中国药学杂志

No.	t_R/ min	Compound	Formula	m/z (Theoretical)	m/z (Measured)	Mass error	m/z(MS²)	Ion mode	Classification	Ascription
1	0.87	Mannitol^[14]	C₆H₁₄O₆	181.070 7	181.071 1	2.21	163.060 4,119.033 3,149.044 8,113.022 9,101.022 7,89.022 6,79.012 2,59.012 3	[M-H]^-	Others	a/b/d/e
2	0.89	Betaine^[15]	C₅H₁₁NO₂	118.086 3	118.086 3	0	59.073 7,58.065 9	[M+H]⁺	Alkaloid	a/b/c/d/e
3	0.89	L-Carnitine^[16]	C₇H₁₅NO₃	162.112 5	162.112 2	-1.85	103.039 3,85.029 0	[M+H]⁺	Alkaloid	b/d
4	0.89	Trigonelline^[15]	C₇H₇NO₂	138.055 0	138.054 7	2.17	110.060 2,94.065 5,92.049 9,78.034 3	[M+H]⁺	Alkaloid	a/e
5	0.92	Sucrose^[17]	C₁₂H₂₂O₁₁	341.107 8	341.109 1	3.81	179.054 6,161.040 1,143.033 4,119.033 3,101.022 8,89.022 6,71.012 1	[M-H]^-	Others	a/b/c
6	0.94	Adenine^1)[18]	C₅H₅N₅	136.061 8	136.061 7	-0.74	119.035 4,94.040 4	[M+H]⁺	Nucleoside	a/b/d/e
7	0.96	Malic acid^[19]	C₄H₆O₅	133.013 1	133.013 2	0.75	115.001 9,89.022 7,71.012 1,59.012 3	[M-H]^-	Organic acid	a/c/e
8	1.23	Pyroglutamic acid^[20]	C₅H₇NO₃	130.049 8	130.049 9	0.77	84.044 0,56.050 3	[M+H]⁺	Amino acid	a/c/d/
9	1.23	Adenosine^1)[19]	C₁₀H₁₃N₄O₅	268.104 0	268.103 9	-0.37	250.107 0,136.061 7,119.035 5	[M+H]⁺	Nucleoside	a/c/e
10	1.51	Gallic acid^1)[21]	C₇H₆O₅	169.013 1	169.013 7	3.55	125.022 6,107.012 0,81.032 9,79.017 3	[M-H]^-	Organic acid	b
11	1.62	Protocatechuic aldehyde^1)[17]	C₇H₆O₃	137.023 3	137.023 7	2.92	109.027 9,93.032 8	[M-H]^-	Aldehyde	a/e
12	1.93	Pyrogallol^[22]	C₆H₆O₃	125.023 3	125.023 3	0	81.032 9	[M-H]^-	Organic acid	d
13	2.06	L-phenylalanine^[23]	C₉H₁₁NO₂	166.086 3	166.086 3	0	149.070 8,131.049 1,120.080 9,103.054 6	[M+H]⁺	Amino acid	a/b/c/d/e
14	2.19	p-Hydroxybenzaldehyde glucoside^[24]	C₁₃H₁₆O₉	315.071 1	315.071 8	2.22	153.017 9,152.009 9,109.028 1,108.019 9	[M-H]^-	Organic acid	b/d/e
15	2.22	N-(9-β-D-ribofuranosyl-9H-purin-6-yl)- D-aspartic acid^[24]	C₁₄H₁₇N₅O₈	384.115 0	384.114 7	-0.78	252.072 5,234.061 8	[M+H]⁺	Amino acid	a
16	2.25	Vanillic acid glucoside^[25]	C₁₄H₁₈O₉	329.086 7	329.085 9	-2.43	167.033 4,152.010 0,123.043 4,108.020 0	[M-H]^-	Organic acid	a/b/d/e
17	2.25	Vanillic acid^[24]	C₈H₈O₄	167.033 9	167.034 3	2.4	152.009 9,123.043 4,120.897 1,108.020 0	[M-H]^-	Organic acid	a/d/e
18	2.46	Methylsuccinic acid^[26]	C₅H₈O₄	131.033 9	131.034 0	0.76	113.022 9,87.043 4,72.99 1	[M-H]^-	Organic acid	a/d/e
19	2.76	Histidylproline^[24]	C₁₁H₁₆N₄O₃	253.129 5	253.129 5	0	236.103 2,225.134 6,208.108 4,191.081 4, 181.144 8,166.086 2,165.102 2,122.096 6, 112.087 2,70.065 9	[M+H]⁺	Amino acid	a/d
20	2.78	Protocatechuic acid^1)[27]	C₇H₆O₄	153.018 2	153.018 4	1.31	109.027 8,108.020 0	[M-H]^-	Organic acid	a/b/d/e
21	3.25	Glucosyringic acid^[28]	C₁₅H₂₀O₁₀	359.097 3	359.099 1	5.01	197.044 2,182.020 5,166.997 1,153.054 2, 138.030 6,123.007 0	[M-H]^-	Organic acid	a/b/d
22	3.41	Neochlorogenic acid^1)[29]	C₁₆H₁₈O₉	353.086 7	353.087 8	3.12	191.054 5,179.033 4,173.044 0,161.022 9, 135.043 4	[M-H]^-	Organic acid	b
23	3.67	Caffeic acid 4-O-glucoside^[24]	C₁₅H₁₈O₉	341.086 7	341.088 2	4.4	179.033 4,135.043 5	[M-H]^-	Organic acid	b
24	4.68	4-Hydroxybenzoic acid^1)[30]	C₇H₆O₃	137.023 3	137.023 4	0.73	109.027 9,93.032 8	[M-H]^-	Organic acid	e
25	4.68	Swertiamarin^[31]	C₁₆H₂₂O₁₀	373.112 9	373.114 7	4.83	211.060 0,179.054 4,167.069 9,193.049 5, 149.059 3,123.043 4,101.022 8,179.054 0, 119.033 2,89.022 6,71.012 2,59.012 3	[M-H]^-	Terpene	b
26	5.05	Loganic acid^[31]	C₁₆H₂₄O₁₀	375.128 6	375.129 2	1.6	213.075 7,169.085 5,151.074 9,143.033 6, 113.022 7,89.022 6,69.032 9	[M-H]^-	Terpene	b
27	5.36	Dihydrophaseic acid-O-glucoside^[24]	C₂₁H₃₂O₁₀	443.191 2	443.192 6	3.16	161.043 9,119.033 3,113.022 7,101.022 7, 89.022 6,71.012 2,59.012 3	[M-H]^-	Organic acid	e
28	5.58	Chlorogenic acid^1)[29]	C₁₆H₁₈O₉	353.086 7	353.087 7	2.83	191.054 5,179.033 5,173.044 0,161.023 0, 135.043 5	[M-H]^-	Organic acid	b
29	5.81	6,7-Dihydroxycoum- arin^[32]	C₉H₆O₄	179.033 9	179.033 9	0	151.038 9,133.028 4,123.044 2	[M+H]⁺	Coumarin	a
30	5.94	Cryptochlorogenic acid^1)[29]	C₁₆H₁₈O₉	353.086 7	353.087 7	2.83	191.054 6,179.033 4,173.043 9,161.022 9, 135.043 4	[M-H]^-	Organic acid	b
31	5.94	Caffeic acid^1)[24]	C₉H₈O₄	179.033 9	179.034 1	1.12	135.043 4,117.032 8,107.048 6,89.037 9	[M-H]^-	Organic acid	a/b/d/e
32	5.94	Shikimic acid^[16]	C₇H₁₀O₅	173.044 5	173.044 7	1.16	155.033 7,137.022 7,128.876 2,111.043 4, 93.032	[M-H]^-	Organic acid	b
33	6.02	Lycoperodine-1^[24]	C₁₂H₁₂N₂O₂	217.097 2	217.097 2	0	144.080 7	[M+H]⁺	Others	a/b/d
34	6.11	Cyclohexanecarboxylic acid^[29]	C₁₆H₁₈O₉	353.086 7	353.088 3	4.53	191.054 6,179.033 4,173.044 0,135.043 4	[M-H]^-	Organic acid	b
35	6.23	Cantleyine^[33]	C₁₁H₁₃NO₃	208.096 7	208.097 6	4.33	190.086 1,176.070 5,158.059 9	[M+H]⁺	Alkaloid	b
36	7.03	5,7-Dihydroxy-4-methylcoumarin^[34]	C₁₀H₈O₄	193.049 5	193.049 4	-0.52	178.025 7,165.054 6,149.096 4,137.059 6	[M+H]⁺	Coumarin	a
37	7.13	Erythricine^[33]	C₁₀H₉NO₂	176.070 6	176.070 3	-1.7	146.059 9,118.065 3,117.057 5	[M+H]⁺	Alkaloid	b
38	7.32	5-Coumariquinic acid^[21]	C₁₆H₁₈O₈	337.091 8	337.093 4	4.75	191.054 5,163.038 5	[M-H]^-	Organic acid	b
39	7.44	Puerarin^[35]	C₂₁H₂₀O₉	415.102 4	415.104 4	4.82	295.060 1,277.049 0,267.065 3	[M-H]^-	Flavonoid	a
40	7.63	Loganin^1)[36]	C₁₇H₂₆O₁₀	435.149 7	435.150 7	2.3	227.091 3,127.038 3,101.022 7	[M+COOH]^-	Terpene	b
41	7.68	Sweroside^[37]	C₁₆H₂₂O₉	403.123 5	403.124 3	1.99	357.118 0,195.064 7,179.054 7,161.044 0, 131.033 4,125.022 6	[M+COOH]^-	Terpene	b
42	7.88	Vanillin^[17]	C₈H₈O₃	153.054 6	153.054 6	0	153.054 5,125.059 8,111.044 3,65.039 4	[M+H]⁺	Aldehyde	a/d/e
43	8.06	2,4-Dihydroxy-6-methoxy-3-methyl acetophenone 4-O-β-D-xylopyranosyl-(1→6)-β-D-glucopyranoside^[36]	C₂₁H₃₀O₁₃	535.165 8	535.168 2	4.49	489.159 9,191.054 3,151.074 9,149.043 9, 125.022 6,81.032 9	[M+COOH]^-	Others	b
44	8.26	Psoralenoside^1)[38]	C₁₇H₁₈O₉	365.086 7	365.087 1	1.1	203.033 7,159.043 5	[M-H]^-	Coumarin	a
45	8.57	Schaftoside/ isomers^[39]	C₂₆H₂₈O₁₄	563.139 5	563.140 4	1.6	503.116 7,473.106 9,443.097 1,383.076 2, 353.065 6,325.070 7,297.075 7,311.05 5	[M-H]^-	Flavonoid	a/d
46	8.57	Luteolin-6-C-glucoside/orientin^[17]	C₂₁H₂₀O₁₁	447.092 2	447.093 6	3.13	429.081 1,411.073 8,393.060 4,357.060 7, 327.050 0,299.055 1,285.039 6,284.031 9, 255.054 2	[M-H]^-	Flavonoid	d
47	8.67	Schaftoside/ isomers^[39]	C₂₆H₂₈O₁₄	563.139 5	563.139 0	-0.89	503.117 7,473.107 2,443.096 4,383.076 1, 353.065 5,325.070 3,311.054 1,294.07 6	[M-H]^-	Flavonoid	a/d
48	8.67	Isopsoralenoside^1)[38]	C₁₇H₁₈O₉	365.086 7	365.087 2	1.37	203.033 7,159.043 5	[M-H]^-	Coumarin	a
49	8.69	Bakuchicin^[40]	C₁₁H₆O₃	187.039 0	187.038 3	-3.74	143.049 0,159.044 0,131.049 1,115.054 4	[M+H]⁺	Coumarin	a
50	8.74	Hydroxyferulic acid^[24]	C₁₀H₁₀O₅	209.044 5	209.045 4	4.31	165.054 0,121.027 7,59.856 8	[M-H]^-	Organic acid	a/e
51	8.82	Luteolin-6-C-glucoside/orientin^[17]	C₂₁H₂₀O₁₁	447.092 5	447.094 5	4.47	429.091 8,411.071 5,357.060 5,327.049 9, 299.054 9,285.039 1,284.032 0,255.054 2	[M-H]^-	Flavonoid	d
52	8.99	Schaftoside/ isomers^[39]	C₂₆H₂₈O₁₄	563.139 5	563.139 5	0	503.117 3,473.107 2,443.096 8,383.076 3, 353.065 7,325.070 7,311.055 0,297.075 8	[M-H]^-	Flavonoid	a/d
53	9.53	1-Hydroxypinoresinol 4'-β-D-glucopyranoside^[36]	C₂₆H₃₂O₁₂	535.181 1	535.183 7	4.86	373.128 0,343.117 5,284.103 8,269.081 1, 254.057 6,193.049 1, 163.038 9,149.059 1, 148.015 0	[M-H]^-	lignan	b
54	9.75	Daidzin^[41]	C₂₁H₂₀O₉	417.118 0	417.117 2	-1.92	297.075 0,255.064 8,227.070 0,199.075 2, 119.049 2,137.023 2	[M+H]⁺	Flavonoid	a
55	9.78	Isovitexin^[42]	C₂₁H₂₀O₁₀	431.097 3	431.099 3	4.64	413.086 3,395.076 6,341.065 6,311.055 3, 283.060 4,269.044 7,161.022 9,117.032 9	[M-H]^-	Flavonoid	d
56	9.83	7-Deoxyloganic acid^[36]	C₁₆H₂₄O₉	359.133 7	359.135 3	4.46	197.080 5,153.090 6,135.079 9,59.012 3	[M-H]^-	Terpene	b
57	9.88	Vitexin^1)[43]	C₂₁H₂₀O₁₀	431.097 3	431.099 1	4.18	341.065 6,311.055 3,283.060 3,269.044 5, 161.022 9,117.032 8	[M-H]^-	Flavonoid	d
58	10.15	Isoquercitrin^[44]	C₂₁H₂₀O₁₂	463.087 1	463.089 4	4.97	301.034 0,300.026 6,271.024 1,255.029 0	[M-H]^-	Flavonoid	a
59	10.46	Swertisin^1)[45]	C₂₂H₂₂O₁₀	445.112 9	445.113 7	1.8	325.070 9,297.039 6,282.052 4	[M-H]^-	Flavonoid	d
60	10.6	Genistin^[41]	C₂₁H₂₀O₁₀	433.112 9	433.111 9	-2.31	271.059 6,253.049 2,243.064 7,215.070 0, 169.064 9,153.018 1	[M+H]⁺	Flavonoid	a
61	10.83	Isoswertisin^[46]	C₂₂H₂₂O₁₀	445.113 2	445.115 3	4.72	325.071 0,297.039 8,282.052 3	[M-H]^-	Flavonoid	d
62	11.10	Salicylic acid^[47]	C₇H₆O₃	137.023 3	137.023 5	1.46	108.898 0,93.032 8,65.038 0	[M-H]^-	Organic acid	a/d/e
63	11.15	Isochlorogenic acid B^1)[48]	C₂₅H₂₄O₁₂	515.118 4	515.119 3	1.75	353.086 8,191.054 6,179.033 4,173.044 0, 135.043 5	[M-H]^-	Organic acid	b
64	11.36	Astragaloside^[49]	C₂₁H₂₀O₁₁	447.092 2	447.093 9	3.8	285.039 1,284.031 8,256.034 7,255.029 0, 227.033 9	[M-H]^-	Flavonoid	a
65	11.39	Isochlorogenic acid A^1)[48]	C₂₅H₂₄O₁₂	515.118 4	515.119 0	1.17	353.087 0,191.054 5,179.033 4,173.044 1, 135.043 4	[M-H]^-	Organic acid	b
66	11.39	Kaempferol^[50]	C₁₅H₁₀O₆	287.055 0	287.054 2	-2.79	259.058 7,241.049 3,213.054 2,165.018 1, 153.018 1,137.023 2	[M+H]⁺	Flavonoid	a
67	11.47	Quercitrin^1)[50]	C₂₁H₂₀O₁₁	447.092 2	447.094 2	4.47	301.033 8,300.026 2,255.028 7,151.001 6	[M-H]^-	Flavonoid	d
68	12.35	Isochlorogenic acid C^1)[48]	C₂₅H₂₄O₁₂	515.118 4	515.119 0	1.17	353.086 9,191.054 6,179.033 4,173.044 0, 135.043 5	[M-H]^-	Organic acid	b
69	13.63	Notoginsenoside M^[51]	C₄₈H₈₂O₁₉	1 007.542 1	1 007.546 9	4.77	961.538 2,799.483 1,637.431 3,619.417 2, 475.378 2	[M+COOH]^-	Saponin	c
70	13.72	Daidzein^[52]	C₁₅H₁₀O₄	255.065 2	255.064 4	-3.14	137.023 2,199.075 2	[M+H]⁺	Flavonoid	a
71	13.9	Notoginsenoside R1^1)[41]	C₄₇H₈₀O₁₈	977.531 6	977.530 6	-1.02	931.528 4,799.484 1,637.431 0,475.377 8, 391.284 7	[M+COOH]^-	Saponin	c
72	14.02	Brosimacutin G^[38]	C₂₀H₂₀O₆	357.133 3	357.132 6	-1.96	255.066 1,237.075 1,147.044 0,119.049 3	[M+H]⁺	Flavonoid	a
73	14.28	Psoralenol^[53]	C₂₀H₁₈O₅	339.122 2	339.122 0	-0.59	321.111 5,291.117 3,279.064 9,267.064 9, 251.070 7,239.070 0,137.023 3	[M+H]⁺	Flavonoid	a
74	14.36	3'-Methoxydaidzein^[52]	C₁₆H₁₂O₅	283.060 3	283.061 6	4.59	268.036 9,239.034 2,211.039 0,148.015 0, 135.007 1	[M-H]^-	Flavonoid	a
75	14.36	Ginsenoside Rf/ isomer^[41]	C₄₂H₇₂O₁₄	845.489 3	845.490 1	0.95	799.484 2,637.430 4,619.419 0,457.377 7, 391.281 5	[M+COOH]^-	Saponin	c
76	14.62	Ginsenoside Rg1^1)[41]	C₄₂H₇₂O₁₄	845.489 3	845.491 6	2.72	799.483 6,637.430 5,619.422 9,475.377 6, 391.284 3	[M+COOH]^-	Saponin	c
77	14.72	Ginsenoside Re^1)[51]	C₄₈H₈₂O₁₈	945.541 7	945.543 6	2.01	945.543 8,637.430 5,619.420 7,475.377 6, 457.366 4,391.284 1	[M+COOH]^-	Saponin	c
78	15.05	Decanedioic acid^[54]	C₁₀H₁₈O₄	201.112 1	201.112 8	3.48	201.112 8,183.101 1,157.121 17,139.111 2	[M-H]^-	Organic acid	d/e
79	15.09	Ginsenoside Rf/ isomer^[41]	C₄₂H₇₂O₁₄	845.489 3	845.493 5	4.97	799.483 8,637.430 6,475.377 4,391.283 3	[M+COOH]^-	Saponin	c
80	15.76	Corylidin/isomer^[40]	C₂₀H₁₆O₇	369.096 9	369.095 3	-4.34	309.038 7,297.039 0,269.044 0,241.049 0	[M+H]⁺	Coumarin	a
81	15.86	Psoralen^1)[40]	C₁₁H₆O₃	187.039 0	187.038 3	-3.74	159.044 0,143.049 1,131.049 2,115.054 5	[M+H]⁺	Coumarin	a
82	15.96	Psoralenol A/psoralenol B/isomer^[55]	C₂₀H₁₈O₆	355.117 6	355.116 2	-3.94	337.106 4,295.096 1,279.064 6,137.023 2	[M+H]⁺	Flavonoid	a
83	16.16	Notoginsenoside G^[56]	C₄₈H₈₀O₁₉	1 005.526 5	1 005.522 8	-3.68	959.521 0,797.468 9,635.414 4,473.364 0	[M+COOH]^-	Saponin	c
84	16.18	Erythrinin A^[40]	C₂₀H₁₆O₄	321.112 1	321.111 4	-2.18	305.085 0,303.101 3,279.065 0,263.070 0, 183.080 4,137.023 3	[M+H]⁺	Flavonoid	a
85	16.48	Angelicin^[32]	C₁₁H₆O₃	187.039 0	187.038 3	-3.74	159.044 0,143.049 0,131.049 1,115.054 4, 103.054 5,77.040 0	[M+H]⁺	Coumarin	a
86	16.48	Psoralenol A/psoralenol/ isomer^[55]	C₂₀H₁₈O₆	355.117 6	355.116 2	-3.94	337.106 6,295.096 2,279.064 9,137.023 3	[M+H]⁺	Flavonoid	a
87	16.59	Genistein^[57]	C₁₅H₁₀O₅	271.060 1	271.059 0	-4.06	253.049 3,243.064 9,197.059 6,169.064 8, 153.018 1	[M+H]⁺	Flavonoid	a
88	17.49	Bavarigenin^[55]	C₂₂H₂₂O₇	399.143 8	399.142 7	-2.76	381.133 0,369.132 7,305.081 6,187.039 0	[M+H]⁺	Flavonoid	a
89	17.79	Corylin^[58]	C₂₀H₁₆O₄	321.112 1	321.111 4	-2.18	306.087 5,279.065 2,211.074 9,183.080 2, 143.085 2,137.023 2	[M+H]⁺	Flavonoid	a
90	18.11	Corylifol B/isomer^[55]	C₂₀H₂₀O₅	341.138 4	341.137 8	-1.76	269.060 5,203.070 1,149.023 3	[M+H]⁺	Flavonoid	a
91	18.44	Asperosaponin Ⅵ^[36]	C₄₇H₇₆O₁₈	973.500 3	973.504 3	4.11	927.497 1,603.388 9,323.097 7 4,179.054 6	[M+COOH]^-	Saponin	b
92	18.84	Neocorylin A/neocorylin B^[55]	C₂₅H₂₆O₅	407.185 3	407.184 1	-2.95	389.173 8,321.111 5,267.064 8,137.023 2	[M+H]⁺	Flavonoid	a
93	18.86	Notoginsenoside R2/ isomer^[51]	C₄₁H₇₀O₁₃	815.478 8	815.481 0	2.7	769.473 5,637.430 3,475.376 9,391.285 0, 161.044 0	[M+COOH]^-	Saponin	c
94	19.12	Notoginsenoside Fa^[59]	C₅₉H₁₀₀O₂₇	1 285.642 3	1 285.647 5	4.05	1 239.638 4,1 107.595 5,945.544 4,783.488 4,621.440 3,459.386 3	[M+COOH]^-	Saponin	c
95	19.12	Ginsenoside Rb1^[60]	C₅₄H₉₂O₂₃	1 153.600 0	1 153.599 4	-0.52	1 107.597 8,945.542 6,783.491 8,621.435 4, 459.383 2	[M+COOH]^-	Saponin	c
96	19.15	Ginsenoside Rg5^[61]	C₄₂H₇₀O₁₂	767.493 0	767.489 9	-4.04	605.439 5,443.386 9,425.375 8,407.365 8, 297.256 7	[M+H]⁺	Saponin	c
97	19.33	Notoginsenoside R2/isomer^[51]	C₄₁H₇₀O₁₃	815.478 8	815.481 3	3.07	769.473 3,637.430 2,475.377 4,391.285 0, 161.044 1	[M+COOH]^-	Saponin	b
98	19.33	Ginsenoside Rg2/isomer^[62]	C₄₂H₇₂O₁₃	829.494 4	829.496 4	2.41	783.492 0,637.430 3,475.377 5,391.284 5	[M+COOH]^-	Saponin	c
99	19.38	4'-O-Asperosaponin Ⅵ^[63]	C₄₉H₇₈O₁₉	1 015.510 8	1 015.514 3	3.45	645.399 8,323.097 2	[M+COOH]^-	Saponin	b
100	19.43	Ginsenoside Rh1/isomer^[64]	C₃₆H₆₂O₉	683.436 5	683.436 8	0.44	637.431 0,475.377 3,391.284 5	[M+COOH]^-	Saponin	c
101	19.53	Ginsenoside Rg2/isomer^[62]	C₄₂H₇₂O₁₃	829.494 4	829.498 4	4.83	783.489 1,637.430 1,475.377 0,391.284 2	[M+COOH]^-	Saponin	c
102	19.61	Bavacoumestan A/ bavacoumestan B/ isomer^[40]	C₂₀H₁₆O₆	353.101 3	353.102 0	1.98	335.090 6,307.095 7,281.044 0,253.049 1, 225.054 3,209.059 4,197.059 4,181.064 7	[M+H]⁺	Flavonoid	a
103	19.64	2'-O-Asperosaponin Ⅵ^[63]	C₄₉H₇₈O₁₉	1 015.510 8	1 015.514 6	3.74	645.399 8,323.097 2	[M+COOH]^-	Saponin	b
104	19.69	Ginsenoside F1/isomer^[65]	C₃₆H₆₂O₉	683.436 5	683.439 2	3.95	637.430 5,475.378 1,161.044 1,113.022 7, 101.022 8	[M+COOH]^-	Saponin	c
105	19.82	Bavacoumestan A/ bavacoumestan B/ isomer^[40]	C₂₀H₁₆O₆	353.101 3	353.102 1	2.27	335.091 2,307.097 0,281.044 6,253.049 2, 225.054 3,209.006 0 2,197.059 4,181.064 7	[M+H]⁺	Flavonoid	a
106	19.95	3'-O-Asperosaponin Ⅵ^[63]	C₄₉H₇₈O₁₉	1 015.510 8	1 015.510 1	-0.69	645.399 9,323.097 3	[M+COOH]^-	Saponin	b
107	20.08	Isoaromadendrene epoxide^[66]	C₁₅H₂₄O	221.190 0	221.189 7	-1.36	203.179 4,147.116 8,119.085 7,105.070 2	[M+H]⁺	Terpene	a
108	20.08	Calamenene^[53]	C₁₅H₂₂	203.179 4	203.179 2	-0.99	147.116 7,133.101 2,119.085 7,105.070 2	[M+H]⁺	Others	a
109	20.22	Dipsacussaponin A^[36]	C₄₂H₆₈O₁₄	841.458 3	841.462 3	4.76	795.456 2,471.346 1,323.096 5,221.066 1, 119.033 5	[M+COOH]^-	Saponin	b
110	20.29	Corylifol C^[67]	C₂₀H₁₈O₅	339.122 7	339.122 1	-1.77	283.059 8,255.065 0,237.054 4,227.070 0, 297.075 3	[M+H]⁺	Flavonoid	a
111	20.43	HN-saponin F^[68]	C₄₁H₆₆O₁₃	811.447 5	811.450 0	3.08	765.442 6,603.389 1,207.049 6,101.022 7	[M+COOH]^-	Saponin	b
112	20.58	Gypenoside XⅦ^[69]	C₄₈H₈₂O₁₈	991.547 2	991.545 7	-1.51	945.544 7,783.489 5,621.435 8	[M+COOH]^-	Saponin	c
113	20.6	Ginsenoside Rd^[41]	C₄₈H₈₂O₁₈	945.541 7	945.546 1	4.66	783.489 0,621.436 3,459.383 0	[M-H]^-	Saponin	c
114	21.2	Ginsenoside Rh3^[70]	C₃₆H₆₀O₇	605.441 2	605.439 5	-2.81	441.372 3,425.376 4,407.366 3,331.264 6	[M+H]⁺	Saponin	c
115	21.21	Notoginsenoside K^[71]	C₄₈H₈₂O₁₈	991.547 2	991.544 6	-2.62	945.544 1,783.487 9,621.436 3,537.342 5, 459.380 8,323.097 3	[M+COOH]^-	Saponin	c
116	21.32	Bavachin^[55]	C₂₀H₂₀O₄	323.127 8	323.128 9	3.41	221.080 9,203.070 1,175.075 1,159.080 1, 119.048 5	[M-H]^-	Flavonoid	a
117	21.72	Neocorylin^[55]	C₂₅H₂₄O₄	389.174 7	389.173 9	-2.06	321.111 5,305.080 8,267.064 9,137.023 3	[M+H]⁺	Flavonoid	a
118	21.72	Neocorylin A/neocorylin B/isomer^[72]	C₂₅H₂₆O₅	407.185 3	407.184 4	-2.21	389.173 8,321.111 2,267.060 5,137.022 3	[M+H]⁺	Flavonoid	a
119	21.78	Bavachromanol^[72]	C₂₀H₂₀O₅	341.138 4	341.137 9	-1.47	323.127 6,221.080 9,203.070 2,149.023 4	[M+H]⁺	Flavonoid	a
120	22.14	Neobavaisoflavone^[40]	C₂₀H₁₈O₄	323.128 0	323.127 6	-1.24	267.065 0,255.065 0,239.07 0,211.059 0,199.075 0,137.023 0	[M+H]⁺	Flavonoid	a
121	22.68	Ginsenoside F4/ isomer^[73]	C₄₂H₇₀O₁₂	811.483 8	811.486 6	3.45	765.478 5,619.420 1,457.369 3	[M+COOH]^-	Saponin	c
122	22.79	4-Dodecylbenzenesulfonic acid^[74]	C₁₈H₃₀SO₃	325.183 3	325.184 4	3.38	183.010 6	[M-H]^-	Others	a/e
123	22.94	Ginsenoside F4/ isomer^[73]	C₄₂H₇₀O₁₂	811.483 8	811.486 5	3.33	765.478 6,619.420 5,457.366 3	[M+COOH]^-	Saponin	c
124	23.05	Ginsenoside Rh4/ isomer^[75]	C₃₆H₆₀O₈	665.425 9	665.426 7	1.2	619.421 5,161.044 0,113.022 7,101.022 7	[M+COOH]^-	Saponin	c
125	23.36	Ginsenoside Rh4/ isomer^[75]	C₃₆H₆₀O₈	665.425 9	665.426 7	1.2	619.420 1,161.044 1,113.023 1,101.022 8	[M+COOH]^-	Saponin	c
126	23.87	Bavachromene^[76]	C₂₀H₁₈O₄	323.127 8	323.127 1	-2.17	305.116 7,281.115 4,253.112 3,221.080 6,203.070 1,175.075 3,147.044 0	[M+H]⁺	Flavonoid	a
127	24.01	Psoralidin^[38]	C₂₀H₁₆O₅	337.107 1	337.106 1	-2.97	309.111 4,281.044 1,253.049 2,237.054 3,225.054 3,209.059 5,197.059 6,181.064 7	[M+H]⁺	Coumarin	a
128	24.2	Ginsenoside Rg3/ isomer^[73]	C₄₂H₇₂O₁₃	829.494 4	829.496 2	2.17	783.489 0,621.436 7,459.382 8,375.288 9,161.044 1	[M+COOH]^-	Saponin	c
129	24.35	Ginsenoside Rg3/ isomer^[73]	C₄₂H₇₂O₁₃	829.494 4	829.496 4	2.41	783.489 3,621.436 2,459.383 2,375.289 5,161.044 1	[M+COOH]^-	Saponin	c
130	24.46	Octadecanedioic acid^[24]	C₁₈H₃₄O₄	313.237 5	313.239 0	4.79	295.226 9,201.111 9,171.101 1	[M-H]^-	Organic acid	a/e
131	25.56	Isobavachalcone^[77]	C₂₀H₂₀O₄	323.127 8	323.128 9	3.41	221.080 9,203.070 1,175.075 4,159.080 0,119.048 5	[M-H]^-	Flavonoid	a
132	26.07	Bavachinin/isomer^[76]	C₂₁H₂₂O₄	339.159 1	339.158 3	-2.36	283.095 9,271.095 9,219.101 4,177.054 6,147.043 9	[M+H]⁺	Flavonoid	a
133	26.75	Corylifol A^[38]	C₂₅H₂₆O₄	391.190 4	391.189 3	-2.81	335.127 0,267.064 8,239.069 8,137.023 2	[M+H]⁺	Flavonoid	a
134	27.03	Dodecyl sulfate^[36]	C₁₂H₂₆O₄S	265.146 8	265.148 1	4.91	96.958 3,95.950 6,79.955 7	[M-H]^-	Others	b
135	27.74	Bavachinin/isomer^[76]	C₂₁H₂₂O₄	339.159 1	339.158 3	-2.36	283.095 8,271.095 9,269.080 5,219.101 3,147.043 9	[M+H]⁺	Flavonoid	a
136	28.16	Neocorylin^[38]	C₂₅H₂₄O₄	389.174 7	389.173 8	-2.31	321.111 4,305.080 1,267.064 7,183.080 4,137.023 0	[M+H]⁺	Flavonoid	a
137	28.79	Bakuchiol^[72]	C₁₈H₂₄O	257.190 0	257.189 5	-1.95	201.127 0,187.111 6,173.096 1,147.080 3,133.064 8,121.064 9,107.049 5	[M+H]⁺	Terpene	a

No.	t_R/ min	Compound	Formula	m/z (Theoretical)	m/z (Measured)	Mass error	m/z(MS²)	Ion mode	Classification	Ascription
1	0.87	Mannitol^[14]	C₆H₁₄O₆	181.070 7	181.071 1	2.21	163.060 4,119.033 3,149.044 8,113.022 9,101.022 7,89.022 6,79.012 2,59.012 3	[M-H]^-	Others	a/b/d/e
2	0.89	Betaine^[15]	C₅H₁₁NO₂	118.086 3	118.086 3	0	59.073 7,58.065 9	[M+H]⁺	Alkaloid	a/b/c/d/e
3	0.89	L-Carnitine^[16]	C₇H₁₅NO₃	162.112 5	162.112 2	-1.85	103.039 3,85.029 0	[M+H]⁺	Alkaloid	b/d
4	0.89	Trigonelline^[15]	C₇H₇NO₂	138.055 0	138.054 7	2.17	110.060 2,94.065 5,92.049 9,78.034 3	[M+H]⁺	Alkaloid	a/e
5	0.92	Sucrose^[17]	C₁₂H₂₂O₁₁	341.107 8	341.109 1	3.81	179.054 6,161.040 1,143.033 4,119.033 3,101.022 8,89.022 6,71.012 1	[M-H]^-	Others	a/b/c
6	0.94	Adenine^1)[18]	C₅H₅N₅	136.061 8	136.061 7	-0.74	119.035 4,94.040 4	[M+H]⁺	Nucleoside	a/b/d/e
7	0.96	Malic acid^[19]	C₄H₆O₅	133.013 1	133.013 2	0.75	115.001 9,89.022 7,71.012 1,59.012 3	[M-H]^-	Organic acid	a/c/e
8	1.23	Pyroglutamic acid^[20]	C₅H₇NO₃	130.049 8	130.049 9	0.77	84.044 0,56.050 3	[M+H]⁺	Amino acid	a/c/d/
9	1.23	Adenosine^1)[19]	C₁₀H₁₃N₄O₅	268.104 0	268.103 9	-0.37	250.107 0,136.061 7,119.035 5	[M+H]⁺	Nucleoside	a/c/e
10	1.51	Gallic acid^1)[21]	C₇H₆O₅	169.013 1	169.013 7	3.55	125.022 6,107.012 0,81.032 9,79.017 3	[M-H]^-	Organic acid	b
11	1.62	Protocatechuic aldehyde^1)[17]	C₇H₆O₃	137.023 3	137.023 7	2.92	109.027 9,93.032 8	[M-H]^-	Aldehyde	a/e
12	1.93	Pyrogallol^[22]	C₆H₆O₃	125.023 3	125.023 3	0	81.032 9	[M-H]^-	Organic acid	d
13	2.06	L-phenylalanine^[23]	C₉H₁₁NO₂	166.086 3	166.086 3	0	149.070 8,131.049 1,120.080 9,103.054 6	[M+H]⁺	Amino acid	a/b/c/d/e
14	2.19	p-Hydroxybenzaldehyde glucoside^[24]	C₁₃H₁₆O₉	315.071 1	315.071 8	2.22	153.017 9,152.009 9,109.028 1,108.019 9	[M-H]^-	Organic acid	b/d/e
15	2.22	N-(9-β-D-ribofuranosyl-9H-purin-6-yl)- D-aspartic acid^[24]	C₁₄H₁₇N₅O₈	384.115 0	384.114 7	-0.78	252.072 5,234.061 8	[M+H]⁺	Amino acid	a
16	2.25	Vanillic acid glucoside^[25]	C₁₄H₁₈O₉	329.086 7	329.085 9	-2.43	167.033 4,152.010 0,123.043 4,108.020 0	[M-H]^-	Organic acid	a/b/d/e
17	2.25	Vanillic acid^[24]	C₈H₈O₄	167.033 9	167.034 3	2.4	152.009 9,123.043 4,120.897 1,108.020 0	[M-H]^-	Organic acid	a/d/e
18	2.46	Methylsuccinic acid^[26]	C₅H₈O₄	131.033 9	131.034 0	0.76	113.022 9,87.043 4,72.99 1	[M-H]^-	Organic acid	a/d/e
19	2.76	Histidylproline^[24]	C₁₁H₁₆N₄O₃	253.129 5	253.129 5	0	236.103 2,225.134 6,208.108 4,191.081 4, 181.144 8,166.086 2,165.102 2,122.096 6, 112.087 2,70.065 9	[M+H]⁺	Amino acid	a/d
20	2.78	Protocatechuic acid^1)[27]	C₇H₆O₄	153.018 2	153.018 4	1.31	109.027 8,108.020 0	[M-H]^-	Organic acid	a/b/d/e
21	3.25	Glucosyringic acid^[28]	C₁₅H₂₀O₁₀	359.097 3	359.099 1	5.01	197.044 2,182.020 5,166.997 1,153.054 2, 138.030 6,123.007 0	[M-H]^-	Organic acid	a/b/d
22	3.41	Neochlorogenic acid^1)[29]	C₁₆H₁₈O₉	353.086 7	353.087 8	3.12	191.054 5,179.033 4,173.044 0,161.022 9, 135.043 4	[M-H]^-	Organic acid	b
23	3.67	Caffeic acid 4-O-glucoside^[24]	C₁₅H₁₈O₉	341.086 7	341.088 2	4.4	179.033 4,135.043 5	[M-H]^-	Organic acid	b
24	4.68	4-Hydroxybenzoic acid^1)[30]	C₇H₆O₃	137.023 3	137.023 4	0.73	109.027 9,93.032 8	[M-H]^-	Organic acid	e
25	4.68	Swertiamarin^[31]	C₁₆H₂₂O₁₀	373.112 9	373.114 7	4.83	211.060 0,179.054 4,167.069 9,193.049 5, 149.059 3,123.043 4,101.022 8,179.054 0, 119.033 2,89.022 6,71.012 2,59.012 3	[M-H]^-	Terpene	b
26	5.05	Loganic acid^[31]	C₁₆H₂₄O₁₀	375.128 6	375.129 2	1.6	213.075 7,169.085 5,151.074 9,143.033 6, 113.022 7,89.022 6,69.032 9	[M-H]^-	Terpene	b
27	5.36	Dihydrophaseic acid-O-glucoside^[24]	C₂₁H₃₂O₁₀	443.191 2	443.192 6	3.16	161.043 9,119.033 3,113.022 7,101.022 7, 89.022 6,71.012 2,59.012 3	[M-H]^-	Organic acid	e
28	5.58	Chlorogenic acid^1)[29]	C₁₆H₁₈O₉	353.086 7	353.087 7	2.83	191.054 5,179.033 5,173.044 0,161.023 0, 135.043 5	[M-H]^-	Organic acid	b
29	5.81	6,7-Dihydroxycoum- arin^[32]	C₉H₆O₄	179.033 9	179.033 9	0	151.038 9,133.028 4,123.044 2	[M+H]⁺	Coumarin	a
30	5.94	Cryptochlorogenic acid^1)[29]	C₁₆H₁₈O₉	353.086 7	353.087 7	2.83	191.054 6,179.033 4,173.043 9,161.022 9, 135.043 4	[M-H]^-	Organic acid	b
31	5.94	Caffeic acid^1)[24]	C₉H₈O₄	179.033 9	179.034 1	1.12	135.043 4,117.032 8,107.048 6,89.037 9	[M-H]^-	Organic acid	a/b/d/e
32	5.94	Shikimic acid^[16]	C₇H₁₀O₅	173.044 5	173.044 7	1.16	155.033 7,137.022 7,128.876 2,111.043 4, 93.032	[M-H]^-	Organic acid	b
33	6.02	Lycoperodine-1^[24]	C₁₂H₁₂N₂O₂	217.097 2	217.097 2	0	144.080 7	[M+H]⁺	Others	a/b/d
34	6.11	Cyclohexanecarboxylic acid^[29]	C₁₆H₁₈O₉	353.086 7	353.088 3	4.53	191.054 6,179.033 4,173.044 0,135.043 4	[M-H]^-	Organic acid	b
35	6.23	Cantleyine^[33]	C₁₁H₁₃NO₃	208.096 7	208.097 6	4.33	190.086 1,176.070 5,158.059 9	[M+H]⁺	Alkaloid	b
36	7.03	5,7-Dihydroxy-4-methylcoumarin^[34]	C₁₀H₈O₄	193.049 5	193.049 4	-0.52	178.025 7,165.054 6,149.096 4,137.059 6	[M+H]⁺	Coumarin	a
37	7.13	Erythricine^[33]	C₁₀H₉NO₂	176.070 6	176.070 3	-1.7	146.059 9,118.065 3,117.057 5	[M+H]⁺	Alkaloid	b
38	7.32	5-Coumariquinic acid^[21]	C₁₆H₁₈O₈	337.091 8	337.093 4	4.75	191.054 5,163.038 5	[M-H]^-	Organic acid	b
39	7.44	Puerarin^[35]	C₂₁H₂₀O₉	415.102 4	415.104 4	4.82	295.060 1,277.049 0,267.065 3	[M-H]^-	Flavonoid	a
40	7.63	Loganin^1)[36]	C₁₇H₂₆O₁₀	435.149 7	435.150 7	2.3	227.091 3,127.038 3,101.022 7	[M+COOH]^-	Terpene	b
41	7.68	Sweroside^[37]	C₁₆H₂₂O₉	403.123 5	403.124 3	1.99	357.118 0,195.064 7,179.054 7,161.044 0, 131.033 4,125.022 6	[M+COOH]^-	Terpene	b
42	7.88	Vanillin^[17]	C₈H₈O₃	153.054 6	153.054 6	0	153.054 5,125.059 8,111.044 3,65.039 4	[M+H]⁺	Aldehyde	a/d/e
43	8.06	2,4-Dihydroxy-6-methoxy-3-methyl acetophenone 4-O-β-D-xylopyranosyl-(1→6)-β-D-glucopyranoside^[36]	C₂₁H₃₀O₁₃	535.165 8	535.168 2	4.49	489.159 9,191.054 3,151.074 9,149.043 9, 125.022 6,81.032 9	[M+COOH]^-	Others	b
44	8.26	Psoralenoside^1)[38]	C₁₇H₁₈O₉	365.086 7	365.087 1	1.1	203.033 7,159.043 5	[M-H]^-	Coumarin	a
45	8.57	Schaftoside/ isomers^[39]	C₂₆H₂₈O₁₄	563.139 5	563.140 4	1.6	503.116 7,473.106 9,443.097 1,383.076 2, 353.065 6,325.070 7,297.075 7,311.05 5	[M-H]^-	Flavonoid	a/d
46	8.57	Luteolin-6-C-glucoside/orientin^[17]	C₂₁H₂₀O₁₁	447.092 2	447.093 6	3.13	429.081 1,411.073 8,393.060 4,357.060 7, 327.050 0,299.055 1,285.039 6,284.031 9, 255.054 2	[M-H]^-	Flavonoid	d
47	8.67	Schaftoside/ isomers^[39]	C₂₆H₂₈O₁₄	563.139 5	563.139 0	-0.89	503.117 7,473.107 2,443.096 4,383.076 1, 353.065 5,325.070 3,311.054 1,294.07 6	[M-H]^-	Flavonoid	a/d
48	8.67	Isopsoralenoside^1)[38]	C₁₇H₁₈O₉	365.086 7	365.087 2	1.37	203.033 7,159.043 5	[M-H]^-	Coumarin	a
49	8.69	Bakuchicin^[40]	C₁₁H₆O₃	187.039 0	187.038 3	-3.74	143.049 0,159.044 0,131.049 1,115.054 4	[M+H]⁺	Coumarin	a
50	8.74	Hydroxyferulic acid^[24]	C₁₀H₁₀O₅	209.044 5	209.045 4	4.31	165.054 0,121.027 7,59.856 8	[M-H]^-	Organic acid	a/e
51	8.82	Luteolin-6-C-glucoside/orientin^[17]	C₂₁H₂₀O₁₁	447.092 5	447.094 5	4.47	429.091 8,411.071 5,357.060 5,327.049 9, 299.054 9,285.039 1,284.032 0,255.054 2	[M-H]^-	Flavonoid	d
52	8.99	Schaftoside/ isomers^[39]	C₂₆H₂₈O₁₄	563.139 5	563.139 5	0	503.117 3,473.107 2,443.096 8,383.076 3, 353.065 7,325.070 7,311.055 0,297.075 8	[M-H]^-	Flavonoid	a/d
53	9.53	1-Hydroxypinoresinol 4'-β-D-glucopyranoside^[36]	C₂₆H₃₂O₁₂	535.181 1	535.183 7	4.86	373.128 0,343.117 5,284.103 8,269.081 1, 254.057 6,193.049 1, 163.038 9,149.059 1, 148.015 0	[M-H]^-	lignan	b
54	9.75	Daidzin^[41]	C₂₁H₂₀O₉	417.118 0	417.117 2	-1.92	297.075 0,255.064 8,227.070 0,199.075 2, 119.049 2,137.023 2	[M+H]⁺	Flavonoid	a
55	9.78	Isovitexin^[42]	C₂₁H₂₀O₁₀	431.097 3	431.099 3	4.64	413.086 3,395.076 6,341.065 6,311.055 3, 283.060 4,269.044 7,161.022 9,117.032 9	[M-H]^-	Flavonoid	d
56	9.83	7-Deoxyloganic acid^[36]	C₁₆H₂₄O₉	359.133 7	359.135 3	4.46	197.080 5,153.090 6,135.079 9,59.012 3	[M-H]^-	Terpene	b
57	9.88	Vitexin^1)[43]	C₂₁H₂₀O₁₀	431.097 3	431.099 1	4.18	341.065 6,311.055 3,283.060 3,269.044 5, 161.022 9,117.032 8	[M-H]^-	Flavonoid	d
58	10.15	Isoquercitrin^[44]	C₂₁H₂₀O₁₂	463.087 1	463.089 4	4.97	301.034 0,300.026 6,271.024 1,255.029 0	[M-H]^-	Flavonoid	a
59	10.46	Swertisin^1)[45]	C₂₂H₂₂O₁₀	445.112 9	445.113 7	1.8	325.070 9,297.039 6,282.052 4	[M-H]^-	Flavonoid	d
60	10.6	Genistin^[41]	C₂₁H₂₀O₁₀	433.112 9	433.111 9	-2.31	271.059 6,253.049 2,243.064 7,215.070 0, 169.064 9,153.018 1	[M+H]⁺	Flavonoid	a
61	10.83	Isoswertisin^[46]	C₂₂H₂₂O₁₀	445.113 2	445.115 3	4.72	325.071 0,297.039 8,282.052 3	[M-H]^-	Flavonoid	d
62	11.10	Salicylic acid^[47]	C₇H₆O₃	137.023 3	137.023 5	1.46	108.898 0,93.032 8,65.038 0	[M-H]^-	Organic acid	a/d/e
63	11.15	Isochlorogenic acid B^1)[48]	C₂₅H₂₄O₁₂	515.118 4	515.119 3	1.75	353.086 8,191.054 6,179.033 4,173.044 0, 135.043 5	[M-H]^-	Organic acid	b
64	11.36	Astragaloside^[49]	C₂₁H₂₀O₁₁	447.092 2	447.093 9	3.8	285.039 1,284.031 8,256.034 7,255.029 0, 227.033 9	[M-H]^-	Flavonoid	a
65	11.39	Isochlorogenic acid A^1)[48]	C₂₅H₂₄O₁₂	515.118 4	515.119 0	1.17	353.087 0,191.054 5,179.033 4,173.044 1, 135.043 4	[M-H]^-	Organic acid	b
66	11.39	Kaempferol^[50]	C₁₅H₁₀O₆	287.055 0	287.054 2	-2.79	259.058 7,241.049 3,213.054 2,165.018 1, 153.018 1,137.023 2	[M+H]⁺	Flavonoid	a
67	11.47	Quercitrin^1)[50]	C₂₁H₂₀O₁₁	447.092 2	447.094 2	4.47	301.033 8,300.026 2,255.028 7,151.001 6	[M-H]^-	Flavonoid	d
68	12.35	Isochlorogenic acid C^1)[48]	C₂₅H₂₄O₁₂	515.118 4	515.119 0	1.17	353.086 9,191.054 6,179.033 4,173.044 0, 135.043 5	[M-H]^-	Organic acid	b
69	13.63	Notoginsenoside M^[51]	C₄₈H₈₂O₁₉	1 007.542 1	1 007.546 9	4.77	961.538 2,799.483 1,637.431 3,619.417 2, 475.378 2	[M+COOH]^-	Saponin	c
70	13.72	Daidzein^[52]	C₁₅H₁₀O₄	255.065 2	255.064 4	-3.14	137.023 2,199.075 2	[M+H]⁺	Flavonoid	a
71	13.9	Notoginsenoside R1^1)[41]	C₄₇H₈₀O₁₈	977.531 6	977.530 6	-1.02	931.528 4,799.484 1,637.431 0,475.377 8, 391.284 7	[M+COOH]^-	Saponin	c
72	14.02	Brosimacutin G^[38]	C₂₀H₂₀O₆	357.133 3	357.132 6	-1.96	255.066 1,237.075 1,147.044 0,119.049 3	[M+H]⁺	Flavonoid	a
73	14.28	Psoralenol^[53]	C₂₀H₁₈O₅	339.122 2	339.122 0	-0.59	321.111 5,291.117 3,279.064 9,267.064 9, 251.070 7,239.070 0,137.023 3	[M+H]⁺	Flavonoid	a
74	14.36	3'-Methoxydaidzein^[52]	C₁₆H₁₂O₅	283.060 3	283.061 6	4.59	268.036 9,239.034 2,211.039 0,148.015 0, 135.007 1	[M-H]^-	Flavonoid	a
75	14.36	Ginsenoside Rf/ isomer^[41]	C₄₂H₇₂O₁₄	845.489 3	845.490 1	0.95	799.484 2,637.430 4,619.419 0,457.377 7, 391.281 5	[M+COOH]^-	Saponin	c
76	14.62	Ginsenoside Rg1^1)[41]	C₄₂H₇₂O₁₄	845.489 3	845.491 6	2.72	799.483 6,637.430 5,619.422 9,475.377 6, 391.284 3	[M+COOH]^-	Saponin	c
77	14.72	Ginsenoside Re^1)[51]	C₄₈H₈₂O₁₈	945.541 7	945.543 6	2.01	945.543 8,637.430 5,619.420 7,475.377 6, 457.366 4,391.284 1	[M+COOH]^-	Saponin	c
78	15.05	Decanedioic acid^[54]	C₁₀H₁₈O₄	201.112 1	201.112 8	3.48	201.112 8,183.101 1,157.121 17,139.111 2	[M-H]^-	Organic acid	d/e
79	15.09	Ginsenoside Rf/ isomer^[41]	C₄₂H₇₂O₁₄	845.489 3	845.493 5	4.97	799.483 8,637.430 6,475.377 4,391.283 3	[M+COOH]^-	Saponin	c
80	15.76	Corylidin/isomer^[40]	C₂₀H₁₆O₇	369.096 9	369.095 3	-4.34	309.038 7,297.039 0,269.044 0,241.049 0	[M+H]⁺	Coumarin	a
81	15.86	Psoralen^1)[40]	C₁₁H₆O₃	187.039 0	187.038 3	-3.74	159.044 0,143.049 1,131.049 2,115.054 5	[M+H]⁺	Coumarin	a
82	15.96	Psoralenol A/psoralenol B/isomer^[55]	C₂₀H₁₈O₆	355.117 6	355.116 2	-3.94	337.106 4,295.096 1,279.064 6,137.023 2	[M+H]⁺	Flavonoid	a
83	16.16	Notoginsenoside G^[56]	C₄₈H₈₀O₁₉	1 005.526 5	1 005.522 8	-3.68	959.521 0,797.468 9,635.414 4,473.364 0	[M+COOH]^-	Saponin	c
84	16.18	Erythrinin A^[40]	C₂₀H₁₆O₄	321.112 1	321.111 4	-2.18	305.085 0,303.101 3,279.065 0,263.070 0, 183.080 4,137.023 3	[M+H]⁺	Flavonoid	a
85	16.48	Angelicin^[32]	C₁₁H₆O₃	187.039 0	187.038 3	-3.74	159.044 0,143.049 0,131.049 1,115.054 4, 103.054 5,77.040 0	[M+H]⁺	Coumarin	a
86	16.48	Psoralenol A/psoralenol/ isomer^[55]	C₂₀H₁₈O₆	355.117 6	355.116 2	-3.94	337.106 6,295.096 2,279.064 9,137.023 3	[M+H]⁺	Flavonoid	a
87	16.59	Genistein^[57]	C₁₅H₁₀O₅	271.060 1	271.059 0	-4.06	253.049 3,243.064 9,197.059 6,169.064 8, 153.018 1	[M+H]⁺	Flavonoid	a
88	17.49	Bavarigenin^[55]	C₂₂H₂₂O₇	399.143 8	399.142 7	-2.76	381.133 0,369.132 7,305.081 6,187.039 0	[M+H]⁺	Flavonoid	a
89	17.79	Corylin^[58]	C₂₀H₁₆O₄	321.112 1	321.111 4	-2.18	306.087 5,279.065 2,211.074 9,183.080 2, 143.085 2,137.023 2	[M+H]⁺	Flavonoid	a
90	18.11	Corylifol B/isomer^[55]	C₂₀H₂₀O₅	341.138 4	341.137 8	-1.76	269.060 5,203.070 1,149.023 3	[M+H]⁺	Flavonoid	a
91	18.44	Asperosaponin Ⅵ^[36]	C₄₇H₇₆O₁₈	973.500 3	973.504 3	4.11	927.497 1,603.388 9,323.097 7 4,179.054 6	[M+COOH]^-	Saponin	b
92	18.84	Neocorylin A/neocorylin B^[55]	C₂₅H₂₆O₅	407.185 3	407.184 1	-2.95	389.173 8,321.111 5,267.064 8,137.023 2	[M+H]⁺	Flavonoid	a
93	18.86	Notoginsenoside R2/ isomer^[51]	C₄₁H₇₀O₁₃	815.478 8	815.481 0	2.7	769.473 5,637.430 3,475.376 9,391.285 0, 161.044 0	[M+COOH]^-	Saponin	c
94	19.12	Notoginsenoside Fa^[59]	C₅₉H₁₀₀O₂₇	1 285.642 3	1 285.647 5	4.05	1 239.638 4,1 107.595 5,945.544 4,783.488 4,621.440 3,459.386 3	[M+COOH]^-	Saponin	c
95	19.12	Ginsenoside Rb1^[60]	C₅₄H₉₂O₂₃	1 153.600 0	1 153.599 4	-0.52	1 107.597 8,945.542 6,783.491 8,621.435 4, 459.383 2	[M+COOH]^-	Saponin	c
96	19.15	Ginsenoside Rg5^[61]	C₄₂H₇₀O₁₂	767.493 0	767.489 9	-4.04	605.439 5,443.386 9,425.375 8,407.365 8, 297.256 7	[M+H]⁺	Saponin	c
97	19.33	Notoginsenoside R2/isomer^[51]	C₄₁H₇₀O₁₃	815.478 8	815.481 3	3.07	769.473 3,637.430 2,475.377 4,391.285 0, 161.044 1	[M+COOH]^-	Saponin	b
98	19.33	Ginsenoside Rg2/isomer^[62]	C₄₂H₇₂O₁₃	829.494 4	829.496 4	2.41	783.492 0,637.430 3,475.377 5,391.284 5	[M+COOH]^-	Saponin	c
99	19.38	4'-O-Asperosaponin Ⅵ^[63]	C₄₉H₇₈O₁₉	1 015.510 8	1 015.514 3	3.45	645.399 8,323.097 2	[M+COOH]^-	Saponin	b
100	19.43	Ginsenoside Rh1/isomer^[64]	C₃₆H₆₂O₉	683.436 5	683.436 8	0.44	637.431 0,475.377 3,391.284 5	[M+COOH]^-	Saponin	c
101	19.53	Ginsenoside Rg2/isomer^[62]	C₄₂H₇₂O₁₃	829.494 4	829.498 4	4.83	783.489 1,637.430 1,475.377 0,391.284 2	[M+COOH]^-	Saponin	c
102	19.61	Bavacoumestan A/ bavacoumestan B/ isomer^[40]	C₂₀H₁₆O₆	353.101 3	353.102 0	1.98	335.090 6,307.095 7,281.044 0,253.049 1, 225.054 3,209.059 4,197.059 4,181.064 7	[M+H]⁺	Flavonoid	a
103	19.64	2'-O-Asperosaponin Ⅵ^[63]	C₄₉H₇₈O₁₉	1 015.510 8	1 015.514 6	3.74	645.399 8,323.097 2	[M+COOH]^-	Saponin	b
104	19.69	Ginsenoside F1/isomer^[65]	C₃₆H₆₂O₉	683.436 5	683.439 2	3.95	637.430 5,475.378 1,161.044 1,113.022 7, 101.022 8	[M+COOH]^-	Saponin	c
105	19.82	Bavacoumestan A/ bavacoumestan B/ isomer^[40]	C₂₀H₁₆O₆	353.101 3	353.102 1	2.27	335.091 2,307.097 0,281.044 6,253.049 2, 225.054 3,209.006 0 2,197.059 4,181.064 7	[M+H]⁺	Flavonoid	a
106	19.95	3'-O-Asperosaponin Ⅵ^[63]	C₄₉H₇₈O₁₉	1 015.510 8	1 015.510 1	-0.69	645.399 9,323.097 3	[M+COOH]^-	Saponin	b
107	20.08	Isoaromadendrene epoxide^[66]	C₁₅H₂₄O	221.190 0	221.189 7	-1.36	203.179 4,147.116 8,119.085 7,105.070 2	[M+H]⁺	Terpene	a
108	20.08	Calamenene^[53]	C₁₅H₂₂	203.179 4	203.179 2	-0.99	147.116 7,133.101 2,119.085 7,105.070 2	[M+H]⁺	Others	a
109	20.22	Dipsacussaponin A^[36]	C₄₂H₆₈O₁₄	841.458 3	841.462 3	4.76	795.456 2,471.346 1,323.096 5,221.066 1, 119.033 5	[M+COOH]^-	Saponin	b
110	20.29	Corylifol C^[67]	C₂₀H₁₈O₅	339.122 7	339.122 1	-1.77	283.059 8,255.065 0,237.054 4,227.070 0, 297.075 3	[M+H]⁺	Flavonoid	a
111	20.43	HN-saponin F^[68]	C₄₁H₆₆O₁₃	811.447 5	811.450 0	3.08	765.442 6,603.389 1,207.049 6,101.022 7	[M+COOH]^-	Saponin	b
112	20.58	Gypenoside XⅦ^[69]	C₄₈H₈₂O₁₈	991.547 2	991.545 7	-1.51	945.544 7,783.489 5,621.435 8	[M+COOH]^-	Saponin	c
113	20.6	Ginsenoside Rd^[41]	C₄₈H₈₂O₁₈	945.541 7	945.546 1	4.66	783.489 0,621.436 3,459.383 0	[M-H]^-	Saponin	c
114	21.2	Ginsenoside Rh3^[70]	C₃₆H₆₀O₇	605.441 2	605.439 5	-2.81	441.372 3,425.376 4,407.366 3,331.264 6	[M+H]⁺	Saponin	c
115	21.21	Notoginsenoside K^[71]	C₄₈H₈₂O₁₈	991.547 2	991.544 6	-2.62	945.544 1,783.487 9,621.436 3,537.342 5, 459.380 8,323.097 3	[M+COOH]^-	Saponin	c
116	21.32	Bavachin^[55]	C₂₀H₂₀O₄	323.127 8	323.128 9	3.41	221.080 9,203.070 1,175.075 1,159.080 1, 119.048 5	[M-H]^-	Flavonoid	a
117	21.72	Neocorylin^[55]	C₂₅H₂₄O₄	389.174 7	389.173 9	-2.06	321.111 5,305.080 8,267.064 9,137.023 3	[M+H]⁺	Flavonoid	a
118	21.72	Neocorylin A/neocorylin B/isomer^[72]	C₂₅H₂₆O₅	407.185 3	407.184 4	-2.21	389.173 8,321.111 2,267.060 5,137.022 3	[M+H]⁺	Flavonoid	a
119	21.78	Bavachromanol^[72]	C₂₀H₂₀O₅	341.138 4	341.137 9	-1.47	323.127 6,221.080 9,203.070 2,149.023 4	[M+H]⁺	Flavonoid	a
120	22.14	Neobavaisoflavone^[40]	C₂₀H₁₈O₄	323.128 0	323.127 6	-1.24	267.065 0,255.065 0,239.07 0,211.059 0,199.075 0,137.023 0	[M+H]⁺	Flavonoid	a
121	22.68	Ginsenoside F4/ isomer^[73]	C₄₂H₇₀O₁₂	811.483 8	811.486 6	3.45	765.478 5,619.420 1,457.369 3	[M+COOH]^-	Saponin	c
122	22.79	4-Dodecylbenzenesulfonic acid^[74]	C₁₈H₃₀SO₃	325.183 3	325.184 4	3.38	183.010 6	[M-H]^-	Others	a/e
123	22.94	Ginsenoside F4/ isomer^[73]	C₄₂H₇₀O₁₂	811.483 8	811.486 5	3.33	765.478 6,619.420 5,457.366 3	[M+COOH]^-	Saponin	c
124	23.05	Ginsenoside Rh4/ isomer^[75]	C₃₆H₆₀O₈	665.425 9	665.426 7	1.2	619.421 5,161.044 0,113.022 7,101.022 7	[M+COOH]^-	Saponin	c
125	23.36	Ginsenoside Rh4/ isomer^[75]	C₃₆H₆₀O₈	665.425 9	665.426 7	1.2	619.420 1,161.044 1,113.023 1,101.022 8	[M+COOH]^-	Saponin	c
126	23.87	Bavachromene^[76]	C₂₀H₁₈O₄	323.127 8	323.127 1	-2.17	305.116 7,281.115 4,253.112 3,221.080 6,203.070 1,175.075 3,147.044 0	[M+H]⁺	Flavonoid	a
127	24.01	Psoralidin^[38]	C₂₀H₁₆O₅	337.107 1	337.106 1	-2.97	309.111 4,281.044 1,253.049 2,237.054 3,225.054 3,209.059 5,197.059 6,181.064 7	[M+H]⁺	Coumarin	a
128	24.2	Ginsenoside Rg3/ isomer^[73]	C₄₂H₇₂O₁₃	829.494 4	829.496 2	2.17	783.489 0,621.436 7,459.382 8,375.288 9,161.044 1	[M+COOH]^-	Saponin	c
129	24.35	Ginsenoside Rg3/ isomer^[73]	C₄₂H₇₂O₁₃	829.494 4	829.496 4	2.41	783.489 3,621.436 2,459.383 2,375.289 5,161.044 1	[M+COOH]^-	Saponin	c
130	24.46	Octadecanedioic acid^[24]	C₁₈H₃₄O₄	313.237 5	313.239 0	4.79	295.226 9,201.111 9,171.101 1	[M-H]^-	Organic acid	a/e
131	25.56	Isobavachalcone^[77]	C₂₀H₂₀O₄	323.127 8	323.128 9	3.41	221.080 9,203.070 1,175.075 4,159.080 0,119.048 5	[M-H]^-	Flavonoid	a
132	26.07	Bavachinin/isomer^[76]	C₂₁H₂₂O₄	339.159 1	339.158 3	-2.36	283.095 9,271.095 9,219.101 4,177.054 6,147.043 9	[M+H]⁺	Flavonoid	a
133	26.75	Corylifol A^[38]	C₂₅H₂₆O₄	391.190 4	391.189 3	-2.81	335.127 0,267.064 8,239.069 8,137.023 2	[M+H]⁺	Flavonoid	a
134	27.03	Dodecyl sulfate^[36]	C₁₂H₂₆O₄S	265.146 8	265.148 1	4.91	96.958 3,95.950 6,79.955 7	[M-H]^-	Others	b
135	27.74	Bavachinin/isomer^[76]	C₂₁H₂₂O₄	339.159 1	339.158 3	-2.36	283.095 8,271.095 9,269.080 5,219.101 3,147.043 9	[M+H]⁺	Flavonoid	a
136	28.16	Neocorylin^[38]	C₂₅H₂₄O₄	389.174 7	389.173 8	-2.31	321.111 4,305.080 1,267.064 7,183.080 4,137.023 0	[M+H]⁺	Flavonoid	a
137	28.79	Bakuchiol^[72]	C₁₈H₂₄O	257.190 0	257.189 5	-1.95	201.127 0,187.111 6,173.096 1,147.080 3,133.064 8,121.064 9,107.049 5	[M+H]⁺	Terpene	a

基于UPLC-QE-Orbitrap-MS/MS的骨康胶囊化学成分分析

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许瑛婕 ¹^,² , 黄鸿运 ¹^,² , 汪洋 ³ , 刘春花 ¹ , 郑林 ³ , 孙佳 ³^,^* , 李勇军 ¹^,²^,³^,^*

中国药学杂志 | 论著 2025,60(3): 290-301

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中国药学杂志 | 论著 2025, 60(3): 290-301

基于UPLC-QE-Orbitrap-MS/MS的骨康胶囊化学成分分析

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许瑛婕¹^,², 黄鸿运¹^,², 汪洋³, 刘春花¹, 郑林³, 孙佳³^,^*, 李勇军¹^,²^,³^,^*

作者信息

¹ 贵州医科大学民族药与中药开发应用教育部工程研究中心, 省部共建药用植物功效与利用国家重点实验室, 贵阳 550004

² 贵州医科大学药学院, 贵阳 550004

³ 贵州医科大学, 贵州省药物制剂重点实验室, 国家苗药工程技术研究中心, 贵阳 550004

许瑛婕,女,硕士研究生研究方向:中药民族药药效物质与质量控制技术研究

通讯作者:

*孙佳,女,博士,教授研究方向:中药代谢与药动学研究 Tel:(0851)86908468;

李勇军,男,博士,教授研究方向:中药制剂工艺、质量标准、药效物质基础 Tel: (0851)86908468

Analysis of Chemical Constituents of Gukang Capsules by UPLC-QE-Orbitrap-MS/MS

Yingjie XU¹^,², Hongyun HUANG¹^,², Yang WANG³, Chunhua LIU¹, Lin ZHENG³, Jia SUN³^,^*, Yongjun LI¹^,²^,³^,^*

Affiliations

¹ State Key Laboratory of Functions and Applications of Medicinal Plants, Guizhou Medical University Engineering Research Center for the Development and Application of Ethnic Medicine and TCM(Ministry of Education), Guiyang 550004, China

² College of Pharmacy, Guizhou Medical University,Guiyang 550004,China

³ Guizhou Provincial Key Laboratory of Pharmaceutics, National Engineering Research Center of Miao's Medicines, Guizhou Medical University, Guiyang 550004, China

出版时间: 2025-02-08 doi: 10.11669/cpj.2025.03.012

文章导航

摘要

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目的采用超高效液相色谱-四极杆静电场轨道阱高分辨质谱(UPLC-QE-Orbitrap-MS/MS)技术分析骨康胶囊的化学成分。方法该药物用体积分数70%甲醇提取液采用Hypersil GOLD C₁₈(2.1 mm×100 mm, 1.9 μm)色谱柱,以0.1%甲酸水溶液-乙腈为流动相梯度洗脱,流速为0.3 mL·min^-1,柱温45 ℃,进样量1 μL。采用电喷雾离子源(ESI),在正、负离子同时扫描模式下采集骨康胶囊的质谱数据,利用软件结合对照品比对、数据库匹配、文献报道及质谱规律对骨康胶囊化学成分进行分析鉴定。结果从骨康胶囊中共鉴定出137个化合物,主要包括黄酮类、皂苷类、有机酸类、香豆素类等,其中27个化合物通过对照品比对鉴定,均明确药材来源归属。结论该方法快速、高效地分析出骨康胶囊的主要化学成分,为其药效物质基础及质量控制的后续研究奠定基础。

关键词

骨康胶囊 / 超高效液相色谱-四极杆静电场轨道阱高分辨质谱 / 黄酮类 / 皂苷类

Abstract

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OBJECTIVE To study the chemical composition of Gukang Capsules by ultra-high performance liquid chromatography-quadrupole/electrostatic field orbitwell high resolution mass spectrometry(UPLC-QE-Orbitrap-MS/MS).METHODS The analysis of 70%methanol extract of the drug was performed on a 45 ℃ thermostatic Hypersil GOLD C₁₈column(2.1 mm×100 mm,1.9 μm)with mobile phase consisting of 0.1%formic acid solution-acetonitrile gradiently eluted at 0.3 mL·min^-1,and the injection volume was 1 μL.The information of the chemical constituents of Gukang Capsules was acquired in positive and negative ion modes by electrospray ion source,and the chemical composition was analyzed and identified by software combined with control comparison,database matching,literature reports and mass spectrometry rules. RESULTS A total of 137 compounds were identified from Gukang Capsules,mainly including flavonoids,saponins,organic acids and coumarins,etc.,among which 27 compounds were identified by comparison with reference substances and their origins of medicinal materials were determined.CONCLUSION In this study,the main chemical composition of Gukang Capsules was identified by this rapid and efficient analytic method,which laid a foundation for further research on pharmacodynamic substance base and quality control.

Key words

Gukang Capsule / UPLC-QE-Orbitrap-MS/MS / flavonoid / saponin

引用本文

许瑛婕, 黄鸿运, 汪洋, 刘春花, 郑林, 孙佳, 李勇军. 基于UPLC-QE-Orbitrap-MS/MS的骨康胶囊化学成分分析. 中国药学杂志, 2025 , 60 (3) : 290 -301 . DOI: 10.11669/cpj.2025.03.012

Yingjie XU, Hongyun HUANG, Yang WANG, Chunhua LIU, Lin ZHENG, Jia SUN, Yongjun LI. Analysis of Chemical Constituents of Gukang Capsules by UPLC-QE-Orbitrap-MS/MS[J]. Chinese Pharmaceutical Journal, 2025 , 60 (3) : 290 -301 . DOI: 10.11669/cpj.2025.03.012

正文

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骨康胶囊是由补骨脂、续断、三七、酢浆草和芭蕉根五味药材制成的复方制剂,来源于贵州苗药民间验方,具有消肿止痛、舒筋通络等功效^[1],在临床上广泛用于治疗由肝肾不足、淤滞阻络引起的骨折、骨性关节炎及骨质疏松症等^[2]。方中补骨脂药材味苦,性温,具有补肾壮阳、温脾止泻等功效^[3];续断味苦、辛,性微温,具有补肝肾、强筋骨、通血脉等功效^[4-5];三七性温,味甘、微苦,具有散瘀止血、消肿定痛的功效^[6];酢浆草味酸性寒,具有清热利湿、凉血消肿、解毒散瘀等功效^[7];芭蕉根味甘,性寒,具清热解毒、止渴、利尿等功效^[8]。目前骨康胶囊在其药效物质基础研究较少,在药理活性及与其他药物的联合使用更多^[9-13],质量控制方面仅以补骨脂素和异补骨脂素作为质控标准,但作为复方制剂不应只以一味药材中某成分作为质控标准,因此本研究运用超高效液相色谱-四极杆静电场轨道阱高分辨质谱(UPLC-QE-Orbitrap-MS/MS)技术对骨康胶囊的化学成分进行鉴别分析,为其药效物质基础及后续质量控制的进一步研究奠定基础。

1 仪器与试药

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1.1 仪器

UltiMate 3000型超高效液相色谱仪、Q-Exactive-Plus四极杆静电场轨道阱质谱、Multifuge X3R高速冷冻离心机(美国Thermo Fisher Scientific公司);Mettler EL204电子分析天平[梅特勒-托利多国际贸易(上海)仪器有限公司];KQ5200E超声波清洗器(昆山市超声仪器有限公司)。

1.2 试药

骨康胶囊(规格:每粒装0.4 g,批号:20210407)、补骨脂(批号:YCOO1-004-20210201)、续断(批号:YCO1-002-20201001)、三七(批号:YCO1-001-20201002)、酢浆草(批号:YCO1-005-20200401)、芭蕉根(批号:YCO1-003-20210101)(贵州维康子帆药业股份有限公司),经贵州医科大学药学院生药学教研室刘春花副教授鉴定为正品;对照品:补骨脂苷(批号:AF21031504)、异补骨脂苷(批号:AF21031505)、异补骨脂素(批号:AF21071801)、补骨脂素(批号:AF21042858)、人参皂苷Re(批号:AF20042104)(成都埃法生物科技有限公司);川续断皂苷Ⅵ(批号:wkq21010703)、马钱苷(批号:wkq21071907)、三七皂苷R1(批号:wkq21 030407)、人参皂苷Rg1(批号:wkq21020401)、人参皂苷Rb1(批号:wkq21010701)、人参皂苷Rd(批号:wkq21042607)、新绿原酸(批号:wkq21010802)、隐绿原酸(批号:wkq20082705)、异绿原酸 A(批号:wkq21020306)、异绿原酸 B(批号:wkq21022206)、异绿原酸 C(批号:wkq21012501)、咖啡酸(批号:wkq21011104)、对羟基苯甲酸(批号:wkq21022204)、腺苷(批号:wkq21030303)、腺嘌呤(批号:wkq21060210)、绿原酸(批号:wkq20042702)(四川省维克奇生物科技有限公司);槲皮苷(批号:181216)、原儿茶醛(批号:200510)、原儿茶酸(批号:191218)、没食子酸(批号:181016)(成都植标化纯生物技术有限公司);牡荆素(批号:M-023-180307)对照品(成都瑞芬思生物科技有限公司);当药黄素对照品为实验室自制,以上所有对照品纯度均≥98%;甲醇、乙腈、甲酸均为质谱级。

2 方法

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2.1 色谱条件

色谱柱为Hypersil GOLD C₁₈(2.1 mm×100 mm,1.9 μm);以体积分数0.1%甲酸水溶液(A)~乙腈(B)为流动相;梯度洗脱(0~1 min,5%B;1~15 min,5%~30%B;15~25 min,30%~60%B;25~28 min,60%~95%B);流速为0.3 mL·min^-1;进样量1 μL;柱温45 ℃。

2.2 质谱条件

电喷雾离子源(ESI)、正负离子检测模式;扫描范围m/z 100~1 500,扫描模式:Full MS/ddMS²;Full MS分辨率:70 000,ddMS²分辨率:17 500,涂喷电压:3.5 kV(正离子模式)和2.5 kV(负离子模式),鞘气压:206.85 kPa,辅助气压:68.95 kPa,毛细管温度:320 ℃,探头加热器温度:350 ℃,碰撞能梯度(NCE):20、40、60 eV。

2.3 对照品溶液的制备

精密称取各对照品适量,加甲醇分别制成每1 mL含1 mg的储备液。精密量取各对照品储备液适量混合,加入甲醇制成含各对照品约10 μg·mL^-1的混合对照品溶液,即得,置4 ℃保存备用。

2.4 供试品溶液的制备

精密称定骨康胶囊内容物2.0 g,置于具塞锥形瓶中,加入体积分数70%甲醇25 mL,称重,超声处理(200 W,40 kHz)30 min,静置,再超声,冷却后再称重,用体积分数70%甲醇补足减失的质量,摇匀,滤过,取续滤液离心(12 000 r·min^-1)10 min,取上清液即得。

2.5 单味药材溶液的制备

分别取补骨脂、三七、续断、酢浆草和芭蕉根药材适量,按骨康胶囊制备工艺制备上述各单味药材单煎液的干浸膏,按照“2.4”项下方法制备各单味药材干浸膏体积分数70%甲醇提取液。

2.6 数据分析

利用Xcalibur 4.1软件进行峰提取,峰匹配,数据文件导入Compound Discoverer 3.2软件,扣除体积分数70%甲醇空白溶剂后,结合在线数据库、本地数据库,初步筛选出与文献比对匹配度高的化合物,根据质谱信息计算相对分子质量,推测其分子式,再结合对照品、相关文献及mzClound、mzVault、Chemical Book等数据库进行化学成分分析,并通过比对制剂与各单味药材中基峰离子流图,将化合物的来源进行药材归属。

3 结果与分析

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骨康胶囊体积分数70%甲醇提取液在正负离子模式下的基峰离子流图见图1,单味药材及混合对照品基峰离子流图见图2。共分析鉴定化合物137个,其中通过对照品比对鉴定确认了27个化合物,且均找到药材来源归属,具体结果见表1。

3.1 黄酮类

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该类成分共鉴定出42种,主要来源于补骨脂、酢浆草,黄酮类化合物在电喷雾离子电源条件下,易脱去H₂O、CO和CH₂O等中性碎片,母核C环也易发生逆狄尔斯-阿德尔反应(RDA)裂解^[78]。峰39在负离子模式下,准分子离子峰m/z 415.104 4[M-H]^-,推测分子式为C₂₁H₂₀O₉,在二级质谱中m/z 415.104 4[M-H]^-失去C₄H₈O₄基团得到m/z 295.060 1[M-H-C₄H₈O₄]^-碎片,分别失去1分子H₂O、CO得到m/z 277.049 0[M-H-C₄H₈O₄-H₂O]^-、267.065 3[M-H-C₄H₈O₄-CO]^-碎片,结合质谱裂解规律与文献参考^[35],推断峰39为葛根素,可能的裂解途径见图3。

3.2 皂苷类

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皂苷类成分共鉴定出32个,主要来源于续断、峰71为例,保留时间t_R=13.90 min,加和离子m/z 977.530 6[M+COOH]^-,加和离子进一步裂解得到m/z 931.528 4[M-H]^-,初步推测分子式为C₄₇H₈₀O₁₈,在二级质谱中m/z 931.528 4[M-H]^-脱去木糖产生m/z 799.484 1[M-H-C₅H₈O₄]^-碎片,再连续脱去葡萄糖产生m/z 637.431 0[M-H-C₅H₈O₄-C₆H₁₀O₅]^-、475.377 8[M-H-C₅H₈O₄-2C₆H₁₀O₅]^-碎片,再脱去C₆H₁₂得到m/z 391.284 7[M-H-C₅H₈O₄-2C₆H₁₀O₅-C₆H₁₂]^-,结合质谱裂解规律、文献参考与对照品比对^[41],推断峰71为三七皂苷R1,其可能的裂解途径见图4。

3.3 有机酸类

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从骨康胶囊中鉴定的有机酸类化合物共鉴定出26种,主要来源于补骨脂、续断、酢浆草和芭蕉根。有机酸类化合物在负离子模式下有较高的响应,主要以[M-H]^-准分子离子峰形式存在,易发生H₂O、COOH、CO₂等中性分子丢失,从而产生相应的特征碎片离子峰^[80]。以峰7为例,保留时间为t_R=0.96 min,准分子离子m/z 133.013 2[M-H]^-,初步推测分子式为C₄H₆O₅,母离子m/z 133.013 2[M-H]^-连续失去1分子H₂O、1分子CO₂得到m/z 115.001 9[M-H-H₂O]^-、m/z 71.012 1[M-H-H₂O-CO₂]^-等碎片离子,结合质谱裂解规律与文献参考^[19],推断峰7为苹果酸,可能的裂解途径见图5。

3.4 香豆素类

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香豆素类化合物共鉴定9种,主要来源于补骨脂药材,香豆素的基本骨架为苯骈α-吡喃酮,很难被裂解,因此该类化合物主要通过丢失-CH₃、-H₂O、-CO、-CO₂等中性小分子基团产生碎片^[79]。以峰81为例,保留时间t_R=15.86 min,准分子离子为m/z 187.038 3[M+H]⁺,推测分子式为C₁₁H₆O₃,准分子离子连续失去CO形成m/z 159.044 0[M+H-CO]⁺、m/z 131.049 1[M+H-2CO]⁺、m/z 103.054 5[M+H-3CO]⁺碎片离子;失去CO₂、CO形成m/z 143.049 1[M+H-CO₂]⁺、m/z 115.054 5[M+H-CO₂-CO]⁺碎片离子。结合质谱裂解规律、参考文献^[40]与对照品比对,推断峰81为补骨脂素,可能的裂解途径为图6。

4 讨论

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本研究采用UPLC-QE-Orbitrap-MS/MS技术共分析鉴定化合物137个,其中黄酮类42个、皂苷类32个、有机酸类26个、香豆素类9个、生物碱类5个、环烯醚萜类5个、氨基酸类4个、醛类2个、核苷类2个、萜类2个、木脂素类1个和其他类7个。由于复方制剂成分复杂,各类成分在不同模式下的响应度高低不同,且各个成分结构与稳定性不同,本研究采用正负离子两种模式以及考察3种(20、40、60 eV)不同碰撞能量,更加全面地检测分析以便得到各个成分较为丰富碎片离子。在对照品选择过程中,特别选择了《中国药典》2020年版收载的补骨脂、续断、三七的指标性成分,例如:补骨脂指标性成分补骨脂素和异补骨脂素,续断指标性成分川续断皂苷Ⅵ,三七指标性成分人参皂苷 Rg1、人参皂苷Rb1及三七皂苷R1,共选择27个对照品,均在骨康胶囊中进行了确证。

据报道补骨脂药材中黄酮类、香豆素类化合物主要有促进骨生长分化、抗炎抗菌等药理活性^[81];三七中的皂苷类成分是发挥活血作用的药效物质基础,能增加成骨细胞活性等作用^[82-83];续断中的川续断总皂苷可促进骨细胞的增殖和分化等^[84],因此,骨康胶囊以补骨脂、续断、三七三味药构成主药,发挥补肾、强筋、通络的主要功效,结合芭蕉根、酢浆草增强解毒、止痛、散瘀的功效^[2],共同发挥骨康胶囊强筋壮骨、通络止痛和滋补肝肾的功效。

综上所述,通过UPLC-QE-Orbitrap-MS/MS法对骨康胶囊化学成分快速高效的分析鉴定,可为该制剂进一步药效物质基础、作用机制和质量控制研究提供实验依据。

基金

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贵州省科技计划项目资助(黔科合中引地〔2023〕006)
贵州省高层次创新型人才培养计划项目资助(〔2016〕5677)
贵阳市科技计划项目资助(筑科合同〔2024〕2-35)

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2025年第60卷第3期

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doi: 10.11669/cpj.2025.03.012

接收时间：2024-08-13
首发时间：2025-10-29
出版时间：2025-02-08

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收稿日期：2024-08-13

基金

贵州省科技计划项目资助(黔科合中引地〔2023〕006)

贵州省高层次创新型人才培养计划项目资助(〔2016〕5677)

贵阳市科技计划项目资助(筑科合同〔2024〕2-35)

作者信息

¹ 贵州医科大学民族药与中药开发应用教育部工程研究中心, 省部共建药用植物功效与利用国家重点实验室, 贵阳 550004

² 贵州医科大学药学院, 贵阳 550004

³ 贵州医科大学, 贵州省药物制剂重点实验室, 国家苗药工程技术研究中心, 贵阳 550004

通讯作者:

*孙佳,女,博士,教授研究方向:中药代谢与药动学研究 Tel:(0851)86908468;

李勇军,男,博士,教授研究方向:中药制剂工艺、质量标准、药效物质基础 Tel: (0851)86908468

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2种不同金属材料的力学参数

科 Family	属数 Number of genus	种数 Number of species	占总种数比例 Percentage of total species (%)	属 Genus	种数 Number of species	占总种数比例 Percentage of total species (%)
鹅膏菌科Amanitaceae	2	11	5.26	鹅膏菌属 Amanita	10	4.78
小菇科 Mycenaceae	2	12	5.74	丝盖伞属 Inocybe	5	2.39
多孔菌科 Polyporaceae	8	14	6.70	蜡蘑属 Laccaria	5	2.39
红菇科 Russulaceae	3	23	11.00	小皮伞属 Marasmius	6	2.87
				小菇属 Mycena	11	5.26
				光柄菇属 Pluteus	5	2.39
				红菇属 Russula	17	8.13
				栓菌属 Trametes	5	2.39

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No.	t_R/ min	Compound	Formula	m/z (Theoretical)	m/z (Measured)	Mass error	m/z(MS²)	Ion mode	Classification	Ascription
1	0.87	Mannitol^[14]	C₆H₁₄O₆	181.070 7	181.071 1	2.21	163.060 4,119.033 3,149.044 8,113.022 9,101.022 7,89.022 6,79.012 2,59.012 3	[M-H]^-	Others	a/b/d/e
2	0.89	Betaine^[15]	C₅H₁₁NO₂	118.086 3	118.086 3	0	59.073 7,58.065 9	[M+H]⁺	Alkaloid	a/b/c/d/e
3	0.89	L-Carnitine^[16]	C₇H₁₅NO₃	162.112 5	162.112 2	-1.85	103.039 3,85.029 0	[M+H]⁺	Alkaloid	b/d
4	0.89	Trigonelline^[15]	C₇H₇NO₂	138.055 0	138.054 7	2.17	110.060 2,94.065 5,92.049 9,78.034 3	[M+H]⁺	Alkaloid	a/e
5	0.92	Sucrose^[17]	C₁₂H₂₂O₁₁	341.107 8	341.109 1	3.81	179.054 6,161.040 1,143.033 4,119.033 3,101.022 8,89.022 6,71.012 1	[M-H]^-	Others	a/b/c
6	0.94	Adenine^1)[18]	C₅H₅N₅	136.061 8	136.061 7	-0.74	119.035 4,94.040 4	[M+H]⁺	Nucleoside	a/b/d/e
7	0.96	Malic acid^[19]	C₄H₆O₅	133.013 1	133.013 2	0.75	115.001 9,89.022 7,71.012 1,59.012 3	[M-H]^-	Organic acid	a/c/e
8	1.23	Pyroglutamic acid^[20]	C₅H₇NO₃	130.049 8	130.049 9	0.77	84.044 0,56.050 3	[M+H]⁺	Amino acid	a/c/d/
9	1.23	Adenosine^1)[19]	C₁₀H₁₃N₄O₅	268.104 0	268.103 9	-0.37	250.107 0,136.061 7,119.035 5	[M+H]⁺	Nucleoside	a/c/e
10	1.51	Gallic acid^1)[21]	C₇H₆O₅	169.013 1	169.013 7	3.55	125.022 6,107.012 0,81.032 9,79.017 3	[M-H]^-	Organic acid	b
11	1.62	Protocatechuic aldehyde^1)[17]	C₇H₆O₃	137.023 3	137.023 7	2.92	109.027 9,93.032 8	[M-H]^-	Aldehyde	a/e
12	1.93	Pyrogallol^[22]	C₆H₆O₃	125.023 3	125.023 3	0	81.032 9	[M-H]^-	Organic acid	d
13	2.06	L-phenylalanine^[23]	C₉H₁₁NO₂	166.086 3	166.086 3	0	149.070 8,131.049 1,120.080 9,103.054 6	[M+H]⁺	Amino acid	a/b/c/d/e
14	2.19	p-Hydroxybenzaldehyde glucoside^[24]	C₁₃H₁₆O₉	315.071 1	315.071 8	2.22	153.017 9,152.009 9,109.028 1,108.019 9	[M-H]^-	Organic acid	b/d/e
15	2.22	N-(9-β-D-ribofuranosyl-9H-purin-6-yl)- D-aspartic acid^[24]	C₁₄H₁₇N₅O₈	384.115 0	384.114 7	-0.78	252.072 5,234.061 8	[M+H]⁺	Amino acid	a
16	2.25	Vanillic acid glucoside^[25]	C₁₄H₁₈O₉	329.086 7	329.085 9	-2.43	167.033 4,152.010 0,123.043 4,108.020 0	[M-H]^-	Organic acid	a/b/d/e
17	2.25	Vanillic acid^[24]	C₈H₈O₄	167.033 9	167.034 3	2.4	152.009 9,123.043 4,120.897 1,108.020 0	[M-H]^-	Organic acid	a/d/e
18	2.46	Methylsuccinic acid^[26]	C₅H₈O₄	131.033 9	131.034 0	0.76	113.022 9,87.043 4,72.99 1	[M-H]^-	Organic acid	a/d/e
19	2.76	Histidylproline^[24]	C₁₁H₁₆N₄O₃	253.129 5	253.129 5	0	236.103 2,225.134 6,208.108 4,191.081 4, 181.144 8,166.086 2,165.102 2,122.096 6, 112.087 2,70.065 9	[M+H]⁺	Amino acid	a/d
20	2.78	Protocatechuic acid^1)[27]	C₇H₆O₄	153.018 2	153.018 4	1.31	109.027 8,108.020 0	[M-H]^-	Organic acid	a/b/d/e
21	3.25	Glucosyringic acid^[28]	C₁₅H₂₀O₁₀	359.097 3	359.099 1	5.01	197.044 2,182.020 5,166.997 1,153.054 2, 138.030 6,123.007 0	[M-H]^-	Organic acid	a/b/d
22	3.41	Neochlorogenic acid^1)[29]	C₁₆H₁₈O₉	353.086 7	353.087 8	3.12	191.054 5,179.033 4,173.044 0,161.022 9, 135.043 4	[M-H]^-	Organic acid	b
23	3.67	Caffeic acid 4-O-glucoside^[24]	C₁₅H₁₈O₉	341.086 7	341.088 2	4.4	179.033 4,135.043 5	[M-H]^-	Organic acid	b
24	4.68	4-Hydroxybenzoic acid^1)[30]	C₇H₆O₃	137.023 3	137.023 4	0.73	109.027 9,93.032 8	[M-H]^-	Organic acid	e
25	4.68	Swertiamarin^[31]	C₁₆H₂₂O₁₀	373.112 9	373.114 7	4.83	211.060 0,179.054 4,167.069 9,193.049 5, 149.059 3,123.043 4,101.022 8,179.054 0, 119.033 2,89.022 6,71.012 2,59.012 3	[M-H]^-	Terpene	b
26	5.05	Loganic acid^[31]	C₁₆H₂₄O₁₀	375.128 6	375.129 2	1.6	213.075 7,169.085 5,151.074 9,143.033 6, 113.022 7,89.022 6,69.032 9	[M-H]^-	Terpene	b
27	5.36	Dihydrophaseic acid-O-glucoside^[24]	C₂₁H₃₂O₁₀	443.191 2	443.192 6	3.16	161.043 9,119.033 3,113.022 7,101.022 7, 89.022 6,71.012 2,59.012 3	[M-H]^-	Organic acid	e
28	5.58	Chlorogenic acid^1)[29]	C₁₆H₁₈O₉	353.086 7	353.087 7	2.83	191.054 5,179.033 5,173.044 0,161.023 0, 135.043 5	[M-H]^-	Organic acid	b
29	5.81	6,7-Dihydroxycoum- arin^[32]	C₉H₆O₄	179.033 9	179.033 9	0	151.038 9,133.028 4,123.044 2	[M+H]⁺	Coumarin	a
30	5.94	Cryptochlorogenic acid^1)[29]	C₁₆H₁₈O₉	353.086 7	353.087 7	2.83	191.054 6,179.033 4,173.043 9,161.022 9, 135.043 4	[M-H]^-	Organic acid	b
31	5.94	Caffeic acid^1)[24]	C₉H₈O₄	179.033 9	179.034 1	1.12	135.043 4,117.032 8,107.048 6,89.037 9	[M-H]^-	Organic acid	a/b/d/e
32	5.94	Shikimic acid^[16]	C₇H₁₀O₅	173.044 5	173.044 7	1.16	155.033 7,137.022 7,128.876 2,111.043 4, 93.032	[M-H]^-	Organic acid	b
33	6.02	Lycoperodine-1^[24]	C₁₂H₁₂N₂O₂	217.097 2	217.097 2	0	144.080 7	[M+H]⁺	Others	a/b/d
34	6.11	Cyclohexanecarboxylic acid^[29]	C₁₆H₁₈O₉	353.086 7	353.088 3	4.53	191.054 6,179.033 4,173.044 0,135.043 4	[M-H]^-	Organic acid	b
35	6.23	Cantleyine^[33]	C₁₁H₁₃NO₃	208.096 7	208.097 6	4.33	190.086 1,176.070 5,158.059 9	[M+H]⁺	Alkaloid	b
36	7.03	5,7-Dihydroxy-4-methylcoumarin^[34]	C₁₀H₈O₄	193.049 5	193.049 4	-0.52	178.025 7,165.054 6,149.096 4,137.059 6	[M+H]⁺	Coumarin	a
37	7.13	Erythricine^[33]	C₁₀H₉NO₂	176.070 6	176.070 3	-1.7	146.059 9,118.065 3,117.057 5	[M+H]⁺	Alkaloid	b
38	7.32	5-Coumariquinic acid^[21]	C₁₆H₁₈O₈	337.091 8	337.093 4	4.75	191.054 5,163.038 5	[M-H]^-	Organic acid	b
39	7.44	Puerarin^[35]	C₂₁H₂₀O₉	415.102 4	415.104 4	4.82	295.060 1,277.049 0,267.065 3	[M-H]^-	Flavonoid	a
40	7.63	Loganin^1)[36]	C₁₇H₂₆O₁₀	435.149 7	435.150 7	2.3	227.091 3,127.038 3,101.022 7	[M+COOH]^-	Terpene	b
41	7.68	Sweroside^[37]	C₁₆H₂₂O₉	403.123 5	403.124 3	1.99	357.118 0,195.064 7,179.054 7,161.044 0, 131.033 4,125.022 6	[M+COOH]^-	Terpene	b
42	7.88	Vanillin^[17]	C₈H₈O₃	153.054 6	153.054 6	0	153.054 5,125.059 8,111.044 3,65.039 4	[M+H]⁺	Aldehyde	a/d/e
43	8.06	2,4-Dihydroxy-6-methoxy-3-methyl acetophenone 4-O-β-D-xylopyranosyl-(1→6)-β-D-glucopyranoside^[36]	C₂₁H₃₀O₁₃	535.165 8	535.168 2	4.49	489.159 9,191.054 3,151.074 9,149.043 9, 125.022 6,81.032 9	[M+COOH]^-	Others	b
44	8.26	Psoralenoside^1)[38]	C₁₇H₁₈O₉	365.086 7	365.087 1	1.1	203.033 7,159.043 5	[M-H]^-	Coumarin	a
45	8.57	Schaftoside/ isomers^[39]	C₂₆H₂₈O₁₄	563.139 5	563.140 4	1.6	503.116 7,473.106 9,443.097 1,383.076 2, 353.065 6,325.070 7,297.075 7,311.05 5	[M-H]^-	Flavonoid	a/d
46	8.57	Luteolin-6-C-glucoside/orientin^[17]	C₂₁H₂₀O₁₁	447.092 2	447.093 6	3.13	429.081 1,411.073 8,393.060 4,357.060 7, 327.050 0,299.055 1,285.039 6,284.031 9, 255.054 2	[M-H]^-	Flavonoid	d
47	8.67	Schaftoside/ isomers^[39]	C₂₆H₂₈O₁₄	563.139 5	563.139 0	-0.89	503.117 7,473.107 2,443.096 4,383.076 1, 353.065 5,325.070 3,311.054 1,294.07 6	[M-H]^-	Flavonoid	a/d
48	8.67	Isopsoralenoside^1)[38]	C₁₇H₁₈O₉	365.086 7	365.087 2	1.37	203.033 7,159.043 5	[M-H]^-	Coumarin	a
49	8.69	Bakuchicin^[40]	C₁₁H₆O₃	187.039 0	187.038 3	-3.74	143.049 0,159.044 0,131.049 1,115.054 4	[M+H]⁺	Coumarin	a
50	8.74	Hydroxyferulic acid^[24]	C₁₀H₁₀O₅	209.044 5	209.045 4	4.31	165.054 0,121.027 7,59.856 8	[M-H]^-	Organic acid	a/e
51	8.82	Luteolin-6-C-glucoside/orientin^[17]	C₂₁H₂₀O₁₁	447.092 5	447.094 5	4.47	429.091 8,411.071 5,357.060 5,327.049 9, 299.054 9,285.039 1,284.032 0,255.054 2	[M-H]^-	Flavonoid	d
52	8.99	Schaftoside/ isomers^[39]	C₂₆H₂₈O₁₄	563.139 5	563.139 5	0	503.117 3,473.107 2,443.096 8,383.076 3, 353.065 7,325.070 7,311.055 0,297.075 8	[M-H]^-	Flavonoid	a/d
53	9.53	1-Hydroxypinoresinol 4'-β-D-glucopyranoside^[36]	C₂₆H₃₂O₁₂	535.181 1	535.183 7	4.86	373.128 0,343.117 5,284.103 8,269.081 1, 254.057 6,193.049 1, 163.038 9,149.059 1, 148.015 0	[M-H]^-	lignan	b
54	9.75	Daidzin^[41]	C₂₁H₂₀O₉	417.118 0	417.117 2	-1.92	297.075 0,255.064 8,227.070 0,199.075 2, 119.049 2,137.023 2	[M+H]⁺	Flavonoid	a
55	9.78	Isovitexin^[42]	C₂₁H₂₀O₁₀	431.097 3	431.099 3	4.64	413.086 3,395.076 6,341.065 6,311.055 3, 283.060 4,269.044 7,161.022 9,117.032 9	[M-H]^-	Flavonoid	d
56	9.83	7-Deoxyloganic acid^[36]	C₁₆H₂₄O₉	359.133 7	359.135 3	4.46	197.080 5,153.090 6,135.079 9,59.012 3	[M-H]^-	Terpene	b
57	9.88	Vitexin^1)[43]	C₂₁H₂₀O₁₀	431.097 3	431.099 1	4.18	341.065 6,311.055 3,283.060 3,269.044 5, 161.022 9,117.032 8	[M-H]^-	Flavonoid	d
58	10.15	Isoquercitrin^[44]	C₂₁H₂₀O₁₂	463.087 1	463.089 4	4.97	301.034 0,300.026 6,271.024 1,255.029 0	[M-H]^-	Flavonoid	a
59	10.46	Swertisin^1)[45]	C₂₂H₂₂O₁₀	445.112 9	445.113 7	1.8	325.070 9,297.039 6,282.052 4	[M-H]^-	Flavonoid	d
60	10.6	Genistin^[41]	C₂₁H₂₀O₁₀	433.112 9	433.111 9	-2.31	271.059 6,253.049 2,243.064 7,215.070 0, 169.064 9,153.018 1	[M+H]⁺	Flavonoid	a
61	10.83	Isoswertisin^[46]	C₂₂H₂₂O₁₀	445.113 2	445.115 3	4.72	325.071 0,297.039 8,282.052 3	[M-H]^-	Flavonoid	d
62	11.10	Salicylic acid^[47]	C₇H₆O₃	137.023 3	137.023 5	1.46	108.898 0,93.032 8,65.038 0	[M-H]^-	Organic acid	a/d/e
63	11.15	Isochlorogenic acid B^1)[48]	C₂₅H₂₄O₁₂	515.118 4	515.119 3	1.75	353.086 8,191.054 6,179.033 4,173.044 0, 135.043 5	[M-H]^-	Organic acid	b
64	11.36	Astragaloside^[49]	C₂₁H₂₀O₁₁	447.092 2	447.093 9	3.8	285.039 1,284.031 8,256.034 7,255.029 0, 227.033 9	[M-H]^-	Flavonoid	a
65	11.39	Isochlorogenic acid A^1)[48]	C₂₅H₂₄O₁₂	515.118 4	515.119 0	1.17	353.087 0,191.054 5,179.033 4,173.044 1, 135.043 4	[M-H]^-	Organic acid	b
66	11.39	Kaempferol^[50]	C₁₅H₁₀O₆	287.055 0	287.054 2	-2.79	259.058 7,241.049 3,213.054 2,165.018 1, 153.018 1,137.023 2	[M+H]⁺	Flavonoid	a
67	11.47	Quercitrin^1)[50]	C₂₁H₂₀O₁₁	447.092 2	447.094 2	4.47	301.033 8,300.026 2,255.028 7,151.001 6	[M-H]^-	Flavonoid	d
68	12.35	Isochlorogenic acid C^1)[48]	C₂₅H₂₄O₁₂	515.118 4	515.119 0	1.17	353.086 9,191.054 6,179.033 4,173.044 0, 135.043 5	[M-H]^-	Organic acid	b
69	13.63	Notoginsenoside M^[51]	C₄₈H₈₂O₁₉	1 007.542 1	1 007.546 9	4.77	961.538 2,799.483 1,637.431 3,619.417 2, 475.378 2	[M+COOH]^-	Saponin	c
70	13.72	Daidzein^[52]	C₁₅H₁₀O₄	255.065 2	255.064 4	-3.14	137.023 2,199.075 2	[M+H]⁺	Flavonoid	a
71	13.9	Notoginsenoside R1^1)[41]	C₄₇H₈₀O₁₈	977.531 6	977.530 6	-1.02	931.528 4,799.484 1,637.431 0,475.377 8, 391.284 7	[M+COOH]^-	Saponin	c
72	14.02	Brosimacutin G^[38]	C₂₀H₂₀O₆	357.133 3	357.132 6	-1.96	255.066 1,237.075 1,147.044 0,119.049 3	[M+H]⁺	Flavonoid	a
73	14.28	Psoralenol^[53]	C₂₀H₁₈O₅	339.122 2	339.122 0	-0.59	321.111 5,291.117 3,279.064 9,267.064 9, 251.070 7,239.070 0,137.023 3	[M+H]⁺	Flavonoid	a
74	14.36	3'-Methoxydaidzein^[52]	C₁₆H₁₂O₅	283.060 3	283.061 6	4.59	268.036 9,239.034 2,211.039 0,148.015 0, 135.007 1	[M-H]^-	Flavonoid	a
75	14.36	Ginsenoside Rf/ isomer^[41]	C₄₂H₇₂O₁₄	845.489 3	845.490 1	0.95	799.484 2,637.430 4,619.419 0,457.377 7, 391.281 5	[M+COOH]^-	Saponin	c
76	14.62	Ginsenoside Rg1^1)[41]	C₄₂H₇₂O₁₄	845.489 3	845.491 6	2.72	799.483 6,637.430 5,619.422 9,475.377 6, 391.284 3	[M+COOH]^-	Saponin	c
77	14.72	Ginsenoside Re^1)[51]	C₄₈H₈₂O₁₈	945.541 7	945.543 6	2.01	945.543 8,637.430 5,619.420 7,475.377 6, 457.366 4,391.284 1	[M+COOH]^-	Saponin	c
78	15.05	Decanedioic acid^[54]	C₁₀H₁₈O₄	201.112 1	201.112 8	3.48	201.112 8,183.101 1,157.121 17,139.111 2	[M-H]^-	Organic acid	d/e
79	15.09	Ginsenoside Rf/ isomer^[41]	C₄₂H₇₂O₁₄	845.489 3	845.493 5	4.97	799.483 8,637.430 6,475.377 4,391.283 3	[M+COOH]^-	Saponin	c
80	15.76	Corylidin/isomer^[40]	C₂₀H₁₆O₇	369.096 9	369.095 3	-4.34	309.038 7,297.039 0,269.044 0,241.049 0	[M+H]⁺	Coumarin	a
81	15.86	Psoralen^1)[40]	C₁₁H₆O₃	187.039 0	187.038 3	-3.74	159.044 0,143.049 1,131.049 2,115.054 5	[M+H]⁺	Coumarin	a
82	15.96	Psoralenol A/psoralenol B/isomer^[55]	C₂₀H₁₈O₆	355.117 6	355.116 2	-3.94	337.106 4,295.096 1,279.064 6,137.023 2	[M+H]⁺	Flavonoid	a
83	16.16	Notoginsenoside G^[56]	C₄₈H₈₀O₁₉	1 005.526 5	1 005.522 8	-3.68	959.521 0,797.468 9,635.414 4,473.364 0	[M+COOH]^-	Saponin	c
84	16.18	Erythrinin A^[40]	C₂₀H₁₆O₄	321.112 1	321.111 4	-2.18	305.085 0,303.101 3,279.065 0,263.070 0, 183.080 4,137.023 3	[M+H]⁺	Flavonoid	a
85	16.48	Angelicin^[32]	C₁₁H₆O₃	187.039 0	187.038 3	-3.74	159.044 0,143.049 0,131.049 1,115.054 4, 103.054 5,77.040 0	[M+H]⁺	Coumarin	a
86	16.48	Psoralenol A/psoralenol/ isomer^[55]	C₂₀H₁₈O₆	355.117 6	355.116 2	-3.94	337.106 6,295.096 2,279.064 9,137.023 3	[M+H]⁺	Flavonoid	a
87	16.59	Genistein^[57]	C₁₅H₁₀O₅	271.060 1	271.059 0	-4.06	253.049 3,243.064 9,197.059 6,169.064 8, 153.018 1	[M+H]⁺	Flavonoid	a
88	17.49	Bavarigenin^[55]	C₂₂H₂₂O₇	399.143 8	399.142 7	-2.76	381.133 0,369.132 7,305.081 6,187.039 0	[M+H]⁺	Flavonoid	a
89	17.79	Corylin^[58]	C₂₀H₁₆O₄	321.112 1	321.111 4	-2.18	306.087 5,279.065 2,211.074 9,183.080 2, 143.085 2,137.023 2	[M+H]⁺	Flavonoid	a
90	18.11	Corylifol B/isomer^[55]	C₂₀H₂₀O₅	341.138 4	341.137 8	-1.76	269.060 5,203.070 1,149.023 3	[M+H]⁺	Flavonoid	a
91	18.44	Asperosaponin Ⅵ^[36]	C₄₇H₇₆O₁₈	973.500 3	973.504 3	4.11	927.497 1,603.388 9,323.097 7 4,179.054 6	[M+COOH]^-	Saponin	b
92	18.84	Neocorylin A/neocorylin B^[55]	C₂₅H₂₆O₅	407.185 3	407.184 1	-2.95	389.173 8,321.111 5,267.064 8,137.023 2	[M+H]⁺	Flavonoid	a
93	18.86	Notoginsenoside R2/ isomer^[51]	C₄₁H₇₀O₁₃	815.478 8	815.481 0	2.7	769.473 5,637.430 3,475.376 9,391.285 0, 161.044 0	[M+COOH]^-	Saponin	c
94	19.12	Notoginsenoside Fa^[59]	C₅₉H₁₀₀O₂₇	1 285.642 3	1 285.647 5	4.05	1 239.638 4,1 107.595 5,945.544 4,783.488 4,621.440 3,459.386 3	[M+COOH]^-	Saponin	c
95	19.12	Ginsenoside Rb1^[60]	C₅₄H₉₂O₂₃	1 153.600 0	1 153.599 4	-0.52	1 107.597 8,945.542 6,783.491 8,621.435 4, 459.383 2	[M+COOH]^-	Saponin	c
96	19.15	Ginsenoside Rg5^[61]	C₄₂H₇₀O₁₂	767.493 0	767.489 9	-4.04	605.439 5,443.386 9,425.375 8,407.365 8, 297.256 7	[M+H]⁺	Saponin	c
97	19.33	Notoginsenoside R2/isomer^[51]	C₄₁H₇₀O₁₃	815.478 8	815.481 3	3.07	769.473 3,637.430 2,475.377 4,391.285 0, 161.044 1	[M+COOH]^-	Saponin	b
98	19.33	Ginsenoside Rg2/isomer^[62]	C₄₂H₇₂O₁₃	829.494 4	829.496 4	2.41	783.492 0,637.430 3,475.377 5,391.284 5	[M+COOH]^-	Saponin	c
99	19.38	4'-O-Asperosaponin Ⅵ^[63]	C₄₉H₇₈O₁₉	1 015.510 8	1 015.514 3	3.45	645.399 8,323.097 2	[M+COOH]^-	Saponin	b
100	19.43	Ginsenoside Rh1/isomer^[64]	C₃₆H₆₂O₉	683.436 5	683.436 8	0.44	637.431 0,475.377 3,391.284 5	[M+COOH]^-	Saponin	c
101	19.53	Ginsenoside Rg2/isomer^[62]	C₄₂H₇₂O₁₃	829.494 4	829.498 4	4.83	783.489 1,637.430 1,475.377 0,391.284 2	[M+COOH]^-	Saponin	c
102	19.61	Bavacoumestan A/ bavacoumestan B/ isomer^[40]	C₂₀H₁₆O₆	353.101 3	353.102 0	1.98	335.090 6,307.095 7,281.044 0,253.049 1, 225.054 3,209.059 4,197.059 4,181.064 7	[M+H]⁺	Flavonoid	a
103	19.64	2'-O-Asperosaponin Ⅵ^[63]	C₄₉H₇₈O₁₉	1 015.510 8	1 015.514 6	3.74	645.399 8,323.097 2	[M+COOH]^-	Saponin	b
104	19.69	Ginsenoside F1/isomer^[65]	C₃₆H₆₂O₉	683.436 5	683.439 2	3.95	637.430 5,475.378 1,161.044 1,113.022 7, 101.022 8	[M+COOH]^-	Saponin	c
105	19.82	Bavacoumestan A/ bavacoumestan B/ isomer^[40]	C₂₀H₁₆O₆	353.101 3	353.102 1	2.27	335.091 2,307.097 0,281.044 6,253.049 2, 225.054 3,209.006 0 2,197.059 4,181.064 7	[M+H]⁺	Flavonoid	a
106	19.95	3'-O-Asperosaponin Ⅵ^[63]	C₄₉H₇₈O₁₉	1 015.510 8	1 015.510 1	-0.69	645.399 9,323.097 3	[M+COOH]^-	Saponin	b
107	20.08	Isoaromadendrene epoxide^[66]	C₁₅H₂₄O	221.190 0	221.189 7	-1.36	203.179 4,147.116 8,119.085 7,105.070 2	[M+H]⁺	Terpene	a
108	20.08	Calamenene^[53]	C₁₅H₂₂	203.179 4	203.179 2	-0.99	147.116 7,133.101 2,119.085 7,105.070 2	[M+H]⁺	Others	a
109	20.22	Dipsacussaponin A^[36]	C₄₂H₆₈O₁₄	841.458 3	841.462 3	4.76	795.456 2,471.346 1,323.096 5,221.066 1, 119.033 5	[M+COOH]^-	Saponin	b
110	20.29	Corylifol C^[67]	C₂₀H₁₈O₅	339.122 7	339.122 1	-1.77	283.059 8,255.065 0,237.054 4,227.070 0, 297.075 3	[M+H]⁺	Flavonoid	a
111	20.43	HN-saponin F^[68]	C₄₁H₆₆O₁₃	811.447 5	811.450 0	3.08	765.442 6,603.389 1,207.049 6,101.022 7	[M+COOH]^-	Saponin	b
112	20.58	Gypenoside XⅦ^[69]	C₄₈H₈₂O₁₈	991.547 2	991.545 7	-1.51	945.544 7,783.489 5,621.435 8	[M+COOH]^-	Saponin	c
113	20.6	Ginsenoside Rd^[41]	C₄₈H₈₂O₁₈	945.541 7	945.546 1	4.66	783.489 0,621.436 3,459.383 0	[M-H]^-	Saponin	c
114	21.2	Ginsenoside Rh3^[70]	C₃₆H₆₀O₇	605.441 2	605.439 5	-2.81	441.372 3,425.376 4,407.366 3,331.264 6	[M+H]⁺	Saponin	c
115	21.21	Notoginsenoside K^[71]	C₄₈H₈₂O₁₈	991.547 2	991.544 6	-2.62	945.544 1,783.487 9,621.436 3,537.342 5, 459.380 8,323.097 3	[M+COOH]^-	Saponin	c
116	21.32	Bavachin^[55]	C₂₀H₂₀O₄	323.127 8	323.128 9	3.41	221.080 9,203.070 1,175.075 1,159.080 1, 119.048 5	[M-H]^-	Flavonoid	a
117	21.72	Neocorylin^[55]	C₂₅H₂₄O₄	389.174 7	389.173 9	-2.06	321.111 5,305.080 8,267.064 9,137.023 3	[M+H]⁺	Flavonoid	a
118	21.72	Neocorylin A/neocorylin B/isomer^[72]	C₂₅H₂₆O₅	407.185 3	407.184 4	-2.21	389.173 8,321.111 2,267.060 5,137.022 3	[M+H]⁺	Flavonoid	a
119	21.78	Bavachromanol^[72]	C₂₀H₂₀O₅	341.138 4	341.137 9	-1.47	323.127 6,221.080 9,203.070 2,149.023 4	[M+H]⁺	Flavonoid	a
120	22.14	Neobavaisoflavone^[40]	C₂₀H₁₈O₄	323.128 0	323.127 6	-1.24	267.065 0,255.065 0,239.07 0,211.059 0,199.075 0,137.023 0	[M+H]⁺	Flavonoid	a
121	22.68	Ginsenoside F4/ isomer^[73]	C₄₂H₇₀O₁₂	811.483 8	811.486 6	3.45	765.478 5,619.420 1,457.369 3	[M+COOH]^-	Saponin	c
122	22.79	4-Dodecylbenzenesulfonic acid^[74]	C₁₈H₃₀SO₃	325.183 3	325.184 4	3.38	183.010 6	[M-H]^-	Others	a/e
123	22.94	Ginsenoside F4/ isomer^[73]	C₄₂H₇₀O₁₂	811.483 8	811.486 5	3.33	765.478 6,619.420 5,457.366 3	[M+COOH]^-	Saponin	c
124	23.05	Ginsenoside Rh4/ isomer^[75]	C₃₆H₆₀O₈	665.425 9	665.426 7	1.2	619.421 5,161.044 0,113.022 7,101.022 7	[M+COOH]^-	Saponin	c
125	23.36	Ginsenoside Rh4/ isomer^[75]	C₃₆H₆₀O₈	665.425 9	665.426 7	1.2	619.420 1,161.044 1,113.023 1,101.022 8	[M+COOH]^-	Saponin	c
126	23.87	Bavachromene^[76]	C₂₀H₁₈O₄	323.127 8	323.127 1	-2.17	305.116 7,281.115 4,253.112 3,221.080 6,203.070 1,175.075 3,147.044 0	[M+H]⁺	Flavonoid	a
127	24.01	Psoralidin^[38]	C₂₀H₁₆O₅	337.107 1	337.106 1	-2.97	309.111 4,281.044 1,253.049 2,237.054 3,225.054 3,209.059 5,197.059 6,181.064 7	[M+H]⁺	Coumarin	a
128	24.2	Ginsenoside Rg3/ isomer^[73]	C₄₂H₇₂O₁₃	829.494 4	829.496 2	2.17	783.489 0,621.436 7,459.382 8,375.288 9,161.044 1	[M+COOH]^-	Saponin	c
129	24.35	Ginsenoside Rg3/ isomer^[73]	C₄₂H₇₂O₁₃	829.494 4	829.496 4	2.41	783.489 3,621.436 2,459.383 2,375.289 5,161.044 1	[M+COOH]^-	Saponin	c
130	24.46	Octadecanedioic acid^[24]	C₁₈H₃₄O₄	313.237 5	313.239 0	4.79	295.226 9,201.111 9,171.101 1	[M-H]^-	Organic acid	a/e
131	25.56	Isobavachalcone^[77]	C₂₀H₂₀O₄	323.127 8	323.128 9	3.41	221.080 9,203.070 1,175.075 4,159.080 0,119.048 5	[M-H]^-	Flavonoid	a
132	26.07	Bavachinin/isomer^[76]	C₂₁H₂₂O₄	339.159 1	339.158 3	-2.36	283.095 9,271.095 9,219.101 4,177.054 6,147.043 9	[M+H]⁺	Flavonoid	a
133	26.75	Corylifol A^[38]	C₂₅H₂₆O₄	391.190 4	391.189 3	-2.81	335.127 0,267.064 8,239.069 8,137.023 2	[M+H]⁺	Flavonoid	a
134	27.03	Dodecyl sulfate^[36]	C₁₂H₂₆O₄S	265.146 8	265.148 1	4.91	96.958 3,95.950 6,79.955 7	[M-H]^-	Others	b
135	27.74	Bavachinin/isomer^[76]	C₂₁H₂₂O₄	339.159 1	339.158 3	-2.36	283.095 8,271.095 9,269.080 5,219.101 3,147.043 9	[M+H]⁺	Flavonoid	a
136	28.16	Neocorylin^[38]	C₂₅H₂₄O₄	389.174 7	389.173 8	-2.31	321.111 4,305.080 1,267.064 7,183.080 4,137.023 0	[M+H]⁺	Flavonoid	a
137	28.79	Bakuchiol^[72]	C₁₈H₂₄O	257.190 0	257.189 5	-1.95	201.127 0,187.111 6,173.096 1,147.080 3,133.064 8,121.064 9,107.049 5	[M+H]⁺	Terpene	a

No.

t_R/
min

Compound

Formula

m/z
(Theoretical)

m/z
(Measured)

Mass
error

m/z(MS²)

Ion
mode

Classification

Ascription

0.87

Mannitol^[14]

C₆H₁₄O₆

181.070 7

181.071 1

2.21

163.060 4,119.033 3,149.044 8,113.022 9,101.022 7,89.022 6,79.012 2,59.012 3

[M-H]^-

Others

a/b/d/e

0.89

Betaine^[15]

C₅H₁₁NO₂

118.086 3

59.073 7,58.065 9

[M+H]⁺

Alkaloid

a/b/c/d/e

0.89

L-Carnitine^[16]

C₇H₁₅NO₃

162.112 5

162.112 2

-1.85

103.039 3,85.029 0

[M+H]⁺

Alkaloid

b/d

0.89

Trigonelline^[15]

C₇H₇NO₂

138.055 0

138.054 7

2.17

110.060 2,94.065 5,92.049 9,78.034 3

[M+H]⁺

Alkaloid

a/e

0.92

Sucrose^[17]

C₁₂H₂₂O₁₁

341.107 8

341.109 1

3.81

179.054 6,161.040 1,143.033 4,119.033 3,101.022 8,89.022 6,71.012 1

[M-H]^-

Others

a/b/c

0.94

Adenine^1)[18]

C₅H₅N₅

136.061 8

136.061 7

-0.74

119.035 4,94.040 4

[M+H]⁺

Nucleoside

a/b/d/e

0.96

Malic acid^[19]

C₄H₆O₅

133.013 1

133.013 2

0.75

115.001 9,89.022 7,71.012 1,59.012 3

[M-H]^-

Organic acid

a/c/e

1.23

Pyroglutamic acid^[20]

C₅H₇NO₃

130.049 8

130.049 9

0.77

84.044 0,56.050 3

[M+H]⁺

Amino acid

a/c/d/

1.23

Adenosine^1)[19]

C₁₀H₁₃N₄O₅

268.104 0

268.103 9

-0.37

250.107 0,136.061 7,119.035 5

[M+H]⁺

Nucleoside

a/c/e

1.51

Gallic acid^1)[21]

C₇H₆O₅

169.013 1

169.013 7

3.55

125.022 6,107.012 0,81.032 9,79.017 3

[M-H]^-

Organic acid

1.62

Protocatechuic
aldehyde^1)[17]

C₇H₆O₃

137.023 3

137.023 7

2.92

109.027 9,93.032 8

[M-H]^-

Aldehyde

a/e

1.93

Pyrogallol^[22]

C₆H₆O₃

125.023 3

81.032 9

[M-H]^-

Organic acid

2.06

L-phenylalanine^[23]

C₉H₁₁NO₂

166.086 3

149.070 8,131.049 1,120.080 9,103.054 6

[M+H]⁺

Amino acid

a/b/c/d/e

2.19

p-Hydroxybenzaldehyde glucoside^[24]

C₁₃H₁₆O₉

315.071 1

315.071 8

2.22

153.017 9,152.009 9,109.028 1,108.019 9

[M-H]^-

Organic acid

b/d/e

2.22

N-(9-β-D-ribofuranosyl-9H-purin-6-yl)-
D-aspartic acid^[24]

C₁₄H₁₇N₅O₈

384.115 0

384.114 7

-0.78

252.072 5,234.061 8

[M+H]⁺

Amino acid

2.25

Vanillic acid
glucoside^[25]

C₁₄H₁₈O₉

329.086 7

329.085 9

-2.43

167.033 4,152.010 0,123.043 4,108.020 0

[M-H]^-

Organic acid

a/b/d/e

2.25

Vanillic acid^[24]

C₈H₈O₄

167.033 9

167.034 3

2.4

152.009 9,123.043 4,120.897 1,108.020 0

[M-H]^-

Organic acid

a/d/e

2.46

Methylsuccinic acid^[26]

C₅H₈O₄

131.033 9

131.034 0

0.76

113.022 9,87.043 4,72.99 1

[M-H]^-

Organic acid

a/d/e

2.76

Histidylproline^[24]

C₁₁H₁₆N₄O₃

253.129 5

236.103 2,225.134 6,208.108 4,191.081 4, 181.144 8,166.086 2,165.102 2,122.096 6, 112.087 2,70.065 9

[M+H]⁺

Amino acid

a/d

2.78

Protocatechuic acid^1)[27]

C₇H₆O₄

153.018 2

153.018 4

1.31

109.027 8,108.020 0

[M-H]^-

Organic acid

a/b/d/e

3.25

Glucosyringic acid^[28]

C₁₅H₂₀O₁₀

359.097 3

359.099 1

5.01

197.044 2,182.020 5,166.997 1,153.054 2, 138.030 6,123.007 0

[M-H]^-

Organic acid

a/b/d

3.41

Neochlorogenic acid^1)[29]

C₁₆H₁₈O₉

353.086 7

353.087 8

3.12

191.054 5,179.033 4,173.044 0,161.022 9, 135.043 4

[M-H]^-

Organic acid

3.67

Caffeic acid 4-O-glucoside^[24]

C₁₅H₁₈O₉

341.086 7

341.088 2

4.4

179.033 4,135.043 5

[M-H]^-

Organic acid

4.68

4-Hydroxybenzoic acid^1)[30]

C₇H₆O₃

137.023 3

137.023 4

0.73

109.027 9,93.032 8

[M-H]^-

Organic acid

4.68

Swertiamarin^[31]

C₁₆H₂₂O₁₀

373.112 9

373.114 7

4.83

211.060 0,179.054 4,167.069 9,193.049 5, 149.059 3,123.043 4,101.022 8,179.054 0, 119.033 2,89.022 6,71.012 2,59.012 3

[M-H]^-

Terpene

5.05

Loganic acid^[31]

C₁₆H₂₄O₁₀

375.128 6

375.129 2

1.6

213.075 7,169.085 5,151.074 9,143.033 6, 113.022 7,89.022 6,69.032 9

[M-H]^-

Terpene

5.36

Dihydrophaseic acid-O-glucoside^[24]

C₂₁H₃₂O₁₀

443.191 2

443.192 6

3.16

161.043 9,119.033 3,113.022 7,101.022 7, 89.022 6,71.012 2,59.012 3

[M-H]^-

Organic acid

5.58

Chlorogenic acid^1)[29]

C₁₆H₁₈O₉

353.086 7

353.087 7

2.83

191.054 5,179.033 5,173.044 0,161.023 0, 135.043 5

[M-H]^-

Organic acid

5.81

6,7-Dihydroxycoum-
arin^[32]

C₉H₆O₄

179.033 9

151.038 9,133.028 4,123.044 2

[M+H]⁺

Coumarin

5.94

Cryptochlorogenic acid^1)[29]

C₁₆H₁₈O₉

353.086 7

353.087 7

2.83

191.054 6,179.033 4,173.043 9,161.022 9, 135.043 4

[M-H]^-

Organic acid

5.94

Caffeic acid^1)[24]

C₉H₈O₄

179.033 9

179.034 1

1.12

135.043 4,117.032 8,107.048 6,89.037 9

[M-H]^-

Organic acid

a/b/d/e

5.94

Shikimic acid^[16]

C₇H₁₀O₅

173.044 5

173.044 7

1.16

155.033 7,137.022 7,128.876 2,111.043 4, 93.032

[M-H]^-

Organic acid

6.02

Lycoperodine-1^[24]

C₁₂H₁₂N₂O₂

217.097 2

144.080 7

[M+H]⁺

Others

a/b/d

6.11

Cyclohexanecarboxylic acid^[29]

C₁₆H₁₈O₉

353.086 7

353.088 3

4.53

191.054 6,179.033 4,173.044 0,135.043 4

[M-H]^-

Organic acid

6.23

Cantleyine^[33]

C₁₁H₁₃NO₃

208.096 7

208.097 6

4.33

190.086 1,176.070 5,158.059 9

[M+H]⁺

Alkaloid

7.03

5,7-Dihydroxy-4-methylcoumarin^[34]

C₁₀H₈O₄

193.049 5

193.049 4

-0.52

178.025 7,165.054 6,149.096 4,137.059 6

[M+H]⁺

Coumarin

7.13

Erythricine^[33]

C₁₀H₉NO₂

176.070 6

176.070 3

-1.7

146.059 9,118.065 3,117.057 5

[M+H]⁺

Alkaloid

7.32

5-Coumariquinic acid^[21]

C₁₆H₁₈O₈

337.091 8

337.093 4

4.75

191.054 5,163.038 5

[M-H]^-

Organic acid

7.44

Puerarin^[35]

C₂₁H₂₀O₉

415.102 4

415.104 4

4.82

295.060 1,277.049 0,267.065 3

[M-H]^-

Flavonoid

7.63

Loganin^1)[36]

C₁₇H₂₆O₁₀

435.149 7

435.150 7

2.3

227.091 3,127.038 3,101.022 7

[M+COOH]^-

Terpene

7.68

Sweroside^[37]

C₁₆H₂₂O₉

403.123 5

403.124 3

1.99

357.118 0,195.064 7,179.054 7,161.044 0, 131.033 4,125.022 6

[M+COOH]^-

Terpene

7.88

Vanillin^[17]

C₈H₈O₃

153.054 6

153.054 5,125.059 8,111.044 3,65.039 4

[M+H]⁺

Aldehyde

a/d/e

8.06

2,4-Dihydroxy-6-methoxy-3-methyl acetophenone 4-O-β-D-xylopyranosyl-(1→6)-β-D-glucopyranoside^[36]

C₂₁H₃₀O₁₃

535.165 8

535.168 2

4.49

489.159 9,191.054 3,151.074 9,149.043 9, 125.022 6,81.032 9

[M+COOH]^-

Others

8.26

Psoralenoside^1)[38]

C₁₇H₁₈O₉

365.086 7

365.087 1

1.1

203.033 7,159.043 5

[M-H]^-

Coumarin

8.57

Schaftoside/
isomers^[39]

C₂₆H₂₈O₁₄

563.139 5

563.140 4

1.6

503.116 7,473.106 9,443.097 1,383.076 2, 353.065 6,325.070 7,297.075 7,311.05 5

[M-H]^-

Flavonoid

a/d

8.57

Luteolin-6-C-glucoside/orientin^[17]

C₂₁H₂₀O₁₁

447.092 2

447.093 6

3.13

429.081 1,411.073 8,393.060 4,357.060 7, 327.050 0,299.055 1,285.039 6,284.031 9, 255.054 2

[M-H]^-

Flavonoid

8.67

Schaftoside/
isomers^[39]

C₂₆H₂₈O₁₄

563.139 5

563.139 0

-0.89

503.117 7,473.107 2,443.096 4,383.076 1, 353.065 5,325.070 3,311.054 1,294.07 6

[M-H]^-

Flavonoid

a/d

8.67

Isopsoralenoside^1)[38]

C₁₇H₁₈O₉

365.086 7

365.087 2

1.37

203.033 7,159.043 5

[M-H]^-

Coumarin

8.69

Bakuchicin^[40]

C₁₁H₆O₃

187.039 0

187.038 3

-3.74

143.049 0,159.044 0,131.049 1,115.054 4

[M+H]⁺

Coumarin

8.74

Hydroxyferulic acid^[24]

C₁₀H₁₀O₅

209.044 5

209.045 4

4.31

165.054 0,121.027 7,59.856 8

[M-H]^-

Organic acid

a/e

8.82

Luteolin-6-C-glucoside/orientin^[17]

C₂₁H₂₀O₁₁

447.092 5

447.094 5

4.47

429.091 8,411.071 5,357.060 5,327.049 9, 299.054 9,285.039 1,284.032 0,255.054 2

[M-H]^-

Flavonoid

8.99

Schaftoside/
isomers^[39]

C₂₆H₂₈O₁₄

563.139 5

503.117 3,473.107 2,443.096 8,383.076 3, 353.065 7,325.070 7,311.055 0,297.075 8

[M-H]^-

Flavonoid

a/d

9.53

1-Hydroxypinoresinol 4'-β-D-glucopyranoside^[36]

C₂₆H₃₂O₁₂

535.181 1

535.183 7

4.86

373.128 0,343.117 5,284.103 8,269.081 1, 254.057 6,193.049 1, 163.038 9,149.059 1, 148.015 0

[M-H]^-

lignan

9.75

Daidzin^[41]

C₂₁H₂₀O₉

417.118 0

417.117 2

-1.92

297.075 0,255.064 8,227.070 0,199.075 2, 119.049 2,137.023 2

[M+H]⁺

Flavonoid

9.78

Isovitexin^[42]

C₂₁H₂₀O₁₀

431.097 3

431.099 3

4.64

413.086 3,395.076 6,341.065 6,311.055 3, 283.060 4,269.044 7,161.022 9,117.032 9

[M-H]^-

Flavonoid

9.83

7-Deoxyloganic acid^[36]

C₁₆H₂₄O₉

359.133 7

359.135 3

4.46

197.080 5,153.090 6,135.079 9,59.012 3

[M-H]^-

Terpene

9.88

Vitexin^1)[43]

C₂₁H₂₀O₁₀

431.097 3

431.099 1

4.18

341.065 6,311.055 3,283.060 3,269.044 5, 161.022 9,117.032 8

[M-H]^-

Flavonoid

10.15

Isoquercitrin^[44]

C₂₁H₂₀O₁₂

463.087 1

463.089 4

4.97

301.034 0,300.026 6,271.024 1,255.029 0

[M-H]^-

Flavonoid

10.46

Swertisin^1)[45]

C₂₂H₂₂O₁₀

445.112 9

445.113 7

1.8

325.070 9,297.039 6,282.052 4

[M-H]^-

Flavonoid

10.6

Genistin^[41]

C₂₁H₂₀O₁₀

433.112 9

433.111 9

-2.31

271.059 6,253.049 2,243.064 7,215.070 0, 169.064 9,153.018 1

[M+H]⁺

Flavonoid

10.83

Isoswertisin^[46]

C₂₂H₂₂O₁₀

445.113 2

445.115 3

4.72

325.071 0,297.039 8,282.052 3

[M-H]^-

Flavonoid

11.10

Salicylic acid^[47]

C₇H₆O₃

137.023 3

137.023 5

1.46

108.898 0,93.032 8,65.038 0

[M-H]^-

Organic acid

a/d/e

11.15

Isochlorogenic acid B^1)[48]

C₂₅H₂₄O₁₂

515.118 4

515.119 3

1.75

353.086 8,191.054 6,179.033 4,173.044 0, 135.043 5

[M-H]^-

Organic acid

11.36

Astragaloside^[49]

C₂₁H₂₀O₁₁

447.092 2

447.093 9

3.8

285.039 1,284.031 8,256.034 7,255.029 0, 227.033 9

[M-H]^-

Flavonoid

11.39

Isochlorogenic acid
A^1)[48]

C₂₅H₂₄O₁₂

515.118 4

515.119 0

1.17

353.087 0,191.054 5,179.033 4,173.044 1, 135.043 4

[M-H]^-

Organic acid

11.39

Kaempferol^[50]

C₁₅H₁₀O₆

287.055 0

287.054 2

-2.79

259.058 7,241.049 3,213.054 2,165.018 1, 153.018 1,137.023 2

[M+H]⁺

Flavonoid

11.47

Quercitrin^1)[50]

C₂₁H₂₀O₁₁

447.092 2

447.094 2

4.47

301.033 8,300.026 2,255.028 7,151.001 6

[M-H]^-

Flavonoid

12.35

Isochlorogenic acid
C^1)[48]

C₂₅H₂₄O₁₂

515.118 4

515.119 0

1.17

353.086 9,191.054 6,179.033 4,173.044 0, 135.043 5

[M-H]^-

Organic acid

13.63

Notoginsenoside M^[51]

C₄₈H₈₂O₁₉

1 007.542 1

1 007.546 9

4.77

961.538 2,799.483 1,637.431 3,619.417 2, 475.378 2

[M+COOH]^-

Saponin

13.72

Daidzein^[52]

C₁₅H₁₀O₄

255.065 2

255.064 4

-3.14

137.023 2,199.075 2

[M+H]⁺

Flavonoid

13.9

Notoginsenoside
R1^1)[41]

C₄₇H₈₀O₁₈

977.531 6

977.530 6

-1.02

931.528 4,799.484 1,637.431 0,475.377 8, 391.284 7

[M+COOH]^-

Saponin

14.02

Brosimacutin G^[38]

C₂₀H₂₀O₆

357.133 3

357.132 6

-1.96

255.066 1,237.075 1,147.044 0,119.049 3

[M+H]⁺

Flavonoid

14.28

Psoralenol^[53]

C₂₀H₁₈O₅

339.122 2

339.122 0

-0.59

321.111 5,291.117 3,279.064 9,267.064 9, 251.070 7,239.070 0,137.023 3

[M+H]⁺

Flavonoid

14.36

3'-Methoxydaidzein^[52]

C₁₆H₁₂O₅

283.060 3

283.061 6

4.59

268.036 9,239.034 2,211.039 0,148.015 0, 135.007 1

[M-H]^-

Flavonoid

14.36

Ginsenoside Rf/
isomer^[41]

C₄₂H₇₂O₁₄

845.489 3

845.490 1

0.95

799.484 2,637.430 4,619.419 0,457.377 7, 391.281 5

[M+COOH]^-

Saponin

14.62

Ginsenoside Rg1^1)[41]

C₄₂H₇₂O₁₄

845.489 3

845.491 6

2.72

799.483 6,637.430 5,619.422 9,475.377 6, 391.284 3

[M+COOH]^-

Saponin

14.72

Ginsenoside Re^1)[51]

C₄₈H₈₂O₁₈

945.541 7

945.543 6

2.01

945.543 8,637.430 5,619.420 7,475.377 6, 457.366 4,391.284 1

[M+COOH]^-

Saponin

15.05

Decanedioic acid^[54]

C₁₀H₁₈O₄

201.112 1

201.112 8

3.48

201.112 8,183.101 1,157.121 17,139.111 2

[M-H]^-

Organic acid

d/e

15.09

Ginsenoside Rf/
isomer^[41]

C₄₂H₇₂O₁₄

845.489 3

845.493 5

4.97

799.483 8,637.430 6,475.377 4,391.283 3

[M+COOH]^-

Saponin

15.76

Corylidin/isomer^[40]

C₂₀H₁₆O₇

369.096 9

369.095 3

-4.34

309.038 7,297.039 0,269.044 0,241.049 0

[M+H]⁺

Coumarin

15.86

Psoralen^1)[40]

C₁₁H₆O₃

187.039 0

187.038 3

-3.74

159.044 0,143.049 1,131.049 2,115.054 5

[M+H]⁺

Coumarin

15.96

Psoralenol A/psoralenol B/isomer^[55]

C₂₀H₁₈O₆

355.117 6

355.116 2

-3.94

337.106 4,295.096 1,279.064 6,137.023 2

[M+H]⁺

Flavonoid

16.16

Notoginsenoside G^[56]

C₄₈H₈₀O₁₉

1 005.526 5

1 005.522 8

-3.68

959.521 0,797.468 9,635.414 4,473.364 0

[M+COOH]^-

Saponin

16.18

Erythrinin A^[40]

C₂₀H₁₆O₄

321.112 1

321.111 4

-2.18

305.085 0,303.101 3,279.065 0,263.070 0, 183.080 4,137.023 3

[M+H]⁺

Flavonoid

16.48

Angelicin^[32]

C₁₁H₆O₃

187.039 0

187.038 3

-3.74

159.044 0,143.049 0,131.049 1,115.054 4, 103.054 5,77.040 0

[M+H]⁺

Coumarin

16.48

Psoralenol A/psoralenol/
isomer^[55]

C₂₀H₁₈O₆

355.117 6

355.116 2

-3.94

337.106 6,295.096 2,279.064 9,137.023 3

[M+H]⁺

Flavonoid

16.59

Genistein^[57]

C₁₅H₁₀O₅

271.060 1

271.059 0

-4.06

253.049 3,243.064 9,197.059 6,169.064 8, 153.018 1

[M+H]⁺

Flavonoid

17.49

Bavarigenin^[55]

C₂₂H₂₂O₇

399.143 8

399.142 7

-2.76

381.133 0,369.132 7,305.081 6,187.039 0

[M+H]⁺

Flavonoid

17.79

Corylin^[58]

C₂₀H₁₆O₄

321.112 1

321.111 4

-2.18

306.087 5,279.065 2,211.074 9,183.080 2, 143.085 2,137.023 2

[M+H]⁺

Flavonoid

18.11

Corylifol B/isomer^[55]

C₂₀H₂₀O₅

341.138 4

341.137 8

-1.76

269.060 5,203.070 1,149.023 3

[M+H]⁺

Flavonoid

18.44

Asperosaponin Ⅵ^[36]

C₄₇H₇₆O₁₈

973.500 3

973.504 3

4.11

927.497 1,603.388 9,323.097 7 4,179.054 6

[M+COOH]^-

Saponin

18.84

Neocorylin A/neocorylin B^[55]

C₂₅H₂₆O₅

407.185 3

407.184 1

-2.95

389.173 8,321.111 5,267.064 8,137.023 2

[M+H]⁺

Flavonoid

18.86

Notoginsenoside R2/
isomer^[51]

C₄₁H₇₀O₁₃

815.478 8

815.481 0

2.7

769.473 5,637.430 3,475.376 9,391.285 0, 161.044 0

[M+COOH]^-

Saponin

19.12

Notoginsenoside Fa^[59]

C₅₉H₁₀₀O₂₇

1 285.642 3

1 285.647 5

4.05

1 239.638 4,1 107.595 5,945.544 4,783.488 4,621.440 3,459.386 3

[M+COOH]^-

Saponin

19.12

Ginsenoside Rb1^[60]

C₅₄H₉₂O₂₃

1 153.600 0

1 153.599 4

-0.52

1 107.597 8,945.542 6,783.491 8,621.435 4, 459.383 2

[M+COOH]^-

Saponin

19.15

Ginsenoside Rg5^[61]

C₄₂H₇₀O₁₂

767.493 0

767.489 9

-4.04

605.439 5,443.386 9,425.375 8,407.365 8, 297.256 7

[M+H]⁺

Saponin

19.33

Notoginsenoside
R2/isomer^[51]

C₄₁H₇₀O₁₃

815.478 8

815.481 3

3.07

769.473 3,637.430 2,475.377 4,391.285 0, 161.044 1

[M+COOH]^-

Saponin

19.33

Ginsenoside
Rg2/isomer^[62]

C₄₂H₇₂O₁₃

829.494 4

829.496 4

2.41

783.492 0,637.430 3,475.377 5,391.284 5

[M+COOH]^-

Saponin

19.38

4'-O-Asperosaponin Ⅵ^[63]

C₄₉H₇₈O₁₉

1 015.510 8

1 015.514 3

3.45

645.399 8,323.097 2

[M+COOH]^-

Saponin

100

19.43

Ginsenoside
Rh1/isomer^[64]

C₃₆H₆₂O₉

683.436 5

683.436 8

0.44

637.431 0,475.377 3,391.284 5

[M+COOH]^-

Saponin

101

19.53

Ginsenoside
Rg2/isomer^[62]

C₄₂H₇₂O₁₃

829.494 4

829.498 4

4.83

783.489 1,637.430 1,475.377 0,391.284 2

[M+COOH]^-

Saponin

102

19.61

Bavacoumestan A/
bavacoumestan B/
isomer^[40]

C₂₀H₁₆O₆

353.101 3

353.102 0

1.98

335.090 6,307.095 7,281.044 0,253.049 1, 225.054 3,209.059 4,197.059 4,181.064 7

[M+H]⁺

Flavonoid

103

19.64

2'-O-Asperosaponin Ⅵ^[63]

C₄₉H₇₈O₁₉

1 015.510 8

1 015.514 6

3.74

645.399 8,323.097 2

[M+COOH]^-

Saponin

104

19.69

Ginsenoside
F1/isomer^[65]

C₃₆H₆₂O₉

683.436 5

683.439 2

3.95

637.430 5,475.378 1,161.044 1,113.022 7, 101.022 8

[M+COOH]^-

Saponin

105

19.82

Bavacoumestan A/
bavacoumestan B/
isomer^[40]

C₂₀H₁₆O₆

353.101 3

353.102 1

2.27

335.091 2,307.097 0,281.044 6,253.049 2, 225.054 3,209.006 0 2,197.059 4,181.064 7

[M+H]⁺

Flavonoid

106

19.95

3'-O-Asperosaponin Ⅵ^[63]

C₄₉H₇₈O₁₉

1 015.510 8

1 015.510 1

-0.69

645.399 9,323.097 3

[M+COOH]^-

Saponin

107

20.08

Isoaromadendrene
epoxide^[66]

C₁₅H₂₄O

221.190 0

221.189 7

-1.36

203.179 4,147.116 8,119.085 7,105.070 2

[M+H]⁺

Terpene

108

20.08

Calamenene^[53]

C₁₅H₂₂

203.179 4

203.179 2

-0.99

147.116 7,133.101 2,119.085 7,105.070 2

[M+H]⁺

Others

109

20.22

Dipsacussaponin A^[36]

C₄₂H₆₈O₁₄

841.458 3

841.462 3

4.76

795.456 2,471.346 1,323.096 5,221.066 1, 119.033 5

[M+COOH]^-

Saponin

110

20.29

Corylifol C^[67]

C₂₀H₁₈O₅

339.122 7

339.122 1

-1.77

283.059 8,255.065 0,237.054 4,227.070 0, 297.075 3

[M+H]⁺

Flavonoid

111

20.43

HN-saponin F^[68]

C₄₁H₆₆O₁₃

811.447 5

811.450 0

3.08

765.442 6,603.389 1,207.049 6,101.022 7

[M+COOH]^-

Saponin

112

20.58

Gypenoside XⅦ^[69]

C₄₈H₈₂O₁₈

991.547 2

991.545 7

-1.51

945.544 7,783.489 5,621.435 8

[M+COOH]^-

Saponin

113

20.6

Ginsenoside Rd^[41]

C₄₈H₈₂O₁₈

945.541 7

945.546 1

4.66

783.489 0,621.436 3,459.383 0

[M-H]^-

Saponin

114

21.2

Ginsenoside Rh3^[70]

C₃₆H₆₀O₇

605.441 2

605.439 5

-2.81

441.372 3,425.376 4,407.366 3,331.264 6

[M+H]⁺

Saponin

115

21.21

Notoginsenoside K^[71]

C₄₈H₈₂O₁₈

991.547 2

991.544 6

-2.62

945.544 1,783.487 9,621.436 3,537.342 5, 459.380 8,323.097 3

[M+COOH]^-

Saponin

116

21.32

Bavachin^[55]

C₂₀H₂₀O₄

323.127 8

323.128 9

3.41

221.080 9,203.070 1,175.075 1,159.080 1, 119.048 5

[M-H]^-

Flavonoid

117

21.72

Neocorylin^[55]

C₂₅H₂₄O₄

389.174 7

389.173 9

-2.06

321.111 5,305.080 8,267.064 9,137.023 3

[M+H]⁺

Flavonoid

118

21.72

Neocorylin A/neocorylin B/isomer^[72]

C₂₅H₂₆O₅

407.185 3

407.184 4

-2.21

389.173 8,321.111 2,267.060 5,137.022 3

[M+H]⁺

Flavonoid

119

21.78

Bavachromanol^[72]

C₂₀H₂₀O₅

341.138 4

341.137 9

-1.47

323.127 6,221.080 9,203.070 2,149.023 4

[M+H]⁺

Flavonoid

120

22.14

Neobavaisoflavone^[40]

C₂₀H₁₈O₄

323.128 0

323.127 6

-1.24

267.065 0,255.065 0,239.07 0,211.059 0,199.075 0,137.023 0

[M+H]⁺

Flavonoid

121

22.68

Ginsenoside F4/
isomer^[73]

C₄₂H₇₀O₁₂

811.483 8

811.486 6

3.45

765.478 5,619.420 1,457.369 3

[M+COOH]^-

Saponin

122

22.79

4-Dodecylbenzenesulfonic acid^[74]

C₁₈H₃₀SO₃

325.183 3

325.184 4

3.38

183.010 6

[M-H]^-

Others

a/e

123

22.94

Ginsenoside F4/
isomer^[73]

C₄₂H₇₀O₁₂

811.483 8

811.486 5

3.33

765.478 6,619.420 5,457.366 3

[M+COOH]^-

Saponin

124

23.05

Ginsenoside Rh4/
isomer^[75]

C₃₆H₆₀O₈

665.425 9

665.426 7

1.2

619.421 5,161.044 0,113.022 7,101.022 7

[M+COOH]^-

Saponin

125

23.36

Ginsenoside Rh4/
isomer^[75]

C₃₆H₆₀O₈

665.425 9

665.426 7

1.2

619.420 1,161.044 1,113.023 1,101.022 8

[M+COOH]^-

Saponin

126

23.87

Bavachromene^[76]

C₂₀H₁₈O₄

323.127 8

323.127 1

-2.17

305.116 7,281.115 4,253.112 3,221.080 6,203.070 1,175.075 3,147.044 0

[M+H]⁺

Flavonoid

127

24.01

Psoralidin^[38]

C₂₀H₁₆O₅

337.107 1

337.106 1

-2.97

309.111 4,281.044 1,253.049 2,237.054 3,225.054 3,209.059 5,197.059 6,181.064 7

[M+H]⁺

Coumarin

128

24.2

Ginsenoside Rg3/
isomer^[73]

C₄₂H₇₂O₁₃

829.494 4

829.496 2

2.17

783.489 0,621.436 7,459.382 8,375.288 9,161.044 1

[M+COOH]^-

Saponin

129

24.35

Ginsenoside Rg3/
isomer^[73]

C₄₂H₇₂O₁₃

829.494 4

829.496 4

2.41

783.489 3,621.436 2,459.383 2,375.289 5,161.044 1

[M+COOH]^-

Saponin

130

24.46

Octadecanedioic
acid^[24]

C₁₈H₃₄O₄

313.237 5

313.239 0

4.79

295.226 9,201.111 9,171.101 1

[M-H]^-

Organic acid

a/e

131

25.56

Isobavachalcone^[77]

C₂₀H₂₀O₄

323.127 8

323.128 9

3.41

221.080 9,203.070 1,175.075 4,159.080 0,119.048 5

[M-H]^-

Flavonoid

132

26.07

Bavachinin/isomer^[76]

C₂₁H₂₂O₄

339.159 1

339.158 3

-2.36

283.095 9,271.095 9,219.101 4,177.054 6,147.043 9

[M+H]⁺

Flavonoid

133

26.75

Corylifol A^[38]

C₂₅H₂₆O₄

391.190 4

391.189 3

-2.81

335.127 0,267.064 8,239.069 8,137.023 2

[M+H]⁺

Flavonoid

134

27.03

Dodecyl sulfate^[36]

C₁₂H₂₆O₄S

265.146 8

265.148 1

4.91

96.958 3,95.950 6,79.955 7

[M-H]^-

Others

135

27.74

Bavachinin/isomer^[76]

C₂₁H₂₂O₄

339.159 1

339.158 3

-2.36

283.095 8,271.095 9,269.080 5,219.101 3,147.043 9

[M+H]⁺

Flavonoid

136

28.16

Neocorylin^[38]

C₂₅H₂₄O₄

389.174 7

389.173 8

-2.31

321.111 4,305.080 1,267.064 7,183.080 4,137.023 0

[M+H]⁺

Flavonoid

137

28.79

Bakuchiol^[72]

C₁₈H₂₄O

257.190 0

257.189 5

-1.95

201.127 0,187.111 6,173.096 1,147.080 3,133.064 8,121.064 9,107.049 5

[M+H]⁺

Terpene