药学学报

No.	t_R /min	Theoretical mass (m/z)	Exact mass (m/z)	Formula	Ion adduction	Error /ppm	Production (m/z)	Compound	Type	Source
1	1.38	155.033 9	155.033 9	C₇H₆O₄	[M+H]⁺	0.32	155.033 9, 109.028 8	3, 4-Dihydroxybenzoic acid	PA	[20]
2	1.49	345.046 3	345.046 6	C₁₃H₁₄O₁₁	[M-H]^-	3.86	193.035 5, 169.014 6	Gallic acyl-3-O-β-D-glucuronide	PA	[11]
3	2.5	149.059 7	149.059 8	C₉H₈O₂	[M+H]⁺	0.83	131.039 3, 103.054 6	Cinnamic acid	PH	[20]
4	3.03	165.054 6	165.054 8	C₉H₈O₃	[M+H]⁺	1.05	147.044 2, 119.049 5	3-p-Hydroxycinnamic acid	PH	[20]
5	3.17	361.112 9	361.113 0	C₁₅H₂₀O₁₀	[M+H]⁺	0.57	199.060 4, 163.060 3	Breviscapine C	F	[21]
6	3.34	241.070 7	241.071 4	C₁₁H₁₂O₆	[M+H]⁺	0.66	241.071 4, 113.023 6	Pyromucic acid glycoside	G	[20]
7	3.4	353.087 8	353.088	C₁₆H₁₈O₉	[M-H]^-	4.13	191.056 2, 179.035 0, 161.024 0, 135.045 2, 109.029 5	3-CQA	PA	[22]
8	3.43	353.087 8	353.088	C₁₆H₁₈O₉	[M-H]^-	3.61	191.055 9, 179.034 6, 173.045 5, 161.024 5, 135.045 0, 109.029 6	1-CQA	PA	[23]
9	3.47	353.087 8	353.088 1	C₁₆H₁₈O₉	[M-H]^-	4.04	191.056 1, 179.034 6, 173.045 7, 161.024 5, 135.045 1, 109.029 5	5-CQA	PA	[23]
10	3.98	341.086 7	341.086 8	C₁₅H₁₆O₉	[M+H]⁺	0.16	341.086 8, 181.049 6, 179.033 9, 162.054 9	Esculin	C	[20]
11	4.28	517.155 2	517.155 8	C₂₂H₂₈O₁₄	[M+H]⁺	1.12	355.102 8, 191.053 4, 163.003 9	5-Caffeoylquinic acid glucoside	PA	[23]
12	4.41	337.092 9	337.093 2	C₁₆H₁₈O₈	[M-H]^-	4.17	191.056 2, 173.045 6, 163.040 1, 119.050 4	5-p-Coumaroylquinic acid	PA	GNPS
13	4.63	381.082 7	381.083	C₁₇H₁₈O₁₀	[M-H]^-	3.55	161.024 1, 135.045 2, 133.029 8	3-CDOA	PA	[23]
14	4.66	397.077 6	397.077 8	C₁₇H₁₈O₁₁	[M-H]^-	3.23	191.056 2, 179.034 7, 161.024 1, 135.045 2	2-COA	PA	[23]
15	4.7	397.077 6	397.077 7	C₁₇H₁₈O₁₁	[M-H]^-	2.92	191.056 2, 179.035 0, 161.045 6, 135.045 2	4-COA	PA	[23]
16	4.76	397.077 6	397.077 7	C₁₇H₁₈O₁₁	[M-H]^-	2.92	191.056 2, 179.034 9, 161.024 2, 135.045 1	3-COA	PA	[23]
17	4.81	355.102 4	355.102 4	C₁₆H₁₈O₉	[M+H]⁺	0.16	355.102 4, 193.049 4	6-Methoxycoumarin-7-O-β-D-glucopyranoside	C	[20]
18	4.83	397.077 6	397.077 6	C₁₇H₁₈O₁₀	[M-H]^-	2.61	191.056 2, 179.024 3, 161.024 3, 135.045 1	9-COA	PA	[23]
19	5.11	353.087 8	353.088	C₁₆H₁₈O₉	[M-H]^-	3.78	191.056 1, 179.034 8, 173.045 5, 161.024 4, 135.045 1, 109.029 5	4-CQA	PA	[22]
20	5.18	325.092 9	325.093 1	C₁₅H₁₈O₈	[M-H]^-	3.95	163.040 2, 146.966 1, 119.050 0	(E)-3-[2-[(2S, 3R, 4S, 5S, 6R)-3, 4, 5-Trihydroxy-6-(hydroxymethyl)oxan-2-yl]oxyphenyl]prop-2-enoic acid	PA	GNPS
21	5.54	381.082 7	381.083	C₁₇H₁₈O₁₀	[M-H]^-	3.63	161.024 2, 135.045 3, 133.029 6	4-CDOA	PA	[23]
22	6.77	381.082 7	381.083	C₁₇H₁₈O₁₀	[M-H]^-	3.55	161.024 1, 135.045 2, 133.029 5	9-CDOA	PA	[23]
23	6.97	195.065 2	195.065 4	C₁₀H₁₀O₄	[M+H]⁺	1.33	177.054 8, 149.059 8	Ferulic acid	PH	[23, 24]
24	7.04	195.065 2	195.065 3	C₁₀H₁₀O₄	[M+H]⁺	0.78	193.049 8, 177.054 8, 163.039 1	Methyl caffeate	PA	[20]
25	8.08	352.101 1	352.101 6	C₁₃H₂₁O₁₁	[M-H]^-	4.4	173.045 8, 111.045 4	Quinic acid glucoside-1	PA	[20]
26	8.36	367.103 5	367.103 6	C₁₇H₂₀O₉	[M-H]^-	3.40	353.088 2, 191.035 1, 179.035 1, 173.045 8	4/5-O-Caffeoylquinic acid methyl ester	PA	[25]
27	8.43	367.103 5	367.103 6	C₁₇H₂₀O₉	[M-H]^-	3.40	193.050 5, 191.056 0, 173.045 4, 134.047 4	3-O-Feruloylquinic acid	PA	GNPS
28	8.54	367.103 5	367.103 6	C₁₇H₂₀O₉	[M-H]^-	3.40	353.087 9, 191.035 2, 179.035 0, 173.045 6	4/5-O-Caffeoylquinic acid methyl ester	PA	[25]
29	8.73	369.118 0	369.118 2	C₁₇H₂₀O₉	[M+H]⁺	0.59	369.118 2, 191.053 1	5-Feruloylquinic acid	PA	[20]
30	8.75	367.103 5	367.103 6	C₁₇H₂₀O₉	[M-H]^-	3.32	353.087 8, 191.035 1, 179.035 1	4/5-O-Caffeoylquinic acid methyl ester	PA	[25]
31	8.95	179.070 3	179.070 3	C₁₀H₁₀O₃	[M+H]⁺	0.06	161.059 8, 133.064 9	p-Methoxycinnamic acid	A	[20]
32	10.15	379.103 5	379.103 2	C₁₈H₂₀O₉	[M-H]^-	2.09	379.103 2, 161.045 6	5-O-Caffeoylquinic acid methyl ester	PA	[20]
33	10.24	155.033 9	155.034 0	C₇H₆O₄	[M+H]⁺	0.42	137.023 5, 109.028 7	Protocatechuic acid	PA	[11]
34	11.58	601.119 9	601.118 0	C₂₈H₂₆O₁₅	[M-H]^-	-1.35	353.088 0, 233.066 8, 195.065 2	1/4-Malonyl-diCQA	PA	[25]
35	11.93	181.049 5	181.049 5	C₉H₈O₄	[M+H]⁺	-0.03	181.049 5, 163.039 0, 135.044 2	3, 4-Dihydroxycinnamic acid	A	[20]
36	12.00	437.107 8	437.107 9	C₂₀H₂₀O₁₁	[M+H]⁺	0.24	163.038 9, 145.028 1	Erigeroside	G	[20]
37	12.02	435.093 3	435.093 3	C₂₀H₂₀O₁₁	[M-H]^-	2.33	323.077 1, 179.035 0, 161.024 3, 135.045 1, 133.029 3	Erigeside Ⅰ	O	[11, 26]
38	12.19	379.103 5	379.103 1	C₁₈H₂₀O₉	[M-H]^-	2.01	379.103 1, 161.045 7	4-O-Caffeoylquinic acid methyl ester	PA	[20]
39	12.26	463.088 2	463.088 6	C₂₁H₂₀O₁₂	[M-H]^-	3.15	301.035 3, 151.040 2, 135.045 3	Quercetin-3-O-β-D-glucopyranoside	F	[25]
40	12.30	463.088 2	463.088 6	C₂₁H₂₀O₁₂	[M-H]^-	3.22	301.035 4, 283.025 3, 151.040 1	Quercetin-3-O-β-D-glucoside	F	[22]
41	12.32	289.070 7	289.070 7	C₁₅H₁₂O₆	[M+H]⁺	0.15	121.028 7	Eriodictyol	F	[20]
42	12.47	477.067 5	477.067 7	C₂₁H₁₈O₁₃	[M-H]^-	2.71	477.067 7, 301.035 2	Quercetin-7-O-glucuronide	F	[11]
43	12.51	477.067 5	477.067 7	C₂₁H₁₈O₁₃	[M-H]^-	2.71	301.035 2, 151.003 5	Quercetin-3-O-glucuronide	F	[20]
44	12.54	477.067 5	477.067 6	C₂₁H₁₈O₁₃	[M-H]^-	2.77	301.035 3, 283.024 6	Galactose-3-O-glucuronate	F	[11]
45	12.58	463.088 2	463.088 4	C₂₁H₂₀O₁₂	[M-H]^-	2.88	301.035 3, 151.040 2, 135.045 3	Quercetin-3-O-β-D-glucopyranoside	F	[25]
46	12.60	479.082 0	479.082 3	C₂₁H₁₈O₁₃	[M+H]⁺	0.6	479.082 3, 303.049 7	Quercetin-3-O-β-galacturonide	F	[23]
47	12.61	461.072 5	461.072 8	C₂₁H₁₈O₁₂	[M-H]^-	2.89	286.043 8, 285.040 4	Kaempferol-3-O-glucuronide	F	GNPS
48	12.63	463.087 1	463.087 4	C₂₁H₁₈O₁₂	[M+H]⁺	0.71	287.054 2, 177.054 7, 121.028 6	Scutellarin*	F	[27]
49	12.70	449.107 8	449.107 9	C₂₁H₂₀O₁₁	[M+H]⁺	0.23	288.057 7, 287.054 3, 269.042 4, 153.018 0	Kaempferol-4′-O-β-D-glucoside	F	GNPS
50	12.73	449.107 8	449.107 9	C₂₁H₂₀O₁₁	[M+H]⁺	0.16	285.039 5	Quercetin-3-O-deoxyhexoside	F	GNPS
51	12.75	477.093 3	477.093 4	C₂₁H₂₀O₁₁	[M-H]^-	2.74	327.050 9, 285.040 4	Kaempferol-3-O-glucoside	F	[20]
52	12.77	463.087 1	463.087 3	C₂₁H₁₈O₁₂	[M+H]⁺	0.52	463.087 3, 287.054 5	Scutellarein-6-O-glucuronide	F	[28]
53	12.78	447.093 3	447.093 3	C₂₁H₂₀O₁₁	[M-H]^-	2.54	353.087 7, 285.040 4, 119.034 9	Scutellarein-7-O-glucoside	F	[25]
54	12.81	461.072 5	461.072 8	C₂₁H₁₈O₁₂	[M-H]^-	2.89	445.078 0, 287.056 1, 285.040 4	Breviscapine	F	[29]
55	12.85	559.109 3	559.109 4	C₂₆H₂₄O₁₄	[M-H]^-	2.15	285.040 3, 191.056 0, 179.056 1, 161.045 6, 135.045 2	3, 9/4.9-COA	PA	[25]
56	12.95	559.109 3	559.109 6	C₂₆H₂₄O₁₄	[M-H]^-	2.37	353.087 8, 285.040 4, 191.056 3, 179.035 1, 161.045 6, 135.045 3	3, 9/4.9-COA	PA	[26]
57	13.53	593.151 2	593.151 6	C₂₇H₃₀O₁₅	[M-H]^-	2.55	287.057 0, 129.055 9	Kaempferol-3-O-rutinoside	F	[20]
58	13.53	417.082 7	417.083 0	C₂₀H₁₈O₁₀	[M-H]^-	3.39	285.040 6, 215.010 0, 161.045 7, 121.029 6	Kaempferol-3-O-arabinoside	F	[25]
59	13.71	515.119 5	515.119 9	C₂₅H₂₄O₁₂	[M-H]^-	2.85	353.087 7, 335.077 5, 191.055 7, 179.035 0, 173.044 9, 161.024 5, 135.045 0	1, 5-diCQA	PA	[27]
60	13.86	179.035 0	179.034 5	C₉H₈O₄	[M-H]^-	3.43	179.035 0, 135.045 2	Caffeic acid	PA	[27]
61	13.92	515.119 5	515.119 8	C₂₅H₂₄O₁₂	[M-H]^-	2.62	353.087 7, 335.077 2, 191.056 0, 179.034 6, 173.045 4, 161.023 9, 135.045 2	1, 3-diCQA	PA	[30]
62	14.07	447.093 3	447.093 5	C₂₁H₂₀O₁₁	[M-H]^-	2.94	429.082 3, 313.071 6, 193.035 5, 131.034 9	Naringenin-7-O-glucuronide	F	[20]
63	14.07	417.082 7	417.082 9	C₂₀H₁₈O₁₀	[M-H]^-	3.10	285.040 5, 215.009 9, 161.045 6, 121.029 6	Kaempferol-3-O-arabinoside	F	[25]
64	14.10	543.114 4	543.114 9	C₂₆H₂₄O₁₃	[M-H]^-	2.86	353.087 7, 179.034 4, 161.045 6, 135.045 2	ErigosterB/4, 9-diCDOA	PA	[25]
65	14.24	543.114 4	543.114 6	C₂₆H₂₄O₁₃	[M-H]^-	2.41	353.088 0, 179.034 9, 161.045 6, 135.044 9	ErigosterB/4, 9-diCDOA	PA	[25]
66	14.36	479.118 4	479.118 7	C₂₂H₂₂O₁₂	[M+H]⁺	0.52	318.068 9, 317.065 7	Isorhamnetin-3-O-glucoside	F	GNPS
67	14.45	447.093 3	447.093 5	C₂₁H₂₀O₁₁	[M-H]^-	2.88	271.061 2, 257.045 2	Naringenin-7-O-glucuronide	F	[11]
68	14.57	433.112 9	433.112 9	C₂₁H₂₀O₁₀	[M+H]⁺	0.61	271.117 1, 254.102 3, 121.028 5	Cosmosiin	F	[23]
69	14.59	431.098 4	431.098 6	C₂₁H₂₀O₁₀	[M-H]^-	3.01	431.098 6, 269.045 4	Scutellarin-7-O-glucoside	F	[20]
70	14.62	431.098 4	431.098 6	C₂₁H₂₀O₁₀	[M-H]^-	3.01	431.098 6, 269.045 5	Baicalein-7-O-β-D-glucopyranoside	F	[20]
71	14.69	445.077 6	445.077 9	C₂₁H₁₈O₁₁	[M-H]^-	3.09	269.045 5, 175.024 8, 129.055 7, 117.018 9, 113.024 4	Breviscapine I	F	[27]
72	14.73	445.077 6	445.077 9	C₂₁H₁₈O₁₁	[M-H]^-	2.95	269.045 4, 117.034 3	Apigenin-7-O-glucuronide*	F	[11]
73	14.80	445.077 6	445.078 0	C₂₁H₁₈O₁₁	[M-H]^-	3.22	271.060 9, 153.019 5, 119.050 2	Apigenin-7-O-β-galacturonide	F	[23]
74	14.80	287.056 1	287.056 2	C₁₅H₁₂O₆	[M-H]^-	4.07	161.045 7, 151.003 7, 135.045 3	Eriodictyol	F	[25]
75	14.87	445.077 6	445.078 0	C₂₁H₁₈O₁₁	[M-H]^-	3.29	429.083 2, 271.061 0, 269.045 5, 113.024 5	Baicalin*	F	[31]
76	15.18	493.097 7	493.098 1	C₂₂H₂₀O₁₃	[M+H]⁺	0.97	318.067 8, 317.064 9, 302.041 1, 153.010 9	Isorhamnetin-3-O-β-D-glucuronide	F	GNPS
77	15.24	515.119 5	515.119 8	C₂₅H₂₄O₁₂	[M-H]^-	2.62	353.087 4, 191.055 7, 179.034 4, 173.045 2, 161.045 6, 135.045 2	1, 4-diCQA	PA	[25]
78	15.28	463.123 5	463.123 4	C₂₂H₂₂O₁₁	[M+H]⁺	-0.10	301.069 8, 287.055 2	6-Methoxykaempferol-4′-O-β-D-glucoside	F	GNPS
79	15.30	515.119 5	515.119 7	C₂₅H₂₄O₁₂	[M-H]^-	2.50	353.087 6, 191.056 0, 179.034 6, 173.045 3, 161.024 1, 135.045 2	3, 4-diCQA*	PA	[27]
80	15.33	515.119 5	515.119 7	C₂₅H₂₄O₁₂	[M-H]^-	2.50	353.087 4, 191.055 9, 179.034 6, 173.045 3, 161.024 2, 135.045 2	3, 5-diCQA*	PA	[27, 30]
81	15.37	515.119 5	515.119 7	C₂₅H₂₄O₁₂	[M-H]^-	2.50	353.087 6, 191.055 9, 179.034 6, 173.045 2, 161.024 2, 135.045 2	4, 5-diCQA*	PA	[27]
82	15.44	475.088 2	475.088 4	C₂₂H₂₀O₁₂	[M-H]^-	2.69	299.056 1, 283.024 7	Kaempferol-7-O-glucuronide	F	[11]
83	15.62	475.088 2	475.088 6	C₂₂H₂₀O₁₂	[M-H]^-	3.14	299.056 1, 283.024 7	Kaempferol-3-O-glucuronide	F	[11]
84	15.75	477.102 8	477.103 1	C₂₂H₂₀O₁₂	[M+H]⁺	0.70	301.069 9, 177.054 9, 113.023 6	6-Methoxyscutellarein-7-O-glucuronide	F	[28]
85	15.95	557.130 1	557.130 6	C₂₇H₂₆O₁₃	[M-H]^-	2.97	381.083 4, 191.056 2, 179.035 1, 161.024 4	Erigoster A	PA	[25]
86	16.06	529.135 1	529.134 3	C₂₆H₂₆O₁₂	[M-H]^-	0.54	353.088 5, 179.034 6, 161.045 6, 135.045 2	3, 4/3, 5-O-Dicaffeoylquinic acid methyl ester	PA	[25]
87	16.2	285.040 5	285.040 6	C₁₅H₁₀O₆	[M-H]^-	4.4	268.037 6, 257.045 5, 239.034 9, 171.045 2, 121.029 4, 117.034 5, 109.029 3	Kaempferol	F	[20]
88	16.25	507.113 3	507.113 5	C₂₃H₂₂O₁₃	[M+H]⁺	0.41	287.055 2, 113.023 6	5, 6, 4′-Trihydroxyflavone-7-O-β-D-glucopyranuronate ethyl ester	F	[20]
89	16.27	285.040 5	285.040 6	C₁₅H₁₀O₆	[M-H]^-	4.40	267.030 1, 239.034 9, 213.055 7, 195.045 2	Scutellarein	F	[20]
90	16.34	287.056 1	287.056 2	C₁₅H₁₂O₆	[M-H]^-	4.40	161.045 6, 151.003 9, 135.045 2	Eriodictyol	F	[25]
91	16.41	285.040 5	285.040 6	C₁₅H₁₀O₆	[M-H]^-	4.4	269.045 9, 245.045 6, 243.029 9, 239.035 2, 229.050 7, 213.056 0, 211.040 3, 201.055 8, 179.035 2, 161.024 4, 137.024 5	Luteolin	F	[20]
92	16.82	557.130 1	557.130 6	C₂₇H₂₆O₁₃	[M-H]^-	2.96	381.082 4, 191.056 3, 179.034 9, 161.024 5	Erigoster A	PA	[25]
93	16.85	529.135 1	529.135 3	C₂₆H₂₆O₁₂	[M-H]^-	2.39	353.088 2, 179.034 9, 161.045 7, 135.045 4	3, 4/3, 5-O-Dicaffeoylquinic acid methyl ester	PA	[25]
94	17.10	501.139 1	501.139 6	C₂₅H₂₄O₁₁	[M+H]⁺	0.90	427.066 9, 271.096 0, 153.054 5	Apigenin-7-O-β-D-glucopyranuronic acid butyl ester	F	[28]
95	17.12	557.130 1	557.130 4	C₂₇H₂₆O₁₃	[M-H]^-	2.52	191.056 3, 179.034 8, 161.045 7	Acetylated-diCQA	PA	[25]
96	17.49	557.130 1	557.130 4	C₂₇H₂₆O₁₃	[M-H]^-	2.52	191.055 8, 179.034 9, 161.024 5	Acetylated-diCQA	PA	[25]
97	17.59	287.056 1	287.056 3	C₁₅H₁₂O₆	[M-H]^-	4.50	287.056 3, 161.045 7, 135.045 2	Eriodictyol	F	[25]
98	17.62	209.080 8	209.080 8	C₁₁H₁₂O₄	[M+H]⁺	0.30	191.070 4, 163.075 5	Ethyl caffeate	PA	[20]
99	17.73	491.118 4	491.119 0	C₂₃H₂₂O₁₂	[M+H]⁺	1.25	287.054 8, 221.081 0, 113.023 6	5, 6, 4′-Trihydroxyflavone-7-O-β-D-glucopyranuronate ethyl ester	F	[28]
100	17.8	491.118 4	491.118 6	C₂₃H₂₂O₁₂	[M+H]⁺	0.45	287.054 9, 221.081 0, 113.023 6	Scutellarin ethyl ester	F	[32]
101	17.93	301.035 4	301.035 5	C₁₅H₁₀O₇	[M-H]^-	4.13	299.019 8, 271.024 9, 151.003 1, 149.024 0, 148.016 1, 133.029 4	3, 5, 6, 7, 4′-Pentahydroxyflavone	F	[20]
102	17.95	481.134 1	481.133 9	C₂₂H₂₄O₁₂	[M+H]⁺	-0.42	481.133 9, 163.038 8	1-(2′-γ-Pyrone)-6-caffeoyl-2-D-glucopyranoside	F	[20]
103	18.00	301.035 4	301.035 5	C₁₅H₁₀O₇	[M-H]^-	4.13	283.024 927 3.0 404, 178.998 2, 151.003 5, 121.029 6	Quercetin	F	[20]
104	18.20	461.107 8	461.108 3	C₂₂H₂₀O₁₁	[M+H]⁺	1.02	301.107 4, 287.055 3, 269.117 0, 189.054 9, 175.075 6, 153.054 8	Scutellarein glucuronide methyl ether	F	[30]
105	18.23	529.135 1	529.135 4	C₂₆H₂₆O₁₂	[M-H]^-	2.50	353.088 2, 179.035 1, 161.045 6, 135.045 2	3, 4/3, 5-O-Dicaffeoylquinic acid methyl ester	PA	[25]
106	18.26	585.125 0	585.125 3	C₂₈H₂₆O₁₄	[M-H]^-	2.43	395.077 0, 353.088 0, 233.154 6, 179.035 0, 137.024 6	1-Malonyl-3, 5-dicaffeoylquinic acid	PA	[23]
107	18.32	459.186 1	459.186 2	C₂₁H₃₀O₁₁	[M+H]⁺	0.15	459.186 2, 297.133 8, 163.060 4	(+)-Syringaresinol-O-β-D-glucopyranoside	C	[20]
108	18.40	557.130 1	557.130 3	C₂₇H₂₆O₁₃	[M-H]^-	2.30	191.056 2, 179.035 0, 161.024 5	Acetylated-diCQA	PA	[25]
109	18.83	207.065 1	207.065 4	C₁₁H₁₀O₄	[M+H]⁺	1.25	189.054 7	Scopoletin	C	[33]
110	18.87	207.065 1	207.065 4	C₁₁H₁₀O₄	[M+H]⁺	0.81	193.049 7, 177.054 9, 163.039 0	Methyl caffeate	PA	[20]
111	19.07	271.061 2	271.061 3	C₁₅H₁₂O₅	[M-H]^-	4.24	177.019 2, 165.019 3, 161.045 6, 145.050 6, 119.049 6	Naringenin*	F	[22]
112	19.08	273.075 8	273.075 7	C₁₅H₁₂O₅	[M+H]⁺	-0.13	271.060 2, 169.977 3, 119.068 8, 119.049 2	5, 7, 4′-Trihydroxyflavanone	F	[20]
113	19.1	269.045 5	269.045 6	C₁₅H₁₀O₅	[M-H]^-	4.36	269.045 6, 252.042	Baicalein*	F	[20]
114	19.13	269.045 5	269.045 6	C₁₅H₁₀O₅	[M-H]^-	4.25	227.034 7, 225.055 6, 201.055 9, 159.044 9, 151.003 7, 117.034 4	Apigenin*	F	[34]
115	19.33	303.086 3	303.086 3	C₁₆H₁₄O₆	[M+H]⁺	-0.04	273.075 6, 169.049 6, 135.044 1	1-Hydroxy-2, 3, 5-trihydroxyxanthone	F	[20]
116	19.34	329.066 7	329.066 8	C₁₇H₁₄O₇	[M-H]^-	3.72	285.040 7, 185.060 8, 178.977 9, 151.040 2	3′, 4′-Dimethoxyquercetin	F	[35]
117	19.36	301.070 7	301.070 8	C₁₆H₁₂O₆	[M+H]⁺	0.45	287.055 0, 177.054 8, 121.028 6	Hispidulin	F	[28]
118	19.4	301.070 7	301.070 8	C₁₆H₁₂O₆	[M+H]⁺	0.55	283.059 2, 271.060 1, 169.049 5, 133.049 6	Scutellarein methyl ether	F	[29]
119	19.56	315.051 0	315.051 2	C₁₆H₁₂O₇	[M-H]^-	4.16	299.019 4, 285.040 6, 243.029 3, 179.034 8, 161.024 5, 137.024 5, 123.008 9	3, 5, 6, 4′-Tetrahydroxy-7-methoxyflavone	F	[20]
120	20.15	455.077 2	455.077 2	C₂₆H₁₆O₈	[M-H]^-	1.87	455.077 2, 191.035 1, 161.024 5	3-O-Caffeoyl-γ-quinlactone	PA	[25]
121	27.8	413.377 8	413.377 8	C₂₉H₄₈O	[M+H]⁺	-0.04	413.377 8, 395.367 3	Stigmasterol	S	[20]
122	27.9	395.330 8	395.331 2	C₂₈H₄₂O	[M+H]⁺	0.77	377.320 8, 271.205 8	Ergosta-7, 22-dien-3-one	S	[20]
123	-	315.051 0	315.051 0	C₁₆H₁₂O₇	[M-H]^-	-	151.002 7, 107.049 7	Isorhamnetin	F	GNPS
124	-	677.151 2	677.151 0	C₃₄H₃₀O₁₅	[M-H]^-	-	515.119 6, 353.087 7, 191.055 9, 179.034 5, 173.045 3, 161.024 2, 135.045 2	3, 4, 5-triCQA	PA	GNPS
125	-	677.151 2	677.172 0	C₃₄H₃₀O₁₅	[M-H]^-	-	515.119 6, 353.087 6, 191.055 9, 179.034 5, 173.045 3, 161.024 2, 135.045 1	3, 4, 5-triCQA or its isomers	PA	GNPS

No.	t_R /min	Theoretical mass (m/z)	Exact mass (m/z)	Formula	Ion adduction	Error /ppm	Production (m/z)	Compound	Type	Source
1	1.38	155.033 9	155.033 9	C₇H₆O₄	[M+H]⁺	0.32	155.033 9, 109.028 8	3, 4-Dihydroxybenzoic acid	PA	[20]
2	1.49	345.046 3	345.046 6	C₁₃H₁₄O₁₁	[M-H]^-	3.86	193.035 5, 169.014 6	Gallic acyl-3-O-β-D-glucuronide	PA	[11]
3	2.5	149.059 7	149.059 8	C₉H₈O₂	[M+H]⁺	0.83	131.039 3, 103.054 6	Cinnamic acid	PH	[20]
4	3.03	165.054 6	165.054 8	C₉H₈O₃	[M+H]⁺	1.05	147.044 2, 119.049 5	3-p-Hydroxycinnamic acid	PH	[20]
5	3.17	361.112 9	361.113 0	C₁₅H₂₀O₁₀	[M+H]⁺	0.57	199.060 4, 163.060 3	Breviscapine C	F	[21]
6	3.34	241.070 7	241.071 4	C₁₁H₁₂O₆	[M+H]⁺	0.66	241.071 4, 113.023 6	Pyromucic acid glycoside	G	[20]
7	3.4	353.087 8	353.088	C₁₆H₁₈O₉	[M-H]^-	4.13	191.056 2, 179.035 0, 161.024 0, 135.045 2, 109.029 5	3-CQA	PA	[22]
8	3.43	353.087 8	353.088	C₁₆H₁₈O₉	[M-H]^-	3.61	191.055 9, 179.034 6, 173.045 5, 161.024 5, 135.045 0, 109.029 6	1-CQA	PA	[23]
9	3.47	353.087 8	353.088 1	C₁₆H₁₈O₉	[M-H]^-	4.04	191.056 1, 179.034 6, 173.045 7, 161.024 5, 135.045 1, 109.029 5	5-CQA	PA	[23]
10	3.98	341.086 7	341.086 8	C₁₅H₁₆O₉	[M+H]⁺	0.16	341.086 8, 181.049 6, 179.033 9, 162.054 9	Esculin	C	[20]
11	4.28	517.155 2	517.155 8	C₂₂H₂₈O₁₄	[M+H]⁺	1.12	355.102 8, 191.053 4, 163.003 9	5-Caffeoylquinic acid glucoside	PA	[23]
12	4.41	337.092 9	337.093 2	C₁₆H₁₈O₈	[M-H]^-	4.17	191.056 2, 173.045 6, 163.040 1, 119.050 4	5-p-Coumaroylquinic acid	PA	GNPS
13	4.63	381.082 7	381.083	C₁₇H₁₈O₁₀	[M-H]^-	3.55	161.024 1, 135.045 2, 133.029 8	3-CDOA	PA	[23]
14	4.66	397.077 6	397.077 8	C₁₇H₁₈O₁₁	[M-H]^-	3.23	191.056 2, 179.034 7, 161.024 1, 135.045 2	2-COA	PA	[23]
15	4.7	397.077 6	397.077 7	C₁₇H₁₈O₁₁	[M-H]^-	2.92	191.056 2, 179.035 0, 161.045 6, 135.045 2	4-COA	PA	[23]
16	4.76	397.077 6	397.077 7	C₁₇H₁₈O₁₁	[M-H]^-	2.92	191.056 2, 179.034 9, 161.024 2, 135.045 1	3-COA	PA	[23]
17	4.81	355.102 4	355.102 4	C₁₆H₁₈O₉	[M+H]⁺	0.16	355.102 4, 193.049 4	6-Methoxycoumarin-7-O-β-D-glucopyranoside	C	[20]
18	4.83	397.077 6	397.077 6	C₁₇H₁₈O₁₀	[M-H]^-	2.61	191.056 2, 179.024 3, 161.024 3, 135.045 1	9-COA	PA	[23]
19	5.11	353.087 8	353.088	C₁₆H₁₈O₉	[M-H]^-	3.78	191.056 1, 179.034 8, 173.045 5, 161.024 4, 135.045 1, 109.029 5	4-CQA	PA	[22]
20	5.18	325.092 9	325.093 1	C₁₅H₁₈O₈	[M-H]^-	3.95	163.040 2, 146.966 1, 119.050 0	(E)-3-[2-[(2S, 3R, 4S, 5S, 6R)-3, 4, 5-Trihydroxy-6-(hydroxymethyl)oxan-2-yl]oxyphenyl]prop-2-enoic acid	PA	GNPS
21	5.54	381.082 7	381.083	C₁₇H₁₈O₁₀	[M-H]^-	3.63	161.024 2, 135.045 3, 133.029 6	4-CDOA	PA	[23]
22	6.77	381.082 7	381.083	C₁₇H₁₈O₁₀	[M-H]^-	3.55	161.024 1, 135.045 2, 133.029 5	9-CDOA	PA	[23]
23	6.97	195.065 2	195.065 4	C₁₀H₁₀O₄	[M+H]⁺	1.33	177.054 8, 149.059 8	Ferulic acid	PH	[23, 24]
24	7.04	195.065 2	195.065 3	C₁₀H₁₀O₄	[M+H]⁺	0.78	193.049 8, 177.054 8, 163.039 1	Methyl caffeate	PA	[20]
25	8.08	352.101 1	352.101 6	C₁₃H₂₁O₁₁	[M-H]^-	4.4	173.045 8, 111.045 4	Quinic acid glucoside-1	PA	[20]
26	8.36	367.103 5	367.103 6	C₁₇H₂₀O₉	[M-H]^-	3.40	353.088 2, 191.035 1, 179.035 1, 173.045 8	4/5-O-Caffeoylquinic acid methyl ester	PA	[25]
27	8.43	367.103 5	367.103 6	C₁₇H₂₀O₉	[M-H]^-	3.40	193.050 5, 191.056 0, 173.045 4, 134.047 4	3-O-Feruloylquinic acid	PA	GNPS
28	8.54	367.103 5	367.103 6	C₁₇H₂₀O₉	[M-H]^-	3.40	353.087 9, 191.035 2, 179.035 0, 173.045 6	4/5-O-Caffeoylquinic acid methyl ester	PA	[25]
29	8.73	369.118 0	369.118 2	C₁₇H₂₀O₉	[M+H]⁺	0.59	369.118 2, 191.053 1	5-Feruloylquinic acid	PA	[20]
30	8.75	367.103 5	367.103 6	C₁₇H₂₀O₉	[M-H]^-	3.32	353.087 8, 191.035 1, 179.035 1	4/5-O-Caffeoylquinic acid methyl ester	PA	[25]
31	8.95	179.070 3	179.070 3	C₁₀H₁₀O₃	[M+H]⁺	0.06	161.059 8, 133.064 9	p-Methoxycinnamic acid	A	[20]
32	10.15	379.103 5	379.103 2	C₁₈H₂₀O₉	[M-H]^-	2.09	379.103 2, 161.045 6	5-O-Caffeoylquinic acid methyl ester	PA	[20]
33	10.24	155.033 9	155.034 0	C₇H₆O₄	[M+H]⁺	0.42	137.023 5, 109.028 7	Protocatechuic acid	PA	[11]
34	11.58	601.119 9	601.118 0	C₂₈H₂₆O₁₅	[M-H]^-	-1.35	353.088 0, 233.066 8, 195.065 2	1/4-Malonyl-diCQA	PA	[25]
35	11.93	181.049 5	181.049 5	C₉H₈O₄	[M+H]⁺	-0.03	181.049 5, 163.039 0, 135.044 2	3, 4-Dihydroxycinnamic acid	A	[20]
36	12.00	437.107 8	437.107 9	C₂₀H₂₀O₁₁	[M+H]⁺	0.24	163.038 9, 145.028 1	Erigeroside	G	[20]
37	12.02	435.093 3	435.093 3	C₂₀H₂₀O₁₁	[M-H]^-	2.33	323.077 1, 179.035 0, 161.024 3, 135.045 1, 133.029 3	Erigeside Ⅰ	O	[11, 26]
38	12.19	379.103 5	379.103 1	C₁₈H₂₀O₉	[M-H]^-	2.01	379.103 1, 161.045 7	4-O-Caffeoylquinic acid methyl ester	PA	[20]
39	12.26	463.088 2	463.088 6	C₂₁H₂₀O₁₂	[M-H]^-	3.15	301.035 3, 151.040 2, 135.045 3	Quercetin-3-O-β-D-glucopyranoside	F	[25]
40	12.30	463.088 2	463.088 6	C₂₁H₂₀O₁₂	[M-H]^-	3.22	301.035 4, 283.025 3, 151.040 1	Quercetin-3-O-β-D-glucoside	F	[22]
41	12.32	289.070 7	289.070 7	C₁₅H₁₂O₆	[M+H]⁺	0.15	121.028 7	Eriodictyol	F	[20]
42	12.47	477.067 5	477.067 7	C₂₁H₁₈O₁₃	[M-H]^-	2.71	477.067 7, 301.035 2	Quercetin-7-O-glucuronide	F	[11]
43	12.51	477.067 5	477.067 7	C₂₁H₁₈O₁₃	[M-H]^-	2.71	301.035 2, 151.003 5	Quercetin-3-O-glucuronide	F	[20]
44	12.54	477.067 5	477.067 6	C₂₁H₁₈O₁₃	[M-H]^-	2.77	301.035 3, 283.024 6	Galactose-3-O-glucuronate	F	[11]
45	12.58	463.088 2	463.088 4	C₂₁H₂₀O₁₂	[M-H]^-	2.88	301.035 3, 151.040 2, 135.045 3	Quercetin-3-O-β-D-glucopyranoside	F	[25]
46	12.60	479.082 0	479.082 3	C₂₁H₁₈O₁₃	[M+H]⁺	0.6	479.082 3, 303.049 7	Quercetin-3-O-β-galacturonide	F	[23]
47	12.61	461.072 5	461.072 8	C₂₁H₁₈O₁₂	[M-H]^-	2.89	286.043 8, 285.040 4	Kaempferol-3-O-glucuronide	F	GNPS
48	12.63	463.087 1	463.087 4	C₂₁H₁₈O₁₂	[M+H]⁺	0.71	287.054 2, 177.054 7, 121.028 6	Scutellarin*	F	[27]
49	12.70	449.107 8	449.107 9	C₂₁H₂₀O₁₁	[M+H]⁺	0.23	288.057 7, 287.054 3, 269.042 4, 153.018 0	Kaempferol-4′-O-β-D-glucoside	F	GNPS
50	12.73	449.107 8	449.107 9	C₂₁H₂₀O₁₁	[M+H]⁺	0.16	285.039 5	Quercetin-3-O-deoxyhexoside	F	GNPS
51	12.75	477.093 3	477.093 4	C₂₁H₂₀O₁₁	[M-H]^-	2.74	327.050 9, 285.040 4	Kaempferol-3-O-glucoside	F	[20]
52	12.77	463.087 1	463.087 3	C₂₁H₁₈O₁₂	[M+H]⁺	0.52	463.087 3, 287.054 5	Scutellarein-6-O-glucuronide	F	[28]
53	12.78	447.093 3	447.093 3	C₂₁H₂₀O₁₁	[M-H]^-	2.54	353.087 7, 285.040 4, 119.034 9	Scutellarein-7-O-glucoside	F	[25]
54	12.81	461.072 5	461.072 8	C₂₁H₁₈O₁₂	[M-H]^-	2.89	445.078 0, 287.056 1, 285.040 4	Breviscapine	F	[29]
55	12.85	559.109 3	559.109 4	C₂₆H₂₄O₁₄	[M-H]^-	2.15	285.040 3, 191.056 0, 179.056 1, 161.045 6, 135.045 2	3, 9/4.9-COA	PA	[25]
56	12.95	559.109 3	559.109 6	C₂₆H₂₄O₁₄	[M-H]^-	2.37	353.087 8, 285.040 4, 191.056 3, 179.035 1, 161.045 6, 135.045 3	3, 9/4.9-COA	PA	[26]
57	13.53	593.151 2	593.151 6	C₂₇H₃₀O₁₅	[M-H]^-	2.55	287.057 0, 129.055 9	Kaempferol-3-O-rutinoside	F	[20]
58	13.53	417.082 7	417.083 0	C₂₀H₁₈O₁₀	[M-H]^-	3.39	285.040 6, 215.010 0, 161.045 7, 121.029 6	Kaempferol-3-O-arabinoside	F	[25]
59	13.71	515.119 5	515.119 9	C₂₅H₂₄O₁₂	[M-H]^-	2.85	353.087 7, 335.077 5, 191.055 7, 179.035 0, 173.044 9, 161.024 5, 135.045 0	1, 5-diCQA	PA	[27]
60	13.86	179.035 0	179.034 5	C₉H₈O₄	[M-H]^-	3.43	179.035 0, 135.045 2	Caffeic acid	PA	[27]
61	13.92	515.119 5	515.119 8	C₂₅H₂₄O₁₂	[M-H]^-	2.62	353.087 7, 335.077 2, 191.056 0, 179.034 6, 173.045 4, 161.023 9, 135.045 2	1, 3-diCQA	PA	[30]
62	14.07	447.093 3	447.093 5	C₂₁H₂₀O₁₁	[M-H]^-	2.94	429.082 3, 313.071 6, 193.035 5, 131.034 9	Naringenin-7-O-glucuronide	F	[20]
63	14.07	417.082 7	417.082 9	C₂₀H₁₈O₁₀	[M-H]^-	3.10	285.040 5, 215.009 9, 161.045 6, 121.029 6	Kaempferol-3-O-arabinoside	F	[25]
64	14.10	543.114 4	543.114 9	C₂₆H₂₄O₁₃	[M-H]^-	2.86	353.087 7, 179.034 4, 161.045 6, 135.045 2	ErigosterB/4, 9-diCDOA	PA	[25]
65	14.24	543.114 4	543.114 6	C₂₆H₂₄O₁₃	[M-H]^-	2.41	353.088 0, 179.034 9, 161.045 6, 135.044 9	ErigosterB/4, 9-diCDOA	PA	[25]
66	14.36	479.118 4	479.118 7	C₂₂H₂₂O₁₂	[M+H]⁺	0.52	318.068 9, 317.065 7	Isorhamnetin-3-O-glucoside	F	GNPS
67	14.45	447.093 3	447.093 5	C₂₁H₂₀O₁₁	[M-H]^-	2.88	271.061 2, 257.045 2	Naringenin-7-O-glucuronide	F	[11]
68	14.57	433.112 9	433.112 9	C₂₁H₂₀O₁₀	[M+H]⁺	0.61	271.117 1, 254.102 3, 121.028 5	Cosmosiin	F	[23]
69	14.59	431.098 4	431.098 6	C₂₁H₂₀O₁₀	[M-H]^-	3.01	431.098 6, 269.045 4	Scutellarin-7-O-glucoside	F	[20]
70	14.62	431.098 4	431.098 6	C₂₁H₂₀O₁₀	[M-H]^-	3.01	431.098 6, 269.045 5	Baicalein-7-O-β-D-glucopyranoside	F	[20]
71	14.69	445.077 6	445.077 9	C₂₁H₁₈O₁₁	[M-H]^-	3.09	269.045 5, 175.024 8, 129.055 7, 117.018 9, 113.024 4	Breviscapine I	F	[27]
72	14.73	445.077 6	445.077 9	C₂₁H₁₈O₁₁	[M-H]^-	2.95	269.045 4, 117.034 3	Apigenin-7-O-glucuronide*	F	[11]
73	14.80	445.077 6	445.078 0	C₂₁H₁₈O₁₁	[M-H]^-	3.22	271.060 9, 153.019 5, 119.050 2	Apigenin-7-O-β-galacturonide	F	[23]
74	14.80	287.056 1	287.056 2	C₁₅H₁₂O₆	[M-H]^-	4.07	161.045 7, 151.003 7, 135.045 3	Eriodictyol	F	[25]
75	14.87	445.077 6	445.078 0	C₂₁H₁₈O₁₁	[M-H]^-	3.29	429.083 2, 271.061 0, 269.045 5, 113.024 5	Baicalin*	F	[31]
76	15.18	493.097 7	493.098 1	C₂₂H₂₀O₁₃	[M+H]⁺	0.97	318.067 8, 317.064 9, 302.041 1, 153.010 9	Isorhamnetin-3-O-β-D-glucuronide	F	GNPS
77	15.24	515.119 5	515.119 8	C₂₅H₂₄O₁₂	[M-H]^-	2.62	353.087 4, 191.055 7, 179.034 4, 173.045 2, 161.045 6, 135.045 2	1, 4-diCQA	PA	[25]
78	15.28	463.123 5	463.123 4	C₂₂H₂₂O₁₁	[M+H]⁺	-0.10	301.069 8, 287.055 2	6-Methoxykaempferol-4′-O-β-D-glucoside	F	GNPS
79	15.30	515.119 5	515.119 7	C₂₅H₂₄O₁₂	[M-H]^-	2.50	353.087 6, 191.056 0, 179.034 6, 173.045 3, 161.024 1, 135.045 2	3, 4-diCQA*	PA	[27]
80	15.33	515.119 5	515.119 7	C₂₅H₂₄O₁₂	[M-H]^-	2.50	353.087 4, 191.055 9, 179.034 6, 173.045 3, 161.024 2, 135.045 2	3, 5-diCQA*	PA	[27, 30]
81	15.37	515.119 5	515.119 7	C₂₅H₂₄O₁₂	[M-H]^-	2.50	353.087 6, 191.055 9, 179.034 6, 173.045 2, 161.024 2, 135.045 2	4, 5-diCQA*	PA	[27]
82	15.44	475.088 2	475.088 4	C₂₂H₂₀O₁₂	[M-H]^-	2.69	299.056 1, 283.024 7	Kaempferol-7-O-glucuronide	F	[11]
83	15.62	475.088 2	475.088 6	C₂₂H₂₀O₁₂	[M-H]^-	3.14	299.056 1, 283.024 7	Kaempferol-3-O-glucuronide	F	[11]
84	15.75	477.102 8	477.103 1	C₂₂H₂₀O₁₂	[M+H]⁺	0.70	301.069 9, 177.054 9, 113.023 6	6-Methoxyscutellarein-7-O-glucuronide	F	[28]
85	15.95	557.130 1	557.130 6	C₂₇H₂₆O₁₃	[M-H]^-	2.97	381.083 4, 191.056 2, 179.035 1, 161.024 4	Erigoster A	PA	[25]
86	16.06	529.135 1	529.134 3	C₂₆H₂₆O₁₂	[M-H]^-	0.54	353.088 5, 179.034 6, 161.045 6, 135.045 2	3, 4/3, 5-O-Dicaffeoylquinic acid methyl ester	PA	[25]
87	16.2	285.040 5	285.040 6	C₁₅H₁₀O₆	[M-H]^-	4.4	268.037 6, 257.045 5, 239.034 9, 171.045 2, 121.029 4, 117.034 5, 109.029 3	Kaempferol	F	[20]
88	16.25	507.113 3	507.113 5	C₂₃H₂₂O₁₃	[M+H]⁺	0.41	287.055 2, 113.023 6	5, 6, 4′-Trihydroxyflavone-7-O-β-D-glucopyranuronate ethyl ester	F	[20]
89	16.27	285.040 5	285.040 6	C₁₅H₁₀O₆	[M-H]^-	4.40	267.030 1, 239.034 9, 213.055 7, 195.045 2	Scutellarein	F	[20]
90	16.34	287.056 1	287.056 2	C₁₅H₁₂O₆	[M-H]^-	4.40	161.045 6, 151.003 9, 135.045 2	Eriodictyol	F	[25]
91	16.41	285.040 5	285.040 6	C₁₅H₁₀O₆	[M-H]^-	4.4	269.045 9, 245.045 6, 243.029 9, 239.035 2, 229.050 7, 213.056 0, 211.040 3, 201.055 8, 179.035 2, 161.024 4, 137.024 5	Luteolin	F	[20]
92	16.82	557.130 1	557.130 6	C₂₇H₂₆O₁₃	[M-H]^-	2.96	381.082 4, 191.056 3, 179.034 9, 161.024 5	Erigoster A	PA	[25]
93	16.85	529.135 1	529.135 3	C₂₆H₂₆O₁₂	[M-H]^-	2.39	353.088 2, 179.034 9, 161.045 7, 135.045 4	3, 4/3, 5-O-Dicaffeoylquinic acid methyl ester	PA	[25]
94	17.10	501.139 1	501.139 6	C₂₅H₂₄O₁₁	[M+H]⁺	0.90	427.066 9, 271.096 0, 153.054 5	Apigenin-7-O-β-D-glucopyranuronic acid butyl ester	F	[28]
95	17.12	557.130 1	557.130 4	C₂₇H₂₆O₁₃	[M-H]^-	2.52	191.056 3, 179.034 8, 161.045 7	Acetylated-diCQA	PA	[25]
96	17.49	557.130 1	557.130 4	C₂₇H₂₆O₁₃	[M-H]^-	2.52	191.055 8, 179.034 9, 161.024 5	Acetylated-diCQA	PA	[25]
97	17.59	287.056 1	287.056 3	C₁₅H₁₂O₆	[M-H]^-	4.50	287.056 3, 161.045 7, 135.045 2	Eriodictyol	F	[25]
98	17.62	209.080 8	209.080 8	C₁₁H₁₂O₄	[M+H]⁺	0.30	191.070 4, 163.075 5	Ethyl caffeate	PA	[20]
99	17.73	491.118 4	491.119 0	C₂₃H₂₂O₁₂	[M+H]⁺	1.25	287.054 8, 221.081 0, 113.023 6	5, 6, 4′-Trihydroxyflavone-7-O-β-D-glucopyranuronate ethyl ester	F	[28]
100	17.8	491.118 4	491.118 6	C₂₃H₂₂O₁₂	[M+H]⁺	0.45	287.054 9, 221.081 0, 113.023 6	Scutellarin ethyl ester	F	[32]
101	17.93	301.035 4	301.035 5	C₁₅H₁₀O₇	[M-H]^-	4.13	299.019 8, 271.024 9, 151.003 1, 149.024 0, 148.016 1, 133.029 4	3, 5, 6, 7, 4′-Pentahydroxyflavone	F	[20]
102	17.95	481.134 1	481.133 9	C₂₂H₂₄O₁₂	[M+H]⁺	-0.42	481.133 9, 163.038 8	1-(2′-γ-Pyrone)-6-caffeoyl-2-D-glucopyranoside	F	[20]
103	18.00	301.035 4	301.035 5	C₁₅H₁₀O₇	[M-H]^-	4.13	283.024 927 3.0 404, 178.998 2, 151.003 5, 121.029 6	Quercetin	F	[20]
104	18.20	461.107 8	461.108 3	C₂₂H₂₀O₁₁	[M+H]⁺	1.02	301.107 4, 287.055 3, 269.117 0, 189.054 9, 175.075 6, 153.054 8	Scutellarein glucuronide methyl ether	F	[30]
105	18.23	529.135 1	529.135 4	C₂₆H₂₆O₁₂	[M-H]^-	2.50	353.088 2, 179.035 1, 161.045 6, 135.045 2	3, 4/3, 5-O-Dicaffeoylquinic acid methyl ester	PA	[25]
106	18.26	585.125 0	585.125 3	C₂₈H₂₆O₁₄	[M-H]^-	2.43	395.077 0, 353.088 0, 233.154 6, 179.035 0, 137.024 6	1-Malonyl-3, 5-dicaffeoylquinic acid	PA	[23]
107	18.32	459.186 1	459.186 2	C₂₁H₃₀O₁₁	[M+H]⁺	0.15	459.186 2, 297.133 8, 163.060 4	(+)-Syringaresinol-O-β-D-glucopyranoside	C	[20]
108	18.40	557.130 1	557.130 3	C₂₇H₂₆O₁₃	[M-H]^-	2.30	191.056 2, 179.035 0, 161.024 5	Acetylated-diCQA	PA	[25]
109	18.83	207.065 1	207.065 4	C₁₁H₁₀O₄	[M+H]⁺	1.25	189.054 7	Scopoletin	C	[33]
110	18.87	207.065 1	207.065 4	C₁₁H₁₀O₄	[M+H]⁺	0.81	193.049 7, 177.054 9, 163.039 0	Methyl caffeate	PA	[20]
111	19.07	271.061 2	271.061 3	C₁₅H₁₂O₅	[M-H]^-	4.24	177.019 2, 165.019 3, 161.045 6, 145.050 6, 119.049 6	Naringenin*	F	[22]
112	19.08	273.075 8	273.075 7	C₁₅H₁₂O₅	[M+H]⁺	-0.13	271.060 2, 169.977 3, 119.068 8, 119.049 2	5, 7, 4′-Trihydroxyflavanone	F	[20]
113	19.1	269.045 5	269.045 6	C₁₅H₁₀O₅	[M-H]^-	4.36	269.045 6, 252.042	Baicalein*	F	[20]
114	19.13	269.045 5	269.045 6	C₁₅H₁₀O₅	[M-H]^-	4.25	227.034 7, 225.055 6, 201.055 9, 159.044 9, 151.003 7, 117.034 4	Apigenin*	F	[34]
115	19.33	303.086 3	303.086 3	C₁₆H₁₄O₆	[M+H]⁺	-0.04	273.075 6, 169.049 6, 135.044 1	1-Hydroxy-2, 3, 5-trihydroxyxanthone	F	[20]
116	19.34	329.066 7	329.066 8	C₁₇H₁₄O₇	[M-H]^-	3.72	285.040 7, 185.060 8, 178.977 9, 151.040 2	3′, 4′-Dimethoxyquercetin	F	[35]
117	19.36	301.070 7	301.070 8	C₁₆H₁₂O₆	[M+H]⁺	0.45	287.055 0, 177.054 8, 121.028 6	Hispidulin	F	[28]
118	19.4	301.070 7	301.070 8	C₁₆H₁₂O₆	[M+H]⁺	0.55	283.059 2, 271.060 1, 169.049 5, 133.049 6	Scutellarein methyl ether	F	[29]
119	19.56	315.051 0	315.051 2	C₁₆H₁₂O₇	[M-H]^-	4.16	299.019 4, 285.040 6, 243.029 3, 179.034 8, 161.024 5, 137.024 5, 123.008 9	3, 5, 6, 4′-Tetrahydroxy-7-methoxyflavone	F	[20]
120	20.15	455.077 2	455.077 2	C₂₆H₁₆O₈	[M-H]^-	1.87	455.077 2, 191.035 1, 161.024 5	3-O-Caffeoyl-γ-quinlactone	PA	[25]
121	27.8	413.377 8	413.377 8	C₂₉H₄₈O	[M+H]⁺	-0.04	413.377 8, 395.367 3	Stigmasterol	S	[20]
122	27.9	395.330 8	395.331 2	C₂₈H₄₂O	[M+H]⁺	0.77	377.320 8, 271.205 8	Ergosta-7, 22-dien-3-one	S	[20]
123	-	315.051 0	315.051 0	C₁₆H₁₂O₇	[M-H]^-	-	151.002 7, 107.049 7	Isorhamnetin	F	GNPS
124	-	677.151 2	677.151 0	C₃₄H₃₀O₁₅	[M-H]^-	-	515.119 6, 353.087 7, 191.055 9, 179.034 5, 173.045 3, 161.024 2, 135.045 2	3, 4, 5-triCQA	PA	GNPS
125	-	677.151 2	677.172 0	C₃₄H₃₀O₁₅	[M-H]^-	-	515.119 6, 353.087 6, 191.055 9, 179.034 5, 173.045 3, 161.024 2, 135.045 1	3, 4, 5-triCQA or its isomers	PA	GNPS

基于HPLC-Q-Exactive Orbitrap MS及网络药理学的益脉康软胶囊治疗缺血性心脑血管疾病的成分及机制研究

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齐娜娜 ¹^,²^,³ , 杨履世 ¹^,²^,³ , 赵子凤 ¹^,²^,³ , 赵卫青 ¹^,²^,³ , 周玉枝 ¹^,²^,³^,^*

药学学报 | 研究论文 2026,61(4): 1345-1360

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药学学报 |研究论文 2026 , 61 (4) : 1345 -1360

基于HPLC-Q-Exactive Orbitrap MS及网络药理学的益脉康软胶囊治疗缺血性心脑血管疾病的成分及机制研究

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齐娜娜¹^,²^,³, 杨履世¹^,²^,³, 赵子凤¹^,²^,³, 赵卫青¹^,²^,³, 周玉枝¹^,²^,³^,^*

作者信息

¹山西大学中医药现代研究中心, 山西太原 030006

²山西大学化学生物学与分子工程教育部重点实验室, 山西太原 030006

³北京黄河颐圣堂中药有限公司, 北京 102600

通讯作者:

周玉枝, E-mail: zhouyuzhi@sxu.edu.cn

作者简介:

作者贡献:

周玉枝、赵子凤、赵卫青负责课题总体设计及文章修改; 齐娜娜负责实验操作、数据处理及论文撰写; 杨履世协助实验完成。

Study on the components and mechanism of Yimaikang Soft Capsules in treating ischemic cardio-cerebrovascular diseases based on HPLC-Q-Exactive Orbitrap MS and network pharmacology

Na-na QI¹^,²^,³, Lv-shi YANG¹^,²^,³, Zi-feng ZHAO¹^,²^,³, Wei-qing ZHAO¹^,²^,³, Yu-zhi ZHOU¹^,²^,³^,^*

Affiliations

¹Modern Research Center for Traditional Chinese Medicine, Shanxi University, Taiyuan 030006, China

²Key Laboratory of Chemical Biology and Molecular Engineering of the Ministry of Education, Shanxi University, Taiyuan 030006, China

³Beijing Huanghe Yishengtang Traditional Chinese Medicine Limited Liability Company, Beijing 102600, China

出版时间: 2026-04-12 doi: 10.16438/j.0513-4870.2025-1226

文章导航

摘要

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益脉康软胶囊是一种用于活血化瘀, 改善微循环的中成药, 用于治疗缺血性心脑血管疾病等, 然而其化学成分及作用机制尚不清晰。本研究采用高效液相色谱-四极杆-静电场轨道阱高分辨质谱(HPLC-Q-Exactive Orbitrap MS) 结合全球天然产物分子网络(global natural products social molecular networking, GNPS) 技术对益脉康软胶囊的化学成分进行系统分析。结果共鉴定出125个体外成分, 其中包括12个首次在益脉康系列制剂及其原料药灯盏细辛中报道的化合物。在此基础上, 进一步通过网络药理学方法, 预测并筛选出125个成分与缺血性脑血管病及冠心病的160个“成分-疾病”交集靶点, 构建“成分-靶点”相互作用网络图和蛋白互作网络图, 识别出核心成分与关键靶点。GO与KEGG通路富集分析表明, 益脉康软胶囊的作用机制主要涉及血管内皮生长因子信号通路、表皮生长因子受体信号通路、晚期糖基化终末产物-受体(advanced glycation end products-receptor for advanced glycation end products, AGE-RAGE) 信号通路等, 这些通路与血管生成、炎症调节及细胞凋亡等生物过程密切相关。分子对接验证显示, 核心成分(如3, 5, 6, 4′-四羟基-7-甲氧基黄酮、七叶树苷和山柰酚) 与对应靶点(phosphatidylinositol-4, 5-bisphosphate 3-kinase catalytic subunit beta, PIK3CB; Harvey rat sarcoma viral oncogene homolog, HRAS; phosphoinositide-3-kinase regulatory subunit 1, PIK3R1) 具有较强的结合活性。本研究初步明确了益脉康软胶囊的潜在药效成分群及其多靶点、多通路的作用机制, 为深入阐释该制剂的现代化药理基础提供了科学依据。

关键词

益脉康软胶囊 / 高效液相色谱-四极杆-静电场轨道阱高分辨质谱 / 全球天然产物社会分子网络 / 网络药理学 / 化学成分

Abstract

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Yimaikang Soft Capsule is a traditional Chinese patent medicine used to promote blood circulation, remove blood stasis and improve microcirculation in the treatment of ischemic cardio-cerebrovascular diseases. However, its chemical composition and mechanism of action remain unclear. In this study, the chemical constituents of Yimaikang Soft Capsules were systematically analyzed using high-performance liquid chromatography coupled with Q-Exactive Orbitrap mass spectrometry (HPLC-Q-Exactive Orbitrap MS) and global natural products social molecular networking (GNPS). A total of 125 in vitro components were identified, including 12 compounds reported for the first time in the Yimaikang series of preparations and its raw material herb Erigeron breviscapus. Subsequently, network pharmacology was employed to predict and screen 160 common targets shared between the 125 identified components and the diseases (ischemic cerebrovascular disease and coronary heart disease). Based on these, a "ingredient-target" interaction network and a protein-protein interaction (PPI) network were constructed to identify the core components and key targets. Gene Ontology (GO) and Kyoto Encyclopedia of Genes and Genomes (KEGG) pathway enrichment analyses revealed that the mechanism of Yimaikang Soft Capsules primarily involves signaling pathways such as the vascular endothelial growth factor (VEGF) signaling pathway, epidermal growth factor receptor (EGFR) signaling pathway and the advanced glycation end-product receptor (AGE-RAGE) signaling pathway. These pathways are closely associated with biological processes including angiogenesis, inflammation regulation, and apoptosis. Molecular docking validation demonstrated strong binding activity between core components (such as 3, 5, 6, 4′-tetrahydroxy-7-methoxyflavone, aesculin and kaempferol) and their corresponding targets (phosphatidylinositol-4, 5-bisphosphate 3-kinase catalytic subunit beta, PIK3CB; Harvey rat sarcoma viral oncogene homolog, HRAS; phosphoinositide-3-kinase regulatory subunit 1, PIK3R1). This study preliminarily identified the potential active ingredient group of Yimaikang Soft Capsules and elucidated its multi-target, multi-pathway mechanism of action, providing a scientific basis for further clarifying the modern pharmacological foundation of this formulation.

Key words

Yimaikang soft capsules / HPLC-Q-Exactive Orbitrap MS / global natural products social molecular networking / network pharmacology / chemical composition

引用本文

齐娜娜, 杨履世, 赵子凤, 赵卫青, 周玉枝. 基于HPLC-Q-Exactive Orbitrap MS及网络药理学的益脉康软胶囊治疗缺血性心脑血管疾病的成分及机制研究. 药学学报, 2026 , 61 (4) : 1345 -1360 . DOI: 10.16438/j.0513-4870.2025-1226

Na-na QI, Lv-shi YANG, Zi-feng ZHAO, Wei-qing ZHAO, Yu-zhi ZHOU. Study on the components and mechanism of Yimaikang Soft Capsules in treating ischemic cardio-cerebrovascular diseases based on HPLC-Q-Exactive Orbitrap MS and network pharmacology[J]. Acta Pharmaceutica Sinica, 2026 , 61 (4) : 1345 -1360 . DOI: 10.16438/j.0513-4870.2025-1226

正文

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脑卒中在全球范围内流行趋势严峻, 发病率居高不下, 已成为成年人群中死亡率第二且致残率最高的疾病^[1]。其中, 脑缺血性卒中约占80%, 主要是由动脉闭塞和持续性低灌注引起, 在年轻群体中的发病率持续攀升, 且女性患者往往病情更为严重, 导致全球社会经济负担急剧上升^[2]。同时, 缺血性脑卒中治疗窗口狭窄且并发症严重, 限制了药物或手术手段进行治疗的临床应用^[3]。目前, 中药在治疗缺血性脑卒中方面的优势日益凸显, 其根本优势源于“整体观”和“辨证论治”相结合的核心思想^[4]。它并非简单的“活血化瘀”, 而是一套针对复杂病理网络、覆盖疾病全过程的整合治疗体系, 特别是在神经功能恢复和改善患者长期生活质量方面, 展现出不可替代的临床价值^[5]。当前, 治疗缺血性脑卒中等疾病常用的中药材有川芎、丹参、银杏叶、灯盏细辛等^[6-9]。

其中, 由灯盏细辛浸膏加工制成的制剂有6种, 包括分散片、滴丸、片剂、胶囊剂、注射液、软胶囊^{[10, 11]}。而软胶囊剂型仅由山西黄河中药有限公司进行生产。益脉康软胶囊(Yimaikang Soft Capsules) 具有活血化瘀、改善脑血循环、增加脑血流量、提高心肌对缺血缺氧的耐受性及改善微循环的作用。临床适用于缺血性脑血管病、脑出血后遗瘫痪、眼底视网膜静脉阻塞、冠心病、血管炎性皮肤病及风湿病等病症。然其质量控制仅以总黄酮作为指标。这种单一的质控策略未能建立在系统、全面的化学成分解析基础之上, 难以全面反映药物的整体质量, 从而导致其在药效物质基础阐释、体内药代动力学行为评估等关键研究层面存在显著局限。同时, 研究深度的不足进一步制约了治疗机制的研究及临床用药的精准性与疗效的稳定性, 阻碍了该制剂在临床应用中的科学优化与合理推广。因此, 系统开展益脉康软胶囊化学成分鉴定工作及其治疗机制预测, 既是阐明其多组分-多靶点药效物质基础、构建与整体药效关联质量控制体系的关键前提, 更是提升产品质量、保障临床用药安全有效, 并为后续药理探索与临床拓展奠定基础的必然路径。

液相色谱-质谱联用技术(LC-MS) 凭借其高效分离与高灵敏度检测的优势, 已成为解析中药复杂化学成分体系的核心工具之一^{[12, 13]}。传统的方法是借助Unifi、Compound discovery等软件, 将检测到的色谱峰与Oracle、Mzcloud、Chemspider等公共数据库进行比对, 以实现化合物鉴定。然而, 由于公共数据库缺乏专一性, 且常伴随着假阳性结果, 需要大量人工甄别, 效率较低。为克服此局限, 当前的研究趋势是构建针对特定研究对象的自建数据库。通过将LC-MS数据与自建库进行靶向比对, 可显著提升化合物鉴定的准确性与效率^[14]。在非靶向分析策略上, 全球天然产物分子网络(global natural product social molecular networking, GNPS) 技术提供了全新的视角^{[15, 16]}。该技术基于MS/MS数据, 将二级质谱图谱相似的化合物自动聚类, 形成可视化网络^{[15, 17]}。其核心优势在于能够同时对单一或多个数据集中、来源于不同生物样本的相同分子、类似物进行系统性的可视化探索, 从而揭示复杂中药体系的物质基础, 并极大地促进了新化合物的发现^[18]。在机制阐释层面, 网络药理学与上述技术形成强大互补。它特别适用于阐释中药复方“多成分-多靶点-多通路”的整体调节作用机制, 在推动中药现代化研究方面展现出显著优势^[19]。这三种技术共同构成了从“化学成分精准解析”到“药理机制系统阐明”的研究链条。

本研究综合运用HPLC-Q-Exactive Orbitrap MS、GNPS及网络药理学技术, 系统分析益脉康软胶囊的化学成分, 并预测其治疗缺血性心脑血管疾病的作用机制。旨在阐明其复杂的化学成分及多靶点作用原理, 为优化该制剂的质量控制标准及推动其临床深度开发提供关键的理论与数据支撑。

材料与方法

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仪器 Ultimate 3000型超高效液相色谱仪: 含双三元梯度泵、自动进样器、柱温箱、DAD检测器(美国Thermo公司); Q Exactive Plus型高分辨率质谱仪: 配有加热电喷雾离子化源(HESI)、Xcalibur4.1化学工作站、Sorvall ST 8R高速离心机(美国Thermo Fisher Scientific公司); BT25S型十万分之一分析天平(美国Sartorius公司); BCD-215 KAGA型4 ℃冰箱(青岛海尔股份有限公司)。

试剂与试药 益脉康软胶囊(批号: Z20050662) 由山西黄河中药有限公司提供; 质谱级乙腈、甲醇和甲酸(Fisher-Scientific, 美国); 娃哈哈水。

黄芩苷(180920)、野黄芩苷(Y-012-171216) 黄芩素(H-018-180426) 均购自成都瑞芬思生物科技有限公司; 芹菜素-7-O-葡萄糖醛酸苷(29741-09-1)、3, 4-双咖啡酰奎宁酸(PS0067-0025MG)、3, 5-双咖啡酰奎宁酸(PS0066-0020)、4, 5-双咖啡酰奎宁酸(PS0068-0020)、柚皮素(PS02400-0025MG)、芹菜素(PS0172-0025MG) 均购自成都普思生物科技有限公司, 所有对照品纯度均不低于98.0%。

对照品溶液的制备 取黄芩苷、野黄芩苷、芹菜素- 7-O-葡萄糖醛酸苷、3, 4, -双咖啡酰奎宁酸、3, 5-双咖啡酰奎宁酸、4, 5-双咖啡酰奎宁酸、黄芩素、柚皮素、芹菜素对照品适量, 加甲醇超声溶解并稀释为0.02 mg·mL^-1, 得到混合对照品溶液。

供试品溶液的制备 取0.45 g益脉康软胶囊的内容物于10 mL量瓶中, 加80%甲醇溶解, 超声30 min, 于3 800 r·min^-1, 4 ℃离心15 min, 过0.22 μm微孔滤膜即得, 于4 ℃冰箱保存。

色谱条件 色谱柱: Hypersil Gold C₁₈ (100 mm × 2.1 mm, 1.8 μm), 流动相: 0.1%甲酸水(A)-乙腈(B), 洗脱梯度: 0~2 min, 95%~90% A; 2~8 min, 90% A; 8~10 min, 90%~82% A; 10~14 min, 82%~80% A; 14~20 min, 80%~45% A; 20~22 min, 45%~30% A; 22~25 min, 30%~25% A; 25~26.5 min, 25%~2% A; 26.5~27 min, 2%A; 27~27.5 min, 2%~95% A; 27.5~30 min, 95% A。流速: 0.25 mL·min^-1, 进样体积: 3 µL, 柱温: 35 ℃。

质谱条件 电喷雾离子源(ESI), 正负离子采集模式。扫描模式: Full Scan/dd-MS²; 喷雾电压正负极分别为3.5、2.5 kV; 毛细管温度: 320 ℃; 鞘气流速: 35 arb, 辅助气流速: 10 arb; m/z采集范围: 100~1 500 Da。

益脉康软胶囊化学成分数据库的建立 系统检索了Web of Science、PubMed、CNKI、Pubchem及HMDB数据库, 共收集到灯盏细辛287个化学成分的化学信息, 包括中英文名称、分子式、结构式、碎片信息、采集模式等, 将这些信息整理成Excel表格, 构建了益脉康软胶囊化学成分数据库。

化合物鉴定 采用Xcalibur4.1软件进行质谱数据处理: 首先输入鉴定化合物的分子式进行峰提取, 设定质量误差允许范围为δ ≤ 5×10^-6, 随后将质谱图中的实际碎片离子与益脉康软胶囊自建数据库中的碎片离子进行比对, 同时结合化合物的裂解规律、色谱保留时间、碎片丰度等特征进行综合分析, 在进一步验证目标化合物的基础上排除假阳性结果, 最终获得可靠数据。

GNPS分子网络的构建 采用Msconvert软件将益脉康软胶囊及其混合对照品溶液的HPLC-Q-Exactive Orbitrap MS质谱数据文件转化为mzML格式, 随后使用Winscp将文件上传至GNPS数据库。在数据库中, 将Precursor Ion Mass Tolerance和Fragment Ion Mass Tolerance的质量误差均设为0.02 Da, 余弦分数阈值设置为0.7, 最小匹配碎片离子数为6, 以此构建GNPS分子网络, 最终使用Cytoscape3.8.0软件对所得数据结果进行可视化处理。

成分靶点、疾病靶点的获取及“成分-靶点”网络的构建 首先, 将益脉康软胶囊体外鉴定出的成分上传到Swiss Target Prediction数据库(http://swisstargetprediction.ch/), 预测其潜在的作用靶点, 作为候选成分靶点集。随后, 分别以“ischemic cerebrovascular disease”和“coronary heart disease”为关键词, 在Gencard数据库(https://www.genecards.org/) 和OMIM数据库(https://www.omim.org/) 中检索相关疾病靶点, 整合检索结果并去除重复项, 构建疾病靶点集。接着, 利用Venny2.1.0在线平台对成分靶点与疾病靶进行分析, 获得交集靶点。最后, 将上述交集靶点及其对应的化学成分导入Cytoscape3.9.1软件, 绘制“成分-靶点”相互作用网络图, 以直观展示潜在的作用关系。

蛋白互作网络构建(protein-protein interaction, PPI) 与核心靶点筛选 将交集靶点导入String数据库(https://string-db.org/), 物种选择“Homo sapiens”, 获取蛋白相互作用信息, 导入Cytoscape3.9.1软件, 通过Cytonca插件进行打分, 将大于中位值的靶点全部选出, 得到核心靶点。

GO和KEGG通路富集 将交集靶点导入DAVID数据库(https://david.ncifcrf.gov/) 进行GO生物功能富集分析和KEGG通路富集分析, 设置P < 0.05进行筛选, 将结果导入微生信可视化平台进行可视化。

分子对接 将得到的核心靶点及其所对应核心成分进行分子对接。从PDB数据库(https://www.pdbus.org/) 获取核心靶点的3D结构作为受体, 利用Pymol软件去除其中的水分子和原配体。从PubChem数据库(https://pubchem.ncbi.nlm.nih.gov/) 下载核心成分的3D结构作为配体。随后, 在Autodock1.5.6软件中, 对受体和配体分子进行加氢、计算电荷等预处理。以原配体所在位置为参考, 定义受体的活性口袋, 运行分子对接以获取结合自由能。最终, 使用Pymol2.6软件对对接结果进行可视化分析。

结果

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1　益脉康软胶囊化学成分分析

采用高效液相色谱-四极杆/静电场轨道阱高分辨质谱联用技术(HPLC-Q-Exactive Orbitrap MS) 结合Xcalibur4.1软件, 共鉴定出113个化合物, 其中包括52个黄酮类成分、47个酚酸类成分、4个香豆素类成分、3个苯丙素类成分以及7个甾醇及其他类成分, 具体结果见表1^{[11, 20-35]}。基峰离子流(base peak ion, BPI) 图如图1所示。

采用GNPS分子网络技术, 结合碎片相似性与质谱裂解规律, 对益脉康软胶囊中的化学成分进行快速鉴定与可视化分析。通过采集正负离子模式下的高分辨质谱数据, 并依据MS/MS碎片离子的相似性构建GNPS分子网络。最终, 通过分子网络分析及二级质谱碎片信息, 共从益脉康软胶囊中鉴定出12个未在益脉康系列制剂及其原料药灯盏细辛中报道的化合物, 其中包括7个黄酮类成分和5个酚酸类成分(表1^{[11, 20-35]})。

1.1　基于GNPS技术对黄酮类化合物进行分析鉴定

益脉康软胶囊中含量最高的成分是黄酮类化合物, 该类化合物均具有C₆-C₃-C₆基本母核, 通过母核上连接甲基、羟基等不同基团, 衍生出黄酮、黄酮苷、黄酮醇苷、黄酮醇、二氢黄酮等多种类型。研究表明^[35], 黄酮类化合物具有丰富的生物活性, 例如野黄芩苷、槲皮素具有抗病毒、抗炎、抗血栓、舒张血管等作用。该类化合物的质谱裂解规律具有显著特征^[36]: 糖苷类成分主要发生糖苷键断裂, 同时伴随中性糖基(C₆H₁₀O₅, 162 Da) 的丢失; 苷元部分则通过逆第尔斯-阿尔德(RDA) 裂解产生特征性互补离子对, 包括A环衍生的m/z 151.00/107.01和B环衍生的m/z 133.02/119.05。另外, 实验^[37]中还观察到一些中性丢失现象, 如丢失CO₂ (44 Da)、C₂O₃ (72 Da) 和C₂H₂O (42 Da), 由此产生的m/z 241.05和m/z 257.04等碎片离子可作为黄酮类化合物鉴定的关键诊断离子, 这种多重裂解路径的组合为黄酮类化合物的结构解析提供了新的质谱识别特征。

以化合物44为例, 该化合物属于黄酮苷类, 在正离子模式下的准分子离子峰为m/z 463.087 4, 推测其分子式为C₂₁H₁₈O₁₂, 二级质谱中观察到m/z 287.054 2 [M+H-176]⁺的碎片离子, 为该化合物丢失1分子葡萄糖醛酸基团(C₆H₈O₆) 后生成苷元—野黄芩素(C₁₅H₁₀O₆), 裂解图见图2A。化合物80 (野黄芩素) 的分子式为C₁₅H₁₀O₆, 在m/z 285.040 5处呈现分子离子峰, 其裂解过程为: 先脱去1分子H₂O生成二级碎片m/z 267.030 1, 继而脱去1分子CO得到m/z 239.034 9; 此外, 野黄芩素还会发生特殊的中性丢失, 先丢失1分子C₂O₃得到m/z 213.055 7, 在此基础上再丢失1分子C₂H₂O得到碎片m/z 195.045 2。

化合物94在负离子模式下的准分子离子峰为m/z 301.035 5, 对应分子式为C₁₅H₁₀O₇。该化合物可分别丢失1分子H₂O和CO产生碎片离子m/z 283.022 7和m/z 273.040 4; 同时, 化合物发生RDA裂解生成178.998 2 [M-H-C₇H₆O₂]^-、151.003 5 [M-H-C₈H₆O₃]^-、121.029 6 [M-H-C₈H₄O₅]^-。结合上述二级碎片裂解规律, 推测其为槲皮素, 其裂解路径见图2B。

化合物105在负离子模式下的准分子离子峰为m/z 269.045 6。进一步的MS/MS分析显示其碎片离子m/z 151.003 7, 提示该化合物可能是黄酮类, 将其碎片信息同对照品进行比对, 确认为芹菜素。

基于GNPS分子网络中碎片离子的相似性及质谱裂解规律, 对益脉康软胶囊化学成分进行鉴定, 推测紫色节点簇可能对应黄酮类及其结构类似物。通过分子网络分析, 推测出山柰酚-4′-O-β-D-葡萄糖苷、山柰酚-3-O-葡萄糖醛酸苷、异鼠李素-3-O-β-D-葡萄糖醛酸苷、异鼠李素-3-O-葡萄糖苷、6-甲氧基山柰酚-4′-O-β-D-葡萄糖苷、槲皮素-3-O-脱氧己糖苷、异鼠李素等7个化合物, 具体分布见图3A、B。在A簇中, 通过与对照品比对, 可以确定m/z 463.088处的化合物为野黄芩苷。基于GNPS分子网络分析, 发现m/z 463.088与449.108的质量差为13.98, 且二者间的余弦值达0.95, 推测m/z 449.108可能由m/z 463.088失去1分子O并获得2分子H形成。该分子在正离子模式下产生碎片离子m/z 288.057 7、287.054 3、269.042 4及m/z 153.018 0, 经与GNPS数据库比对, 推测其为山柰酚-4′-O-β-D-葡萄糖苷。此外, m/z 461.073与463.088相差2.015, 两者分子式均为C₂₁H₁₈O₁₂, 且余弦值为0.86, 其在负离子模式下产生碎片离子m/z 286.043 8、285.040 4, 与GNPS数据库比对, 推测其为山柰酚-3-O-葡萄糖醛酸苷。而m/z 479.083与463.088相差15.995, 被推测为槲皮素-3-O-β-D-葡萄糖醛酸苷; m/z 493.098与479.083相差14.015, 两者间余弦值为0.82, 推测m/z 493.098可能由m/z 479.083得到1分子CH₂形成, 且m/z 493.098在正离子模式下的碎片离子为m/z 318.067 8、317.064 9、302.041 1、153.010 9, 与GNPS数据库比对后, 推测为异鼠李素-3-O-β-D-葡萄糖醛酸苷。m/z 479.119与493.098相差13.979, 两者间余弦值为0.93, 推测m/z 479.119可能由m/z 493.098失去1分子O并获得2分子H形成, 其正离子模式下的碎片离子为m/z 318.068 9、317.065 7, 故推测该化合物为异鼠李素-3-O-葡萄糖苷。m/z 463.124与479.119相差15.995, 两者间余弦值为0.87, 推测m/z 463.124可能由m/z 479.119失去1分子O形成, 且正离子模式下的碎片离子为m/z 301.069 8、287.055 2与GNPS数据库比对后推测为6-甲氧基山柰酚-4′-O-β-D-葡萄糖苷。另一化合物m/z 447.094在正离子模式下产生碎片离子m/z 285.039 5, 与GNPS数据库比对后, 推测其为槲皮素-3-O-脱氧己糖苷。在B簇中, 通过对照品确认m/z 269.046为芹菜素。化合物m/z 315.051在负离子模式下的碎片离子为m/z151.002 7、107.049 7, 经GNPS数据库比对推测为异鼠李素。

1.2　基于GNPS技术对酚酸类化合物进行分析鉴定

酚酸类化合物是益脉康软胶囊中的一类重要成分, 具有抗氧化、抗菌、抗炎等生物活性^{[23, 36]}。本文以咖啡酰奎宁酸类化合物为例进行说明: 该类化合物及其异构体是由不同数目的咖啡酰基与奎宁酸通过酯化反应缩合而成, 包括咖啡酰奎宁酸(CQA)、咖啡酰-2, 7-脱氢-2-辛酮糖酸(COA)、咖啡酰-2, 7-脱氢-3-脱氧-2-辛酮糖酸(CDOA) 及咖啡酰-1-(2′-λ-吡喃酮) (CPO) 四类, 其质谱裂解主要围绕酯键展开。

在负离子模式下, 于保留时间3.40、3.43、3.47、5.11 min检测到4个异构体, 其分子式均为C₁₆H₁₇O₉, 均由1分子咖啡酸和1分子奎宁酸经酯化反应生成。以3-CQA为例, 其二级质谱的主要信号离子包括母离子m/z 353.088 1, 以及子离子m/z 191.056 2 [M-H-174]^-、179.035 0 [M-H-162]^-、161.024 0 [M-H-18]^-、135.045 2 [M-H-44]^-。3-CQA与其异构体的差异在于咖啡酸和奎宁酸的酯化位置不同, 因此裂解时均会发生酯键断裂, 生成咖啡酸离子(m/z 179.035 0) 和奎宁酸离子(m/z 191.056 2), 其中咖啡酸离子可进一步失去1分子H₂O (形成m/z 161.024 0) 和1分子CO₂ (形成m/z 135.045 2)。据此推测, 上述化合物为单咖啡酰基奎宁酸及其异构体; 结合保留时间顺序及碎片丰度, 化合物7~9、18分别被推测为3-CQA、1-CQA、5-CQA和4-CQA。

化合物13~15和17在负离子模式下均于m/z 397.077 6处出现分子离子峰, 对应分子式C₁₇H₁₈O₁₁。MS/MS数据显示, 该类化合物的特征碎片离子包括m/z 191.056 2 [M-H-207]^-、179.034 7 [M-H-218]^-、161.024 1 [M-H-18]^-和135.045 2 [M-H-44]^-, 据此推测其为咖啡酰-2, 7-脱水-2-辛基吡咯烷酮酸及其异构体。结合保留时间及碎片丰度差异, 化合物13~15和17分别为被推测为2-COA、4-COA、3-COA和9-COA。化合物12、19和20的分子式为C₁₇H₁₈O₁₀, 其MS/MS谱图中均出现碎片离子m/z 161.024 2 [M-H-220]^-, 推测该类化合物为咖啡酰-2, 7-脱水-3-脱氧-2-辛基吡咯烷酮酸及其异构体。结合其保留时间, 化合物12、19和20分别被推测为3-CDOA、4-CDOA、9-CDOA。

此外, 化合物53、55、70~72的在[M-H]^-模式下的分子离子峰为m/z 515.119 5, 对应分子式C₂₅H₂₄O₁₂, 推测为二咖啡酰奎宁酸及其异构体, 该类化合物是由2分子咖啡酸和1分子奎宁酸经酯化反应生成。以4, 5-diCQA为例(图4), 其MS/MS数据显示特征碎片离子包括m/z 353.087 6 [M-H-162]^-、191.055 9 [M-H-162]^-、179.034 6 [M-H-12]^-、173.045 2 [M-H-12]^-、161.024 2 [M-H-18]^-和135.045 2 [M-H-44]^-, 均符合二咖啡酰奎宁酸及其异构体的典型碎片特征。与单咖啡酰奎宁酸相比, 二咖啡酰奎宁酸的二级裂解规律表现为: 优先失去1分子咖啡酸酰基(162 Da), 生成m/z 353.087 6的碎片离子, 该离子进一步裂解产生m/z 191.055 9 (奎宁酸离子) 和m/z 179.034 6 (咖啡酸离子); 其中m/z 191.055 9可继续裂解为m/z 173.045 2, m/z 179.034 6则进一步丢失1分子H₂O和1分子CO₂, 生成161.024 2 [M-H-18]^-和135.045 2 [M-H-44]^-。结合保留时间及对照品碎片信息, 化合物70~72被确认为3, 4-diCQA、3, 5-diCQA和4, 5-diCQA; 化合物53、55推测为1, 5-diCQA、1, 3-diCQA。

基于GNPS分子网络中碎片离子的相似性与质谱裂解规律, 对益脉康软胶囊化学成分进行进一步鉴定, 推测蓝色节点簇可能为酚酸类及其类似化合物, 分子网络中共推测出5个化合物, 包括3, 4, 5-triCQA及其异构、(E)-3-(2-((2S, 3R, 4S, 5S, 6R)-3, 4, 5-三羟基-6-(羟甲基)氧杂环己烷-2-基)氧基苯基)丙-2-烯酸、3-O-阿魏酰奎宁酸、5-对香豆酰奎宁酸, 见图5。对照品验证m/z 515.141处的化合物为3, 5-diCQA。该离子丢失1分子咖啡酸酰基(162.053 Da) 生成m/z 353.088, 二者间余弦值为0.92, 结合m/z 353.088在负离子模式下的碎片离子m/z 191.055 9、179.034 1、173.045 3、161.024 2、135.045 2及GNPS数据库比对, 推测其为4-CQA。m/z 337.093与353.088的质量差为15.995, 两者余弦值为0.85, 提示可能丢失1分子OH形成, 结合其负离子模式下的碎片离子为m/z 191.056 2、173.045 6、163.040 1、119.050 4, 经与GNPS数据库比对, 推测该化合物为5-对香豆酰奎宁酸。此外, m/z 515.141与515.120质量差为0.021, 余弦值为0.86, 表明二者互为同分异构体, 结合其负离子模式下的碎片离子m/z 353.087 4、191.055 7、179.034 4、173.045 0、161.024 2、135.045 0及GNPS技术, 推测m/z 515.120为1, 3-diCQA。m/z 515.141进一步获取1分子咖啡酸酰基(162.053 Da) 生成m/z 677.151, 二者间余弦值为0.80, 结合其负离子模式下的碎片离子m/z 515.119 6、353.087 7、191.055 9、179.034 5、173.045 3、161.024 2、135.045 2, 推测该化合物为3, 4, 5-triCQA。m/z 677.172与677.151质量差为0.021, 余弦值为0.93, 提示二者互为同分异构体。此外, 基于GNPS数据库发现, 母离子m/z 325.093在负离子模式下的碎片离子为m/z 163.040 2、146.966 1、119.050 0; 母离子m/z 367.104在负离子模式下的碎片离子m/z 191.056 0、173.045 4、134.047 4, 推测m/z 325.093和m/z 367.104分别为(E)-3-(2-((2S, 3R, 4S, 5S, 6R)-3, 4, 5-三羟基-6-(羟甲基)氧杂环己烷-2-基)氧基苯基)丙-2-烯酸、3-O-阿魏酰奎宁酸。

1.3　香豆素、苯丙素类、甾醇类裂解规律

化合物10推测为香豆素类成分七叶树苷, 分子式为C₁₅H₁₆O₉。在正离子模式下于m/z 341.086 7处出现其分子离子峰, 其二级质谱显示依次丢失1分子C₆H₁₀O₅ (162 Da) 和C₉H₆O₄ (179 Da), 生成碎片离子m/z 179.033 9 [M+H-162]^-和m/z 162.054 9 [M+H-179]^-。化合物100的分子式为C₁₁H₁₀O₄, 正离子模式下在m/z207.065 4处出现其分子离子峰, 经连续丢失2分子O生成碎片离子m/z 189.054 7, 推测为东莨菪素。

化合物3推测为肉桂酸, 正离子模式下分子离子峰为m/z 149.059 7, 丢失1分子中性碎片COOH (45 Da), 生成苯乙烯基阳离子碎片m/z 103.054 6, 同时, 该分子离子峰还丢失1分子H₂O生成m/z 131.049 3。

化合物87分子式为C₂₈H₄₂O, 推测属于甾醇类的麦角甾-7, 22-二烯-3-酮, 正离子模式下分子离子峰m/z 395.330 8遵循甾体化合物的典型裂解规律(Diels烃规则), 优先断裂C环和D环之间的键, 生成特征碎片m/z 271.205 8; 同时, 分子离子峰丢失1分子H₂O生成二级碎片m/z 377.320 8。

1.4　其他类化合物裂解规律

除上述化学成分类型外, 本研究还鉴定出1个其他类的化合物。化合物34在负离子模式下的分子离子峰为m/z 435.093 2, 对应分子式为C₂₀H₂₀O₁₁。其裂解规律如下: 母离子m/z 435.093 2先丢失1分子C₅H₄O₃ (122 Da) 生成碎片离子m/z 323.077 1 [M-H-122]^-; 该离子进一步丢失1分子C₆H₈O₄ (144 Da), 生成m/z 179.035 0 [M-H-144]^-, 随后m/z 179.035 0 [M-H-144]^-分别丢失1分子H₂O (18 Da)、CO₂ (44 Da) 和C₂H₂O₂ (58 Da), 依次生成碎片离子m/z 161.024 3 [M-H-18]^-、135.045 1 [M-H-44]^-和133.029 3 [M-H-58]^-。结合上述裂解特征及文献^[23]报道, 推测该化合物为erigeside Ⅰ。

2　网络药理学分析

2.1　核心靶点网络构建

通过成分靶点预测, 获得益脉康软胶囊体外化学成分的潜在作用靶点359个, 通过疾病数据库检索得到缺血性心脑血管疾病相关靶点2 418个。进一步对两者取交集, 通过韦恩图分析得到160个潜在治疗靶点。在此基础上, 构建了“成分-靶点”相互作用网络(图6A), 以可视化其复杂关联。随后, 基于该靶点集构建PPI网络(图6B), 其中节点颜色深度与大小表征其网络连接度的高低。最后, 通过综合计算Betweenness、Closeness、Degree等参数, 并以其中位数为阈值进行筛选, 确定了7个关键核心靶点(图6C)。

2.2　核心靶点GO功能富集和KEGG信号通路分析

将得到的交集靶点在DAVID数据库中进行GO和KEGG富集分析。以P < 0.05为筛选条件得到益脉康软胶囊治疗缺血性心脑血管疾病的GO分析结果中生物学过程(biology process, BP)、细胞组分(cellular component, CC) 和分子功能(molecular function, MF) 相关条目分别为450、85和155个, 选取每组前10个结果进行绘图(图7A)。结果发现, 益脉康软胶囊治疗缺血性心脑血管疾病的靶点蛋白主要参与表皮生长因子受体信号通路、血管内皮生长因子信号通路、血小板衍生生长因子受体信号通路等生物过程, 作用于质膜、神经元胞体等细胞组分, 调节蛋白酪氨酸激酶活性、蛋白激酶活性与ATP结合、巨噬细胞集落刺激因子受体活性等功能。

以P < 0.05为筛选条件得到155个KEGG通路, 选择前20个重要通路绘制气泡图, 以富集到该通路的核心靶点数和P值来衡量其富集程度(图7B)。结果表明, 益脉康软胶囊治疗缺血性心脑血管疾病主要包括脂质与动脉粥样硬化、晚期糖基化终末产物-晚期糖基化终末产物受体(advanced glycation end products-receptor for advanced glycation end products, AGE-RAGE)、血管内皮细胞生长因子(vascular endothelial growth factor, VEGF) 等通路。

2.3　分子对接结果

筛选出益脉康软胶囊治疗缺血性心脑血管疾病的核心靶点有7个, 分别为磷脂酰肌醇-4, 5-二磷酸3-激酶催化亚基α (phosphatidylinositol-4, 5-bisphosphate3-kinase catalytic subunit alpha, PIK3CA)、磷脂酰肌醇-4, 5-二磷酸3-激酶催化亚基β (phosphatidylinositol-4, 5-bisphosphate 3-kinase catalytic subunit β, PIK3CB)、磷脂酰肌醇-4, 5-二磷酸3-激酶催化亚基δ (phosphatidylinositol-4, 5-bisphosphate 3-kinase catalytic subunit δ, PIK3CD)、Harvey大鼠肉瘤病毒癌基因同源物(Harvey rat sarcoma viral oncogene homolog, HRAS)、表皮生长因子受体(epidermal growth factor receptor, EGFR)、磷酸肌醇-3-激酶调节亚基1 (phosphoinositide-3-kinase regulatory subunit 1, PIK3R1)、SRC (sarcoma, SRC) 原癌基因非受体酪氨酸激酶, 其对应的核心成分共有4个, 分别为3, 5, 6, 4′-四羟基-7-甲氧基黄酮、七叶树苷、野黄芩苷、山柰酚; 分子对接结果见图8。其中3, 5, 6, 4′-四羟基-7-甲氧基黄酮与PIK3CB、七叶树苷与HRAS以及山柰酚与PIK3R1结合良好, 结合能分别为-9.5、-9.7、-8.5 kcal·mol^-1。

讨论

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本研究整合了HPLC-Q-Exactive Orbitrap MS、GNPS及网络药理学技术, 对益脉康软胶囊的化学成分及治疗缺血性心脑血管疾病的潜在作用机制进行了综合分析。基于特征碎片离子及化合物裂解规律, 共鉴定出125个化合物, 包括黄酮类成分59个、酚酸类成分52个、香豆素类成分4个、苯丙素类成分3个、甾醇及其他类成分共7个; 进一步通过网络药理学分析筛选出160个潜在作用靶点, 富集分析表明这些靶点主要参与炎症反应、细胞凋亡和氧化应激等生物过程的调控, 其作用机制与VEGF、AGE-RAGE等信号通路的调节密切相关。

目前, 已有药理研究表明, 这些成分具有明确的生物活性: 野黄芩苷^[38]可发挥神经保护作用, 减轻脑损伤并改善神经功能; 咖啡酰奎宁酸^[39]具有较强的抗氧化活性, 可缓解心肌缺血再灌注损伤; 七叶树苷^[40]在体内外均表现出显著抗炎作用; 苯丙素类^[41]成分具有抗氧化、抗炎及神经保护等多重活性; erigeside Ⅰ^[42]亦具有抗炎、抗氧化和神经保护作用。上述成分可协同发挥神经保护、心脑血管保护、抗氧化与抗炎等综合疗效, 共同支撑益脉康软胶囊的临床效用。同时, Zhuang等^[43]研究首次揭示, 黄酮类化合物野黄芩苷能够通过上调组织蛋白酶D, 恢复在心脏缺血/再灌注损伤中被破坏的溶酶体流与自噬流, 从而有效改善内皮功能障碍, 减轻心肌损伤并改善心脏功能, 该发现阐明了野黄芩苷治疗心脏缺血/再灌注损伤的一种新型作用机制。Duan等^[44]通过整合计算机模拟与实验验证的研究策略, 首次系统阐明黄酮类化合物野黄芩苷可通过激活PI3K/AKT (phosphoinositide 3-kinase/protein kinase B, PI3K/AKT) 信号通路, 调控Bcl-2/Bax/Caspase-3等关键凋亡相关蛋白的表达平衡, 抑制神经元凋亡, 从而在缺血性脑卒中模型中发挥明确的神经保护作用。Cheng等^[45]采用血管紧张素II诱导的人脐静脉内皮细胞损伤模型并运用灰色关联分析、偏最小二乘回归分析和Pearson相关分析评估药效与成分的关联性, 结果表明, 木犀草素-7-O-β-D-葡萄糖苷、3, 4-diCQA、1, 5-diCQA和3, 5-diCQA是菊花发挥心血管保护作用的关键药效物质。Tong等^[39]通过体外离体心脏模型发现, 3-CQA异构体隐绿原酸能显著改善缺血心肌组织的血流动力学功能、相关指标、细胞形态、显著增加线粒体生物合成。由此可见, 本研究开展的益脉康软胶囊化学成分全面、系统的分析鉴定, 对下一步阐释药效物质基础及拓展临床应用具有重要意义。

在技术方法层面, GNPS平台凭借其高效的数据处理能力、先进的分子网络分析技术及丰富的数据库资源, 显著提升了化合物识别的效率与准确性, 不仅能够快速实现已知成分的鉴别, 也为新化合物的发现提供了有力支持^{[17, 18]}。而网络药理学则从系统生物学视角出发, 通过整合多源数据与构建分子网络, 突破了传统“单靶点”研究模式的局限, 能够系统揭示中药多成分、多靶点、多通路的协同作用机制, 为阐释中药整体药效提供重要方法学支撑^[19]。

综上所述, 本研究系统解析了益脉康软胶囊的化学成分群, 并揭示其通过多成分、多靶点、多通路协同作用机制治疗心脑血管疾病的科学内涵, 为阐明其效物质基础、揭示其“多成分-多靶点”作用机制、提升质量控制水平及临床拓展提供了系统的实验依据与方法学支撑, 有力推动了益脉康软胶囊的现代化研究进程。

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2026年第61卷第4期

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doi: 10.16438/j.0513-4870.2025-1226

接收时间：2025-10-15
首发时间：2026-09-21
出版时间：2026-04-12

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收稿日期：2025-10-15
修回日期：2025-12-29

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¹山西大学中医药现代研究中心, 山西太原 030006

²山西大学化学生物学与分子工程教育部重点实验室, 山西太原 030006

³北京黄河颐圣堂中药有限公司, 北京 102600

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周玉枝, E-mail: zhouyuzhi@sxu.edu.cn

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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	Theoretical mass (m/z)	Exact mass (m/z)	Formula	Ion adduction	Error /ppm	Production (m/z)	Compound	Type	Source
1	1.38	155.033 9	155.033 9	C₇H₆O₄	[M+H]⁺	0.32	155.033 9, 109.028 8	3, 4-Dihydroxybenzoic acid	PA	[20]
2	1.49	345.046 3	345.046 6	C₁₃H₁₄O₁₁	[M-H]^-	3.86	193.035 5, 169.014 6	Gallic acyl-3-O-β-D-glucuronide	PA	[11]
3	2.5	149.059 7	149.059 8	C₉H₈O₂	[M+H]⁺	0.83	131.039 3, 103.054 6	Cinnamic acid	PH	[20]
4	3.03	165.054 6	165.054 8	C₉H₈O₃	[M+H]⁺	1.05	147.044 2, 119.049 5	3-p-Hydroxycinnamic acid	PH	[20]
5	3.17	361.112 9	361.113 0	C₁₅H₂₀O₁₀	[M+H]⁺	0.57	199.060 4, 163.060 3	Breviscapine C	F	[21]
6	3.34	241.070 7	241.071 4	C₁₁H₁₂O₆	[M+H]⁺	0.66	241.071 4, 113.023 6	Pyromucic acid glycoside	G	[20]
7	3.4	353.087 8	353.088	C₁₆H₁₈O₉	[M-H]^-	4.13	191.056 2, 179.035 0, 161.024 0, 135.045 2, 109.029 5	3-CQA	PA	[22]
8	3.43	353.087 8	353.088	C₁₆H₁₈O₉	[M-H]^-	3.61	191.055 9, 179.034 6, 173.045 5, 161.024 5, 135.045 0, 109.029 6	1-CQA	PA	[23]
9	3.47	353.087 8	353.088 1	C₁₆H₁₈O₉	[M-H]^-	4.04	191.056 1, 179.034 6, 173.045 7, 161.024 5, 135.045 1, 109.029 5	5-CQA	PA	[23]
10	3.98	341.086 7	341.086 8	C₁₅H₁₆O₉	[M+H]⁺	0.16	341.086 8, 181.049 6, 179.033 9, 162.054 9	Esculin	C	[20]
11	4.28	517.155 2	517.155 8	C₂₂H₂₈O₁₄	[M+H]⁺	1.12	355.102 8, 191.053 4, 163.003 9	5-Caffeoylquinic acid glucoside	PA	[23]
12	4.41	337.092 9	337.093 2	C₁₆H₁₈O₈	[M-H]^-	4.17	191.056 2, 173.045 6, 163.040 1, 119.050 4	5-p-Coumaroylquinic acid	PA	GNPS
13	4.63	381.082 7	381.083	C₁₇H₁₈O₁₀	[M-H]^-	3.55	161.024 1, 135.045 2, 133.029 8	3-CDOA	PA	[23]
14	4.66	397.077 6	397.077 8	C₁₇H₁₈O₁₁	[M-H]^-	3.23	191.056 2, 179.034 7, 161.024 1, 135.045 2	2-COA	PA	[23]
15	4.7	397.077 6	397.077 7	C₁₇H₁₈O₁₁	[M-H]^-	2.92	191.056 2, 179.035 0, 161.045 6, 135.045 2	4-COA	PA	[23]
16	4.76	397.077 6	397.077 7	C₁₇H₁₈O₁₁	[M-H]^-	2.92	191.056 2, 179.034 9, 161.024 2, 135.045 1	3-COA	PA	[23]
17	4.81	355.102 4	355.102 4	C₁₆H₁₈O₉	[M+H]⁺	0.16	355.102 4, 193.049 4	6-Methoxycoumarin-7-O-β-D-glucopyranoside	C	[20]
18	4.83	397.077 6	397.077 6	C₁₇H₁₈O₁₀	[M-H]^-	2.61	191.056 2, 179.024 3, 161.024 3, 135.045 1	9-COA	PA	[23]
19	5.11	353.087 8	353.088	C₁₆H₁₈O₉	[M-H]^-	3.78	191.056 1, 179.034 8, 173.045 5, 161.024 4, 135.045 1, 109.029 5	4-CQA	PA	[22]
20	5.18	325.092 9	325.093 1	C₁₅H₁₈O₈	[M-H]^-	3.95	163.040 2, 146.966 1, 119.050 0	(E)-3-[2-[(2S, 3R, 4S, 5S, 6R)-3, 4, 5-Trihydroxy-6-(hydroxymethyl)oxan-2-yl]oxyphenyl]prop-2-enoic acid	PA	GNPS
21	5.54	381.082 7	381.083	C₁₇H₁₈O₁₀	[M-H]^-	3.63	161.024 2, 135.045 3, 133.029 6	4-CDOA	PA	[23]
22	6.77	381.082 7	381.083	C₁₇H₁₈O₁₀	[M-H]^-	3.55	161.024 1, 135.045 2, 133.029 5	9-CDOA	PA	[23]
23	6.97	195.065 2	195.065 4	C₁₀H₁₀O₄	[M+H]⁺	1.33	177.054 8, 149.059 8	Ferulic acid	PH	[23, 24]
24	7.04	195.065 2	195.065 3	C₁₀H₁₀O₄	[M+H]⁺	0.78	193.049 8, 177.054 8, 163.039 1	Methyl caffeate	PA	[20]
25	8.08	352.101 1	352.101 6	C₁₃H₂₁O₁₁	[M-H]^-	4.4	173.045 8, 111.045 4	Quinic acid glucoside-1	PA	[20]
26	8.36	367.103 5	367.103 6	C₁₇H₂₀O₉	[M-H]^-	3.40	353.088 2, 191.035 1, 179.035 1, 173.045 8	4/5-O-Caffeoylquinic acid methyl ester	PA	[25]
27	8.43	367.103 5	367.103 6	C₁₇H₂₀O₉	[M-H]^-	3.40	193.050 5, 191.056 0, 173.045 4, 134.047 4	3-O-Feruloylquinic acid	PA	GNPS
28	8.54	367.103 5	367.103 6	C₁₇H₂₀O₉	[M-H]^-	3.40	353.087 9, 191.035 2, 179.035 0, 173.045 6	4/5-O-Caffeoylquinic acid methyl ester	PA	[25]
29	8.73	369.118 0	369.118 2	C₁₇H₂₀O₉	[M+H]⁺	0.59	369.118 2, 191.053 1	5-Feruloylquinic acid	PA	[20]
30	8.75	367.103 5	367.103 6	C₁₇H₂₀O₉	[M-H]^-	3.32	353.087 8, 191.035 1, 179.035 1	4/5-O-Caffeoylquinic acid methyl ester	PA	[25]
31	8.95	179.070 3	179.070 3	C₁₀H₁₀O₃	[M+H]⁺	0.06	161.059 8, 133.064 9	p-Methoxycinnamic acid	A	[20]
32	10.15	379.103 5	379.103 2	C₁₈H₂₀O₉	[M-H]^-	2.09	379.103 2, 161.045 6	5-O-Caffeoylquinic acid methyl ester	PA	[20]
33	10.24	155.033 9	155.034 0	C₇H₆O₄	[M+H]⁺	0.42	137.023 5, 109.028 7	Protocatechuic acid	PA	[11]
34	11.58	601.119 9	601.118 0	C₂₈H₂₆O₁₅	[M-H]^-	-1.35	353.088 0, 233.066 8, 195.065 2	1/4-Malonyl-diCQA	PA	[25]
35	11.93	181.049 5	181.049 5	C₉H₈O₄	[M+H]⁺	-0.03	181.049 5, 163.039 0, 135.044 2	3, 4-Dihydroxycinnamic acid	A	[20]
36	12.00	437.107 8	437.107 9	C₂₀H₂₀O₁₁	[M+H]⁺	0.24	163.038 9, 145.028 1	Erigeroside	G	[20]
37	12.02	435.093 3	435.093 3	C₂₀H₂₀O₁₁	[M-H]^-	2.33	323.077 1, 179.035 0, 161.024 3, 135.045 1, 133.029 3	Erigeside Ⅰ	O	[11, 26]
38	12.19	379.103 5	379.103 1	C₁₈H₂₀O₉	[M-H]^-	2.01	379.103 1, 161.045 7	4-O-Caffeoylquinic acid methyl ester	PA	[20]
39	12.26	463.088 2	463.088 6	C₂₁H₂₀O₁₂	[M-H]^-	3.15	301.035 3, 151.040 2, 135.045 3	Quercetin-3-O-β-D-glucopyranoside	F	[25]
40	12.30	463.088 2	463.088 6	C₂₁H₂₀O₁₂	[M-H]^-	3.22	301.035 4, 283.025 3, 151.040 1	Quercetin-3-O-β-D-glucoside	F	[22]
41	12.32	289.070 7	289.070 7	C₁₅H₁₂O₆	[M+H]⁺	0.15	121.028 7	Eriodictyol	F	[20]
42	12.47	477.067 5	477.067 7	C₂₁H₁₈O₁₃	[M-H]^-	2.71	477.067 7, 301.035 2	Quercetin-7-O-glucuronide	F	[11]
43	12.51	477.067 5	477.067 7	C₂₁H₁₈O₁₃	[M-H]^-	2.71	301.035 2, 151.003 5	Quercetin-3-O-glucuronide	F	[20]
44	12.54	477.067 5	477.067 6	C₂₁H₁₈O₁₃	[M-H]^-	2.77	301.035 3, 283.024 6	Galactose-3-O-glucuronate	F	[11]
45	12.58	463.088 2	463.088 4	C₂₁H₂₀O₁₂	[M-H]^-	2.88	301.035 3, 151.040 2, 135.045 3	Quercetin-3-O-β-D-glucopyranoside	F	[25]
46	12.60	479.082 0	479.082 3	C₂₁H₁₈O₁₃	[M+H]⁺	0.6	479.082 3, 303.049 7	Quercetin-3-O-β-galacturonide	F	[23]
47	12.61	461.072 5	461.072 8	C₂₁H₁₈O₁₂	[M-H]^-	2.89	286.043 8, 285.040 4	Kaempferol-3-O-glucuronide	F	GNPS
48	12.63	463.087 1	463.087 4	C₂₁H₁₈O₁₂	[M+H]⁺	0.71	287.054 2, 177.054 7, 121.028 6	Scutellarin*	F	[27]
49	12.70	449.107 8	449.107 9	C₂₁H₂₀O₁₁	[M+H]⁺	0.23	288.057 7, 287.054 3, 269.042 4, 153.018 0	Kaempferol-4′-O-β-D-glucoside	F	GNPS
50	12.73	449.107 8	449.107 9	C₂₁H₂₀O₁₁	[M+H]⁺	0.16	285.039 5	Quercetin-3-O-deoxyhexoside	F	GNPS
51	12.75	477.093 3	477.093 4	C₂₁H₂₀O₁₁	[M-H]^-	2.74	327.050 9, 285.040 4	Kaempferol-3-O-glucoside	F	[20]
52	12.77	463.087 1	463.087 3	C₂₁H₁₈O₁₂	[M+H]⁺	0.52	463.087 3, 287.054 5	Scutellarein-6-O-glucuronide	F	[28]
53	12.78	447.093 3	447.093 3	C₂₁H₂₀O₁₁	[M-H]^-	2.54	353.087 7, 285.040 4, 119.034 9	Scutellarein-7-O-glucoside	F	[25]
54	12.81	461.072 5	461.072 8	C₂₁H₁₈O₁₂	[M-H]^-	2.89	445.078 0, 287.056 1, 285.040 4	Breviscapine	F	[29]
55	12.85	559.109 3	559.109 4	C₂₆H₂₄O₁₄	[M-H]^-	2.15	285.040 3, 191.056 0, 179.056 1, 161.045 6, 135.045 2	3, 9/4.9-COA	PA	[25]
56	12.95	559.109 3	559.109 6	C₂₆H₂₄O₁₄	[M-H]^-	2.37	353.087 8, 285.040 4, 191.056 3, 179.035 1, 161.045 6, 135.045 3	3, 9/4.9-COA	PA	[26]
57	13.53	593.151 2	593.151 6	C₂₇H₃₀O₁₅	[M-H]^-	2.55	287.057 0, 129.055 9	Kaempferol-3-O-rutinoside	F	[20]
58	13.53	417.082 7	417.083 0	C₂₀H₁₈O₁₀	[M-H]^-	3.39	285.040 6, 215.010 0, 161.045 7, 121.029 6	Kaempferol-3-O-arabinoside	F	[25]
59	13.71	515.119 5	515.119 9	C₂₅H₂₄O₁₂	[M-H]^-	2.85	353.087 7, 335.077 5, 191.055 7, 179.035 0, 173.044 9, 161.024 5, 135.045 0	1, 5-diCQA	PA	[27]
60	13.86	179.035 0	179.034 5	C₉H₈O₄	[M-H]^-	3.43	179.035 0, 135.045 2	Caffeic acid	PA	[27]
61	13.92	515.119 5	515.119 8	C₂₅H₂₄O₁₂	[M-H]^-	2.62	353.087 7, 335.077 2, 191.056 0, 179.034 6, 173.045 4, 161.023 9, 135.045 2	1, 3-diCQA	PA	[30]
62	14.07	447.093 3	447.093 5	C₂₁H₂₀O₁₁	[M-H]^-	2.94	429.082 3, 313.071 6, 193.035 5, 131.034 9	Naringenin-7-O-glucuronide	F	[20]
63	14.07	417.082 7	417.082 9	C₂₀H₁₈O₁₀	[M-H]^-	3.10	285.040 5, 215.009 9, 161.045 6, 121.029 6	Kaempferol-3-O-arabinoside	F	[25]
64	14.10	543.114 4	543.114 9	C₂₆H₂₄O₁₃	[M-H]^-	2.86	353.087 7, 179.034 4, 161.045 6, 135.045 2	ErigosterB/4, 9-diCDOA	PA	[25]
65	14.24	543.114 4	543.114 6	C₂₆H₂₄O₁₃	[M-H]^-	2.41	353.088 0, 179.034 9, 161.045 6, 135.044 9	ErigosterB/4, 9-diCDOA	PA	[25]
66	14.36	479.118 4	479.118 7	C₂₂H₂₂O₁₂	[M+H]⁺	0.52	318.068 9, 317.065 7	Isorhamnetin-3-O-glucoside	F	GNPS
67	14.45	447.093 3	447.093 5	C₂₁H₂₀O₁₁	[M-H]^-	2.88	271.061 2, 257.045 2	Naringenin-7-O-glucuronide	F	[11]
68	14.57	433.112 9	433.112 9	C₂₁H₂₀O₁₀	[M+H]⁺	0.61	271.117 1, 254.102 3, 121.028 5	Cosmosiin	F	[23]
69	14.59	431.098 4	431.098 6	C₂₁H₂₀O₁₀	[M-H]^-	3.01	431.098 6, 269.045 4	Scutellarin-7-O-glucoside	F	[20]
70	14.62	431.098 4	431.098 6	C₂₁H₂₀O₁₀	[M-H]^-	3.01	431.098 6, 269.045 5	Baicalein-7-O-β-D-glucopyranoside	F	[20]
71	14.69	445.077 6	445.077 9	C₂₁H₁₈O₁₁	[M-H]^-	3.09	269.045 5, 175.024 8, 129.055 7, 117.018 9, 113.024 4	Breviscapine I	F	[27]
72	14.73	445.077 6	445.077 9	C₂₁H₁₈O₁₁	[M-H]^-	2.95	269.045 4, 117.034 3	Apigenin-7-O-glucuronide*	F	[11]
73	14.80	445.077 6	445.078 0	C₂₁H₁₈O₁₁	[M-H]^-	3.22	271.060 9, 153.019 5, 119.050 2	Apigenin-7-O-β-galacturonide	F	[23]
74	14.80	287.056 1	287.056 2	C₁₅H₁₂O₆	[M-H]^-	4.07	161.045 7, 151.003 7, 135.045 3	Eriodictyol	F	[25]
75	14.87	445.077 6	445.078 0	C₂₁H₁₈O₁₁	[M-H]^-	3.29	429.083 2, 271.061 0, 269.045 5, 113.024 5	Baicalin*	F	[31]
76	15.18	493.097 7	493.098 1	C₂₂H₂₀O₁₃	[M+H]⁺	0.97	318.067 8, 317.064 9, 302.041 1, 153.010 9	Isorhamnetin-3-O-β-D-glucuronide	F	GNPS
77	15.24	515.119 5	515.119 8	C₂₅H₂₄O₁₂	[M-H]^-	2.62	353.087 4, 191.055 7, 179.034 4, 173.045 2, 161.045 6, 135.045 2	1, 4-diCQA	PA	[25]
78	15.28	463.123 5	463.123 4	C₂₂H₂₂O₁₁	[M+H]⁺	-0.10	301.069 8, 287.055 2	6-Methoxykaempferol-4′-O-β-D-glucoside	F	GNPS
79	15.30	515.119 5	515.119 7	C₂₅H₂₄O₁₂	[M-H]^-	2.50	353.087 6, 191.056 0, 179.034 6, 173.045 3, 161.024 1, 135.045 2	3, 4-diCQA*	PA	[27]
80	15.33	515.119 5	515.119 7	C₂₅H₂₄O₁₂	[M-H]^-	2.50	353.087 4, 191.055 9, 179.034 6, 173.045 3, 161.024 2, 135.045 2	3, 5-diCQA*	PA	[27, 30]
81	15.37	515.119 5	515.119 7	C₂₅H₂₄O₁₂	[M-H]^-	2.50	353.087 6, 191.055 9, 179.034 6, 173.045 2, 161.024 2, 135.045 2	4, 5-diCQA*	PA	[27]
82	15.44	475.088 2	475.088 4	C₂₂H₂₀O₁₂	[M-H]^-	2.69	299.056 1, 283.024 7	Kaempferol-7-O-glucuronide	F	[11]
83	15.62	475.088 2	475.088 6	C₂₂H₂₀O₁₂	[M-H]^-	3.14	299.056 1, 283.024 7	Kaempferol-3-O-glucuronide	F	[11]
84	15.75	477.102 8	477.103 1	C₂₂H₂₀O₁₂	[M+H]⁺	0.70	301.069 9, 177.054 9, 113.023 6	6-Methoxyscutellarein-7-O-glucuronide	F	[28]
85	15.95	557.130 1	557.130 6	C₂₇H₂₆O₁₃	[M-H]^-	2.97	381.083 4, 191.056 2, 179.035 1, 161.024 4	Erigoster A	PA	[25]
86	16.06	529.135 1	529.134 3	C₂₆H₂₆O₁₂	[M-H]^-	0.54	353.088 5, 179.034 6, 161.045 6, 135.045 2	3, 4/3, 5-O-Dicaffeoylquinic acid methyl ester	PA	[25]
87	16.2	285.040 5	285.040 6	C₁₅H₁₀O₆	[M-H]^-	4.4	268.037 6, 257.045 5, 239.034 9, 171.045 2, 121.029 4, 117.034 5, 109.029 3	Kaempferol	F	[20]
88	16.25	507.113 3	507.113 5	C₂₃H₂₂O₁₃	[M+H]⁺	0.41	287.055 2, 113.023 6	5, 6, 4′-Trihydroxyflavone-7-O-β-D-glucopyranuronate ethyl ester	F	[20]
89	16.27	285.040 5	285.040 6	C₁₅H₁₀O₆	[M-H]^-	4.40	267.030 1, 239.034 9, 213.055 7, 195.045 2	Scutellarein	F	[20]
90	16.34	287.056 1	287.056 2	C₁₅H₁₂O₆	[M-H]^-	4.40	161.045 6, 151.003 9, 135.045 2	Eriodictyol	F	[25]
91	16.41	285.040 5	285.040 6	C₁₅H₁₀O₆	[M-H]^-	4.4	269.045 9, 245.045 6, 243.029 9, 239.035 2, 229.050 7, 213.056 0, 211.040 3, 201.055 8, 179.035 2, 161.024 4, 137.024 5	Luteolin	F	[20]
92	16.82	557.130 1	557.130 6	C₂₇H₂₆O₁₃	[M-H]^-	2.96	381.082 4, 191.056 3, 179.034 9, 161.024 5	Erigoster A	PA	[25]
93	16.85	529.135 1	529.135 3	C₂₆H₂₆O₁₂	[M-H]^-	2.39	353.088 2, 179.034 9, 161.045 7, 135.045 4	3, 4/3, 5-O-Dicaffeoylquinic acid methyl ester	PA	[25]
94	17.10	501.139 1	501.139 6	C₂₅H₂₄O₁₁	[M+H]⁺	0.90	427.066 9, 271.096 0, 153.054 5	Apigenin-7-O-β-D-glucopyranuronic acid butyl ester	F	[28]
95	17.12	557.130 1	557.130 4	C₂₇H₂₆O₁₃	[M-H]^-	2.52	191.056 3, 179.034 8, 161.045 7	Acetylated-diCQA	PA	[25]
96	17.49	557.130 1	557.130 4	C₂₇H₂₆O₁₃	[M-H]^-	2.52	191.055 8, 179.034 9, 161.024 5	Acetylated-diCQA	PA	[25]
97	17.59	287.056 1	287.056 3	C₁₅H₁₂O₆	[M-H]^-	4.50	287.056 3, 161.045 7, 135.045 2	Eriodictyol	F	[25]
98	17.62	209.080 8	209.080 8	C₁₁H₁₂O₄	[M+H]⁺	0.30	191.070 4, 163.075 5	Ethyl caffeate	PA	[20]
99	17.73	491.118 4	491.119 0	C₂₃H₂₂O₁₂	[M+H]⁺	1.25	287.054 8, 221.081 0, 113.023 6	5, 6, 4′-Trihydroxyflavone-7-O-β-D-glucopyranuronate ethyl ester	F	[28]
100	17.8	491.118 4	491.118 6	C₂₃H₂₂O₁₂	[M+H]⁺	0.45	287.054 9, 221.081 0, 113.023 6	Scutellarin ethyl ester	F	[32]
101	17.93	301.035 4	301.035 5	C₁₅H₁₀O₇	[M-H]^-	4.13	299.019 8, 271.024 9, 151.003 1, 149.024 0, 148.016 1, 133.029 4	3, 5, 6, 7, 4′-Pentahydroxyflavone	F	[20]
102	17.95	481.134 1	481.133 9	C₂₂H₂₄O₁₂	[M+H]⁺	-0.42	481.133 9, 163.038 8	1-(2′-γ-Pyrone)-6-caffeoyl-2-D-glucopyranoside	F	[20]
103	18.00	301.035 4	301.035 5	C₁₅H₁₀O₇	[M-H]^-	4.13	283.024 927 3.0 404, 178.998 2, 151.003 5, 121.029 6	Quercetin	F	[20]
104	18.20	461.107 8	461.108 3	C₂₂H₂₀O₁₁	[M+H]⁺	1.02	301.107 4, 287.055 3, 269.117 0, 189.054 9, 175.075 6, 153.054 8	Scutellarein glucuronide methyl ether	F	[30]
105	18.23	529.135 1	529.135 4	C₂₆H₂₆O₁₂	[M-H]^-	2.50	353.088 2, 179.035 1, 161.045 6, 135.045 2	3, 4/3, 5-O-Dicaffeoylquinic acid methyl ester	PA	[25]
106	18.26	585.125 0	585.125 3	C₂₈H₂₆O₁₄	[M-H]^-	2.43	395.077 0, 353.088 0, 233.154 6, 179.035 0, 137.024 6	1-Malonyl-3, 5-dicaffeoylquinic acid	PA	[23]
107	18.32	459.186 1	459.186 2	C₂₁H₃₀O₁₁	[M+H]⁺	0.15	459.186 2, 297.133 8, 163.060 4	(+)-Syringaresinol-O-β-D-glucopyranoside	C	[20]
108	18.40	557.130 1	557.130 3	C₂₇H₂₆O₁₃	[M-H]^-	2.30	191.056 2, 179.035 0, 161.024 5	Acetylated-diCQA	PA	[25]
109	18.83	207.065 1	207.065 4	C₁₁H₁₀O₄	[M+H]⁺	1.25	189.054 7	Scopoletin	C	[33]
110	18.87	207.065 1	207.065 4	C₁₁H₁₀O₄	[M+H]⁺	0.81	193.049 7, 177.054 9, 163.039 0	Methyl caffeate	PA	[20]
111	19.07	271.061 2	271.061 3	C₁₅H₁₂O₅	[M-H]^-	4.24	177.019 2, 165.019 3, 161.045 6, 145.050 6, 119.049 6	Naringenin*	F	[22]
112	19.08	273.075 8	273.075 7	C₁₅H₁₂O₅	[M+H]⁺	-0.13	271.060 2, 169.977 3, 119.068 8, 119.049 2	5, 7, 4′-Trihydroxyflavanone	F	[20]
113	19.1	269.045 5	269.045 6	C₁₅H₁₀O₅	[M-H]^-	4.36	269.045 6, 252.042	Baicalein*	F	[20]
114	19.13	269.045 5	269.045 6	C₁₅H₁₀O₅	[M-H]^-	4.25	227.034 7, 225.055 6, 201.055 9, 159.044 9, 151.003 7, 117.034 4	Apigenin*	F	[34]
115	19.33	303.086 3	303.086 3	C₁₆H₁₄O₆	[M+H]⁺	-0.04	273.075 6, 169.049 6, 135.044 1	1-Hydroxy-2, 3, 5-trihydroxyxanthone	F	[20]
116	19.34	329.066 7	329.066 8	C₁₇H₁₄O₇	[M-H]^-	3.72	285.040 7, 185.060 8, 178.977 9, 151.040 2	3′, 4′-Dimethoxyquercetin	F	[35]
117	19.36	301.070 7	301.070 8	C₁₆H₁₂O₆	[M+H]⁺	0.45	287.055 0, 177.054 8, 121.028 6	Hispidulin	F	[28]
118	19.4	301.070 7	301.070 8	C₁₆H₁₂O₆	[M+H]⁺	0.55	283.059 2, 271.060 1, 169.049 5, 133.049 6	Scutellarein methyl ether	F	[29]
119	19.56	315.051 0	315.051 2	C₁₆H₁₂O₇	[M-H]^-	4.16	299.019 4, 285.040 6, 243.029 3, 179.034 8, 161.024 5, 137.024 5, 123.008 9	3, 5, 6, 4′-Tetrahydroxy-7-methoxyflavone	F	[20]
120	20.15	455.077 2	455.077 2	C₂₆H₁₆O₈	[M-H]^-	1.87	455.077 2, 191.035 1, 161.024 5	3-O-Caffeoyl-γ-quinlactone	PA	[25]
121	27.8	413.377 8	413.377 8	C₂₉H₄₈O	[M+H]⁺	-0.04	413.377 8, 395.367 3	Stigmasterol	S	[20]
122	27.9	395.330 8	395.331 2	C₂₈H₄₂O	[M+H]⁺	0.77	377.320 8, 271.205 8	Ergosta-7, 22-dien-3-one	S	[20]
123	-	315.051 0	315.051 0	C₁₆H₁₂O₇	[M-H]^-	-	151.002 7, 107.049 7	Isorhamnetin	F	GNPS
124	-	677.151 2	677.151 0	C₃₄H₃₀O₁₅	[M-H]^-	-	515.119 6, 353.087 7, 191.055 9, 179.034 5, 173.045 3, 161.024 2, 135.045 2	3, 4, 5-triCQA	PA	GNPS
125	-	677.151 2	677.172 0	C₃₄H₃₀O₁₅	[M-H]^-	-	515.119 6, 353.087 6, 191.055 9, 179.034 5, 173.045 3, 161.024 2, 135.045 1	3, 4, 5-triCQA or its isomers	PA	GNPS

No.

t_R
/min

Theoretical mass (m/z)

Exact mass
(m/z)

Formula

Ion adduction

Error
/ppm

Production (m/z)

Compound

Type

Source

1.38

155.033 9

C₇H₆O₄

[M+H]⁺

0.32

155.033 9, 109.028 8

3, 4-Dihydroxybenzoic acid

[20]

1.49

345.046 3

345.046 6

C₁₃H₁₄O₁₁

[M-H]^-

3.86

193.035 5, 169.014 6

Gallic acyl-3-O-β-D-glucuronide

[11]

2.5

149.059 7

149.059 8

C₉H₈O₂

[M+H]⁺

0.83

131.039 3, 103.054 6

Cinnamic acid

[20]

3.03

165.054 6

165.054 8

C₉H₈O₃

[M+H]⁺

1.05

147.044 2, 119.049 5

3-p-Hydroxycinnamic acid

[20]

3.17

361.112 9

361.113 0

C₁₅H₂₀O₁₀

[M+H]⁺

0.57

199.060 4, 163.060 3

Breviscapine C

[21]

3.34

241.070 7

241.071 4

C₁₁H₁₂O₆

[M+H]⁺

0.66

241.071 4, 113.023 6

Pyromucic acid glycoside

[20]

3.4

353.087 8

353.088

C₁₆H₁₈O₉

[M-H]^-

4.13

191.056 2, 179.035 0, 161.024 0, 135.045 2, 109.029 5

3-CQA

[22]

3.43

353.087 8

353.088

C₁₆H₁₈O₉

[M-H]^-

3.61

191.055 9, 179.034 6, 173.045 5, 161.024 5, 135.045 0, 109.029 6

1-CQA

[23]

3.47

353.087 8

353.088 1

C₁₆H₁₈O₉

[M-H]^-

4.04

191.056 1, 179.034 6, 173.045 7, 161.024 5, 135.045 1, 109.029 5

5-CQA

[23]

3.98

341.086 7

341.086 8

C₁₅H₁₆O₉

[M+H]⁺

0.16

341.086 8, 181.049 6, 179.033 9, 162.054 9

Esculin

[20]

4.28

517.155 2

517.155 8

C₂₂H₂₈O₁₄

[M+H]⁺

1.12

355.102 8, 191.053 4, 163.003 9

5-Caffeoylquinic acid glucoside

[23]

4.41

337.092 9

337.093 2

C₁₆H₁₈O₈

[M-H]^-

4.17

191.056 2, 173.045 6, 163.040 1, 119.050 4

5-p-Coumaroylquinic acid

GNPS

4.63

381.082 7

381.083

C₁₇H₁₈O₁₀

[M-H]^-

3.55

161.024 1, 135.045 2, 133.029 8

3-CDOA

[23]

4.66

397.077 6

397.077 8

C₁₇H₁₈O₁₁

[M-H]^-

3.23

191.056 2, 179.034 7, 161.024 1, 135.045 2

2-COA

[23]

4.7

397.077 6

397.077 7

C₁₇H₁₈O₁₁

[M-H]^-

2.92

191.056 2, 179.035 0, 161.045 6, 135.045 2

4-COA

[23]

4.76

397.077 6

397.077 7

C₁₇H₁₈O₁₁

[M-H]^-

2.92

191.056 2, 179.034 9, 161.024 2, 135.045 1

3-COA

[23]

4.81

355.102 4

C₁₆H₁₈O₉

[M+H]⁺

0.16

355.102 4, 193.049 4

6-Methoxycoumarin-7-O-β-D-glucopyranoside

[20]

4.83

397.077 6

C₁₇H₁₈O₁₀

[M-H]^-

2.61

191.056 2, 179.024 3, 161.024 3, 135.045 1

9-COA

[23]

5.11

353.087 8

353.088

C₁₆H₁₈O₉

[M-H]^-

3.78

191.056 1, 179.034 8, 173.045 5,
161.024 4, 135.045 1, 109.029 5

4-CQA

[22]

5.18

325.092 9

325.093 1

C₁₅H₁₈O₈

[M-H]^-

3.95

163.040 2, 146.966 1, 119.050 0

(E)-3-[2-[(2S, 3R, 4S, 5S, 6R)-3, 4, 5-Trihydroxy-6-(hydroxymethyl)oxan-2-yl]oxyphenyl]prop-2-enoic acid

GNPS

5.54

381.082 7

381.083

C₁₇H₁₈O₁₀

[M-H]^-

3.63

161.024 2, 135.045 3, 133.029 6

4-CDOA

[23]

6.77

381.082 7

381.083

C₁₇H₁₈O₁₀

[M-H]^-

3.55

161.024 1, 135.045 2, 133.029 5

9-CDOA

[23]

6.97

195.065 2

195.065 4

C₁₀H₁₀O₄

[M+H]⁺

1.33

177.054 8, 149.059 8

Ferulic acid

[23, 24]

7.04

195.065 2

195.065 3

C₁₀H₁₀O₄

[M+H]⁺

0.78

193.049 8, 177.054 8, 163.039 1

Methyl caffeate

[20]

8.08

352.101 1

352.101 6

C₁₃H₂₁O₁₁

[M-H]^-

4.4

173.045 8, 111.045 4

Quinic acid glucoside-1

[20]

8.36

367.103 5

367.103 6

C₁₇H₂₀O₉

[M-H]^-

3.40

353.088 2, 191.035 1, 179.035 1, 173.045 8

4/5-O-Caffeoylquinic acid methyl ester

[25]

8.43

367.103 5

367.103 6

C₁₇H₂₀O₉

[M-H]^-

3.40

193.050 5, 191.056 0, 173.045 4, 134.047 4

3-O-Feruloylquinic acid

GNPS

8.54

367.103 5

367.103 6

C₁₇H₂₀O₉

[M-H]^-

3.40

353.087 9, 191.035 2, 179.035 0, 173.045 6

4/5-O-Caffeoylquinic acid methyl ester

[25]

8.73

369.118 0

369.118 2

C₁₇H₂₀O₉

[M+H]⁺

0.59

369.118 2, 191.053 1

5-Feruloylquinic acid

[20]

8.75

367.103 5

367.103 6

C₁₇H₂₀O₉

[M-H]^-

3.32

353.087 8, 191.035 1, 179.035 1

4/5-O-Caffeoylquinic acid methyl ester

[25]

8.95

179.070 3

C₁₀H₁₀O₃

[M+H]⁺

0.06

161.059 8, 133.064 9

p-Methoxycinnamic acid

[20]

10.15

379.103 5

379.103 2

C₁₈H₂₀O₉

[M-H]^-

2.09

379.103 2, 161.045 6

5-O-Caffeoylquinic acid methyl ester

[20]

10.24

155.033 9

155.034 0

C₇H₆O₄

[M+H]⁺

0.42

137.023 5, 109.028 7

Protocatechuic acid

[11]

11.58

601.119 9

601.118 0

C₂₈H₂₆O₁₅

[M-H]^-

-1.35

353.088 0, 233.066 8, 195.065 2

1/4-Malonyl-diCQA

[25]

11.93

181.049 5

C₉H₈O₄

[M+H]⁺

-0.03

181.049 5, 163.039 0, 135.044 2

3, 4-Dihydroxycinnamic acid

[20]

12.00

437.107 8

437.107 9

C₂₀H₂₀O₁₁

[M+H]⁺

0.24

163.038 9, 145.028 1

Erigeroside

[20]

12.02

435.093 3

C₂₀H₂₀O₁₁

[M-H]^-

2.33

323.077 1, 179.035 0, 161.024 3, 135.045 1, 133.029 3

Erigeside Ⅰ

[11, 26]

12.19

379.103 5

379.103 1

C₁₈H₂₀O₉

[M-H]^-

2.01

379.103 1, 161.045 7

4-O-Caffeoylquinic acid methyl ester

[20]

12.26

463.088 2

463.088 6

C₂₁H₂₀O₁₂

[M-H]^-

3.15

301.035 3, 151.040 2, 135.045 3

Quercetin-3-O-β-D-glucopyranoside

[25]

12.30

463.088 2

463.088 6

C₂₁H₂₀O₁₂

[M-H]^-

3.22

301.035 4, 283.025 3, 151.040 1

Quercetin-3-O-β-D-glucoside

[22]

12.32

289.070 7

C₁₅H₁₂O₆

[M+H]⁺

0.15

121.028 7

Eriodictyol

[20]

12.47

477.067 5

477.067 7

C₂₁H₁₈O₁₃

[M-H]^-

2.71

477.067 7, 301.035 2

Quercetin-7-O-glucuronide

[11]

12.51

477.067 5

477.067 7

C₂₁H₁₈O₁₃

[M-H]^-

2.71

301.035 2, 151.003 5

Quercetin-3-O-glucuronide

[20]

12.54

477.067 5

477.067 6

C₂₁H₁₈O₁₃

[M-H]^-

2.77

301.035 3, 283.024 6

Galactose-3-O-glucuronate

[11]

12.58

463.088 2

463.088 4

C₂₁H₂₀O₁₂

[M-H]^-

2.88

301.035 3, 151.040 2, 135.045 3

Quercetin-3-O-β-D-glucopyranoside

[25]

12.60

479.082 0

479.082 3

C₂₁H₁₈O₁₃

[M+H]⁺

0.6

479.082 3, 303.049 7

Quercetin-3-O-β-galacturonide

[23]

12.61

461.072 5

461.072 8

C₂₁H₁₈O₁₂

[M-H]^-

2.89

286.043 8, 285.040 4

Kaempferol-3-O-glucuronide

GNPS

12.63

463.087 1

463.087 4

C₂₁H₁₈O₁₂

[M+H]⁺

0.71

287.054 2, 177.054 7, 121.028 6

Scutellarin*

[27]

12.70

449.107 8

449.107 9

C₂₁H₂₀O₁₁

[M+H]⁺

0.23

288.057 7, 287.054 3, 269.042 4, 153.018 0

Kaempferol-4′-O-β-D-glucoside

GNPS

12.73

449.107 8

449.107 9

C₂₁H₂₀O₁₁

[M+H]⁺

0.16

285.039 5

Quercetin-3-O-deoxyhexoside

GNPS

12.75

477.093 3

477.093 4

C₂₁H₂₀O₁₁

[M-H]^-

2.74

327.050 9, 285.040 4

Kaempferol-3-O-glucoside

[20]

12.77

463.087 1

463.087 3

C₂₁H₁₈O₁₂

[M+H]⁺

0.52

463.087 3, 287.054 5

Scutellarein-6-O-glucuronide

[28]

12.78

447.093 3

C₂₁H₂₀O₁₁

[M-H]^-

2.54

353.087 7, 285.040 4, 119.034 9

Scutellarein-7-O-glucoside

[25]

12.81

461.072 5

461.072 8

C₂₁H₁₈O₁₂

[M-H]^-

2.89

445.078 0, 287.056 1, 285.040 4

Breviscapine

[29]

12.85

559.109 3

559.109 4

C₂₆H₂₄O₁₄

[M-H]^-

2.15

285.040 3, 191.056 0, 179.056 1, 161.045 6, 135.045 2

3, 9/4.9-COA

[25]

12.95

559.109 3

559.109 6

C₂₆H₂₄O₁₄

[M-H]^-

2.37

353.087 8, 285.040 4, 191.056 3, 179.035 1, 161.045 6, 135.045 3

3, 9/4.9-COA

[26]

13.53

593.151 2

593.151 6

C₂₇H₃₀O₁₅

[M-H]^-

2.55

287.057 0, 129.055 9

Kaempferol-3-O-rutinoside

[20]

13.53

417.082 7

417.083 0

C₂₀H₁₈O₁₀

[M-H]^-

3.39

285.040 6, 215.010 0, 161.045 7, 121.029 6

Kaempferol-3-O-arabinoside

[25]

13.71

515.119 5

515.119 9

C₂₅H₂₄O₁₂

[M-H]^-

2.85

353.087 7, 335.077 5, 191.055 7, 179.035 0, 173.044 9, 161.024 5, 135.045 0

1, 5-diCQA

[27]

13.86

179.035 0

179.034 5

C₉H₈O₄

[M-H]^-

3.43

179.035 0, 135.045 2

Caffeic acid

[27]

13.92

515.119 5

515.119 8

C₂₅H₂₄O₁₂

[M-H]^-

2.62

353.087 7, 335.077 2, 191.056 0, 179.034 6, 173.045 4, 161.023 9, 135.045 2

1, 3-diCQA

[30]

14.07

447.093 3

447.093 5

C₂₁H₂₀O₁₁

[M-H]^-

2.94

429.082 3, 313.071 6, 193.035 5, 131.034 9

Naringenin-7-O-glucuronide

[20]

14.07

417.082 7

417.082 9

C₂₀H₁₈O₁₀

[M-H]^-

3.10

285.040 5, 215.009 9, 161.045 6, 121.029 6

Kaempferol-3-O-arabinoside

[25]

14.10

543.114 4

543.114 9

C₂₆H₂₄O₁₃

[M-H]^-

2.86

353.087 7, 179.034 4, 161.045 6, 135.045 2

ErigosterB/4, 9-diCDOA

[25]

14.24

543.114 4

543.114 6

C₂₆H₂₄O₁₃

[M-H]^-

2.41

353.088 0, 179.034 9, 161.045 6, 135.044 9

ErigosterB/4, 9-diCDOA

[25]

14.36

479.118 4

479.118 7

C₂₂H₂₂O₁₂

[M+H]⁺

0.52

318.068 9, 317.065 7

Isorhamnetin-3-O-glucoside

GNPS

14.45

447.093 3

447.093 5

C₂₁H₂₀O₁₁

[M-H]^-

2.88

271.061 2, 257.045 2

Naringenin-7-O-glucuronide

[11]

14.57

433.112 9

C₂₁H₂₀O₁₀

[M+H]⁺

0.61

271.117 1, 254.102 3, 121.028 5

Cosmosiin

[23]

14.59

431.098 4

431.098 6

C₂₁H₂₀O₁₀

[M-H]^-

3.01

431.098 6, 269.045 4

Scutellarin-7-O-glucoside

[20]

14.62

431.098 4

431.098 6

C₂₁H₂₀O₁₀

[M-H]^-

3.01

431.098 6, 269.045 5

Baicalein-7-O-β-D-glucopyranoside

[20]

14.69

445.077 6

445.077 9

C₂₁H₁₈O₁₁

[M-H]^-

3.09

269.045 5, 175.024 8, 129.055 7, 117.018 9, 113.024 4

Breviscapine I

[27]

14.73

445.077 6

445.077 9

C₂₁H₁₈O₁₁

[M-H]^-

2.95

269.045 4, 117.034 3

Apigenin-7-O-glucuronide*

[11]

14.80

445.077 6

445.078 0

C₂₁H₁₈O₁₁

[M-H]^-

3.22

271.060 9, 153.019 5, 119.050 2

Apigenin-7-O-β-galacturonide

[23]

14.80

287.056 1

287.056 2

C₁₅H₁₂O₆

[M-H]^-

4.07

161.045 7, 151.003 7, 135.045 3

Eriodictyol

[25]

14.87

445.077 6

445.078 0

C₂₁H₁₈O₁₁

[M-H]^-

3.29

429.083 2, 271.061 0, 269.045 5, 113.024 5

Baicalin*

[31]

15.18

493.097 7

493.098 1

C₂₂H₂₀O₁₃

[M+H]⁺

0.97

318.067 8, 317.064 9, 302.041 1, 153.010 9

Isorhamnetin-3-O-β-D-glucuronide

GNPS

15.24

515.119 5

515.119 8

C₂₅H₂₄O₁₂

[M-H]^-

2.62

353.087 4, 191.055 7, 179.034 4, 173.045 2, 161.045 6, 135.045 2

1, 4-diCQA

[25]

15.28

463.123 5

463.123 4

C₂₂H₂₂O₁₁

[M+H]⁺

-0.10

301.069 8, 287.055 2

6-Methoxykaempferol-4′-O-β-D-glucoside

GNPS

15.30

515.119 5

515.119 7

C₂₅H₂₄O₁₂

[M-H]^-

2.50

353.087 6, 191.056 0, 179.034 6, 173.045 3, 161.024 1, 135.045 2

3, 4-diCQA*

[27]

15.33

515.119 5

515.119 7

C₂₅H₂₄O₁₂

[M-H]^-

2.50

353.087 4, 191.055 9, 179.034 6, 173.045 3, 161.024 2, 135.045 2

3, 5-diCQA*

[27, 30]

15.37

515.119 5

515.119 7

C₂₅H₂₄O₁₂

[M-H]^-

2.50

353.087 6, 191.055 9, 179.034 6, 173.045 2, 161.024 2, 135.045 2

4, 5-diCQA*

[27]

15.44

475.088 2

475.088 4

C₂₂H₂₀O₁₂

[M-H]^-

2.69

299.056 1, 283.024 7

Kaempferol-7-O-glucuronide

[11]

15.62

475.088 2

475.088 6

C₂₂H₂₀O₁₂

[M-H]^-

3.14

299.056 1, 283.024 7

Kaempferol-3-O-glucuronide

[11]

15.75

477.102 8

477.103 1

C₂₂H₂₀O₁₂

[M+H]⁺

0.70

301.069 9, 177.054 9, 113.023 6

6-Methoxyscutellarein-7-O-glucuronide

[28]

15.95

557.130 1

557.130 6

C₂₇H₂₆O₁₃

[M-H]^-

2.97

381.083 4, 191.056 2, 179.035 1, 161.024 4

Erigoster A

[25]

16.06

529.135 1

529.134 3

C₂₆H₂₆O₁₂

[M-H]^-

0.54

353.088 5, 179.034 6, 161.045 6, 135.045 2

3, 4/3, 5-O-Dicaffeoylquinic acid methyl ester

[25]

16.2

285.040 5

285.040 6

C₁₅H₁₀O₆

[M-H]^-

4.4

268.037 6, 257.045 5, 239.034 9, 171.045 2, 121.029 4, 117.034 5, 109.029 3

Kaempferol

[20]

16.25

507.113 3

507.113 5

C₂₃H₂₂O₁₃

[M+H]⁺

0.41

287.055 2, 113.023 6

5, 6, 4′-Trihydroxyflavone-7-O-β-D-glucopyranuronate ethyl ester

[20]

16.27

285.040 5

285.040 6

C₁₅H₁₀O₆

[M-H]^-

4.40

267.030 1, 239.034 9, 213.055 7, 195.045 2

Scutellarein

[20]

16.34

287.056 1

287.056 2

C₁₅H₁₂O₆

[M-H]^-

4.40

161.045 6, 151.003 9, 135.045 2

Eriodictyol

[25]

16.41

285.040 5

285.040 6

C₁₅H₁₀O₆

[M-H]^-

4.4

269.045 9, 245.045 6, 243.029 9, 239.035 2, 229.050 7, 213.056 0, 211.040 3, 201.055 8, 179.035 2, 161.024 4, 137.024 5

Luteolin

[20]

16.82

557.130 1

557.130 6

C₂₇H₂₆O₁₃

[M-H]^-

2.96

381.082 4, 191.056 3, 179.034 9, 161.024 5

Erigoster A

[25]

16.85

529.135 1

529.135 3

C₂₆H₂₆O₁₂

[M-H]^-

2.39

353.088 2, 179.034 9, 161.045 7, 135.045 4

3, 4/3, 5-O-Dicaffeoylquinic acid methyl ester

[25]

17.10

501.139 1

501.139 6

C₂₅H₂₄O₁₁

[M+H]⁺

0.90

427.066 9, 271.096 0, 153.054 5

Apigenin-7-O-β-D-glucopyranuronic acid butyl ester

[28]

17.12

557.130 1

557.130 4

C₂₇H₂₆O₁₃

[M-H]^-

2.52

191.056 3, 179.034 8, 161.045 7

Acetylated-diCQA

[25]

17.49

557.130 1

557.130 4

C₂₇H₂₆O₁₃

[M-H]^-

2.52

191.055 8, 179.034 9, 161.024 5

Acetylated-diCQA

[25]

17.59

287.056 1

287.056 3

C₁₅H₁₂O₆

[M-H]^-

4.50

287.056 3, 161.045 7, 135.045 2

Eriodictyol

[25]

17.62

209.080 8

C₁₁H₁₂O₄

[M+H]⁺

0.30

191.070 4, 163.075 5

Ethyl caffeate

[20]

17.73

491.118 4

491.119 0

C₂₃H₂₂O₁₂

[M+H]⁺

1.25

287.054 8, 221.081 0, 113.023 6

5, 6, 4′-Trihydroxyflavone-7-O-β-D-glucopyranuronate ethyl ester

[28]

100

17.8

491.118 4

491.118 6

C₂₃H₂₂O₁₂

[M+H]⁺

0.45

287.054 9, 221.081 0, 113.023 6

Scutellarin ethyl ester

[32]

101

17.93

301.035 4

301.035 5

C₁₅H₁₀O₇

[M-H]^-

4.13

299.019 8, 271.024 9, 151.003 1,
149.024 0, 148.016 1, 133.029 4

3, 5, 6, 7, 4′-Pentahydroxyflavone

[20]

102

17.95

481.134 1

481.133 9

C₂₂H₂₄O₁₂

[M+H]⁺

-0.42

481.133 9, 163.038 8

1-(2′-γ-Pyrone)-6-caffeoyl-2-D-glucopyranoside

[20]

103

18.00

301.035 4

301.035 5

C₁₅H₁₀O₇

[M-H]^-

4.13

283.024 927 3.0 404, 178.998 2, 151.003 5, 121.029 6

Quercetin

[20]

104

18.20

461.107 8

461.108 3

C₂₂H₂₀O₁₁

[M+H]⁺

1.02

301.107 4, 287.055 3, 269.117 0, 189.054 9, 175.075 6, 153.054 8

Scutellarein glucuronide methyl ether

[30]

105

18.23

529.135 1

529.135 4

C₂₆H₂₆O₁₂

[M-H]^-

2.50

353.088 2, 179.035 1, 161.045 6, 135.045 2

3, 4/3, 5-O-Dicaffeoylquinic acid methyl ester

[25]

106

18.26

585.125 0

585.125 3

C₂₈H₂₆O₁₄

[M-H]^-

2.43

395.077 0, 353.088 0, 233.154 6, 179.035 0, 137.024 6

1-Malonyl-3, 5-dicaffeoylquinic acid

[23]

107

18.32

459.186 1

459.186 2

C₂₁H₃₀O₁₁

[M+H]⁺

0.15

459.186 2, 297.133 8, 163.060 4

(+)-Syringaresinol-O-β-D-glucopyranoside

[20]

108

18.40

557.130 1

557.130 3

C₂₇H₂₆O₁₃

[M-H]^-

2.30

191.056 2, 179.035 0, 161.024 5

Acetylated-diCQA

[25]

109

18.83

207.065 1

207.065 4

C₁₁H₁₀O₄

[M+H]⁺

1.25

189.054 7

Scopoletin

[33]

110

18.87

207.065 1

207.065 4

C₁₁H₁₀O₄

[M+H]⁺

0.81

193.049 7, 177.054 9, 163.039 0

Methyl caffeate

[20]

111

19.07

271.061 2

271.061 3

C₁₅H₁₂O₅

[M-H]^-

4.24

177.019 2, 165.019 3, 161.045 6, 145.050 6, 119.049 6

Naringenin*

[22]

112

19.08

273.075 8

273.075 7

C₁₅H₁₂O₅

[M+H]⁺

-0.13

271.060 2, 169.977 3, 119.068 8, 119.049 2

5, 7, 4′-Trihydroxyflavanone

[20]

113

19.1

269.045 5

269.045 6

C₁₅H₁₀O₅

[M-H]^-

4.36

269.045 6, 252.042

Baicalein*

[20]

114

19.13

269.045 5

269.045 6

C₁₅H₁₀O₅

[M-H]^-

4.25

227.034 7, 225.055 6, 201.055 9, 159.044 9, 151.003 7, 117.034 4

Apigenin*

[34]

115

19.33

303.086 3

C₁₆H₁₄O₆

[M+H]⁺

-0.04

273.075 6, 169.049 6, 135.044 1

1-Hydroxy-2, 3, 5-trihydroxyxanthone

[20]

116

19.34

329.066 7

329.066 8

C₁₇H₁₄O₇

[M-H]^-

3.72

285.040 7, 185.060 8, 178.977 9, 151.040 2

3′, 4′-Dimethoxyquercetin

[35]

117

19.36

301.070 7

301.070 8

C₁₆H₁₂O₆

[M+H]⁺

0.45

287.055 0, 177.054 8, 121.028 6

Hispidulin

[28]

118

19.4

301.070 7

301.070 8

C₁₆H₁₂O₆

[M+H]⁺

0.55

283.059 2, 271.060 1, 169.049 5, 133.049 6

Scutellarein methyl ether

[29]

119

19.56

315.051 0

315.051 2

C₁₆H₁₂O₇

[M-H]^-

4.16

299.019 4, 285.040 6, 243.029 3, 179.034 8, 161.024 5, 137.024 5, 123.008 9

3, 5, 6, 4′-Tetrahydroxy-7-methoxyflavone

[20]

120

20.15

455.077 2

C₂₆H₁₆O₈

[M-H]^-

1.87

455.077 2, 191.035 1, 161.024 5

3-O-Caffeoyl-γ-quinlactone

[25]

121

27.8

413.377 8

C₂₉H₄₈O

[M+H]⁺

-0.04

413.377 8, 395.367 3

Stigmasterol

[20]

122

27.9

395.330 8

395.331 2

C₂₈H₄₂O

[M+H]⁺

0.77

377.320 8, 271.205 8

Ergosta-7, 22-dien-3-one

[20]

123

315.051 0

C₁₆H₁₂O₇

[M-H]^-

151.002 7, 107.049 7

Isorhamnetin

GNPS

124

677.151 2

677.151 0

C₃₄H₃₀O₁₅

[M-H]^-

515.119 6, 353.087 7, 191.055 9, 179.034 5, 173.045 3, 161.024 2, 135.045 2

3, 4, 5-triCQA

GNPS

125

677.151 2

677.172 0

C₃₄H₃₀O₁₅

[M-H]^-

515.119 6, 353.087 6, 191.055 9, 179.034 5, 173.045 3, 161.024 2, 135.045 1

3, 4, 5-triCQA or its isomers

GNPS