基于UPLC-QTOF-MS/MS分析的芪葵颗粒化学成分系统筛选与识别

李长印; 陆明霞; 廖健城; 黄莉吉; 居文政; 邹建东

doi:10.14148/j.issn.1672-0482.2023.0057

基于UPLC-QTOF-MS/MS分析的芪葵颗粒化学成分系统筛选与识别

doi: 10.14148/j.issn.1672-0482.2023.0057

1.
南京中医药大学附属医院, 江苏省中医院临床药理实验室, 江苏南京 210029
2.
南京中医药大学附属医院, 江苏省中医院内分泌科, 江苏南京 210029

基金项目:

江苏省自然科学基金面上项目 BK20201502

“333高层次人才培养工程”科研资助项目 BRA2020384

江苏省中医院高峰人才项目 y2018rc22

江苏省中医院高峰人才项目 y2021rc31

江苏高校优势学科建设工程资助项目苏政办发〔2018〕87号

南京中医药大学中医学优势学科三期项目开放课题 ZYX03KF030

详细信息

作者简介:
李长印, 男, 副研究员, E-mail: fsyy00612@njucm.edu.cn

通讯作者:
邹建东, 男, 研究员, 主要从事中医药临床研究数据管理和统计研究, E-mail: jdzou2000@163.com

中图分类号: R284
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- 被引次数: 0
出版历程
- 收稿日期: 2021-11-06
- 网络出版日期: 2023-01-18
- 发布日期: 2023-01-10

Systematic Screening and Identification of Chemical Constituents in Qikui Granules Based on UPLC-QTOF-MS/MS Analysis

1.
Department of Clinical Pharmacology, Jiangsu Province Hospital of Chinese Medicine, The Affiliated Hospital of Nanjing University of Chinese Medicine, Nanjing 210029, China
2.
Department of Endocrinology, Jiangsu Province Hospital of Chinese Medicine, The Affiliated Hospital of Nanjing University of Chinese Medicine, Nanjing 210029, China

摘要

摘要: 目的系统定性表征芪葵颗粒(黄芪、制首乌、黄蜀葵花)中的化学成分。方法采用超高效液相色谱-四级杆飞行时间质谱(UPLC-QTOF-MS/MS)联用分析方法对芪葵颗粒水提液进行分离检测, 获取正、负离子模式下的原始分析数据; 借助AB Sciex PeakView软件, 综合采用靶向和非靶向的筛选方法, 对获得的原始分析数据进行处理, 系统筛选鉴定芪葵颗粒中的化学成分; 以不少于2个准分子离子的同时出现, 排除碎片离子的干扰, 锁定筛选所得目标化合物; 依据准分子离子及特征二级子离子质谱信息, 结合标准品比对, 并参考数据库搜索匹配和文献数据比对, 对锁定的化合物进行鉴定或合理归属。结果从芪葵颗粒中共筛选出89个化合物, 鉴定出71个化合物, 包括黄酮类45个, 皂苷类14个, 蒽醌类4个, 二苯乙烯苷类3个, 多糖类2个, 有机酸类3个。鉴定结果表明羟基化、糖基化、葡萄糖醛酸化、乙酰化、甲基化、丙二酰化等多种转化反应参与了芪葵颗粒多样化学成分的形成。结论基于UPLC-QTOF-MS/MS靶向和非靶向相结合的筛选鉴定方法可快速全面表征芪葵颗粒中的主要化学成分及其涉及的转化反应, 为深入探讨芪葵颗粒的质量控制、组方优化和药效物质等奠定了基础。
- 芪葵颗粒 /
- UPLC-QTOF-MS/MS /
- 系统筛选 /
- 成分鉴定 /
- 黄芪 /
- 制首乌 /
- 黄蜀葵花
Abstract: OBJECTIVE To systematically characterize the chemical constituents of Qikui Granules. METHODS Aqueous extract of Qikui Granules was analyzed by ultra-performance liquid chromatography coupled with quadrupole time-of-flight mass spectrometry (UPLC-QTOF-MS/MS) in both positive and negative ion modes. Aiding by PeakView software, both targeted and non-targeted approaches were employed to systematically screen and identify the chemical constituents from the obtained UPLC-QTOF-MS/MS raw data. Each screened compound was finally locked by the simultaneous occurrence of its corresponding quasimolecular ions. They were tentatively characterized or assigned according to its quasimolecular ions and diagnostic product ions, and then were confirmed by comparison with authentic standard, related database and literatures. RESULT Totally 89 compounds were screened, and 71 of them were identified, including 45 flavonoids, 14 saponins, 4 anthraquinones, 3 stilbene glycosides, 2 polysaccharides and 3 organic acids. The results indicated that conversion reactions including hydroxylation, glucuronidation, acetylation, methylation, malonylation, as well as glycosidation (by the addition of one hexose, pentose, or tetrose), were involved in the formation of chemical constituents of Qikui Granules. CONCLUSION UPLC-QTOF-MS/MS based targeted and non-targeted compound screening approaches can clearly characterized the major constituents in Qikui Granules, providing a foundation for further researches on Qikui Granules such as quality control, preparation optimization and pharmacodynamics.
- Qikui Granules /
- UPLC-QTOF-MS/MS /
- systematic screening /
- compound identification /
- astragali radix /
- radix polygoni multiflori preparata /
- flos abelmoschus manihot

HTML全文

图 1 芪葵颗粒水提液的UPLC-QTOF-MS色谱图

注：a.负离子模式下TIC图；b.正离子模式下TIC图；c.负离子模式下XIC图；d.正离子模式下XIC图；1~71.已鉴定化学成分LC1~LC71;U1~U18.未鉴定化学成分

Figure 1. The UPLC-QTOF-MS chromatograms from the aqueous extract of Qikui Granules

下载: 全尺寸图片幻灯片

图 2 毛蕊异黄酮(a)、大黄素甲醚(b)、毛蕊异黄酮苷(c)和大黄素甲醚-8-O-β-D-葡萄糖苷(d)的二级子离子图谱

注：a和b源自对照品溶液; c和d源自芪葵颗粒水提液, 对应编号为LC14和LC49的目标化合物。

Figure 2. Product ion mass spectra of calycosin (a), physcion (b), calycosin-7-O-β-D-glucoside (c) and physcion-8-O-β-D-glucoside (d)

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图 3 芪葵颗粒中主要化学成分的可能化学结构及其可能涉及的转化反应

注：(1)羟基化; (2)六碳糖基化; (3)葡萄糖醛酸化; (4)乙酰化; (5)去甲基化; (6)甲基化; (7)四碳糖基化; (8)丙二酰化; (9)五碳糖基化; 蓝色表示经标准品比对确认的化合物

Figure 3. The candidate structures of the identified compounds and their possible related conversion reactions

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表 1 芪葵颗粒20个主要化学成分对照品信息

Table 1. General information of 20 authentic standards for major constituents in Qikui Granules

编号	名称	生产厂家	批号
1	芦丁	成都曼斯特生物科技有限公司	MUST-17122001
2	毛蕊异黄酮苷	中国药品生物制品检定所	111920-201102
3	二苯乙烯苷	成都曼斯特生物科技有限公司	MUST-18051611
4	金丝桃苷	成都曼斯特生物科技有限公司	MUST-17101605
5	异槲皮苷	上海源叶生物科技有限公司	P25J9F65872
6	棉纤维素	上海源叶生物科技有限公司	Z14M8H30302
7	棉皮苷	上海源叶生物科技有限公司	T01J11Z117171
8	杨梅素	上海源叶生物科技有限公司	YM0311YA13
9	棉皮素	法国EXTRASYNTHESE公司	14110601
10	刺芒柄花苷	上海源叶生物科技有限公司	P03A10F84910
11	毛蕊异黄酮	上海源叶生物科技有限公司	Y05J11H115098
12	黄芪紫檀烷苷	上海源叶生物科技有限公司	P21N9F75533
13	槲皮素	成都曼斯特生物科技有限公司	MUST-17101104
14	黄芪异黄烷苷	成都曼斯特生物科技有限公司	MUST-19102620
15	芒柄花素	中国药品生物制品检定所	111703-200602
16	黄芪甲苷	中国药品生物制品检定所	0781-200109
17	黄芪紫檀烷	上海源叶生物科技有限公司	Y28M10H84302
18	黄芪异黄烷	上海源叶生物科技有限公司	Y28M10H84303
19	大黄素甲醚	中国药品生物制品检定所	110758-201013
20	大黄素	南京聚康医药化工有限公司	181215

下载: 导出CSV

表 2 芪葵颗粒中鉴定出的71个化合物的详细信息

Table 2. The detailed information of 71 identified compounds in Qikui Granules

编号	t_R/min	分子式	[M-H]^-	[M+HCO OH-H]^-	[M+HN O₃-H]^-	[M+H]⁺	[M+Na]⁺	^△强度/ cps	^△主要特征子离子m/z(峰面积/%)	化合物名称	来源
LC1	1.16	C₁₂H₂₂O₁₁	341.108 8 (-0.4)^△	387.113 6 (0.7)	404.103 5 (0.1)	343.123 7 (0.7)	365.105 6 (-1)	387 105	341.110 7(18.15), 179.056 4(6.29), 143.036 4(2.22), 119.035 4(10.81), 113.024 6(5.53), 101.024 8(5.47), 89.025 3(16.27), 71.015 9(8.32)	蔗糖(Sucrose)/松二糖(Turanose)^#	1, 2, 3
LC2	1.27	C₆H₈O₇	191.019 9 (0.8)^△			193.034 2 (-0.4)	215.016 2 (-2.9)	953 702	191.018 7(6.46), 129.019 5(3.43), 111.009 2(25.4), 87.009 9(23.51), 85.030 7(14.9), 67.021 1(5.12), 57.037 6(3.94), 41.007 0(1.98)	异柠檬酸盐(Isocitrate)/柠檬酸(Citrate)^#	1, 2, 3
LC3	1.51	C₆H₈O₇	191.020 0 (1.2)^△			193.034 3 (0.2)	215.016 2 (-2.9)	826 587	191.020 6(5.2), 129.019 8(2.27), 111.010 1(25.81), 87.010 5(27.44), 85.031 3(14.15), 67.021 3(6.85), 57.038 2(4.44), 41.007 4(2.57)	异柠檬酸盐(Isocitrate)/柠檬酸(Citrate)^#	1, 2, 3
LC4	1.71	C₇H₆O₅	169.014 4 (1.1)^△					168 945	169.014 7(15.2), 125.025 0(42.59), 124.016 5(5.23), 97.030 6(2.99), 81.036 1(3.61), 79.020 0(9.26), 69.036 5(2.99), 51.027 3(2.59)	没食子酸(Gallic acid)^#	3
LC5	8.28	C₂₇H₂₈O₁₉	655.114 9 (-0.4)^△			657.129 7 (0)	679.113 7 (3)	33 921	655.114 8(52.8), 479.082 8(26.2), 316.022 0(9.59), 287.0194 4(1.14), 271.022 3(1.06)	棉皮苷-3-O-葡萄糖苷(Gossypetin-8-O-β-D-glu-3-O-glc)	2
LC6	9.85	C₂₆H₃₂O₁₄	567.171 6 (-0.5)	613.176 1 (-0.3)^△	630.165 7 (-1.2)			14 460	613.160 4(1.8), 567.167 0(6.93), 405.118 1(58.83)3, 243.065 8(26.55)	二苯乙烯苷-O-葡萄糖苷(2, 3, 5, 4'-THDPE-2-O-glc-O-glc)	3
LC7	10.17	C₂₃H₂₈O₁₁	479.155 4 (-1.1)	525.160 0 (-0.5)^△	542.150 3 (-0.2)		503.154 1 (3.3)	7 166	525.165 9(20.22), 479.162 0(9.62), 449.147 2(36.87), 431.128 3(2.85), 327.111 0(9.19), 165.054 5(2.77), 121.029 0(14.27), 77.041 2(2.72)	羟基黄芪异黄烷苷(Hydroxy-isomucronulatol-7-O-β-D-glc)	1
LC8	10.92	C₂₁H₂₀O₁₃	479.082 5 (-1.2)^△		542.076 9 (-1.5)	481.097 6 (-0.1)	503.079 0 (-1.2)	20 568	479.084 2(44.7), 317.026 4(4.75), 316.020 4(29.83), 287.020 9(2.61), 271.024 5(7.13), 179.002 4(1.37)	棉皮素-3-O-半乳糖苷(Gossypetin-3-O-galactoside)	2
LC9	11.19	C₂₁H₂₀O₁₃	479.082 5 (-1.4)^△	525.087 6 (0.2)	542.078 0 (0.6)	481.097 7 (0.2)		45 526	479.083 9(47.25), 317.027 9(5.25), 316.021 5(25.36), 287.016 5(4.15), 271.023 7(6.85), 214.024 3(1.23), 151.005 9(0.48)	棉皮素-3-O-吡喃葡萄糖苷(Gossypetin-3-O-glucopyranoside)	2
LC10	11.59	C₂₆H₂₈O₁₆	595.130 0 (-0.8)^△		658.125 5 (0.8)	597.144 6 (-0.7)	619.127 4 (0.8)	40 051	595.134 0(56.53), 301.035 9(2.18), 300.028 1(23.84), 271.023 0(4.34), 255.031 9(3.5)	槲皮素-3-O-葡萄糖苷-戊糖苷(Quercetin-3-O-glc-pentose)	2
LC11	11.70	C₂₂H₂₂O₁₀		491.118 7 (0.6)^△	508.109 1 (1)	447.128 9 (0.8)	469.109 6 (-1.9)	2 865	445.108 0(36.77), 283.063 4(30.91), 268.035 0(7.71), 267.029 5(12.32), 239.034 2(2.91)	毛蕊异黄酮葡萄糖苷(Calycosin-O-glc)	1
LC12	12.46	C₂₆H₃₂O₁₄	567.176 1 (-0.6)^△	613.175 8 (-0.8)	630.166 5 (0)	569.186 2 (-0.6)	591.168 4 (-0.1)	18 935	567.171 5(64.47), 243.062 9(22.8)	四羟基二苯乙烯-2-O-双葡萄糖苷(2, 3, 5, 4'-THDPE-2-O-diglc)	3
LC13^*	12.55	C₂₇H₃₀O₁₆	609.145 2 (-1.6)^△		672.140 2 (-0.6)	611.161 3 (1.1)	633.141 9 (-1.1)	84 754	609.147 2(51.33), , 300.026 7(22.37), 271.026 2(4.39), 255.031 5(2.02), 178.998 5(0.83), 151.005 2(1.21), 121.030 6(0.16)	芦丁(Rutin)^#	2
LC14^*	12.69	C₂₂H₂₂O₁₀		491.118 5 (0.2)^△	508.108 3 (-0.6)	447.129 0 (0.9)	469.111 0 (1)	217 163	491.117 3(9.13), 283.061 2(52.44), 268.038 0(23.8), 267.033 2(1.22)	毛蕊异黄酮苷(Calycosin-7-O-β-D-glc)^#	1
LC15^*	12.75	C₂₀H₂₂O₉	405.118 7 (-1.1)^△	451.123 4 (-0.3)	468.113 4 (-0.6)		429.115 9 (0.7)	1 420 070	405.120 8(6.09), 243.067 1(37.07), 225.056 0(2.68), 215.070 4(1.53), 173.061 0(4.44), 145.065 7(1.7), 137.025 2(4.21), 131.049 6(1.59), 109.029 9(2.25), 93.035 2(2.19)	二苯乙烯苷(2, 3, 5, 4'-THDPE-2-O-glc)^#	3
LC16^*	12.90	C₂₁H₂₀O₁₂	463.087 2 (-2.1)^△		526.082 9 (0.2)	465.102 8 (0.2)	487.084 7 (0.1)	276 602	463.087 6(24.63), 301.034 7(14.76), 300.026 7(25.35), 271.023 4(12.69), 255.028 4(6.12), 243.029 3(2.36), 151.001 7(1.59)	金丝桃苷(Hyperoside)	2
LC17^*	13.21	C₂₁H₂₀O₁₂	463.087 2 (-2.3)^△		526.082 9 (0.2)	465.102 6 (-0.3)		284 469	463.086 5(35.33), 301.035 3(12.76), 300.025 1(21.97), 271.022 9(11.77), 255.030 2(4.74), 243.025 4(1.29), 178.994 3(0.71), 151.001 7(1.38)	异槲皮苷(Isoquercitrin)^#	2
LC18	13.34	C₂₈H₃₂O₁₅	607.166 4 (-0.8)^△	653.172 2 (1.5)	670.159 2 (-3.3)	609.182 9 (2.4)	631.164 3 (1.5)	7 650	607.164 7(42.25), 413.108 0(4.17), 193.049 2(33.39), 178.023 5(5.02), 137.023 7(6.41), 134.041 8(2.38), 93.034 0(1.32)	毛蕊异黄酮双葡萄糖苷异构体(Calycosin-diglc isomer)	12
LC19^*	13.47	C₂₁H₂₀O₁₃	479.081 9 (-2.6)^△		542.077 2 (-0.8)			43 035	479.084 4(53.82), 317.030 7(24.34), 299.009 8(0.26), 271.025 8(2.68), 178.999 3(6.88), 151.004 8(4.21), 137.024 7(1.39)	棉纤维素(Gossypin)	2
LC20	13.58	C₂₁H₂₀O₁₀	431.096 9 (-3.4)	477.102 4 (-0.7)^△	494.092 6 (-0.6)	433.113 0 (0.3)		8 577	431.097 6(51.75), 269.044 2(34.54), 268.038 9(10.77)	4'-去甲基毛蕊异黄酮苷(4'-Demethylcalycosin-7-O-β-D-glc)	1
LC21	14.31	C₂₂H₂₂O₁₁		507.113 0 (-0.7)^△	524.102 9 (-1.2)	463.124 8 (2.8)		2 782	507.124 4(9.94), 461.106 1(37.93), 446.078 9(2.66), 299.054 9(29.52), 298.047 3(6.53), 284.032 9(2.13), 255.031 5(4.03)	5-羟基毛蕊异黄酮苷(5-Hydroxy-calycosin-7-O-β-D-glc)	1
LC22^*	14.48	C₂₁H₁₈O₁₄	493.061 5 (-1.9)^△			495.077 3 (0.7)	517.059 1 (0.5)	310 887	493.062 7(22.69), 317.030 6(39.6), 299.021 6(2.21), 271.024 7(1.79), 194.994 0(2.13), 166.998 1(3.85), 139.003 7(2.7)	棉皮苷(Gossypetin-8-O-β-D-glu)	2
LC23	14.71	C₃₁H₄₀O₁₆	667.223 8 (-0.9)^△		730.221 6 (3.7)	669.240 9 (2.9)		2 772	667.226 0(64.47), 505.154 4(7.29), 417.155 3(19.88), 181.050 7(2.91), 87.010 3(3.03)	丙二酰黄芪异黄烷苷-四碳糖苷(Malonyl-isomucronulatol-7-O-β-D-glc-tetrose)	1
LC24	14.78	C₂₂H₂₂O₁₂	477.102 8 (-2.2)^△		540.098 2 (-0.4)			1 350	477.106 5(29.28), 314.045 6(31.68)	5, 2'-双羟基毛蕊异黄酮苷(5, 2'-Dihydroxy-calycosin-7-O-β-D-glc)	1
LC25^*	14.96	C₁₅H₁₀O₈	317.030 0 (-0.9)^△		380.024 9 (0.1)	319.044 8 (-0.1)		1 829	-	杨梅素(Myricetin)	2
LC26	14.96	C₂₉H₃₈O₁₅	625.212 5 (-2.1)	671.217 9 (-0.4)^△	688.208 8 (0.6)	627.231 2 (4.5)	649.211 0 (1)	5 890	625.223 8(2.56), 625.198 9(8.05), 463.159 9(41.85), 301.105 8(28.16), 286.095 6(9.27)	黄芪异黄烷-7, 2'-双葡萄糖苷(Isomucronulatol-7, 2'-diglc)	1
LC27	15.10	C₂₂H₂₂O₁₁	461.107 3 (-3.6)	507.113 3 (-0.1)^△	524.103 0 (-1)	463.123 9 (0.9)		18 771	507.105 8(3.05), 461.104 4(3.62), 446.102 9(2.55), 341.066 1(2.23), 299.054 7(61.02), 284.033 0(26.07), 255.027 3(1.46)	2'-羟基毛蕊异黄酮苷(2'-Hydroxy-calycosin-7-O-β-D-glc)	1
LC28	15.12	C₂₂H₂₄O₁₀	447.128 6 (-2.3)	493.133 7 (-0.7)^△	510.124 2 (-0.1)	449.143 0 (-2.7)	471.126 5 (0.8)	3 906	493.065 2(13.39), 447.116 4(16.51), 405.125 3(1.43), 317.031 4(1.26), 285.074 6(34.98), 285.042 7(3.59), 270.053 4(25.83)	9-去甲基黄芪紫檀烷苷(9-Demethyl-9, 10-DiMOPTC-3-O-β-D-glc)	1
LC29^*	15.25	C₁₅H₁₀O₈	317.030 2 (-0.4)^△		380.024 1 (-1.9)			38 192	317.031 0(51.85), 193.021 0(1.96), 179.002 3(10.64), 151.000 3(11.29), 137.025 7(9.64), 109.030 7(7.41), 107.013 1(3.65)	棉皮素(Gossypetin)	2
LC30	15.66	C₁₂H₂₂O₁₁	341.108 0 (-2.8)^△	387.113 1 (-0.5)	404.103 0 (-1.3)			37 837	-	蔗糖(Sucrose)/松二糖(Turanose)	1, 2, 3
LC31	15.79	C₂₁H₂₀O₁₂	463.087 5 (-1.5)^△	509.092 3 (-0.6)	526.082 4 (-0.6)	465.102 7 (-0.2)	487.085 4 (1.5)	165 903	463.090 1(36.5), 301.035 8(40.31), 300.028 9(1.14), 273.033 9(1.1), 178.999 1(5.09), 151.004 2(9.57), 121.029 6(1.94), 107.014 4(1.41)	槲皮素-3'-O-葡萄糖苷(Quercetin-3'-O-glc)^#	2
LC32	15.80	C₂₂H₂₄O₁₀	447.129 4 (-0.6)	493.132 0 (-4.2)	510.121 7 (-4.9)^△	449.143 6 (-1.5)	471.127 1 (2)	1 454	464.089 0(57.26), 302.039 3(17.51), 301.032 2(10.05), 273.028 4(0.61), 178.996 6(3.23), 152.003 4(2.06), 151.002 5(4.79), 61.989 6(1.61)	10-去甲基黄芪紫檀烷苷(10-Demethyl-9, 10-DiMOPTC-3-O-β-D-glc)	1
LC33^*	16.54	C₂₂H₂₂O₉	429.118 7 (-1.1)	475.123 0 (-1)^△	492.113 2 (-0.9)	431.133 9 (0.7)	453.115 9 (0.6)	185 601	475.124 8(11.91), 267.066 1(62.97), 252.043 1(15.04), 224.046 8(0.34), 223.036 5(0.56), 195.050 5(0.29), 132.023 4(0.18), 45.001 3(4.66)	芒柄花苷(Formononetin-7-O-β-D-glc)^#	1
LC34	16.68	C₂₄H₂₄O₁₁	487.122 6 (-4.1)	533.128 6 (-0.8)^△	550.118 7 (-0.8)	489.139 2 (0)	511.123 2 (4.2)	36 288	533.121 4(16.24), 325.067 4(1.12), 285.069 4(3.28), 284.074 1(1.05), 283.059 1(55.1), 268.032 5(16.95), 267.024 3(1.01), 45.001 4(5.25)	3'-乙酰基-毛蕊异黄酮苷(3'-Acetyl-calycosin-7-O-β-D-glc)	1
LC35	16.84	C₂₈H₃₄O₁₄	593.186 8 (-1.3)^△	639.191 6 (-0.6)		595.202 6 (0.7)	617.182 5 (-2.5)	8 395	593.189 6(51.94), 505.173 7(12.35), 417.153 9(9.9), 402.133 3(2.54), 387.116 3(3.32), 299.056 4(5.1), 181.051 6(4.25), 87.007 8(3.56)	黄芪紫檀烷苷-戊糖苷(9, 10-DiMOPTC-3-O-β-D-glc-pentose)	1
LC36	17.02	C₂₈H₃₄O₁₄	593.187 2 (-0.7)^△	639.192 6 (1)	656.182 2 (0.1)	595.202 5 (0.5)	617.184 6 (0.9)	5 613	593.191 6(68.73), 299.095 7(18.06), 284.073 4(13.2)	黄芪紫檀烷苷-戊糖苷(9, 10-DiMOPTC-3-O-β-D-glc-pentose)	1
LC37	17.48	C₁₆H₁₂O₅	283.061 2 (-0.1)^△			285.075 5 (-1)	307.058 3 (1.9)	11 503	283.065 8(33.08), 268.039 5(29.79), 239.026 7(3.07), 211.044 4(8.31), 195.049 4(5.6), 183.043 5(2.69), 148.019 1(3.02), 91.020 1(2.85)	毛蕊异黄酮同分异构体(Calycosin isomer)	1
LC38^*	17.51	C₂₃H₂₆O₁₀	461.145 3 (-0.1)	507.149 8 (0.2)^△	524.139 8 (0)	463.159 6 (-0.6)	485.142 0 (0.4)	131 258	507.152 7(33.88), 461.147 9(3.1), 299.092 6(29.1), 298.297 0(0.79), 284.068 5(5.19), 269.046 7(5.22), 45.001 5(17.84)	黄芪紫檀烷苷(9, 10-DiMOPTC-3-O-β-D-glc)	1
LC39^*	17.76	C₁₅H₁₀O₇	301.035 2 (-0.7)^△		364.029 0 (-2.6)	303.049 4 (-1.7)	325.030 6 (-3.8)	62 825	301.034 9(38.21), 273.043 3(1.48), 178.998 3(8.86), 151.003 3(20.59), 133.028 4(1.5), 121.029 7(5.75), 107.013 6(4.57)	槲皮素(Quercetin)^#	2
LC40^*	17.95	C₁₆H₁₂O₅	283.061 1 (-0.4)^△	329.067 0 (4.4)	346.055 8 (0.2)	285.075 5 (-0.8)	307.057 5 (-0.5)	638 440	283.060 8(13.08), 268.037 6(26.72), 240.042 0(2.9), 239.034 3(6.44), 211.040 2(11.84), 195.045 7(2.85), 183.044 4(2.51), 148.016 4(2.3), 135.009 1(2.6), 91.020 3(3.76)	毛蕊异黄酮(Calycosin)	1
LC41^*	18.01	C₂₃H₂₈O₁₀	463.160 8 (-0.3)^△	509.165 5 (0.3)	526.155 3 (-0.5)	465.175 6 (0.1)	487.157 9 (0.9)	34 853	463.157 2(12.73), 301.106 8(58.23), 286.079 5(3.05), 271.060 9(3.98), 164.046 5(2.96), 135.043 8(4.8), 121.027 4(3.84), 109.028 5(1.42)	黄芪异黄烷苷(Isomucronulatol-7-O-β-D-glc)	1
LC42	18.39	C₂₁H₂₀O₁₀	431.097 6 (-1.8)^△		494.093 8 (1.9)		455.093 8 (-2.3)	37 321	431.099 2(48.75), 293.043 0(0.89), 269.044 8(36.39), 241.051 0(2.18), 240.046 0(1.28), 225.058 2(5.66), 210.030 3(0.65)	大黄素-8-O-β-D-葡萄糖苷(Emodin-8-O-β-D-glc)^#	3
LC43	18.92	C₂₂H₂₂O₁₀		491.117 7 (-1.4)^△	508.107 6 (-1.9)	447.127 5 (-2.5)		2 753	491.117 7(11.87), 445.120 5(2.26), 329.241 2(9.72), 283.061 2(59.08), 268.034 4(10.52)	毛蕊异黄酮葡萄糖苷(Calycosin-O-glc)	1
LC44	19.49	C₁₅H₁₀O₅	269.045 3 (-0.9)^△		332.038 9 (-3.5)	271.061 1 (3.8)		23 026	269.046 0(62.52), 225.055 5(2.41), 197.059 0(1.13), 183.047 1(1.45), 181.066 7(1.49), 159.045 7(2.08), 107.014 6(1.14), 63.025 5(1.43)	大黄素同分异构体(Emodin isomer)	3
LC45	19.85	C₁₇H₁₆O₆	315.087 2 (-0.7)^△		378.083 0 (2.6)	317.102 0 (0.1)	339.083 3 (-1.9)	19 835	315.088 0(20.41), 297.039 7(2.25), 285.040 0(2.04), 163.003 2(2.97), 109.030 2(61.88), 67.020 1(1.67), 65.041 7(3.82), 41.007 8(1.41)	2-羟基黄芪紫檀烷(2, 3-Dihydroxy-9, 10-DiMOPTC)	1
LC46	19.91	C₄₇H₇₈O₁₉	945.503 1 (-3.6)	991.511 5 (0.7)^△		947.520 8 (-0.2)	969.507 3 (4.5)	4 160	991.518 6(23.87), 946.518 6(9.11), 945.507 3(61.81), 783.492 3(0.98), 783.462 6(0.49), 59.012 9(0.2)	黄芪皂苷Ⅴ/Ⅵ/Ⅶ同分异构体(Astragaloside Ⅴ/Ⅵ/Ⅶ isomer)	1
LC47	20.00	C₁₆H₁₂O₆	299.055 8 (-1)^△		362.051 1 (1.3)			13 358	299.054 5(34.81), 284.031 3(32.94), 256.036 7(2.99), 255.028 0(4.54), 227.033 1(2.81), 211.035 4(0.9), 199.037 9(1), 183.044 6(1.08), 148.014 2(3.35)	5-羟基毛蕊异黄酮(5-Hydroxy-calycosin)	1
LC48	20.01	C₁₇H₁₄O₅	297.076 8 (-0.2)^△	343.081 9 (1.9)			321.074 2 (2.8)	6 855	297.079 6(27.68), 282.055 8(13.32), 281.046 6(17.64), 267.028 2(11.44), 253.057 0(5.81), 239.035 9(16.53), 211.038 1(2.65), 195.039 8(1.7), 91.018 6(1.45)	3'-甲基毛蕊异黄酮(3'-Methyl-calycosin)	1
LC49	20.17	C₂₂H₂₂O₁₀	445.112 8 (-2.7)	491.118 0 (-0.8)^△	508.107 9 (-1.3)			2 819	491.118 0(6.76), 427.105 7(6.76), 325.074 6(8.84), 283.060 3(64.09), 240.038 0(9.66)	大黄素甲醚-8-O-β-D-葡萄糖苷(Physcion-8-O-β-D-glc)	3
LC50	20.40	C₁₆H₁₂O₆	299.056 0 (-0.4)^△	345.061 1 (1.7)	362.051 8 (3)	301.070 7 (0.1)	323.051 3 (-3.9)	48 015	299.054 8(29.7), 284.032 2(31.38), 255.025 2(4.54), 239.039 8(1.47), 227.032 4(8.13), 211.040 4(1.53), 199.044 2(4.01), 148.017 0(1.41)	2'-羟基毛蕊异黄酮(2'-Hydroxy-calycosin)	1
LC51	20.61	C₄₁H₆₈O₁₄	783.453 1 (-0.6)	829.458 4 (0.5)^△	846.447 6 (-0.7)	785.467 6 (-0.8)	807.450 0 (-0.2)	1 960	830.486 2(0.7), 829.459 1(22.58), 784.472 8(2.74), 783.456 6(71.2), 119.030 7(1.07)	黄芪甲苷同分异构体(Astragaloside Ⅳ isomer)	1
LC52	20.75	C₂₅H₃₀O₁₁	505.169 7 (-3.6)	551.174 8 (-2.1)^△	568.165 9 (-0.3)	507.184 7 (-2.7)	529.167 7 (-0.6)	1 325	551.181 4(7.82), 505.168 7(42.31), 301.109 2(35.19), 164.044 5(3.1), 135.042 8(2.29), 121.031 7(2.5)	黄芪异黄烷-乙酰葡萄糖苷(Isomucronulatol-acetyl-glc)	1
LC53	21.34	C₄₇H₇₈O₁₉	945.504 9 (-1.6)	991.510 9 (0)^△			969.500 2 (-2.9)	6 507	991.518 7(53.75), 946.511 5(6.66), 945.510 8(24.73), 783.448 6(1.54), 161.046 0(0.32), 119.034 4(0.13)	黄芪皂苷Ⅴ/Ⅵ/Ⅶ同分异构体(Astragaloside Ⅴ/Ⅵ/Ⅶ isomer)	1
LC54^*	21.65	C₁₆H₁₂O₄	267.066 2 (-0.3)^△		330.060 8 (-0.2)	269.080 9 (0.3)	291.062 7 (-0.1)	518 951	267.065 4(15.05), 252.042 3(23.58), 223.040 0(13.26), 208.052 6(1.97), 195.045 0(10.65), 167.050 1(2.44), 135.008 8(2.29), 132.022 0(4.27), 104.027 3(1.27), 91.020 1(3.09)	芒柄花素(Formononetin)^#	1
LC55	21.65	C₄₁H₆₈O₁₄		829.456 5 (-1.9)^△	846.446 7 (-1.7)			1 377	-	黄芪甲苷同分异构体(Astragaloside Ⅳ isomer)	1
LC56^*	22.07	C₄₁H₆₈O₁₄		829.458 8 (1)^△	846.449 2 (1.2)	785.468 1 (-0.1)	807.453 8 (4.6)	38 167	829.461 1(80.16), 827.184 2(3.18), 783.462 7(3.57), 179.054 6(0.36), 45.001 5(0.67)	黄芪甲苷(Astragaloside Ⅳ)^#	1
LC57^*	22.08	C₁₇H₁₆O₅	299.092 3 (-0.7)^△	345.095 6 (-3.6)		301.107 1 (0.1)	323.088 6 (-1.4)	22 053	299.091 1(15.76), 284.067 4(19.25), 269.045 9(31.61), 241.049 0(9.19), 225.055 7(1.94), 199.037 5(2.03), 185.065 1(1.96), 133.027 6(1.33), 115.055 0(1.39)	黄芪紫檀烷(3-Hydroxy-9, 10-DiMOPTC)^#	1
LC58	22.09	C₁₇H₁₄O₅	297.076 9 (0)^△			299.089 4 (-6.6)		1 713	297.044 2(54.62), 281.020 4(23.18), 251.163 7(10.5), 160.982 1(11.7)	7-甲基毛蕊异黄酮(7-Methyl-calycosin)	1
LC59	22.26	C₄₁H₆₈O₁₄	783.451 9 (-2.2)	829.458 3 (0.3)^△	846.448 1 (-0.1)		807.449 9 (-0.3)	17 637	829.461 2(39.31), 783.458 2(52.7), 161.044 1(0.88), 113.023 4(0.6), 101.023 2(0.94)	黄芪甲苷同分异构体(Astragaloside Ⅳ isomer)	1
LC60^*	22.49	C₁₇H₁₈O₅	301.107 9 (-0.9)^△			303.122 9 (0.6)		2 856	301.105 2(30.35), 286.092 6(11.83), 271.065 2(18.24), 256.038 4(11.19), 229.044 9(7.06), 227.074 1(1.76), 149.025 2(6.41), 135.044 0(5.42), 124.015 8(3.9), 121.033 9(3.85)	黄芪异黄烷(Isomucronulatol)	1
LC61	23.02	C₁₇H₁₆O₅	299.091 3 (-4.2)^△			301.107 5 (1.6)		567	299.093 0(30.09), 284.067 4(31.28), 269.054 5(20.93), 269.042 4(16.17), 171.047 2(1.52)	黄芪紫檀烷异构体(Hydroxy-diMOPTC)	1
LC62	23.14	C₄₈H₇₈O₁₈	941.511 2 (-0.4)	987.516 5 (0.6)^△				8 065	987.519 2(6.47), 941.518 5(77.91), 615.392 1(0.33), 512.464 8(0.13), 85.031 8(0.11)	大豆皂苷(Soyasaponin)	1
LC63	23.29	C₄₃H₇₀O₁₅		871.468 8 (0.3)^△	888.459 4 (0.8)	827.478 8 (0)	849.461 2 (0.6)	73 219	871.470 3(74.22), 825.462 1(3.98), 765.435 8(1.02), 179.055 4(0.16), 161.048 2(0.2), 113.022 5(0.22), 45.000 8(0.94)	黄芪皂苷Ⅱ同分异构体(Astragaloside Ⅱ isomer)	1
LC64	24.08	C₄₃H₇₀O₁₅		871.469 4 (0.9)^△	888.458 7 (-0.1)	827.479 0 (0.3)	849.460 0 (-0.8)	26 480	871.472 7(84.22), 825.471 1(1.15), 765.440 4(0.58), 101.023 2(0.05), 89.023 5(0.09), 59.014 8(0.11), 45.001 5(0.84)	黄芪皂苷Ⅱ同分异构体(Astragaloside Ⅱ isomer)	1
LC65	24.33	C₁₆H₁₂O₅	283.061 1 (-0.5)^△			285.077 0 (4.4)		7 407	283.060 2(34.59), 268.037 5(28.16), 240.041 6(1.38), 239.035 5(3.99), 211.039 3(4.49), 195.043 1(1.37), 183.045 7(1.44), 135.009 0(0.35), 132.021 7(1.77)	毛蕊异黄酮同分异构体(Calycosin isomer)	1
LC66	24.68	C₄₃H₇₀O₁₅		871.468 6 (0.1)^△	888.459 5 (0.8)	827.478 7 (0)	849.460 7 (0)	22 811	871.473 4(80.78), 825.490 9(0.82), 825.468 6(1.34), 825.444 4(0.21), 765.445 4(0.41), 119.036 8(0.12), 89.025 0(0.05), 45.001 0(0.94)	黄芪皂苷Ⅱ同分异构体(Astragaloside Ⅱ isomer)	1
LC67	25.45	C₄₅H₇₂O₁₆		913.479 4 (0.2)^△	930.468 7 (-0.6)	869.489 6 (0.4)	891.472 4 (1.2)	60 681	913.485 1(80.09), 867.484 4(1.94), 825.469 8(0.5), 807.450 5(0.13), 119.035 6(0.05), 59.016 6(0.1), 45.001 8(1.04)	黄芪皂苷Ⅰ同分异构体(Astragaloside Ⅰ isomer)^#	1
LC68	26.04	C₄₅H₇₂O₁₆		913.479 0 (-0.2)^△	930.471 3 (2.1)	869.489 0 (-0.4)	891.473 1 (2.1)	54 160	913.485 1(75.47), 867.521 3(0.25), 867.475 7(1.61), 825.467 3(0.37), 807.448 6(0.82), 89.023 7(0.11), 59.018 4(0.07), 45.001 4(1.06)	黄芪皂苷Ⅰ同分异构体(Astragaloside Ⅰ isomer)^#	1
LC69^*	26.16	C₁₅H₁₀O₅	269.045 5 (-0.3)^△			271.058 9 (-4.4)		364 991	269.044 5(37.17), 241.049 3(5.98), 225.054 9(13.29), 210.030 9(2.39), 197.060 7(2.69), 195.044 7(2.7), 185.059 5(2.29), 182.036 1(3.41), 171.044 0(1.41)	大黄素(Emodin)	3
LC70	26.78	C₄₅H₇₂O₁₆		913.479 9 (0.8)^△	930.467 7 (-1.8)	869.488 6 (-0.8)	891.469 6 (-1.9)	12 211	913.482 8(84.71), 867.468 7(1.74), 825.465 3(0.36), 807.464 2(0.28), 112.986 3(0.05), 89.025 5(0.07), 45.002 2(0.77)	黄芪皂苷Ⅰ同分异构体(Astragaloside Ⅰ isomer)^#	1
LC71	28.00	C₄₇H₇₄O₁₇		955.489 7 (0)^△	972.478 6 (-1.3)			1 700	955.491 7(81.83), 909.508 8(1.71), 161.038 5(0.1), 146.967 3(0.69), 112.984 8(0.34), 45.000 3(0.84)	乙酰黄芪皂苷Ⅰ(Acetyl astragaloside Ⅰ)	1
注: ^*标准品比对确认; ^#AB Sciex中药高分辨质谱数据库比对; ^△产生特征碎片离子的准分子离子及其峰强度; 1.黄芪; 2.黄蜀葵花; 3.何首乌; THDPE.四羟基二苯乙烯; HPTC.羟基紫檀烷; MOPTC.甲氧基紫檀烷; glc.葡萄糖; glu.葡萄糖醛酸。

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参考文献(20)

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