paliurus contained flavonoids, organic acids, triterpenoids, coumarins, amino acids, and other compounds, and malic acid, hesperidin, rosin, 6,7-dihydroxycoumarin, 6-methylcoumarin, 5,7-dimethoxycoumarin are found in Cyclocarya paliurus for the first time. This study can lay a foundation for further clarifying the material basis of Cyclocarya paliurus. It provides a theoretical basis for the development of relevant products of Cyclocarya paliurus.

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图 1 青钱柳嫩叶渗漉提取液的UHPLC-Q-TOF-MS/MS总离子流图

Figure 1. Total ion current chromatograms of percolation extraction of Cyclocarya paliurus tender leaves by UHPLC-Q-TOF-MS/MS

注：A.负离子模式；B.正离子模式；编号1~94为鉴定出的化合物对应的响应强度峰。

下载: 全尺寸图片幻灯片

图 2 3-咖啡酰奎宁酸在负离子模式下的一、二级质谱及可能裂解规律

Figure 2. Mass spectra and possible fragment pathways of 3-caffeoylquinic acid in negative ion mode

下载: 全尺寸图片幻灯片

图 3 金丝桃苷在负离子模式下的一、二级质谱及可能裂解规律

Figure 3. Mass spectra and possible fragment pathways of hiperoside in negative ion mode

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图 4 青钱柳苷H-Cui在负离子模式下的一、二级质谱及可能裂解规律

Figure 4. Mass spectra and possible fragment pathways of cyclocarioside H-Cui in negative ion mode

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表 1 正、负模式下青钱柳渗漉液中各成分二级质谱碎片信息

Table 1. The secondary mass spectrometry fragments information in Cyclocarya paliurus percolate in positive and negativeion mode

分类	序号	t_R（min）	分子式	准分子离子峰（m/z）				MS/MS特征碎片信息	推测化合物
分类	序号	t_R（min）	分子式	离子模式	实测值	理论值	误差（ppm）	MS/MS特征碎片信息	推测化合物
有机酸类	1	1.588	C₄H₈O₅	[M-H]⁻	135.0299	135.0299	0	59.0137,135.0276	苏糖酸^[7−9] （Threonic acid）
	2	1.707	C₄H₆O₅	[M-H]⁻	133.0148	133.0142	4.5	71.0132，133.0117	苹果酸^[7−9] （Malic acid）
	3	1.843	C₆H₈O₇	[M-H]⁻	191.0197	191.0197	0	85.0280，87.0071，111.0077，191.0170	异柠檬酸^[7−9] （Isocitric acid）
	4	2.406	C₆H₈O₇	[M-H]⁻	191.0197	191.0197	0	111.0075，173.0067	柠檬酸^[7−10] （Citric acid）
	5	4.689	C₇H₁₀O₇	[M-H]⁻	205.0352	205.0354	−1	59.0130，73.0272，87.0074，205.0320	高柠檬酸^[7−9] （Homoisocitrate）
	6	4.178	C₇H₆O₅	[M-H]⁻	169.0143	169.0142	0.6	69.0337，71.0122，95.0122，123.0065，125.0222	没食子酸^[5,7−9] （Gallic acid）
	7	9.513	C₇H₆O₃	[M-H]⁻	137.0248	137.0244	2.9	65.0383，93.0325	水杨酸^[11] （Salicylic acid）
	8	10.817	C₇H₆O₄	[M-H]⁻	153.0195	153.0193	1.3	53.0384，109.0227，153.0165	原儿茶酸^[11] （Protocatechuic acid）
	9	12.734	C₁₆H₁₈O₈	[M-H]⁻	337.0909	337.0929	−5.9	137.0216，163.0375，191.0527	3-O-对香豆酰奎尼酸^[8] （3-O-Coumaroylquinic acid）
	10	13.612	C₉H₈O₄	[M-H]⁻	179.0358	179.035	4.5	79.0543，89.0378，106.0405，134.0344，179.0318	咖啡酸^[7−9] （Caffeic acid）
	11	13.791	C₁₆H₁₈O₉	[M-H]⁻	353.0832	353.0878	−13	135.0424，173.0422，179.0335，191.0527	3-咖啡酰奎宁酸^[12] （Chlorogenic Acid）
	12	15.631	C₁₆H₁₈O₉	[M-H]⁻	353.0879	353.0878	0.3	93.0326，135.0422，191.0532	4-咖啡酰奎宁酸^[12] （Cyclohexanecarboxylic acid）
	13	18.392	C₁₆H₁₈O₉	[M-H]⁻	353.0871	353.0878	−2	93.0323，191.0525	5-咖啡酰奎宁酸^[12] （Neochlorogenic acid）
	14^*	19.619	C₇H₁₀O₅	[M-H]⁻	173.0454	173.0455	−0.6	55.0177，57.0340，59.0133，69.0331，173.042 4	莽草酸（Shikimic Acid）
	15	20.284	C₁₀H₁₀O₄	[M-H]⁻	193.0482	193.0506	−12.4	89.0389，93.0328，103.0540，117.0327，145.0274	阿魏酸^[12] （Ferulic acid）
	16^*	20.846	C₉H₈O₃	[M-H]⁻	163.0401	163.0401	0	93.0325，119.0478，163.0371	对香豆酸（P-Coumaric acid）
	17	21.247	C₉H₁₀O₅	[M-H]⁻	197.0553	197.0528	12.6	79.0166，81.0340，95.0135，97.0288，125.0221	丁香酸^[5] （Syringic acid）
	18^*	22.687	C₇H₁₂O₆	[M-H]⁻	191.0565	191.0561	2.1	71.0123，73.0275，87.0078，127.0365，191.0529	奎宁酸（Quinic acid）
	19	33.186	C₂₅H₂₄O₁₂	[M-H]⁻	515.1131	515.1195	−12.4	173.0421，179.0319，191.0526	3,4-O-二咖啡酰奎宁酸^[13] （3,4-O-Dicaffenoylquinate）
有机酸类	20^*	47.613	C₃₄H₃₀O₁₅	[M-H]⁻	677.1535	677.1512	3.4	173.0451，179.0314，191.0568，353.0833	1,3,5-三咖啡酰奎宁酸（1,3,5-Tricaffeoylquinic acid）
	21^*	55.683	C₁₈H₁₆O₈	[M-H]⁻	359.0774	359.0772	0.6	109.0291，359.0724	迷迭香酸（Rosmarinic acid）
	22^*	103.907	C₁₈H₃₀O₂	[M-H]⁻	277.2171	277.2173	−0.7	277.2131	α−亚麻酸（α−Linolenic acid）
	23	4.388	C₁₆H₁₈O₉	[M+H]⁺	355.1022	355.1024	−0.6	135.0479，163.0428	1-咖啡酰奎宁酸^[7−9] （1-O-Caffeoylquinic Acid）
	24^*	51.751	C₈H₈O₄	[M+Na]⁺	191.0316	191.0315	0.5	121.0290	香草酸（Vanillic acid）
	25	69.610	C₁₆H₃₂O₂	[M+NH₄]⁺	274.2742	274.2741	0.4	57.0703，71.0854，85.1019	棕榈酸^[7−9] （Palmitic acid）
黄酮类	26^*	7.706	C₁₅H₁₄O₇	[M-H]⁻	305.0667	305.0667	0	57.0333，83.0123，109.0272，125.0219，137.0218	（-）-表没食子儿茶素[（-）-Epigallocatechin]
	27^*	19.279	C₁₅H₁₄O₆	[M-H]⁻	289.0715	289.0718	−1	93.0324，105.0340，123.0424，137.0239，139.033 0	儿茶素（Catechin）
	28	24.665	C₂₁H₂₀O₁₃	[M-H]⁻	479.0832	479.0831	0.2	108.0180，133.0265，147.0056，201.0190，214.0205，271.0174，316.0211，317.0198	杨梅素-3-O-半乳糖苷^[14] （Myricetin-3-O-Galactoside）
	29^*	26.931	C₁₅H₁₀O₇	[M-H]⁻	301.0356	301.0354	0.7	107.0121，109.0254，121.0273，151.0013，271.0283	槲皮素（Quercetin）
	30	27.945	C₂₁H₂₀O₁₂	[M-H]⁻	463.0827	463.0882	−11.9	151.0014，178.9955，255.0243，271.0213，300.0232，301.2371	异槲皮苷^{[7−9,15-16]} （Isoquercitrin）
	31	28.636	C₂₁H₁₈O₁₃	[M-H]⁻	477.0620	477.0675	−11.5	151.0001，175.0224，301.0302	槲皮素-3-O-葡萄糖醛酸苷^[4] （Quercetin-3-O-α−D-glucuronide）
	32	28.891	C₂₁H₂₀O₁₂	[M-H]⁻	463.0828	463.0882	−11.7	255.0254，271.0206，272.0243，300.0229	槲皮素-7-葡萄糖苷^{[7−9,15-16]} （Quercetin 7-glucoside）
	33	29.139	C₂₁H₂₀O₁₂	[M-H]⁻	463.0826	463.0882	−12.1	101.0224，178.9962，243.0253，255.0296，271.0249，300.0276，301.0267，302.030 2	金丝桃苷^{[7−9,15-16]} （Hiperoside）
	34	30.868	C₂₀H₁₈O₁₁	[M-H]⁻	433.0719	433.0776	−13.2	150.9979，271.0203，301.0260	槲皮素-3-O-α−L−阿拉伯糖苷^[5] （Quercetin-3-O-α−L−arabinoside）
	35	31.175	C₂₁H₂₀O₁₁	[M-H]⁻	447.0874	447.0933	−13.2	227.0306，228.0349，255.0264，258.0314，285.031 4	山柰酚-3-O-葡萄糖苷^[17] （Kaempferol-3-O-glucoside）
黄酮类	36^*	31.431	C₁₅H₁₂O₇	[M-H]⁻	303.0495	303.051	−4.9	105.0346，119.0476，123.0443，125.0226，145.0274，151.0385	二氢槲皮^[7−9] （Dihydroquercetin）
	37	32.964	C₂₁H₂₀O₁₁	[M-H]⁻	447.0870	447.0933	−14.1	93.0315，119.0477，145.0266，149.0220，177.016 0	柚皮素-7-O-葡糖苷酸^[7−9] （Naringenin-7-O-glucoside）
	38	34.268	C₁₅H₁₀O₈	[M-H]⁻	317.0260	317.0303	−13.6	65.0022，83.0124，109.0265，137.0215	杨梅素^[14] （Myricetin）
	39^*	37.14	C₂₁H₂₀O₁₀	[M-H]⁻	431.0931	431.0984	−12.3	228.0347，256.0296，285.0326	阿福豆苷^[18] （Afzelin）
	40	37.379	C₂₁H₂₀O₁₀	[M-H]⁻	431.0930	431.0984	−12.5	59.0132，135.0053，151.0026，227.0311	染料木素-5-葡萄糖苷^[7−9] （Genistein-5-glucoside）
	41	47.434	C₂₃H₂₂O₁₁	[M-H]⁻	473.1024	473.1089	−13.7	59.0146，255.0264，285.0320	4''-乙酰基阿福豆苷^[7−9] （4''-O-Acetylafzelin）
	42^*	47.758	C₁₇H₁₄O₇	[M-H]⁻	329.0660	329.0667	−2.1	161.0255，227.0306，272.0249，300.0222，313.0322	苜蓿素（Tricin）
	43	49.804	C₁₅H₁₀O₆	[M-H]⁻	285.0369	285.0405	−12.6	119.0107，135.0086，211.0376，255.0299	山柰酚^[14,18] （Kaempferol）
	44	52.224	C₁₅H₁₂O₅	[M-H]⁻	271.0609	271.0612	−1.1	91.0179，117.0312，145.0261，159.0409，187.036 6	柚皮素^[7−9] （Naringenin）
	45	57.098	C₁₆H₁₄O₆	[M-H]⁻	301.0717	301.0718	−0.3	121.0283，134.0353，135.0422，199.0336	橙皮素^[7−9] （Hesperetin）
	46	59.024	C₃₀H₂₆O₁₂	[M-H]⁻	577.1290	577.1346	−9.7	145.0272，163.0368，285.0353	山柰酚-3-O-α−L−（3-反式-p-肉桂酰基-鼠李糖苷）^[4] [Kaempferol 3-O-α−L-（3-trans-p-coumaroyl-rhamnopyranoside）]
	47^*	7.525	C₁₅H₁₄O₇	[M+H]⁺	307.0815	307.0812	1	139.0421	（+）-没食子儿茶素^[4] [（+）-Gallocatechin]
	48^*	13.382	C₁₅H₁₄O₆	[M+H]⁺	291.0866	291.0863	1	139.0424，147.0480	（-）-表儿茶素 [（-）-Epicatechin]
	49	23.722	C₂₁H₂₀O₁₃	[M+H]⁺	481.1000	481.0977	4.8	273.0461，319.0532	杨梅素-3-O-D-吡喃葡萄糖苷^[7−9] （Myricetin 3-O-β−D-Galactopyranoside）
	50	33.184	C₂₁H₁₈O₁₂	[M+H]⁺	463.0932	463.0871	13.2	287.0582	山柰酚-3-O-β−葡萄糖醛苷酸^[4] （Kaempferol-3-O-β−glucuronoside）
	51	38.350	C₂₂H₂₀O₁₂	[M+H]⁺	477.1075	477.1028	9.9	153.0200，287.0575	木犀草素-7-甲基葡萄糖醛酸^[7−9] （Luteolin 7-methylglucuronide）
	52	40.243	C₁₅H₁₂O₆	[M+H]⁺	289.0703	289.0707	−1.4	83.0167，135.0477	二氢山柰酚^[7−9] （Dihydrokaempferol）
	53	56.977	C₁₆H₁₄O₆	[M+H]⁺	303.0855	303.0863	−2.6	117.0320，145.0285，163.0331	7-O-甲基圣草酚^[7−9] （Sterubin）
	54	60.446	C₂₇H₃₀O₁₄	[M+H]⁺	579.1650	579.1708	−10	129.0541，287.0627	山柰酚-3,7-二-O-α−L- 鼠李糖苷^[7−9] （Kaempferitrin）
三萜类	55	66.455	C₄₁H₇₀O₁₃	[M+COOH]⁻	815.4711	815.4798	−10.7	509.3316，609.4230，671.3817，771.4723，815.4710	青钱柳苷Z18- Li C（Cyclocarioside Z18-Li C）
	56	71.176	C₄₀H₆₈O₁₂	[M+COOH]⁻	785.461	785.4693	−10.6	477.3780，609.4226，741.4624， 785.4610	青钱柳苷F-Li[（20S,24R）-epoxydammarane-（3β,12β）-25-hydroxyl-12-O-α−L−arabinopyranoyl-3-O-α−L−arabinofuranoside]
	57	75.3	C₃₇H₆₀O₁₁	[M-H]⁻	679.3965	679.4058	−13.7	603.3963，639.4408，679.3989	青钱柳苷Q-Qin[（24R）-12β,20-dihydroxy-24-hydroperoxy-3,4-seco-dammara-4（28）,25-diene-3-oic acid 20-O-（5-O-acetyl）-α−L−arabinofuranoside]
	58	76.655	C₄₁H₇₀O₁₂	[M+COOH]⁻	799.4765	799.4841	−9.5	477.3773，609.4194，755.4784， 799.4765	青钱柳苷N-Cui[（20S,24R）-（3β,12β）-20,24-epoxydammara-25-ol-12-O-β−D−quinovopyranosyl-3-O-α−L−arabinopyranoside]
	59	78.385	C₄₃H₇₄O₁₄	[M+COOH]⁻	859.4973	859.5061	−10.2	494.3838，626.4224，771.5400，773.6733，814.4968，815.4978	青钱柳苷Z10[Dammarane-（20S,24R,25）-penthydroxyl-11-O-β−D−quinovopyranosyl-3-O-（5'-O-acetyl）-α−L−arabinofuranoside]
	60	87.034	C₄₃H₇₂O₁₃	[M+COOH]⁻	841.4868	841.4955	10.33	524.3514，623.4338，755.4787， 797.4861，841.4873	青钱柳苷H-Cui [（20S,24R）-（3β,12β）-20,24-epoxydammara-25-ol-12-O-β−D−quinovopyranosyl-3-O-（5-O-acetyl）-α−L-arabinopyranoside]
	61	87.81	C₃₅H₅₈O₉	[M-H]⁻	621.394	621.4003	−10.1	489.3513，522.3109	pterocaryoside B
	62	92.719	C₃₆H₆₀O₉	[M-H]⁻	635.4104	635.4156	−8.2	489.3530，535.3222	pterocaryoside A
	63	95.829	C₄₄H₇₄O₁₃	[M+COOH]⁻	855.5027	855.5111	−9.8	474.3492，621.0097，769.4955， 811.5031，855.5027	青钱柳苷N-Wu[（20S,24R）-epoxydammarane （3β,12β）-25-hydroxyl-12-O-β−D−quinovopyranosyl-3-O-（4′-O-acetyl）-β−D−quinovopyranoside]
	64	96.689	C₃₅H₅₈O₉	[M-H]⁻	621.3942	621.4003	−9.8	489.3536，523.3233，595.9477	青钱柳苷J[（12R,20S,24S）-20,24-dihydroxy-3,4-secodammara-4（28）,25-dien-3-oic acid-12-O- a-L−arabinopyranoside]
	65	98.308	C₃₀H₄₈O₄	[M+COOH]⁻	517.3527	517.3535	−1.5	473.3576，517.3470	2α−羟基乌苏酸（2α−hydroxyursolic acid）
	66	99.962	C₃₆H₆₀O₉	[M-H]⁻	635.4094	635.4156	−9.8	489.3518	青钱柳苷III（Cyclocarioside III）
	67	100.32	C₃₅H₅₆O₈	[M-H]⁻	603.3893	603.3897	−0.7	471.3426，521.3055	青钱柳苷II（Cyclocarioside II）
三萜类	68	76.813	C₄₃H₇₂O₁₄	[M+NH₄]⁺	830.5244	830.5260	−1.9	772.5202，830.5244	青钱柳苷Z19[（20S,24R）-epoxydammarane-（3α,11α）-25-hydroxyl-11-O-β−D−glucopyranoside-3-O-（5′-O-acetyl）-α−L−arabinofuranoside]
	69	93.215	C₄₂H₇₀O₁₃	[M+NH₄]⁺	800.5211	800.5155	7	652.4207，742.5142，800.5211	青钱柳苷C[（20S,24R）-epoxydammarane （3β, 12β）-25-hydroxyl-12-O-α−L−arabinopyranosyl-3-O-（5'-O-acetyl）-α−L−arabinofuranoside]
	70	96.173	C₃₀H₄₈O₄	[M+H]⁺	473.3615	473.3625	−2.1	107.0875，119.0869，145.1030，147.1198	山楂酸（Maslinic acid）
香豆素类	71^*	9.385	C₉H₆O₃	[M-H]⁻	161.0245	161.0244	0.6	117.0321，132.0189，160.0126	伞形酮（Umbelliferone）
	72	27.119	C₁₄H₆O₈	[M-H]⁻	300.9948	300.9990	−14	201.0141，213.0112，226.9960，254.9890，257.0033，270.9838，282.9879，300.9925	鞣花酸^[7−9] （Ellagic acid）
	73	65.406	C₂₀H₁₄O₇	[M-H]⁻	365.0666	365.0667	−0.3	189.0159，235.0336	瑞香素甲醚^[7−9] （Daphnoretin methyl ether）
	74	19.236	C₁₀H₈O₃	[M-H]⁻	175.0391	175.0401	−5.7	93.0333，131.0464，175.0327	4-甲基伞形酮^[7−9] （4-Methylumbelliferone）
	75	8.863	C₉H₆O₄	[M+H]⁺	179.0332	179.0339	−3.9	77.0403，105.0354	6,7-二羟基香豆^[7−9] （6,7-Dihydroxycoumarin）
	76	16.970	C₁₀H₈O₂	[M+H]⁺	161.0595	161.0597	−1.2	91.0570，105.0725，133.0654	6-甲基香豆^[7−9] （6-Methylcoumarin）
	77^*	22.784	C₉H₆O₂	[M+H]⁺	147.045	147.0441	6.1	75.0541，77.0387，103.0540	香豆素（Coumarin）
	78	34.429	C₁₁H₁₀O₄	[M+H]⁺	207.0642	207.0652	−4.8	63.0223，121.0279，149.0228	5,7-二甲氧基香豆^[7−9] （Citropten）
糖类	79	22.432	C₆H₁₂O₆	[M-H]⁻	179.0568	179.0561	3.9	59.0124，71.0136，85.0278，179.0528	D-葡萄糖^[7−9] （D-glucopyranoside）
酚苷类	80	17.728	C₁₅H₁₈O₈	[M-H]⁻	325.0928	325.0929	−0.3	73.0263，103.0530，117.0323， 145.0273，163.0400	顺式苜蓿甙^[7−9] （Cis-Melilotoside）
	81	23.352	C₁₆H₁₈O₈	[M-H]⁻	337.0907	337.0929	−6.5	59.0128，109.0284，133.0256，145.0272	水胡桃苷^[7−9] （Hydrojuglone glucoside）
	82	24.477	C₁₆H₁₆O₈	[M-H]⁻	335.0722	335.0741	−5.7	59.0127，71.0125，93.0324，145.0266	胡桃苷^[7−9] （Juglone Glucoside）
生物碱类	83	2.235	C₅H₅N₅	[M-H]⁻	134.0478	134.0472	4.5	92.0230，107.0335，134.0448	腺嘌呤^[19] （Adenine）
氨基酸类	84	2.534	C₅H₇NO₃	[M-H]⁻	128.0352	128.0353	−0.8	52.0201，128.0330	焦谷氨酸^[7−9] （Pyroglutamic acid）
	85^*	10.577	C₁₁H₁₂N₂O₂	[M+H]⁺	205.1001	205.0972	14.1	118.0679，146.0641	L-色氨酸（L-Tryptophan）
	86	41.922	C₉H₁₁NO₂	[M+H]⁺	166.0861	166.0863	−1.2	65.0397，91.0565，120.0834	苯丙氨酸^[20] （Phenylalanine）
萜烯类	87	26.007	C₁₁H₁₆O₃	[M+H]⁺	197.1195	197.1172	11.7	91.0555，105.0714，133.1027	地芰普内酯^[7−9] （Loliolide）
倍半萜类	88	41.675	C₁₅H₂₂	[M+H]⁺	203.1809	203.1794	7.4	57.0716，77.0398，91.0562，103.0578	α−姜黄^[7−9] （α−Curcumene）
	89	52.407	C₁₅H₂₀O₂	[M+H]⁺	233.1525	233.1536	−4.7	81.0686，91.0536，103.0545，117.0699	姜黄素β ^[7−9] （Turmeronol β）
单萜类	90	53.788	C₁₅H₂₂O	[M+H]⁺	219.1760	219.1743	7.8	79.0543，91.0543，105.0703	松脂素^[7−9] （Dendrolasin）
	91	31.897	C₁₁H₁₄O₅	[M+H]⁺	227.0912	227.0914	−0.9	141.0554	京尼平^[7−9] （Genipin）
鞣质类	92	5.507	C₁₃H₁₆O₁₀	[M-H]⁻	331.0678	331.0671	2.1	55.0180，107.0100，123.0077，125.0212，137.0226	2-没食子酰葡萄糖^[5] （2-Galloylglucose）
	93	32.010	C₂₀H₂₀O₁₃	[M-H]⁻	467.0782	467.0831	−10.5	59.0125，123.0070，125.0218，151.0027，169.0107	3,4,5-三羟基苯甲醛-3-O-（6′-O-没食子酸-β−D-吡喃葡萄糖甙）^[7−9] （Castamollissin）
甾体类	94	75.731	C₂₈H₄₈O	[M+Na]⁺	423.3616	423.3597	4.5	135.1164，147.1153，161.1311	菜油甾醇^[7−9] （Campesterol）
注：*经安捷伦中药对照品成分数据库（Agilent TCM library-V20-04-17.cdb）质谱比对；[序号]经对应序号的参考文献质谱信息比对的化合物。

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参考文献(32)

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