药学学报

No.	t_R/min	Identification	Formula	Ion mode	Observed (m/z)	Error (×10^-6)	Fragment	Structure class	Origin
1	1.12	Histamine	C₅H₉N₃	[M+H]⁺	112.087 3	3.09	95.060 8, 83.060 9, 68.049 2	g	D
2	1.12	1-Deoxynojirimycin	C₆H₁₃NO₄	[M+H]⁺	164.091 8	0.46	146.081 0, 128.070 2, 68.049 1	b	S
3	1.15	Arginine	C₆H₁₄N₄O₂	[M-H]^-	173.104 4	-0.59	156.076 5, 131.081 1, 114.054 5	c	S/D/G
4	1.16	Valinol	C₅H₁₃NO	[M+H]⁺	104.107 2	2.2	87.084 5, 71.029 9, 60.081 6	b	S/G
5^△	1.24	Xylonic acid	C₅H₁₀O₆	[M-H]^-	165.039 1	-1.54	147.028 5, 129.017 9, 87.007 1, 75.007 0	c	S/D/G
6	1.26	Sugar acid	C₆H₁₀O₈	[M-H]^-	209.030 3	1.9	191.018 8, 133.012 8, 129.017 9, 85.027 8	c	S/D/G
7	1.27	Quinic acid	C₇H₁₂O₆	[M-H]^-	191.056 1	0.92	173.044 3, 127.038 6, 111.007 2, 85.027 8	c	S/D
8	1.34	Betaine	C₅H₁₁NO₂	[M+H]⁺	118.086 4	0.97	94.365 8, 72.081 5, 59.073 7, 58.065 8	b	S/D/G
9	1.86	Malic acid	C₄H₆O₅	[M-H]^-	133.013 1	-0.52	115.002 1, 89.022 8, 73.002 2	c	S/D/G
10^*	1.98	Adenine	C₅H₅N₅	[M+H]⁺	136.061 6	-1.61	119.035 3, 109.064 9, 100.274 0	g	S/D/G
11	1.99	Guanine	C₅H₅N₅O	[M+H]⁺	152.056 5	-1.42	135.033 0, 134.033 3, 110.035 0	g	S/D/G
12	1.99	Malic acid isomer	C₄H₆O₅	[M-H]^-	133.012 6	-3.53	115.002 1, 89.022 8, 72.991 4	c	S/D/G
13^△	1.99	Dehydroascorbic acid	C₆H₆O₆	[M-H]^-	173.009 2	-1.88	111.007 2, 85.028 7, 67.017 2	c	S/D/G
14^△	2.01	2-Acetamidoacrylic acid	C₅H₇NO₃	[M+H]⁺	130.049 5	2.45	112.087 1, 84.044 8, 70.065 7	c	S/D/G
15	2.02	Citric acid	C₆H₈O₇	[M-H]^-	191.018 9	1.21	173.088 1, 129.017 9, 111.007 2, 87.007 1	c	S/D/G
16	2.03	Stachydrine	C₇H₁₃NO₂	[M+H]⁺	144.101 9	-0.38	126.091 4, 98.096 8, 84.061 2, 70.062 5	b	G
17	2.07	Uridine	C₉H₁₂N₂O₆	[M-H]^-	243.062 3	3.24	200.055 8, 152.034 0, 110.023 2, 82.028 3	g	S/D/G
18	2.17	Suberic acid	C₈H₁₄O₄	[M-H]^-	173.081 9	0.46	129.017 9, 111.007 2, 85.027 8, 72.991 5	c	S/D
19	2.17	N-Acetyl-L-glutamic acid	C₇H₁₁NO₅	[M-H]^-	188.056 4	1.36	170.044 8, 144.065 3, 128.033 9, 102.054 5	c	S/D
20	2.27	Adenosine	C₁₀H₁₃N₅O₄	[M+H]⁺	268.104 0	-1.46	206.107 8, 152.648 5, 136.061 7	g	S/D/G
21	2.41	δ-Ribosyl-1,4-lactone	C₅H₈O₅	[M-H]^-	147.028 6	-1.5	129.018 0, 102.947 2, 87.007 1, 59.012 2	c	S/D/G
22	2.49	4-Hydroxyphenethylamine	C₈H₁₁NO	[M+H]⁺	138.091 3	-0.66	121.064 9, 111.007 9, 93.070 3	b	D
23	2.49	Isoleucine	C₆H₁₃NO₂	[M+H]⁺	132.101 9	-0.04	113.963 8, 86.096 9, 69.070 5	c	D/G
24	2.55	Guanosine	C₁₀H₁₃N₅O₅	[M-H]^-	282.084 4	4.59	178.900 8, 152.040 8, 126.029 4	g	S/D/G
25	2.56	Trigonelline	C₇H₇NO₂	[M+H]⁺	138.055 4	3.37	110.060 2, 94.056 3, 68.997 8	b	S/G
26	4.12	Cytisine	C₁₁H₁₄N₂O	[M+H]⁺	191.117 8	-0.57	162.090 8, 122.060 0, 105.963 0	b	D
27	5.08	Protocatechuic acid 4-O-β-glucoside	C₁₃H₁₆O₉	[M-H]^-	315.072 5	4.79	152.010 1, 125.256 2, 109.027 9	c	S/D/G
28^*	6.15	Vanillic acid 4-β-D-glucoside	C₁₄H₁₈O₉	[M-H]^-	329.088 0	1.27	167.033 8, 152.010 3, 123.043 7	c	S/D/G
29	6.98	Catechol	C₆H₆O₂	[M-H]^-	109.028 0	-3.62	108.020 4, 79.029 0, 67.029 1	c	S/D/G
30	7.02	Protocatechuic acid	C₇H₆O₄	[M-H]^-	153.019 3	-1.08	135.044 1, 109.028 0, 91.017 3	c	S/D/G
31^△	7.29	Daphneside	C₂₁H₂₆O₁₄	[M-H]^-	501.125 5	3.33	381.082 7, 219.029 3, 191.034 1	d	S/G
32^*	7.64	Caffeoylputrescine	C₁₃H₁₈N₂O₃	[M+H]⁺	251.139 0	-0.56	234.111 7, 163.038 6, 145.028 1, 89.107 7	b	D
33	7.95	Syringic acid glucoside	C₁₅H₂₀O₁₀	[M-H]^-	359.099 0	4.73	197.044 8, 182.022 1, 138.030 9	c	D
34^△*	8.57	Mulberroside A+Glc	C₃₃H₄₄O₂₁	[M-H]^-	775.231 3	2.13	729.225 3, 567.172 0, 405.119 1, 243.009 0	e	S
35^*	8.59	Oxyresveratrol-6-O-D-glucopyranosyl-D-glucopyranoside isomer	C₃₂H₄₂O₁₉	[M-H]^-	729.225 9	3.07	567.172 6, 405.112 5, 243.066 1, 225.055 2	e	S
36^*	8.78	Neochlorogenic acid	C₁₆H₁₈O₉	[M-H]^-	353.088 1	1.18	191.055 3, 179.034 0, 135.043 8	d	S
37	8.87	Indole-3-acrylic acid	C₁₁H₉NO₂	[M+H]⁺	188.070 4	-1.3	170.059 7, 146.059 8, 118.065 2, 88.022 0	b	S/D/G
38	9.01	Tryptophan	C₁₁H₁₂N₂O₂	[M-H]^-	203.082 6	2.15	186.055 2, 159.091 6, 116.049 1	c	D
39	9.4	8-Hydroxyquinoline	C₉H₇NO	[M+H]⁺	146.059 9	-1.24	128.950 7, 118.065 3, 99.044 4	b	D/G
40	10.13	Salicylic acid	C₇H₆O₃	[M-H]^-	137.023 1	-1.9	119.012 6, 93.033 3, 65.038 0	c	S/D/G
41	10.54	2-Isopropylmalic acid	C₇H₁₂O₅	[M-H]^-	175.061 2	0.4	146.959 9, 115.038 6, 85.064 3	c	G
42^△*	10.85	Unknown	C₃₂H₅₀N₇O₁₀	[M+H]⁺	693.369 1	-0.16	657.343 4, 474.257 4, 293.185 8, 222.112 1	b	D
43^*	11.	Kukoamine A	C₂₈H₄₂N₄O₆	[M+H]⁺	531.317 1	-0.45	293.185 6, 222.112 1, 165.054 5, 123.043 9	b	D
44	11.13	Phenyllactic acid	C₉H₁₀O₃	[M-H]^-	165.054 6	-0.43	121.064 5, 93.033 0, 59.012 2	d	S/D/G
45^*	11.14	Kukoamine B	C₂₈H₄₂N₄O₆	[M+H]⁺	531.317 3	-0.57	293.185 5, 222.122 0, 165.054 5, 123.043 9	b	D
46	11.2	6-Methylquinoline	C₁₀H₉N	[M+H]⁺	144.080 6	-1.14	117.065 4, 98.331 1, 84.081 2	b	D
47	11.28	Esculin	C₁₅H₁₆O₉	[M-H]^-	339.071 8	2.22	249.040 5, 219.029 3, 191.034 2	d	S
48^*	11.98	Caffeoylagmatine	C₁₄H₂₀N₄O₃	[M+H]⁺	293.160 4	-0.45	276.134 7, 163.038 7, 131.092 5, 114.102 7	b	D
49^*	12.62	Feruloylputrescine	C₁₄H₂₀N₂O₃	[M+H]⁺	265.154 3	-0.34	177.054 4, 163.039 5, 145.028 3, 89.107 8	b	D
50	12.94	7-Hydroxycoumarin	C₉H₆O₃	[M+H]⁺	163.038 7	-0.24	145.028 3, 135.044 1, 119.033 9, 104.049 4	d	S/G
51	12.98	Dihydrocaffeic acid	C₉H₁₀O₄	[M-H]^-	181.050 6	0.63	163.038 9, 137.059 4, 121.027 9, 109.028 0, 93.069 3	c	G
52^*	13.15	N¹-Caffeoyl-N¹⁰-dihydro caffeoylspermine	C₂₈H₄₀N₄O₆	[M+H]⁺	529.301 9	-0.34	511.471 6, 367.271 4, 293.186 5, 220.096 5, 163.038 7	b	D
53^*	13.21	Chlorogenic acid	C₁₆H₁₈O₉	[M-H]^-	353.087 8	3.34	191.055 2, 179.034 0, 161.023 2	d	S
54^*	13.31	N¹-Caffeoyl-N¹⁴-dihydro caffeoylspermine	C₂₈H₄₀N₄O₆	[M+H]⁺	529.301 9	-0.18	511.472 2, 458.227 0, 367.270 0, 293.184 7, 220.096 5, 163.038 7	b	D
55^△	13.36	Sinapic acid glucuronide	C₁₇H₂₀O₁₁	[M-H]^-	399.093 0	2.16	221.702 8, 192.037 4	d	S/G
56^△*	13.45	Multiflorin A	C₂₉H₃₂O₁₆	[M-H]^-	635.156 6	-4.04	567.171 9, 405.120 3, 243.066 0, 225.056 1	a	S
57^*	13.48	N⁵-3-Acetyldihydrocaffeoyl-N¹⁰-dihydrocaffeoylspermine	C₂₈H₄₀N₄O₆	[M+H]⁺	529.301 9	-0.12	291.170 1, 220.096 7, 163.038 8, 147.069 4	b	D
58^△*	13.55	Mulberroside A +2H₂O	C₂₆H₃₆O₁₆	[M-H]^-	603.146 4	1.23	567.172 3, 405.119 3, 243.066 1	e	S
59^△*	13.57	Leiocarposide	C₂₇H₃₄O₁₆	[M-H]^-	613.176 7	0.39	567.172 2, 405.119 4, 243.066 1, 225.055 4	e	S
60^*	13.61	Mulberroside A	C₂₆H₃₂O₁₄	[M-H]^-	567.172 4	2.69	405.119 3, 243.006 1, 225.055 3, 199.075 7	e	S
61^*	13.63	Glucosyl-3-O-β-D-apiosyl-(1→6)-O-β-D-glucoside	C₃₁H₄₀O₁₈	[M-H]^-	699.216 1	3.1	537.159 9, 405.119 2, 243.066 1, 225.055 4	e	S
62^△*	13.67	Mulberroside A dimer	C₅₂H₆₄O₂₈	[M-H]^-	1 135.343 7	-4.58	567.172 1, 405.119 1, 243.066 0, 225.055 1	e	S
63^△*	14.1	L-Leucyl-L-tyrosine	C₁₅H₂₂N₂O₄	[M+H]⁺	295.164 8	-0.4	207.065 0, 175.038 8, 147.039 9, 119.049 3	b	D
64^△	14.29	Capsaicin	C₁₃H₂₇N₈O₃	[M+H]⁺	344.228 3	1.11	327.200 9, 283.174 7, 177.112 0, 133.086 0, 89.068 2	b	D
65^*	14.49	Cryptochlorogenic acid	C₁₆H₁₈O₉	[M-H]^-	353.087 9	3.34	191.055 3, 179.034 0, 161.023 4, 135.043 8	d	S
66	14.61	4-Hydroxybenzaldehyde	C₇H₆O₂	[M-H]^-	121.028 0	-3.11	108.020 1, 93.020 9, 69.985 5	g	S/G
67	14.71	N¹-Dihydrocaffeoyl-N⁵ dihydroferuoylspermine	C₂₉H₄₄N₄O₆	[M+H]⁺	545.330 0	-0.35	307.200 9, 293.185 2, 236.127 8, 222.112 2, 179.070 7, 137.059 7	b	D
68	14.79	Scopoletin	C₁₀H₈O₄	[M+H]⁺	193.049 4	-0.75	178.027 5, 165.054 4, 149.059 3, 133.028 4, 127.298 6	d	D
69	14.95	α-Rhamnosyl-(1→6)-O-β-D-glucoside	C₂₁H₂₆O₁₃	[M-H]^-	485.130 1	1.31	363.248 8, 293.088 3, 191.034 2, 176.010 4	d	S
70^*	15.02	Oxyresveratrol-6-O-D-glucopyranosyl-D-glucopyranoside	C₃₂H₄₂O₁₉	[M-H]^-	729.227 2	4.9	567.171 8, 243.066 1, 225.055 1	e	S
71^△*	15.13	Hydroxyprolyl-tryptophan	C₁₆H₁₉N₃O₄	[M+H]⁺	318.144 4	-1.42	207.065 1, 175.038 7, 147.043 4	b	D
72^#	15.37	Quercetin-3-O-sophoroside	C₂₇H₃₀O₁₇	[M-H]^-	625.141 2	1.99	463.088 4, 299.020 1, 151.002 4, 125.002 9	a	S
73^*	16.92	N¹,N¹⁰-Bis(dihydrocaffeoyl)spermidine	C₂₅H₃₅N₃O₆	[M+H]⁺	474.259 7	-0.16	293.185 9, 222.112 2, 165.054 5, 123.044 1	b	D
74^#	17.67	Glucoliquiritin apioside	C₃₂H₄₀O₁₈	[M-H]^-	711.214 7	2.21	711.216 5, 549.160 5, 255.065 8, 153.018 5, 135.008 6, 119.048 7	a	G
75	17.8	3-p-Coumaroylquinic acid	C₁₆H₁₈O₈	[M-H]^-	337.092 4	1.74	191.055 2, 163.038 7, 119.048 8, 93.033 0	c	S
76^△#*	17.88	Hydroxysafflor yellow A	C₂₇H₃₂O₁₆	[M-H]^-	611.162 0	2.17	565.156 3, 403.103 4, 241.050 3, 197.060 2	a	S
77^#*	17.93	Glabranin	C₂₀H₂₀O₄	[M-H]^-	323.125 4	-2.36	257.678 3, 203.081 4, 189.066 0, 175.086 9	a	G
78	18.46	Riboflavin	C₁₇H₂₀N₄O₆	[M+H]⁺	377.145 1	-1.2	359.134 3, 243.087 4, 172.086 8	b	D
79	18.93	N⁵-Dihydrocaffeoyl-N¹⁰ caffeoylspermidine	C₂₅H₃₃N₃O₆	[M+H]⁺	472.243 8	-0.41	455.214 8, 310.212 0, 293.185 4, 236.127 6, 220.096 5, 163.038 7	b	D
80^△*	19.02	Unknown	C₂₇H₄₀N₇O₆	[M+H]⁺	559.311 5	0.42	321.179 8, 293.185 5, 222.122 0, 165.054 6, 123.044 2	b	D
81	19.18	Magnoflorine	C₂₀H₂₃NO₄	[M+H]⁺	342.168 8	-3.58	297.110 6, 265.084 5, 237.090 6, 183.521 0, 177.054 2, 115.076 2	b	D
82	19.34	Esculetin	C₉H₆O₄	[M-H]^-	177.018 2	-0.01	149.023 3, 133.028 1, 105.032 9, 89.038 1	d	S/G
83	19.83	Vicenin-2	C₂₇H₃₀O₁₅	[M-H]^-	593.151 1	1.73	473.104 7, 383.075 9, 353.066 7, 325.073 0, 297.076 6	a	G
84^△*	19.93	Unknown	C₂₆H₁₈O₇	[M-H]^-	441.094 3	-5.78	405.119 3, 243.066 1, 225.056 2, 199.076 3, 175.074 9	e	S
85^△*	19.97	Catechin-7-O-β-D-glucopyranoside	C₂₁H₂₄O₁₁	[M-H]^-	451.124 8	1.3	405.119 3, 243.066 1, 225.055 2, 199.075 8, 175.075 5, 157.064 7	e	S
86^△*	19.98	6"-O-Acetylgenistin	C₂₃H₂₂O₁₁	[M-H]^-	473.106 1	-1.7	405.119 3, 243.066 2, 225.055 6, 175.075 3	e	S
87^*	20.01	2,3,5,4′-Tetrahydroxy stilbene-2-Ο-β-D-glucoside isomer	C₂₀H₂₂O₉	[M-H]^-	405.119 1	2.79	243.066 1, 225.055 2, 199.075 7, 175.075 3, 157.064 5	e	S/G
88^△*	20.22	Acremonidin D	C₃₃H₂₈O₁₄	[M-H]^-	647.139 4	-0.2	449.109 3, 287.057 6, 161.023 4, 125.023 0	a	S
89^*	20.24	N¹-3-Acetyldihydrocaffeoyl-N¹⁰-dihydrocaffeoyl spermine	C₃₀H₄₄N₄O₇	[M+H]⁺	573.327 7	-1.01	475.269 6, 335.196 6, 293.184 1, 222.112 2, 208.681 9, 165.054 3	b	D
90^△*	20.44	Unknown	C₂₈H₃₄O₁₈	[M-H]^-	657.167 8	1.65	611.162 0, 449.109 1, 287.056 2, 125.023 0	a	S
91	20.77	N-Acetyl-L-phenylalanine	C₁₁H₁₃NO₃	[M-H]^-	206.082 3	2.23	192.005 5, 164.070 5, 147.043 8, 118.991 6, 91.053 7	c	D
92^△#	21.05	Diosmetin-7-O-glucoside	C₂₂H₂₂O₁₁	[M-H]^-	461.329 1	0.92	415.161 4, 299.057 2, 191.055 3, 149.099 3, 131.033 7, 89.022 8	a	S
93^△*	21.28	Unknown	C₂₈H₃₄O₁₈	[M-H]^-	657.168 2	2.11	611.162 8, 449.109 2, 287.056 2, 161.023 3, 125.023 1	a	S
94^△#*	21.45	Unknown	C₃₂H₄₀O₂₀	[M-H]^-	743.202 6	-0.38	700.649 8, 449.111 5, 405.341 5, 287.056 7, 161.023 2, 125.022 9	a	S
95^△*	21.48	Plantagoside	C₂₁H₂₂O₁₂	[M-H]^-	465.103 7	0.92	303.105 8, 151.002 8, 125.023 0	a	S
96^*	21.73	2,3,5,4′-Tetrahydroxy stilbene-2-Ο-β-D-glucoside	C₂₀H₂₂O₉	[M-H]^-	405.119 1	2.79	243.066 1, 225.055 2, 199.075 8, 175.075 4, 159.044 0	e	S/G
97^△#	21.94	Unknown	C₂₁H₂₉O₁₄	[M-H]^-	504.147 3	3.89	412.140 9, 301.831 4, 192.067 1, 165.054 8	a	S
98^#	22.18	Daidzin	C₂₁H₂₀O₉	[M+H]⁺	417.117 8	-0.5	255.064 8, 237.054 6, 199.074 3, 149.717 5	a	G
99^△*	22.96	N-Acetyl-1-O-benzyl-α-muramyl-α-aminoisobutyryl-D-isoglutamine benzyl ester	C₃₄H₄₆N₄O₁₁	[M+H]⁺	687.322 5	0.3	449.191 0, 293.185 9, 222.121 6, 165.054 1	b	D
100^*	22.98	Hyperoside	C₂₁H₂₀O₁₂	[M-H]^-	463.088 5	3.08	301.033 5, 273.040 3, 255.030 0, 151.002 4, 125.002 9	a	S
101^#	23.44	Schaftoside	C₂₆H₂₈O₁₄	[M-H]^-	563.140 8	2.38	473.106 1, 443.098 0, 383.077 7, 353.066 4, 325.071 8, 297.076 7	a	G
102	23.5	Isoscopoletin	C₁₀H₈O₄	[M+H]⁺	193.049 4	-0.15	178.025 0, 165.054 7, 149.056 9, 137.059 7, 133.024 8	d	D
103	24.21	Ferulic acid	C₁₀H₁₀O₄	[M-H]^-	193.050 0	2.51	178.026 1, 149.059 5, 134.036 0	c	S/D/G
104^#	25.35	Tetrahydroxychalcone 4′-O-glucoside	C₂₁H₂₂O₁₀	[M-H]^-	433.113 6	-1.	271.061 0, 151.003 6, 135.008 7, 119.050 2	a	G
105^*	25.75	Isoliquiritin	C₂₁H₂₂O₉	[M-H]^-	417.118 5	-1.45	255.065 5, 148.016 4, 135.008 6, 119.050 1	a	G
106^△#*	25.85	Unknown	C₂₀H₂₂O₁₂	[M-H]^-	453.095 4	-7.35	417.119 3, 255.066 7, 153.018 1, 135.007 6, 119.048 6	a	G
107	26.08	Dihydro-N-caffeoyltyramine	C₁₇H₁₉NO₄	[M+H]⁺	302.138 4	-0.29	165.054 3, 143.572 4, 138.091 3, 121.064 9	b	D
108^*	26.17	Isoliquiritin apioside	C₂₆H₃₀O₁₃	[M-H]^-	549.160 3	-1.95	429.104 2, 297.077 5, 255.065 7, 135.008 5, 119.050 0	a	G
109^△#*	26.17	Eriocitrin isomer	C₂₇H₃₂O₁₅	[M-H]^-	595.167 2	1.49	255.066 1, 135.007 6, 119.049 0	a	S
110^△*	26.2	Unknown	C₂₅H₃₀O₁₆	[M-H]^-	585.135 9	-6.16	429.102 8, 255.066 3, 135.007 5	a	G
111^*	26.38	N¹,N⁵-Bis(dihydroferuloyl)spermidine	C₂₇H₃₉N₃O₆	[M+H]⁺	502.291 2	0.04	388.415 9, 250.142 4, 236.127 8, 179.070 5, 137.059 7	b	D
112^#*	26.47	Liquiritin	C₂₁H₂₂O₉	[M-H]^-	417.119 3	3.28	255.066 2, 163.018 0, 148.015 0, 135.007 4, 119.048 7	a	G
113^△#	26.54	Tetrahydroxychalcone 4′-O-glucoside isomer	C₂₁H₂₂O₁₀	[M-H]^-	433.113 9	2.3	271.061 3, 151.002 4, 135.008 7, 119.050 3	a	S
114^#*	26.68	Naringenin-7-O-glucoside	C₂₁H₂₂O₁₀	[M-H]^-	433.114 2	3.02	271.061 5, 151.002 4, 119.048 7	a	G
115^*	26.74	N¹,N⁵,N¹⁰-tris(di hydrocaffeoyl) spermine	C₃₇H₅₀N₄O₉	[M+H]⁺	695.363 3	-2.5	678.344 1, 457.234 3, 293.185 9, 222.112 3	b	D
116^△*	26.75	Liquiritin apioside	C₂₆H₃₀O₁₃	[M-H]^-	549.161 3	2.02	417.119 3, 255.066 1, 153.018 0, 135.007 3, 119.048 6, 91.017 3	a	G
117^△*	26.79	Unknown	C₂₅H₃₀O₁₆	[M-H]^-	585.138 9	-0.49	549.161 8, 429.102 8, 255.066 3, 153.017 7, 135.007 5	a	G
118^#	27.19	Dihydromorin	C₁₅H₁₂O₇	[M-H]^-	303.052 2	7.66	275.056 3, 177.018 2, 125.023 0	a	S
119^#*	27.76	Eriodictyol-7-O-glucoside	C₂₁H₂₂O₁₁	[M-H]^-	449.109 9	4.57	287.056 7, 269.136 8, 197.059 8, 125.022 9	a	S
120^#	27.89	6′′-O-Acetylliquiritin isomer	C₂₃H₂₄O₁₀	[M-H]^-	459.130 0	3.04	339.087 5, 255.044 6, 153.010 3	a	G
121^△*	27.97	Unknown	C₃₄H₄₆N₄O₈	[M+H]⁺	639.338 6	-0.35	621.330 1, 293.185 9, 222.112 2	b	D
122	28.79	Oxyresveratrol	C₁₄H₁₂O₄	[M-H]^-	243.066 1	3.76	225.055 1, 199.075 8, 175.075 3	e	S
123^#	28.91	6′′-O-Acetylliquiritin isomer	C₂₃H₂₄O₁₀	[M-H]^-	459.129 3	1.16	339.087 4, 263.056 7, 255.045 2, 153.010 0	a	G
124^#	29.13	Naringenin chalcone	C₁₅H₁₂O₅	[M-H]^-	271.061 4	4.91	151.002 3, 140.975 4, 119.048 9	a	G
125	29.14	Mulberroside F	C₂₆H₃₀O₁₄	[M-H]^-	565.156 2	1.78	433.112 0, 335.243 8, 271.061 4, 227.071 2, 151.002 4, 119.048 7	e	S
126^*	29.21	trans-N-Caffeoyltyramine	C₁₇H₁₇NO₄	[M+H]⁺	300.122 8	-0.78	163.038 7, 121.064 9, 89.060 1	b	D
127	29.23	Azelaic acid	C₉H₁₆O₄	[M-H]^-	187.096 5	-0.03	169.085 7, 143.106 5, 125.095 7	c	S/D/G
128^△#	29.25	Tetrahydroxychalcone 4′-O-glucoside isomer	C₂₁H₂₂O₁₀	[M-H]^-	433.113 1	0.41	271.061 4, 151.002 4, 135.008 7, 119.050 4	a	S
129^*	29.77	Lyciumin A	C₄₂H₅₁N₉O₁₂	[M+H]⁺	874.372 6	-0.5	856.363 7, 486.198 1, 468.187 6, 136.075 7	b	D
130^#	29.78	Eriodictyol	C₁₅H₁₂O₆	[M-H]^-	287.056 1	3.85	259.061 4, 243.067 2, 151.002 3, 125.022 9	a	S
131^△	29.9	4-Oxododecanedioic acid	C₁₂H₂₀O₅	[M-H]^-	243.123 8	2.88	225.112 8, 207.102 2, 181.122 5, 146.959 9	c	S/D/G
132	30.04	7-O-β-D-Apiosyl-3-O-p-coumaroylkaempferol	C₂₇H₃₀O₁₃	[M-H]^-	561.161 6	2.41	309.076 8, 267.066 4, 252.042 8	d	G
133^△*	30.17	Eriodictyol isomer	C₂₇H₃₂O₁₅	[M-H]^-	595.167 6	1.85	351.069 3, 255.066 2, 135.007 4, 119.048 8, 91.017 2	a	S
134^△#	30.47	Isoformononetin	C₁₆H₁₂O₄	[M-H]^-	269.080 4	-1.69	254.055 9, 237.054 2, 213.091 2, 119.041 4	a	S
135^*	30.9	Neoisoliquiritin	C₂₁H₂₂O₉	[M-H]^-	417.111 9	-4.7	255.066 2, 153.019 1, 148.015 4, 135.007 1, 119.048 7	a	G
136^#	30.92	Liquiritin B	C₃₅H₃₆O₁₅	[M-H]^-	695.198 8	2.51	531.152 5, 255.066 3, 119.048 8, 72.991 5	a	G
137	30.94	N-p-trans-Coumaroyltyramine	C₁₇H₁₇NO₃	[M+H]⁺	284.128 1	0.07	239.149 7, 147.043 9, 121.064 8, 119.049 2	b	D
138^#	31.08	Liquiritin A	C₃₆H₃₈O₁₆	[M-H]^-	725.210 0	3.24	531.152 7, 255.066 0, 193.049 5, 135.007 5	a	G
139^#	31.25	Morin	C₁₅H₁₀O₇	[M-H]^-	301.035 6	4.42	273.042 0, 229.050 2, 151.002 4, 125.023 0	a	S
140^*	31.34	Feruloyltyramine	C₁₈H₁₉NO₄	[M+H]⁺	314.138 5	-0.52	292.079 3, 177.054 4, 145.028 3, 117.033 6	b	D
141^△*	31.41	Baicalin	C₂₁H₁₈O₁₁	[M-H]^-	445.077 0	3.46	269.045 8, 235.303 8, 175.023 9, 113.022 9	a	S
142	31.43	Lyciumin B	C₄₄H₅₂N₁₀O₁₁	[M+H]⁺	897.388 7	-0.34	689.307 3, 486.198 0, 468.187 5, 159.091 5	b	D
143^*	31.62	N-Feruloyl-3-methoxy tyramine	C₁₉H₂₁NO₅	[M+H]⁺	344.148 7	-1.74	177.054 4, 145.028 4, 117.033 6	b	D
144^△#	31.62	Licorice saponin J2 isomer	C₄₂H₆₄O₁₆	[M-H]^-	823.413 2	2.61	671.079 0, 351.057 4, 193.034 9, 113.002 9	f	G
145^#	31.65	4′,7-Dihydroxyflavanone	C₁₅H₁₂O₄	[M-H]^-	255.062 5	-7.28	219.845 1, 153.018 1, 135.007 2, 119.004 2	a	G
146^△#	31.71	24-Hydroxy-licorice saponin A3	C₄₈H₇₂O₂₂	[M-H]^-	999.445 6	2.41	837.388 9, 377.540 1, 351.056 2, 193.034 4, 113.022 9	f	G
147^#	31.8	Liquiritigenin	C₁₅H₁₂O₄	[M-H]^-	255.065 0	4.57	219.844 9, 153.018 1, 135.007 2, 119.004 8	a	G
148^△*	31.85	Chrysin-7-O-β-D-glucuronide	C₂₁H₁₈O₁₀	[M-H]^-	429.082 1	4.5	253.050 6, 175.023 9, 113.022 9	a	S
149	31.86	Sebacic acid	C₁₀H₁₈O₄	[M-H]^-	201.113 2	1.76	183.101 7, 139.111 5, 111.080 1	c	S/D
150^△*	31.91	Diosmetin-7-glucuronide	C₂₂H₂₀O₁₂	[M-H]^-	475.087 6	2.49	299.056 5, 284.032 9, 217.056 7, 113.022 6	a	S
151	31.99	7-Hydroxy-1-(3,4-dihydroxyphenyl)-N²,N³-bis(4-hydroxyphenethyl)-6,8-dimethoxy-1,2-dihydronaphthalene-2,3-dicarboxamide	C₃₆H₃₆N₂O₉	[M+H]⁺	641.245 3	-6.33	504.163 9, 476.167 8, 339.086 8	b	D
152	32.07	Lyciumin C	C₄₉H₅₇N₉O₁₂	[M+H]⁺	964.419 9	-0.09	593.273 4, 576.246 5, 389.181 5, 257.128 1, 188.070 4	b	D
153^△*	32.1	3,7-Bis(2-hydroxyethyl) icaritin	C₂₅H₂₈O₈	[M-H]^-	455.170 9	0.83	371.217 2, 213.221 2, 153.349 6, 125.022 9	a	S
154^△#	32.4	22-Hydroxy-licorice saponin G2	C₄₂H₆₂O₁₈	[M-H]^-	853.387 2	2.3	351.056 6, 193.034 6, 175.024 5, 113.022 8	f	G
155^*	32.53	Licorice saponin A3	C₄₈H₇₂O₂₁	[M-H]^-	983.450 5	2.3	821.398 5, 645.365 0, 469.335 2, 351.056 9, 193.034 5, 113.022 9	f	G
156^△*	32.94	Rhaglycyrrhizin	C₄₈H₇₂O₂₀	[M-H]^-	969.461 1	-0.15	601.403 5, 351.056 9, 193.034 9, 113.022 9	f	G
157^#*	33.25	Licorice saponin G2 isomer	C₄₂H₆₂O₁₇	[M-H]^-	837.391 8	1.74	485.330 3, 351.056 9, 235.046 4, 193.034 3, 113.022 9	f	G
158^*	33.26	Glycyrrhetinic acid	C₃₀H₄₆O₄	[M+H]⁺	471.346 4	-0.95	453.335 7, 317.210 8, 135.116 7	f	G
159	33.28	Glabrolide	C₃₀H₄₄O₄	[M+H]⁺	469.330 6	-1.29	451.319 3, 405.315 1, 243.137 3, 175.147 9	d	G
160	33.39	(11E,15Z)-9,10,13-Trihydroxy-11,15-octadecadienoic acid	C₁₈H₃₂O₅	[M-H]^-	327.218 0	4.15	309.207 6, 211.133 3, 171.101 6, 85.027 9	c	S/D
161^△#	33.48	Licorice saponin J2 isomer	C₄₂H₆₄O₁₆	[M-H]^-	823.411 2	0.16	759.278 1, 351.056 9, 193.034 7, 113.022 9	f	G
162^#*	33.68	Naringenin	C₁₅H₁₂O₅	[M-H]^-	271.061 5	5.02	225.222 1, 177.018 1, 151.00 24, 119.048 6	a	G
163^△	33.77	Hedione	C₁₃H₂₂O₃	[M-H]^-	225.149 6	3.24	207.138 5, 181.159 0, 167.106 8, 125.095 7	c	S/D/G
164^#*	34.25	Licorice saponin G2 isomer	C₄₂H₆₂O₁₇	[M-H]^-	837.392 5	1.09	351.057 1, 193.034 6, 175.024 1, 113.022 9	f	G
165^#*	34.81	Licorice saponin G2 isomer	C₄₂H₆₂O₁₇	[M-H]^-	837.391 5	1.45	351.056 6, 193.034 3, 175.023 1, 113.022 9	f	G
166^#*	34.9	Glycyrrhizic acid	C₄₂H₆₂O₁₆	[M-H]^-	821.397 6	2.71	645.365 8, 351.057 1, 193.034 6, 174.023 8, 113.022 9	f	G
167^*	34.95	Oleaside E	C₄₂H₆₄O₁₇	[M-H]^-	839.409 2	3.2	351.057 3, 193.034 6, 175.024 0, 113.023 0	f	G
168^#	35.12	Licorice saponin H2	C₄₂H₆₂O₁₆	[M-H]^-	821.397 5	2.52	351.057 1, 193.034 6, 175.023 7, 113.022 9	f	G
169^#*	35.16	Isoliquiritigenin	C₁₅H₁₂O₄	[M-H]^-	255.065 0	3.56	219.845 2, 153.018 1, 135.007 4, 119.004 9, 91.017 3	a	G
170^△#	35.47	Licorice saponin B2 isomer	C₄₂H₆₄O₁₅	[M-H]^-	807.416 1	3.16	351.057 1, 193.034 4, 175.023 7, 113.022 9	f	G
171^#*	35.48	Formononetin	C₁₆H₁₂O₄	[M+H]⁺	269.080 3	-1.8	254.057 3, 237.054 7, 213.090 7, 154.026 0	a	G
172^△#	35.96	Licorice saponin K2	C₄₂H₆₂O₁₆	[M-H]^-	821.397 6	2.23	643.293 9, 351.057 1, 193.034 7, 175.023 9, 113.023 0	f	G
173^△#*	36.33	Kushenol L	C₂₅H₂₈O₇	[M-H]^-	439.177 1	1.93	151.005 2, 125.023 0, 92.089 7	a	S
174^△#	36.44	Kuwanon G	C₂₅H₂₆O₇	[M-H]^-	437.161 4	4.42	401.187 3, 174.185 5, 152.994 9, 125.022 9	a	S
175^△#	36.46	Licorice saponin C2	C₄₂H₆₂O₁₅	[M-H]^-	805.401 2	0.75	573.278 4, 351.057 1, 295.579 1, 193.034 7, 113.022 9	f	G
176^△#	36.6	Licorice saponin B2 isomer	C₄₂H₆₄O₁₅	[M-H]^-	807.415 9	-0.25	351.057 2, 193.034 0, 175.023 9, 113.023 1	f	G
177^#*	36.86	Glycycoumarin	C₂₁H₂₀O₆	[M-H]^-	367.118 5	0.89	297.040 3, 139.038 8	a	G
178^#	36.93	Ononin	C₂₂H₂₂O₉	[M-H]^-	429.113 0	-3.2	361.163 4, 293.176 5, 236.105 2, 221.154 1	a	G
179	36.97	3,5-Di-tert-butylcatechol	C₁₄H₂₂O₂	[M-H]^-	221.154 7	2.28	205.071 6, 177.039 4, 135.969 8, 91.952 1	c	S/D/G
180	37.06	(±)9-HpODE	C₁₈H₃₂O₄	[M-H]^-	311.222 8	4.	293.176 2, 267.196 8, 223.170 0, 99.007 2	c	S/D/G
181	37.85	Morusin P	C₁₉H₁₈O₅	[M-H]^-	325.104 3	-2.74	249.131 9, 235.248 0, 193.506 0	e	S
182^△#	38.25	Cyclomorusin	C₂₅H₂₄O₆	[M+H]⁺	421.164 2	-0.67	365.101 7, 347.090 8, 311.054 7, 137.291 7	a	S
183	38.63	Glycycoumarin isomer	C₂₁H₂₀O₆	[M-H]^-	367.118 4	2.41	313.071 0, 263.538 2, 139.038 8, 111.810 5	d	G
184	39.15	Oleic acid	C₁₈H₃₄O₂	[M-H]^-	281.248 6	4.74	192.471 9, 152.055 1, 134.683 8, 95.195 3	c	S/D/G
185	39.25	Stearic acid	C₁₈H₃₆O₂	[M-H]^-	283.264 3	4.85	167.095 3, 139.668 7, 66.418 6	c	S/D/G

No.	t_R/min	Identification	Formula	Ion mode	Observed (m/z)	Error (×10^-6)	Fragment	Structure class	Origin
1	1.12	Histamine	C₅H₉N₃	[M+H]⁺	112.087 3	3.09	95.060 8, 83.060 9, 68.049 2	g	D
2	1.12	1-Deoxynojirimycin	C₆H₁₃NO₄	[M+H]⁺	164.091 8	0.46	146.081 0, 128.070 2, 68.049 1	b	S
3	1.15	Arginine	C₆H₁₄N₄O₂	[M-H]^-	173.104 4	-0.59	156.076 5, 131.081 1, 114.054 5	c	S/D/G
4	1.16	Valinol	C₅H₁₃NO	[M+H]⁺	104.107 2	2.2	87.084 5, 71.029 9, 60.081 6	b	S/G
5^△	1.24	Xylonic acid	C₅H₁₀O₆	[M-H]^-	165.039 1	-1.54	147.028 5, 129.017 9, 87.007 1, 75.007 0	c	S/D/G
6	1.26	Sugar acid	C₆H₁₀O₈	[M-H]^-	209.030 3	1.9	191.018 8, 133.012 8, 129.017 9, 85.027 8	c	S/D/G
7	1.27	Quinic acid	C₇H₁₂O₆	[M-H]^-	191.056 1	0.92	173.044 3, 127.038 6, 111.007 2, 85.027 8	c	S/D
8	1.34	Betaine	C₅H₁₁NO₂	[M+H]⁺	118.086 4	0.97	94.365 8, 72.081 5, 59.073 7, 58.065 8	b	S/D/G
9	1.86	Malic acid	C₄H₆O₅	[M-H]^-	133.013 1	-0.52	115.002 1, 89.022 8, 73.002 2	c	S/D/G
10^*	1.98	Adenine	C₅H₅N₅	[M+H]⁺	136.061 6	-1.61	119.035 3, 109.064 9, 100.274 0	g	S/D/G
11	1.99	Guanine	C₅H₅N₅O	[M+H]⁺	152.056 5	-1.42	135.033 0, 134.033 3, 110.035 0	g	S/D/G
12	1.99	Malic acid isomer	C₄H₆O₅	[M-H]^-	133.012 6	-3.53	115.002 1, 89.022 8, 72.991 4	c	S/D/G
13^△	1.99	Dehydroascorbic acid	C₆H₆O₆	[M-H]^-	173.009 2	-1.88	111.007 2, 85.028 7, 67.017 2	c	S/D/G
14^△	2.01	2-Acetamidoacrylic acid	C₅H₇NO₃	[M+H]⁺	130.049 5	2.45	112.087 1, 84.044 8, 70.065 7	c	S/D/G
15	2.02	Citric acid	C₆H₈O₇	[M-H]^-	191.018 9	1.21	173.088 1, 129.017 9, 111.007 2, 87.007 1	c	S/D/G
16	2.03	Stachydrine	C₇H₁₃NO₂	[M+H]⁺	144.101 9	-0.38	126.091 4, 98.096 8, 84.061 2, 70.062 5	b	G
17	2.07	Uridine	C₉H₁₂N₂O₆	[M-H]^-	243.062 3	3.24	200.055 8, 152.034 0, 110.023 2, 82.028 3	g	S/D/G
18	2.17	Suberic acid	C₈H₁₄O₄	[M-H]^-	173.081 9	0.46	129.017 9, 111.007 2, 85.027 8, 72.991 5	c	S/D
19	2.17	N-Acetyl-L-glutamic acid	C₇H₁₁NO₅	[M-H]^-	188.056 4	1.36	170.044 8, 144.065 3, 128.033 9, 102.054 5	c	S/D
20	2.27	Adenosine	C₁₀H₁₃N₅O₄	[M+H]⁺	268.104 0	-1.46	206.107 8, 152.648 5, 136.061 7	g	S/D/G
21	2.41	δ-Ribosyl-1,4-lactone	C₅H₈O₅	[M-H]^-	147.028 6	-1.5	129.018 0, 102.947 2, 87.007 1, 59.012 2	c	S/D/G
22	2.49	4-Hydroxyphenethylamine	C₈H₁₁NO	[M+H]⁺	138.091 3	-0.66	121.064 9, 111.007 9, 93.070 3	b	D
23	2.49	Isoleucine	C₆H₁₃NO₂	[M+H]⁺	132.101 9	-0.04	113.963 8, 86.096 9, 69.070 5	c	D/G
24	2.55	Guanosine	C₁₀H₁₃N₅O₅	[M-H]^-	282.084 4	4.59	178.900 8, 152.040 8, 126.029 4	g	S/D/G
25	2.56	Trigonelline	C₇H₇NO₂	[M+H]⁺	138.055 4	3.37	110.060 2, 94.056 3, 68.997 8	b	S/G
26	4.12	Cytisine	C₁₁H₁₄N₂O	[M+H]⁺	191.117 8	-0.57	162.090 8, 122.060 0, 105.963 0	b	D
27	5.08	Protocatechuic acid 4-O-β-glucoside	C₁₃H₁₆O₉	[M-H]^-	315.072 5	4.79	152.010 1, 125.256 2, 109.027 9	c	S/D/G
28^*	6.15	Vanillic acid 4-β-D-glucoside	C₁₄H₁₈O₉	[M-H]^-	329.088 0	1.27	167.033 8, 152.010 3, 123.043 7	c	S/D/G
29	6.98	Catechol	C₆H₆O₂	[M-H]^-	109.028 0	-3.62	108.020 4, 79.029 0, 67.029 1	c	S/D/G
30	7.02	Protocatechuic acid	C₇H₆O₄	[M-H]^-	153.019 3	-1.08	135.044 1, 109.028 0, 91.017 3	c	S/D/G
31^△	7.29	Daphneside	C₂₁H₂₆O₁₄	[M-H]^-	501.125 5	3.33	381.082 7, 219.029 3, 191.034 1	d	S/G
32^*	7.64	Caffeoylputrescine	C₁₃H₁₈N₂O₃	[M+H]⁺	251.139 0	-0.56	234.111 7, 163.038 6, 145.028 1, 89.107 7	b	D
33	7.95	Syringic acid glucoside	C₁₅H₂₀O₁₀	[M-H]^-	359.099 0	4.73	197.044 8, 182.022 1, 138.030 9	c	D
34^△*	8.57	Mulberroside A+Glc	C₃₃H₄₄O₂₁	[M-H]^-	775.231 3	2.13	729.225 3, 567.172 0, 405.119 1, 243.009 0	e	S
35^*	8.59	Oxyresveratrol-6-O-D-glucopyranosyl-D-glucopyranoside isomer	C₃₂H₄₂O₁₉	[M-H]^-	729.225 9	3.07	567.172 6, 405.112 5, 243.066 1, 225.055 2	e	S
36^*	8.78	Neochlorogenic acid	C₁₆H₁₈O₉	[M-H]^-	353.088 1	1.18	191.055 3, 179.034 0, 135.043 8	d	S
37	8.87	Indole-3-acrylic acid	C₁₁H₉NO₂	[M+H]⁺	188.070 4	-1.3	170.059 7, 146.059 8, 118.065 2, 88.022 0	b	S/D/G
38	9.01	Tryptophan	C₁₁H₁₂N₂O₂	[M-H]^-	203.082 6	2.15	186.055 2, 159.091 6, 116.049 1	c	D
39	9.4	8-Hydroxyquinoline	C₉H₇NO	[M+H]⁺	146.059 9	-1.24	128.950 7, 118.065 3, 99.044 4	b	D/G
40	10.13	Salicylic acid	C₇H₆O₃	[M-H]^-	137.023 1	-1.9	119.012 6, 93.033 3, 65.038 0	c	S/D/G
41	10.54	2-Isopropylmalic acid	C₇H₁₂O₅	[M-H]^-	175.061 2	0.4	146.959 9, 115.038 6, 85.064 3	c	G
42^△*	10.85	Unknown	C₃₂H₅₀N₇O₁₀	[M+H]⁺	693.369 1	-0.16	657.343 4, 474.257 4, 293.185 8, 222.112 1	b	D
43^*	11.	Kukoamine A	C₂₈H₄₂N₄O₆	[M+H]⁺	531.317 1	-0.45	293.185 6, 222.112 1, 165.054 5, 123.043 9	b	D
44	11.13	Phenyllactic acid	C₉H₁₀O₃	[M-H]^-	165.054 6	-0.43	121.064 5, 93.033 0, 59.012 2	d	S/D/G
45^*	11.14	Kukoamine B	C₂₈H₄₂N₄O₆	[M+H]⁺	531.317 3	-0.57	293.185 5, 222.122 0, 165.054 5, 123.043 9	b	D
46	11.2	6-Methylquinoline	C₁₀H₉N	[M+H]⁺	144.080 6	-1.14	117.065 4, 98.331 1, 84.081 2	b	D
47	11.28	Esculin	C₁₅H₁₆O₉	[M-H]^-	339.071 8	2.22	249.040 5, 219.029 3, 191.034 2	d	S
48^*	11.98	Caffeoylagmatine	C₁₄H₂₀N₄O₃	[M+H]⁺	293.160 4	-0.45	276.134 7, 163.038 7, 131.092 5, 114.102 7	b	D
49^*	12.62	Feruloylputrescine	C₁₄H₂₀N₂O₃	[M+H]⁺	265.154 3	-0.34	177.054 4, 163.039 5, 145.028 3, 89.107 8	b	D
50	12.94	7-Hydroxycoumarin	C₉H₆O₃	[M+H]⁺	163.038 7	-0.24	145.028 3, 135.044 1, 119.033 9, 104.049 4	d	S/G
51	12.98	Dihydrocaffeic acid	C₉H₁₀O₄	[M-H]^-	181.050 6	0.63	163.038 9, 137.059 4, 121.027 9, 109.028 0, 93.069 3	c	G
52^*	13.15	N¹-Caffeoyl-N¹⁰-dihydro caffeoylspermine	C₂₈H₄₀N₄O₆	[M+H]⁺	529.301 9	-0.34	511.471 6, 367.271 4, 293.186 5, 220.096 5, 163.038 7	b	D
53^*	13.21	Chlorogenic acid	C₁₆H₁₈O₉	[M-H]^-	353.087 8	3.34	191.055 2, 179.034 0, 161.023 2	d	S
54^*	13.31	N¹-Caffeoyl-N¹⁴-dihydro caffeoylspermine	C₂₈H₄₀N₄O₆	[M+H]⁺	529.301 9	-0.18	511.472 2, 458.227 0, 367.270 0, 293.184 7, 220.096 5, 163.038 7	b	D
55^△	13.36	Sinapic acid glucuronide	C₁₇H₂₀O₁₁	[M-H]^-	399.093 0	2.16	221.702 8, 192.037 4	d	S/G
56^△*	13.45	Multiflorin A	C₂₉H₃₂O₁₆	[M-H]^-	635.156 6	-4.04	567.171 9, 405.120 3, 243.066 0, 225.056 1	a	S
57^*	13.48	N⁵-3-Acetyldihydrocaffeoyl-N¹⁰-dihydrocaffeoylspermine	C₂₈H₄₀N₄O₆	[M+H]⁺	529.301 9	-0.12	291.170 1, 220.096 7, 163.038 8, 147.069 4	b	D
58^△*	13.55	Mulberroside A +2H₂O	C₂₆H₃₆O₁₆	[M-H]^-	603.146 4	1.23	567.172 3, 405.119 3, 243.066 1	e	S
59^△*	13.57	Leiocarposide	C₂₇H₃₄O₁₆	[M-H]^-	613.176 7	0.39	567.172 2, 405.119 4, 243.066 1, 225.055 4	e	S
60^*	13.61	Mulberroside A	C₂₆H₃₂O₁₄	[M-H]^-	567.172 4	2.69	405.119 3, 243.006 1, 225.055 3, 199.075 7	e	S
61^*	13.63	Glucosyl-3-O-β-D-apiosyl-(1→6)-O-β-D-glucoside	C₃₁H₄₀O₁₈	[M-H]^-	699.216 1	3.1	537.159 9, 405.119 2, 243.066 1, 225.055 4	e	S
62^△*	13.67	Mulberroside A dimer	C₅₂H₆₄O₂₈	[M-H]^-	1 135.343 7	-4.58	567.172 1, 405.119 1, 243.066 0, 225.055 1	e	S
63^△*	14.1	L-Leucyl-L-tyrosine	C₁₅H₂₂N₂O₄	[M+H]⁺	295.164 8	-0.4	207.065 0, 175.038 8, 147.039 9, 119.049 3	b	D
64^△	14.29	Capsaicin	C₁₃H₂₇N₈O₃	[M+H]⁺	344.228 3	1.11	327.200 9, 283.174 7, 177.112 0, 133.086 0, 89.068 2	b	D
65^*	14.49	Cryptochlorogenic acid	C₁₆H₁₈O₉	[M-H]^-	353.087 9	3.34	191.055 3, 179.034 0, 161.023 4, 135.043 8	d	S
66	14.61	4-Hydroxybenzaldehyde	C₇H₆O₂	[M-H]^-	121.028 0	-3.11	108.020 1, 93.020 9, 69.985 5	g	S/G
67	14.71	N¹-Dihydrocaffeoyl-N⁵ dihydroferuoylspermine	C₂₉H₄₄N₄O₆	[M+H]⁺	545.330 0	-0.35	307.200 9, 293.185 2, 236.127 8, 222.112 2, 179.070 7, 137.059 7	b	D
68	14.79	Scopoletin	C₁₀H₈O₄	[M+H]⁺	193.049 4	-0.75	178.027 5, 165.054 4, 149.059 3, 133.028 4, 127.298 6	d	D
69	14.95	α-Rhamnosyl-(1→6)-O-β-D-glucoside	C₂₁H₂₆O₁₃	[M-H]^-	485.130 1	1.31	363.248 8, 293.088 3, 191.034 2, 176.010 4	d	S
70^*	15.02	Oxyresveratrol-6-O-D-glucopyranosyl-D-glucopyranoside	C₃₂H₄₂O₁₉	[M-H]^-	729.227 2	4.9	567.171 8, 243.066 1, 225.055 1	e	S
71^△*	15.13	Hydroxyprolyl-tryptophan	C₁₆H₁₉N₃O₄	[M+H]⁺	318.144 4	-1.42	207.065 1, 175.038 7, 147.043 4	b	D
72^#	15.37	Quercetin-3-O-sophoroside	C₂₇H₃₀O₁₇	[M-H]^-	625.141 2	1.99	463.088 4, 299.020 1, 151.002 4, 125.002 9	a	S
73^*	16.92	N¹,N¹⁰-Bis(dihydrocaffeoyl)spermidine	C₂₅H₃₅N₃O₆	[M+H]⁺	474.259 7	-0.16	293.185 9, 222.112 2, 165.054 5, 123.044 1	b	D
74^#	17.67	Glucoliquiritin apioside	C₃₂H₄₀O₁₈	[M-H]^-	711.214 7	2.21	711.216 5, 549.160 5, 255.065 8, 153.018 5, 135.008 6, 119.048 7	a	G
75	17.8	3-p-Coumaroylquinic acid	C₁₆H₁₈O₈	[M-H]^-	337.092 4	1.74	191.055 2, 163.038 7, 119.048 8, 93.033 0	c	S
76^△#*	17.88	Hydroxysafflor yellow A	C₂₇H₃₂O₁₆	[M-H]^-	611.162 0	2.17	565.156 3, 403.103 4, 241.050 3, 197.060 2	a	S
77^#*	17.93	Glabranin	C₂₀H₂₀O₄	[M-H]^-	323.125 4	-2.36	257.678 3, 203.081 4, 189.066 0, 175.086 9	a	G
78	18.46	Riboflavin	C₁₇H₂₀N₄O₆	[M+H]⁺	377.145 1	-1.2	359.134 3, 243.087 4, 172.086 8	b	D
79	18.93	N⁵-Dihydrocaffeoyl-N¹⁰ caffeoylspermidine	C₂₅H₃₃N₃O₆	[M+H]⁺	472.243 8	-0.41	455.214 8, 310.212 0, 293.185 4, 236.127 6, 220.096 5, 163.038 7	b	D
80^△*	19.02	Unknown	C₂₇H₄₀N₇O₆	[M+H]⁺	559.311 5	0.42	321.179 8, 293.185 5, 222.122 0, 165.054 6, 123.044 2	b	D
81	19.18	Magnoflorine	C₂₀H₂₃NO₄	[M+H]⁺	342.168 8	-3.58	297.110 6, 265.084 5, 237.090 6, 183.521 0, 177.054 2, 115.076 2	b	D
82	19.34	Esculetin	C₉H₆O₄	[M-H]^-	177.018 2	-0.01	149.023 3, 133.028 1, 105.032 9, 89.038 1	d	S/G
83	19.83	Vicenin-2	C₂₇H₃₀O₁₅	[M-H]^-	593.151 1	1.73	473.104 7, 383.075 9, 353.066 7, 325.073 0, 297.076 6	a	G
84^△*	19.93	Unknown	C₂₆H₁₈O₇	[M-H]^-	441.094 3	-5.78	405.119 3, 243.066 1, 225.056 2, 199.076 3, 175.074 9	e	S
85^△*	19.97	Catechin-7-O-β-D-glucopyranoside	C₂₁H₂₄O₁₁	[M-H]^-	451.124 8	1.3	405.119 3, 243.066 1, 225.055 2, 199.075 8, 175.075 5, 157.064 7	e	S
86^△*	19.98	6"-O-Acetylgenistin	C₂₃H₂₂O₁₁	[M-H]^-	473.106 1	-1.7	405.119 3, 243.066 2, 225.055 6, 175.075 3	e	S
87^*	20.01	2,3,5,4′-Tetrahydroxy stilbene-2-Ο-β-D-glucoside isomer	C₂₀H₂₂O₉	[M-H]^-	405.119 1	2.79	243.066 1, 225.055 2, 199.075 7, 175.075 3, 157.064 5	e	S/G
88^△*	20.22	Acremonidin D	C₃₃H₂₈O₁₄	[M-H]^-	647.139 4	-0.2	449.109 3, 287.057 6, 161.023 4, 125.023 0	a	S
89^*	20.24	N¹-3-Acetyldihydrocaffeoyl-N¹⁰-dihydrocaffeoyl spermine	C₃₀H₄₄N₄O₇	[M+H]⁺	573.327 7	-1.01	475.269 6, 335.196 6, 293.184 1, 222.112 2, 208.681 9, 165.054 3	b	D
90^△*	20.44	Unknown	C₂₈H₃₄O₁₈	[M-H]^-	657.167 8	1.65	611.162 0, 449.109 1, 287.056 2, 125.023 0	a	S
91	20.77	N-Acetyl-L-phenylalanine	C₁₁H₁₃NO₃	[M-H]^-	206.082 3	2.23	192.005 5, 164.070 5, 147.043 8, 118.991 6, 91.053 7	c	D
92^△#	21.05	Diosmetin-7-O-glucoside	C₂₂H₂₂O₁₁	[M-H]^-	461.329 1	0.92	415.161 4, 299.057 2, 191.055 3, 149.099 3, 131.033 7, 89.022 8	a	S
93^△*	21.28	Unknown	C₂₈H₃₄O₁₈	[M-H]^-	657.168 2	2.11	611.162 8, 449.109 2, 287.056 2, 161.023 3, 125.023 1	a	S
94^△#*	21.45	Unknown	C₃₂H₄₀O₂₀	[M-H]^-	743.202 6	-0.38	700.649 8, 449.111 5, 405.341 5, 287.056 7, 161.023 2, 125.022 9	a	S
95^△*	21.48	Plantagoside	C₂₁H₂₂O₁₂	[M-H]^-	465.103 7	0.92	303.105 8, 151.002 8, 125.023 0	a	S
96^*	21.73	2,3,5,4′-Tetrahydroxy stilbene-2-Ο-β-D-glucoside	C₂₀H₂₂O₉	[M-H]^-	405.119 1	2.79	243.066 1, 225.055 2, 199.075 8, 175.075 4, 159.044 0	e	S/G
97^△#	21.94	Unknown	C₂₁H₂₉O₁₄	[M-H]^-	504.147 3	3.89	412.140 9, 301.831 4, 192.067 1, 165.054 8	a	S
98^#	22.18	Daidzin	C₂₁H₂₀O₉	[M+H]⁺	417.117 8	-0.5	255.064 8, 237.054 6, 199.074 3, 149.717 5	a	G
99^△*	22.96	N-Acetyl-1-O-benzyl-α-muramyl-α-aminoisobutyryl-D-isoglutamine benzyl ester	C₃₄H₄₆N₄O₁₁	[M+H]⁺	687.322 5	0.3	449.191 0, 293.185 9, 222.121 6, 165.054 1	b	D
100^*	22.98	Hyperoside	C₂₁H₂₀O₁₂	[M-H]^-	463.088 5	3.08	301.033 5, 273.040 3, 255.030 0, 151.002 4, 125.002 9	a	S
101^#	23.44	Schaftoside	C₂₆H₂₈O₁₄	[M-H]^-	563.140 8	2.38	473.106 1, 443.098 0, 383.077 7, 353.066 4, 325.071 8, 297.076 7	a	G
102	23.5	Isoscopoletin	C₁₀H₈O₄	[M+H]⁺	193.049 4	-0.15	178.025 0, 165.054 7, 149.056 9, 137.059 7, 133.024 8	d	D
103	24.21	Ferulic acid	C₁₀H₁₀O₄	[M-H]^-	193.050 0	2.51	178.026 1, 149.059 5, 134.036 0	c	S/D/G
104^#	25.35	Tetrahydroxychalcone 4′-O-glucoside	C₂₁H₂₂O₁₀	[M-H]^-	433.113 6	-1.	271.061 0, 151.003 6, 135.008 7, 119.050 2	a	G
105^*	25.75	Isoliquiritin	C₂₁H₂₂O₉	[M-H]^-	417.118 5	-1.45	255.065 5, 148.016 4, 135.008 6, 119.050 1	a	G
106^△#*	25.85	Unknown	C₂₀H₂₂O₁₂	[M-H]^-	453.095 4	-7.35	417.119 3, 255.066 7, 153.018 1, 135.007 6, 119.048 6	a	G
107	26.08	Dihydro-N-caffeoyltyramine	C₁₇H₁₉NO₄	[M+H]⁺	302.138 4	-0.29	165.054 3, 143.572 4, 138.091 3, 121.064 9	b	D
108^*	26.17	Isoliquiritin apioside	C₂₆H₃₀O₁₃	[M-H]^-	549.160 3	-1.95	429.104 2, 297.077 5, 255.065 7, 135.008 5, 119.050 0	a	G
109^△#*	26.17	Eriocitrin isomer	C₂₇H₃₂O₁₅	[M-H]^-	595.167 2	1.49	255.066 1, 135.007 6, 119.049 0	a	S
110^△*	26.2	Unknown	C₂₅H₃₀O₁₆	[M-H]^-	585.135 9	-6.16	429.102 8, 255.066 3, 135.007 5	a	G
111^*	26.38	N¹,N⁵-Bis(dihydroferuloyl)spermidine	C₂₇H₃₉N₃O₆	[M+H]⁺	502.291 2	0.04	388.415 9, 250.142 4, 236.127 8, 179.070 5, 137.059 7	b	D
112^#*	26.47	Liquiritin	C₂₁H₂₂O₉	[M-H]^-	417.119 3	3.28	255.066 2, 163.018 0, 148.015 0, 135.007 4, 119.048 7	a	G
113^△#	26.54	Tetrahydroxychalcone 4′-O-glucoside isomer	C₂₁H₂₂O₁₀	[M-H]^-	433.113 9	2.3	271.061 3, 151.002 4, 135.008 7, 119.050 3	a	S
114^#*	26.68	Naringenin-7-O-glucoside	C₂₁H₂₂O₁₀	[M-H]^-	433.114 2	3.02	271.061 5, 151.002 4, 119.048 7	a	G
115^*	26.74	N¹,N⁵,N¹⁰-tris(di hydrocaffeoyl) spermine	C₃₇H₅₀N₄O₉	[M+H]⁺	695.363 3	-2.5	678.344 1, 457.234 3, 293.185 9, 222.112 3	b	D
116^△*	26.75	Liquiritin apioside	C₂₆H₃₀O₁₃	[M-H]^-	549.161 3	2.02	417.119 3, 255.066 1, 153.018 0, 135.007 3, 119.048 6, 91.017 3	a	G
117^△*	26.79	Unknown	C₂₅H₃₀O₁₆	[M-H]^-	585.138 9	-0.49	549.161 8, 429.102 8, 255.066 3, 153.017 7, 135.007 5	a	G
118^#	27.19	Dihydromorin	C₁₅H₁₂O₇	[M-H]^-	303.052 2	7.66	275.056 3, 177.018 2, 125.023 0	a	S
119^#*	27.76	Eriodictyol-7-O-glucoside	C₂₁H₂₂O₁₁	[M-H]^-	449.109 9	4.57	287.056 7, 269.136 8, 197.059 8, 125.022 9	a	S
120^#	27.89	6′′-O-Acetylliquiritin isomer	C₂₃H₂₄O₁₀	[M-H]^-	459.130 0	3.04	339.087 5, 255.044 6, 153.010 3	a	G
121^△*	27.97	Unknown	C₃₄H₄₆N₄O₈	[M+H]⁺	639.338 6	-0.35	621.330 1, 293.185 9, 222.112 2	b	D
122	28.79	Oxyresveratrol	C₁₄H₁₂O₄	[M-H]^-	243.066 1	3.76	225.055 1, 199.075 8, 175.075 3	e	S
123^#	28.91	6′′-O-Acetylliquiritin isomer	C₂₃H₂₄O₁₀	[M-H]^-	459.129 3	1.16	339.087 4, 263.056 7, 255.045 2, 153.010 0	a	G
124^#	29.13	Naringenin chalcone	C₁₅H₁₂O₅	[M-H]^-	271.061 4	4.91	151.002 3, 140.975 4, 119.048 9	a	G
125	29.14	Mulberroside F	C₂₆H₃₀O₁₄	[M-H]^-	565.156 2	1.78	433.112 0, 335.243 8, 271.061 4, 227.071 2, 151.002 4, 119.048 7	e	S
126^*	29.21	trans-N-Caffeoyltyramine	C₁₇H₁₇NO₄	[M+H]⁺	300.122 8	-0.78	163.038 7, 121.064 9, 89.060 1	b	D
127	29.23	Azelaic acid	C₉H₁₆O₄	[M-H]^-	187.096 5	-0.03	169.085 7, 143.106 5, 125.095 7	c	S/D/G
128^△#	29.25	Tetrahydroxychalcone 4′-O-glucoside isomer	C₂₁H₂₂O₁₀	[M-H]^-	433.113 1	0.41	271.061 4, 151.002 4, 135.008 7, 119.050 4	a	S
129^*	29.77	Lyciumin A	C₄₂H₅₁N₉O₁₂	[M+H]⁺	874.372 6	-0.5	856.363 7, 486.198 1, 468.187 6, 136.075 7	b	D
130^#	29.78	Eriodictyol	C₁₅H₁₂O₆	[M-H]^-	287.056 1	3.85	259.061 4, 243.067 2, 151.002 3, 125.022 9	a	S
131^△	29.9	4-Oxododecanedioic acid	C₁₂H₂₀O₅	[M-H]^-	243.123 8	2.88	225.112 8, 207.102 2, 181.122 5, 146.959 9	c	S/D/G
132	30.04	7-O-β-D-Apiosyl-3-O-p-coumaroylkaempferol	C₂₇H₃₀O₁₃	[M-H]^-	561.161 6	2.41	309.076 8, 267.066 4, 252.042 8	d	G
133^△*	30.17	Eriodictyol isomer	C₂₇H₃₂O₁₅	[M-H]^-	595.167 6	1.85	351.069 3, 255.066 2, 135.007 4, 119.048 8, 91.017 2	a	S
134^△#	30.47	Isoformononetin	C₁₆H₁₂O₄	[M-H]^-	269.080 4	-1.69	254.055 9, 237.054 2, 213.091 2, 119.041 4	a	S
135^*	30.9	Neoisoliquiritin	C₂₁H₂₂O₉	[M-H]^-	417.111 9	-4.7	255.066 2, 153.019 1, 148.015 4, 135.007 1, 119.048 7	a	G
136^#	30.92	Liquiritin B	C₃₅H₃₆O₁₅	[M-H]^-	695.198 8	2.51	531.152 5, 255.066 3, 119.048 8, 72.991 5	a	G
137	30.94	N-p-trans-Coumaroyltyramine	C₁₇H₁₇NO₃	[M+H]⁺	284.128 1	0.07	239.149 7, 147.043 9, 121.064 8, 119.049 2	b	D
138^#	31.08	Liquiritin A	C₃₆H₃₈O₁₆	[M-H]^-	725.210 0	3.24	531.152 7, 255.066 0, 193.049 5, 135.007 5	a	G
139^#	31.25	Morin	C₁₅H₁₀O₇	[M-H]^-	301.035 6	4.42	273.042 0, 229.050 2, 151.002 4, 125.023 0	a	S
140^*	31.34	Feruloyltyramine	C₁₈H₁₉NO₄	[M+H]⁺	314.138 5	-0.52	292.079 3, 177.054 4, 145.028 3, 117.033 6	b	D
141^△*	31.41	Baicalin	C₂₁H₁₈O₁₁	[M-H]^-	445.077 0	3.46	269.045 8, 235.303 8, 175.023 9, 113.022 9	a	S
142	31.43	Lyciumin B	C₄₄H₅₂N₁₀O₁₁	[M+H]⁺	897.388 7	-0.34	689.307 3, 486.198 0, 468.187 5, 159.091 5	b	D
143^*	31.62	N-Feruloyl-3-methoxy tyramine	C₁₉H₂₁NO₅	[M+H]⁺	344.148 7	-1.74	177.054 4, 145.028 4, 117.033 6	b	D
144^△#	31.62	Licorice saponin J2 isomer	C₄₂H₆₄O₁₆	[M-H]^-	823.413 2	2.61	671.079 0, 351.057 4, 193.034 9, 113.002 9	f	G
145^#	31.65	4′,7-Dihydroxyflavanone	C₁₅H₁₂O₄	[M-H]^-	255.062 5	-7.28	219.845 1, 153.018 1, 135.007 2, 119.004 2	a	G
146^△#	31.71	24-Hydroxy-licorice saponin A3	C₄₈H₇₂O₂₂	[M-H]^-	999.445 6	2.41	837.388 9, 377.540 1, 351.056 2, 193.034 4, 113.022 9	f	G
147^#	31.8	Liquiritigenin	C₁₅H₁₂O₄	[M-H]^-	255.065 0	4.57	219.844 9, 153.018 1, 135.007 2, 119.004 8	a	G
148^△*	31.85	Chrysin-7-O-β-D-glucuronide	C₂₁H₁₈O₁₀	[M-H]^-	429.082 1	4.5	253.050 6, 175.023 9, 113.022 9	a	S
149	31.86	Sebacic acid	C₁₀H₁₈O₄	[M-H]^-	201.113 2	1.76	183.101 7, 139.111 5, 111.080 1	c	S/D
150^△*	31.91	Diosmetin-7-glucuronide	C₂₂H₂₀O₁₂	[M-H]^-	475.087 6	2.49	299.056 5, 284.032 9, 217.056 7, 113.022 6	a	S
151	31.99	7-Hydroxy-1-(3,4-dihydroxyphenyl)-N²,N³-bis(4-hydroxyphenethyl)-6,8-dimethoxy-1,2-dihydronaphthalene-2,3-dicarboxamide	C₃₆H₃₆N₂O₉	[M+H]⁺	641.245 3	-6.33	504.163 9, 476.167 8, 339.086 8	b	D
152	32.07	Lyciumin C	C₄₉H₅₇N₉O₁₂	[M+H]⁺	964.419 9	-0.09	593.273 4, 576.246 5, 389.181 5, 257.128 1, 188.070 4	b	D
153^△*	32.1	3,7-Bis(2-hydroxyethyl) icaritin	C₂₅H₂₈O₈	[M-H]^-	455.170 9	0.83	371.217 2, 213.221 2, 153.349 6, 125.022 9	a	S
154^△#	32.4	22-Hydroxy-licorice saponin G2	C₄₂H₆₂O₁₈	[M-H]^-	853.387 2	2.3	351.056 6, 193.034 6, 175.024 5, 113.022 8	f	G
155^*	32.53	Licorice saponin A3	C₄₈H₇₂O₂₁	[M-H]^-	983.450 5	2.3	821.398 5, 645.365 0, 469.335 2, 351.056 9, 193.034 5, 113.022 9	f	G
156^△*	32.94	Rhaglycyrrhizin	C₄₈H₇₂O₂₀	[M-H]^-	969.461 1	-0.15	601.403 5, 351.056 9, 193.034 9, 113.022 9	f	G
157^#*	33.25	Licorice saponin G2 isomer	C₄₂H₆₂O₁₇	[M-H]^-	837.391 8	1.74	485.330 3, 351.056 9, 235.046 4, 193.034 3, 113.022 9	f	G
158^*	33.26	Glycyrrhetinic acid	C₃₀H₄₆O₄	[M+H]⁺	471.346 4	-0.95	453.335 7, 317.210 8, 135.116 7	f	G
159	33.28	Glabrolide	C₃₀H₄₄O₄	[M+H]⁺	469.330 6	-1.29	451.319 3, 405.315 1, 243.137 3, 175.147 9	d	G
160	33.39	(11E,15Z)-9,10,13-Trihydroxy-11,15-octadecadienoic acid	C₁₈H₃₂O₅	[M-H]^-	327.218 0	4.15	309.207 6, 211.133 3, 171.101 6, 85.027 9	c	S/D
161^△#	33.48	Licorice saponin J2 isomer	C₄₂H₆₄O₁₆	[M-H]^-	823.411 2	0.16	759.278 1, 351.056 9, 193.034 7, 113.022 9	f	G
162^#*	33.68	Naringenin	C₁₅H₁₂O₅	[M-H]^-	271.061 5	5.02	225.222 1, 177.018 1, 151.00 24, 119.048 6	a	G
163^△	33.77	Hedione	C₁₃H₂₂O₃	[M-H]^-	225.149 6	3.24	207.138 5, 181.159 0, 167.106 8, 125.095 7	c	S/D/G
164^#*	34.25	Licorice saponin G2 isomer	C₄₂H₆₂O₁₇	[M-H]^-	837.392 5	1.09	351.057 1, 193.034 6, 175.024 1, 113.022 9	f	G
165^#*	34.81	Licorice saponin G2 isomer	C₄₂H₆₂O₁₇	[M-H]^-	837.391 5	1.45	351.056 6, 193.034 3, 175.023 1, 113.022 9	f	G
166^#*	34.9	Glycyrrhizic acid	C₄₂H₆₂O₁₆	[M-H]^-	821.397 6	2.71	645.365 8, 351.057 1, 193.034 6, 174.023 8, 113.022 9	f	G
167^*	34.95	Oleaside E	C₄₂H₆₄O₁₇	[M-H]^-	839.409 2	3.2	351.057 3, 193.034 6, 175.024 0, 113.023 0	f	G
168^#	35.12	Licorice saponin H2	C₄₂H₆₂O₁₆	[M-H]^-	821.397 5	2.52	351.057 1, 193.034 6, 175.023 7, 113.022 9	f	G
169^#*	35.16	Isoliquiritigenin	C₁₅H₁₂O₄	[M-H]^-	255.065 0	3.56	219.845 2, 153.018 1, 135.007 4, 119.004 9, 91.017 3	a	G
170^△#	35.47	Licorice saponin B2 isomer	C₄₂H₆₄O₁₅	[M-H]^-	807.416 1	3.16	351.057 1, 193.034 4, 175.023 7, 113.022 9	f	G
171^#*	35.48	Formononetin	C₁₆H₁₂O₄	[M+H]⁺	269.080 3	-1.8	254.057 3, 237.054 7, 213.090 7, 154.026 0	a	G
172^△#	35.96	Licorice saponin K2	C₄₂H₆₂O₁₆	[M-H]^-	821.397 6	2.23	643.293 9, 351.057 1, 193.034 7, 175.023 9, 113.023 0	f	G
173^△#*	36.33	Kushenol L	C₂₅H₂₈O₇	[M-H]^-	439.177 1	1.93	151.005 2, 125.023 0, 92.089 7	a	S
174^△#	36.44	Kuwanon G	C₂₅H₂₆O₇	[M-H]^-	437.161 4	4.42	401.187 3, 174.185 5, 152.994 9, 125.022 9	a	S
175^△#	36.46	Licorice saponin C2	C₄₂H₆₂O₁₅	[M-H]^-	805.401 2	0.75	573.278 4, 351.057 1, 295.579 1, 193.034 7, 113.022 9	f	G
176^△#	36.6	Licorice saponin B2 isomer	C₄₂H₆₄O₁₅	[M-H]^-	807.415 9	-0.25	351.057 2, 193.034 0, 175.023 9, 113.023 1	f	G
177^#*	36.86	Glycycoumarin	C₂₁H₂₀O₆	[M-H]^-	367.118 5	0.89	297.040 3, 139.038 8	a	G
178^#	36.93	Ononin	C₂₂H₂₂O₉	[M-H]^-	429.113 0	-3.2	361.163 4, 293.176 5, 236.105 2, 221.154 1	a	G
179	36.97	3,5-Di-tert-butylcatechol	C₁₄H₂₂O₂	[M-H]^-	221.154 7	2.28	205.071 6, 177.039 4, 135.969 8, 91.952 1	c	S/D/G
180	37.06	(±)9-HpODE	C₁₈H₃₂O₄	[M-H]^-	311.222 8	4.	293.176 2, 267.196 8, 223.170 0, 99.007 2	c	S/D/G
181	37.85	Morusin P	C₁₉H₁₈O₅	[M-H]^-	325.104 3	-2.74	249.131 9, 235.248 0, 193.506 0	e	S
182^△#	38.25	Cyclomorusin	C₂₅H₂₄O₆	[M+H]⁺	421.164 2	-0.67	365.101 7, 347.090 8, 311.054 7, 137.291 7	a	S
183	38.63	Glycycoumarin isomer	C₂₁H₂₀O₆	[M-H]^-	367.118 4	2.41	313.071 0, 263.538 2, 139.038 8, 111.810 5	d	G
184	39.15	Oleic acid	C₁₈H₃₄O₂	[M-H]^-	281.248 6	4.74	192.471 9, 152.055 1, 134.683 8, 95.195 3	c	S/D/G
185	39.25	Stearic acid	C₁₈H₃₆O₂	[M-H]^-	283.264 3	4.85	167.095 3, 139.668 7, 66.418 6	c	S/D/G

结合多点筛查质量亏损过滤和分子网络的泻白散成分表征

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纪思齐 ¹ , 王小明 ² , 周严严 ¹ , 许悦 ³ , 马致洁 ³ , 代云桃 ¹^,^*

药学学报 | 研究论文 2026,61(4): 1361-1379

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药学学报 |研究论文 2026 , 61 (4) : 1361 -1379

结合多点筛查质量亏损过滤和分子网络的泻白散成分表征

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纪思齐¹, 王小明², 周严严¹, 许悦³, 马致洁³, 代云桃¹^,^*

作者信息

¹中国中医科学院, 中药研究所, 北京 100700

²山东中医药大学, 山东济南 250355

³首都医科大学附属北京地坛医院药学部, 北京 100015

通讯作者:

代云桃, E-mail: ytdai@icmm.ac.cn

作者简介:

作者贡献:

纪思齐负责完成实验、数据分析及文章撰写; 王小明、周严严负责文章校对; 代云桃、许悦、马致洁负责课题整体设计及文章修改。

Comprehensive characterization of chemical components in Xie Bai San by integrating multi-point screening mass defect filtering and molecular networking

Si-qi JI¹, Xiao-ming WANG², Yan-yan ZHOU¹, Yue XU³, Zhi-jie MA³, Yun-tao DAI¹^,^*

Affiliations

¹Institute of Chinese Materia Medica, China Academy of Chinese Medical Sciences, Beijing 100700, China

²Shandong University of Traditional Chinese Medicine, Jinan 250355, China

³Department of Pharmacy, Beijing Ditan Hospital, Capital Medical University, Beijing 100015, China

出版时间: 2026-04-12 doi: 10.16438/j.0513-4870.2025-1318

文章导航

摘要

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对经典名方化学成分进行快速和准确指认是经典名方现代化研究中的重要内容之一。联合多点筛查质量亏损过滤(mass defect filtering, MDF)和分子网络技术(molecular network, MN), 建立快速鉴定经典名方泻白散质谱数据中化学成分的方法, 以实现泻白散成分的准确和全面鉴定。采用超高效液相色谱-四极杆-静电场轨道阱串联质谱法(UHPLC-Q-Orbitrap-MS/MS)在正负离子模式下对泻白散汤剂进行质谱数据采集。采用MDF方法, 通过设置多点筛查质量亏损过滤窗口以实现结构相似的化学成分的鉴定。采用MN方法, 通过MS/MS碎片模式的相似性创建GNPS分子网络, 运用Cytoscape3.6.1软件确定结构相似的分子簇, 通过探针分子达到同类成分的鉴定。通过上述方法, 结合保留时间、精确分子质量、二级质谱碎片特征, 基于数据库及相关文献信息, 在泻白散汤剂中鉴定出185个成分, 包括54个黄酮类成分、42个生物碱类成分、17个皂苷类成分、16个芪类成分、34个有机酸成分、15个苯丙素类成分和7个其他类成分, 其中46个成分为在泻白散复方及其药味中首次报道的成分。该研究实现了快速、准确、全面表征泻白散汤剂成分, 为泻白散复方制剂的药效物质基础和质量控制研究提供了化学成分基础, 也为中药复杂体系物化学成分的快速鉴定提供方法参考。

关键词

泻白散 / UHPLC-Q-Orbitrap-MS/MS / 质量亏损过滤 / 分子网络 / 化学成分

Abstract

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Rapid and accurate identification of chemical components in classical famous formulas is a crucial aspect of their modern research. This study aimed to establish a method for the rapid identification of chemical components in the mass spectrometry data of Xie Bai San by integrating multi-point mass defect filtering (MDF) and molecular networking (MN) techniques, to achieve accurate and comprehensive characterization of its constituents. The mass spectrometric data of Xie Bai San decoction was acquired using ultra-high performance liquid chromatography coupled with quadrupole-Orbitrap tandem mass spectrometry (UHPLC-Q-Orbitrap-MS/MS) in both positive and negative ion modes. The MDF method was employed, utilizing set multi-point mass defect filtering windows to identify structurally similar compounds. The MN approach was applied to create a GNPS molecular network based on the similarity of MS/MS fragmentation patterns, and Cytoscape 3.6.1 software was used to identify clusters of structurally similar molecules, enabling the identification of homologous components via probe molecules. Using the aforementioned methods, combined with retention time, accurate molecular mass, and secondary MS/MS fragmentation characteristics, and based on database and relevant literature information, a total of 185 compounds were identified in the Xie Bai San decoction. These included 54 flavonoids, 42 alkaloids, 17 saponins, 16 stilbenes, 34 organic acids, 15 phenylpropanoids, and 7 other types of compounds. Among these, 46 compounds were reported for the first time in the Xie Bai San formula or its constituent herbs. This study successfully achieved the rapid, accurate, and comprehensive characterization of the chemical components in Xie Bai San decoction. It provides a chemical component foundation for research on the pharmacodynamic material basis and quality control of Xie Bai San compound preparations, and also offers a methodological reference for the rapid identification of chemical components in complex traditional Chinese medicine systems.

Key words

Xie Bai San / UHPLC-Q-Orbitrap-MS/MS / mass defect filtering / molecular networking / chemical component

引用本文

纪思齐, 王小明, 周严严, 许悦, 马致洁, 代云桃. 结合多点筛查质量亏损过滤和分子网络的泻白散成分表征. 药学学报, 2026 , 61 (4) : 1361 -1379 . DOI: 10.16438/j.0513-4870.2025-1318

Si-qi JI, Xiao-ming WANG, Yan-yan ZHOU, Yue XU, Zhi-jie MA, Yun-tao DAI. Comprehensive characterization of chemical components in Xie Bai San by integrating multi-point screening mass defect filtering and molecular networking[J]. Acta Pharmaceutica Sinica, 2026 , 61 (4) : 1361 -1379 . DOI: 10.16438/j.0513-4870.2025-1318

正文

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经典名方泻白散源自宋代医学家钱乙的《小儿药证直诀·卷下诸方》, 由炒桑白皮、焙地骨皮、炙甘草和粳米四味中药组成, 是治疗肺热喘咳的经典方剂^[1]。该方以桑白皮为君药, 地骨皮为臣药, 甘草与粳米共为佐使, 具有治疗肺热咳喘的功效。临床广泛应用于肺系疾病, 如肺炎、哮喘、支气管扩张症^[2]等疾病的治疗。泻白散化学成分复杂多样: 桑白皮主要含黄酮及芪类成分, 地骨皮以生物碱类成分为主, 甘草则富含黄酮与皂苷类成分^[3]。目前, 该方的实验研究多集中于制备工艺^[4]、药效评价和作用机制研究^[5-7], 而其系统的物质基础的研究仍相对薄弱; 现有鉴定方法较为单一, 导致已鉴定的成分数量有限, 鉴定结果缺乏不同技术间的相互验证^{[3, 5, 8]}, 无法实现对复方化学成分的全面系统表征。因此, 亟需整合现代分析技术与多维度质谱数据处理策略, 以提升泻白散物质基础的解析精度与效率, 为后续揭示其药效机制及质量控制提供科学依据。

超高效液相色谱-四极杆-静电场轨道阱高分辨质谱法(UHPLC-Q-Orbitrap-MS/MS)凭借其高分辨率、高灵敏度和快速扫描的优势, 已广泛用于中药复方的化学成分表征^{[9, 10]}。然而, 中药化学成分复杂, 单次分析产生大量质谱数据, 传统解析方式耗时且易遗漏低丰度成分。质量亏损过滤(mass defect filtering, MDF)技术可根据母核结构相似性, 通过设定质量亏损范围选择性筛选同类成分, 显著提高相似结构类型成分的辨识效率^[11-16], 达到一类成分同时被识别和辨认。分子网络分析(molecular network, MN)是一种通过质谱数据将结构相似的分子可视化为互连节点, 从而揭示化学成分间结构关系及代谢通路的分析方法。全球天然产物社会分子网络(global natural products social molecular networking, GNPS)平台通过构建质谱可视化分子网络, 支持大规模成分数据的比对与归类, 近年来已成为分析复杂体系化学成分质谱数据的重要工具^[17-23]。GNPS通过质谱碎片模式将不同的分子联系起来, 从而可视化复杂混合物中化学成分之间的关系, 从而提高了质谱鉴定的效率和准确性。分子网络技术已广泛应用于天然产物研究领域, 包括成分的鉴定、相似地方的追踪、新型未知成分的发现、目标样品活性成分的筛选与分离等方面发挥重要作用。本研究整合UHPLC-Q-Orbitrap-MS/MS、MDF与GNPS三种策略, 系统、高效地解析泻白散汤剂中的化学成分, 旨在为其药效物质基础的阐明及质量控制研究提供研究基础。

材料与方法

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仪器 Thermo Scientific Orbitrap Exploris 120高分辨液质联用仪(美国Thermo Fisher公司); 涡旋混合器Vortex-2 Genie (Scientific Industries); 超声波清洗器WD-9415C (北京市六一仪器厂); 医用离心机(湖南湘仪实验室仪器开发有限公司); ME204/02型电子分析天平(d = 0.000 1 g)、XSR105 /A型精密天平(d = 0.000 01 g), 梅特勒托利多科技(中国)有限公司; N-1100旋转蒸发仪、OSB-2100型油浴锅, 上海爱朗仪器有限公司。

材料与试剂 地骨皮(批号: YL-216-2008-002, 产地为宁夏)、炒桑白皮(批号: YL-124-2008-003, 产地为安徽亳州)、炒甘草(批号: YL-051-2011-010, 产地为新疆)由企业提供, 粳米购自中粮米业有限公司。药材基原经本课题组前期鉴定分别为茄科植物枸杞Lycium chinense Mill.的干燥根皮, 桑科植物桑Morus alba L.的干燥根皮, 豆科植物甘草Glycyrrhiza uralensis Fisch.的干燥根和根茎和禾本科植物稻Oryza sativa L.的干燥成熟种子。焙地骨皮为实验室采用地骨皮饮片, 根据古代经典名方关键信息(25首方剂)中泻白散关键信息, 参照地方标准《安徽省中药炮制规范》(2005年版)中的焙法进行炮制。色谱级乙腈、甲醇、甲酸购于美国Fisher公司, 水为娃哈哈纯净水。

泻白散汤剂的制备 遵循国家中医药管理局发布的《古代经典名方目录(第一批)》中泻白散的制备工艺“上锉散, 入粳米一撮, 水二小盏, 煎七分, 食前服”, 按照古代经典名方关键信息(25首方剂)中泻白散的制备工艺“每次取6.20 g, 加粳米2 g, 以水300 mL, 煎取180 mL”, 经实验室优化工艺参数后确定了泻白散汤剂制备方法, 即首先将三味药材粉碎为粗颗粒, 取炒桑白皮2.95 g、焙地骨皮2.95 g、炒甘草0.3 g和粳米2 g放入煎药壶中, 加入300 mL水浸泡30 min。以武火加热煮沸, 然后以文火保持微沸30 min至液体量约为180 mL, 200目涤纶趁热过滤, 滤液补足至180 mL即得。

供试品溶液的制备 取制备的汤剂, 于80 ℃减压浓缩至50 mL。取复方汤剂50 μL, 加入5 mL 80%甲醇水溶液(甲醇-水, 80∶20), 涡旋混合5 min, 14 000 r·min^-1离心10 min, 取上清0.8 mL置于离心管中, 再次离心, 取上清置入进样瓶中, 待UHPLC-MS/MS分析。

液相色谱条件 Waters UPLC HSS T3色谱柱(100 mm × 2.1 mm, 1.8 μm); 流动相为0.1%甲酸水溶液(A)和0.1%甲酸乙腈溶液(B); 梯度洗脱(0~10 min, 100%~70% B; 10~25 min, 70%~60% B; 25~30 min, 60%~50% B; 30~40 min, 50%~30% B; 40~45 min, 30%~0% B); 柱温35 ℃; 流速0.3 mL·min^-1; 进样量: 10 μL。

质谱条件 碰撞气体和鞘气/辅助气体分别为超高纯氮气和氮气发生器系统提供的氮气(纯度 > 99.99%), 鞘气流速40 arb, 辅助气流速15 arb; 采用电喷雾离子(ESI)源分别在正负离子模式下进行扫描, 扫描模式为Full MS/dd-MS2, 正、负离子模式电压分别为3.2、3.0 kV, 质量扫描范围m/z 100~1 500, 传输管温度320 ℃, 加热器温度350 ℃。

基于数据库鉴定方法的建立 数据库鉴定基于高分辨质谱数据与已知成分信息的匹配, 通过比对精确分子量及二级质谱碎片等信息, 实现化学成分的快速识别。依据现有文献报道的泻白散各药味的化学成分信息, 实验室建立了泻白散本地数据库。所建的数据库包含了404种泻白散各药味中可能的成分, 并收集了各成分名称、分子式、结构式、精确分子量等结构信息。采用Xcalibur 4.2软件分析质谱数据中化学成分的保留时间、一级质谱、二级质谱, 根据ChemSpider、PubChem等网络数据库以及实验室自建库, 运用Compound Discoverer (CD) 3.2软件进行处理, 建立工作流, 利用mzCloud、mzVault和Mass List数据库进行二级质谱匹配, 设置最大峰面积≥ 1×10⁶、匹配分数≥ 70, 通过比对分子式、保留时间、质谱碎片信息以及裂解规律对化学成分进行结构鉴定。

多点筛查MDF过滤方法的建立 MDF技术基于化学成分骨架相似时其质量亏损值分布相对集中的特性, 通过设定特定过滤窗口, 筛选具有相似结构类型的潜在成分, 能够高效识别泻白散中结构相关的成分类别, 如黄酮类、皂苷类。

首先使用开源软件MZmine 4.5对UPLC-Q-Orbitrap-MS/MS获得的RAW原始质谱数据进行预处理并提取特征峰信息。MZmine是目前分析质谱数据使用最广泛的一种工具, 其运行相对稳定, 操作简单, 对计算机性能的要求相对较低, 可对质谱原始数据进行准确、高效地处理^[24]。依次使用MZmine的质量检测、色谱图构建、局部最小特征解析、¹³C同位素过滤、峰对齐和特征离子过滤功能, 并导出为CSV文件, 导入至Excel中进行质量亏损过滤分析。

确定准确的过滤窗口是获得高质量母离子的关键步骤。为了全面表征泻白散汤剂中的成分, 对泻白散中的代表性成分黄酮类成分、皂苷类成分设置了过滤窗口。基于上述成分主要出现在负离子模式下, 查阅相关文献^[25-29], 分别确定了两类成分负离子模式下的模板化合物。黄酮类成分的MDF过滤窗口由5个化合物(A~E)组成(图1A), A点为泻白散中相对分子质量最小的黄酮类化合物(m/z 255.066 2, C₁₅H₁₂O₄, 甘草素^[30])、B点为泻白散中质量亏损最小的化合物(m/z 303.051 0, C₁₅H₁₂O₇, 二氢槲皮素^[25])、C点为泻白散中母核结构最大且质量亏损为正的化合物(m/z 607.160 9, C₃₅H₂₈O₁₀, guangsangon G^[31])、D点为泻白散中相对分子质量最大且质量亏损最大的化合物(m/z 839.307 3, C₅₀H₄₈O₁₂, kuwanon M^[32])、E点为泻白散中母核结构小且取代基质量亏损为正的化合物(m/z 423.181 3, C₂₅H₂₈O₆, sanggenol Q^[33]); 同理, 构建皂苷类化合物的MDF过滤窗口, 由4个模板化合物(F~I)组成(图1B), 分别为C₃₀H₄₆O₄、C₄₂H₆₂O₁₇、C₄₈H₇₂O₂₂、C₄₂H₆₄O₁₅。由于皂苷类成分的取代情况更有规律, 结构共性更强, 本研究只选取了4个点足以构成一个高效的四边形过滤窗口。最终各形成两个应用于各类成分的过滤窗口。再将获得的化合物精确质荷比拆分, 在Excel中建立质量亏损分析模型: 以整数质量(Da)为横坐标, 十进制质量(mDa)为纵坐标构建二维散点图, 使用GraphPad Prism 8.0.2进行可视化。设定线性方程定义MDF窗口边界(图1中红色外框), 利用IF函数筛选位于窗口内的目标母离子。使用Xcalibur工作站的mass range功能提取目标离子^[21], 验证其峰形完整性及保留时间准确性。再结合母离子预测对应的化学分子式, 并分析其二级质谱碎片信息, 结合不饱和度(RDB)、诊断离子碎片、中性丢失等信息初步鉴定潜在的目标成分, 并筛除假阳性结果。

MN分析方法建立 分子网络分析是一种通过质谱数据将结构相似的分子可视化为互连节点, 从而揭示成分间结构关系, 有效提高化学成分鉴定的效率和准确性。GNPS是基于化学成分的MS/MS碎片模式相似性创建分子网络的公共平台, 通过计算每个成分二级碎片的相似性关系来创建一个可视化的网络图, 以反映质谱实验中捕获分子的聚类关系和多样性^[34]。首先, 使用MsConvert软件将原始的LC-MS/MS数据转换为mgf格式, 并通过WinSCP软件上传至GNPS生成分子网络库(https://gnps.ucsd.edu), 余弦分数阈值设置为0.7, 最小匹配碎片离子为6, topK设置为10, 母离子之间的最大质量偏差为0.02 Da, 碎片离子的质量偏差为0.5 Da, 其余为默认值。将后缀为graphml的结果导出后运用Cytoscape 3.6.1软件可视化分析结果。分子网络图中每一个节点表示一个成分, 点与节点之间的连线表示成分之间的相关性, 其中结构类似的成分分子会在一个分子网络中聚集成簇, 可直观显示泻白散汤剂中所有未知成分与标准成分之间的结构相似度。结合m/z和相对分子质量差异, 以及GNPS平台通过在线数据库匹配得到的成分以及已鉴定的明确成分作为探针, 利用其在网络中的位置, 筛选出与之结构相似的未知成分节点; 通过比对两者之间的质荷比差异、诊断离子碎片或中性丢失, 推断这些未知成分可能发生的结构修饰类型, 从而实现其他未知成分的推测。基于GNPS平台和Cytoscape软件, 按照上述的工作流程处理泻白散二级质谱数据, 获得泻白散汤剂中化学成分的分子网络, 可视化图见图2。

结果

收起

1　三种方法整合鉴定泻白散汤剂质谱数据

泻白散汤剂正负离子模式下的UPLC-Q-Orbitrap-MS基峰离子流图, 见图3。基于网络数据库与自建数据库的检索与比对, 本研究从泻白散中初步鉴定出12个黄酮类成分、15个生物碱类成分、4个皂苷类成分、3个芪类成分、34个有机酸类成分及12个苯丙素类成分, 并通过对照品比对进一步确定了甘草酸、甘草次酸、甘草苷、芹糖苷草苷、桑皮苷A、地骨皮乙素, 为后续其余成分的鉴定与验证提供了探针分子。

以负离子模式下采集的MS¹精确质荷比的整数部分作为横坐标, 十进制小数部分作为纵坐标作二维散点图, 共采集得到1 492个m/z信号, 黑色圆点表示, 见图1。多边形内的一级质谱信号为对象, 调取二级质谱信号, 推断裂解规律, 通过与文献比对, 最终从黄酮类MDF过滤窗口中鉴定出35个成分, 其中11个成分为在泻白散及其药味中首次报道的成分; 从皂苷类MDF过滤窗口中鉴定出11个成分, 其中8个为在泻白散及其药味中首次报道的成分。

基于分子网络数据库, 划分出6类分子簇, 分别为桑白皮中黄酮类(A)和芪类(B)、地骨皮亚精胺型酚酰胺类(C)和丁二胺型酚酰胺类(D)、甘草中黄酮类(E)和甘草皂苷类(F), 见图2。分别以每个分子簇中的已知成分桑色素、桑皮苷A、地骨皮甲素、咖啡酰丁二胺、甘草苷、甘草酸为探针分子, 通过分析每个分子簇中探针成分周围的节点, 并检索其二级碎片, 推测这些节点所代表的成分。最终从分子网络中共鉴定出74个成分, 31个为在泻白散及其药味中首次报道的成分。

基于上述成分解析方法, 共从泻白散汤剂中鉴定出185个成分, 包括54个黄酮类成分、42个生物碱类成分、17个皂苷类成分、16个芪类成分、34个有机酸成分、15个苯丙素类成分和7个其他类成分。成分鉴定结果和相关信息见表1。

2　代表成分解析

2.1　黄酮类成分

黄酮类成分主要来源于桑白皮和甘草, 本文通过对比自建数据库和查阅相关文献, 结合MDF过滤和分子网络簇分析, 从泻白散汤剂中鉴定出54个黄酮类成分。

以成分139和112为例对泻白散中黄酮类成分裂解途径进行阐述。成分139的准分子离子峰为m/z 301.035 6 [M-H]^-, 推测其分子式为C₁₅H₁₀O₇, 二级质谱主要发生逆狄尔斯-阿德尔(RDA)反应, 并产生一系列碎片离子m/z 151.002 4、125.023 0, 经文献^[35]对照确认其为桑色素, 来源于桑白皮, 根据二级质谱信息推测其裂解途径(图4A、B), 并根据该类成分的裂解规律总结该类成分的特征碎片作为诊断离子m/z 273 [M-H-CO₂]^-、151。成分112的准分子离子峰为m/z 417.119 4 [M-H]^-, 推测其分子式为C₂₁H₂₂O₉, 与成分139类似, 先丢失1分子Glc, 产生碎片离子m/z 255.066 3 [M-H-162]^-, 在此基础上发生RDA裂解, 产生一系列碎片离子m/z 163.018 0、148.015 0、135.007 4、119.048 7, 经文献^[30]对照确认其为甘草苷, 来源于甘草, 根据二级质谱信息推测其裂解途径(图4C、D), 并总结该类成分的诊断离子有m/z 135、119、91。

成分114的准分子离子峰m/z 433.114 2 [M-H]^-在黄酮MDF过滤窗口被筛出, 通过其碎片离子m/z 151、119确认其为黄酮类成分, 同时, 在分子网络簇(图2E)中与成分112连接, 提示其可能来源于甘草, 并推测其分子式为C₂₁H₂₂O₁₀。二级质谱图显示其碎片信息m/z 271.061 5 [M-H-C₆H₁₂O₅]^-, 即丢失1分子葡萄糖, 再发生RDA裂解, 产生碎片m/z 151.002 4、119.048 7, 经文献^[36]对照确认其为柚皮素-7-O-葡萄糖苷, 来源于甘草, 该成分首次在泻白散复方中报道。

成分95在分子网络簇(图2A)中, 根据其碎片离子m/z 303、151、125推测其可能为黄酮类成分, 且和成分139在同一个分子簇中, 推测其来源于桑白皮。根据其准分子离子峰m/z 465.103 7 [M-H]^-, 推测其分子式为C₂₁H₂₂O₁₂, 丢失1分子葡萄糖产生二级质谱图碎片m/z 303.105 8 [M-H-C₆H₁₂O₅]^-, 再发生RDA裂解, 产生碎片m/z 151.002 8、125.023 0, 经文献^{[3, 37]}对照初步鉴定其为车前子苷, 来源于桑白皮, 该成分首次在泻白散复方中报道。

成分93与已知来源于甘草的成分112聚集于同一簇(图2E), 提示其可能共同具有黄酮类骨架, 特征碎片离子m/z 255、135进一步验证该推断; 成分94与已知来源于桑白皮的成分139聚集于同一簇(图2A), 提示其可能共同具有黄酮类骨架, 特征碎片离子m/z 287、125进一步验证该推断。然而, 这两个成分在现有报告的质谱数据库中未获得匹配, 且在药材中首次报道, 其确切结构暂未能指认, 有待后续确认。

2.2　皂苷类成分解析

皂苷类成分在中草药中分布很广, 主要由皂苷元和糖基组合而成。泻白散汤剂中的皂苷类成分来源于甘草, 属于五环三萜类皂苷, 苷元为齐墩果烷型五环三萜。本文通过对比自建数据库和查阅相关文献^{[26, 29, 38]}, 结合MDF过滤和分子网络簇分析, 从泻白散汤剂中鉴定出17个皂苷类成分。通过分析皂苷类成分在质谱中的裂解行为发现, 皂苷类成分易先脱去葡萄糖醛酸基团(GlcA)、葡萄糖基团(Glc), 分别产生m/z 176、m/z 162的中性丢失碎片, 并产生m/z 351、193、113的诊断离子碎片。

以成分166为例对泻白散中皂苷类成分裂解途径进行阐述。成分166的准分子离子峰为m/z 821.397 6 [M-H]^-, 推测其分子式为C₄₂H₆₂O₁₆, 二级质谱图显示其碎片离子645.365 8 [M-H-176]^-为其失去1分子GlcA产生, 469.335 8 [M-H-176-176]^-为其失去2分子GlcA产生, 经文献^[30]对照确认其为甘草酸, 根据二级质谱信息推测其裂解途径(图5), 并总结该类成分的诊断离子有m/z 351、193、113。

成分166在分子网络簇(图2F)中与附近准分子离子峰为m/z 983.450 5[M-H]^-的成分155的二级质谱图有相同碎片离子m/z 351.05, 且分子簇显示两者具有结构相似性, 提示其为齐墩果烷型五环三萜, 推测其分子式为C₄₈H₇₂O₂₁, 从质谱中提取该成分的二级质谱信息, 可观察到一系列碎片离子信息983.450 5 [M-H]^-、821.398 5 [M-H-162]^-、645.365 0 [M-H-162-176]^-、469.335 2 [M-H-162-176-176]^-, 中性丢失依次为162、176、176, 提示其依次丢失1分子Glc和2分子GlcA, 结合文献^[37]数据, 推断其为甘草皂苷A3。

同样, 该分子网络簇中找到准分子离子为m/z 837.392的成分164, 同样有诊断离子碎片m/z 351, 提示其为齐墩果烷型五环三萜, 且在皂苷类MDF过滤窗口中出现该准分子离子峰信息。根据其二级质谱信息, 观察到一系列碎片离子信息837.392 [M-H]^-、661 [M-H-176]^-、485 [M-H-176-176]^-、467 [M-H-176-176-18]^-、449 [M-H-176-176-18-18]^-, 中性丢失依次为176、176、16、18, 提示其依次丢失2分子GlcA、2分子H₂O, 结合文献^[37]数据, 推测其为甘草皂苷G2。

2.3　芪类成分解析

芪类成分具有二苯乙烯母核, 泻白散中的芪类成分来源于桑白皮。本文通过对比自建数据库和查阅相关文献, 结合分子网络簇分析, 从泻白散汤剂中鉴定出16个皂苷类成分。

以成分60为例对泻白散中芪类成分分裂途径进行阐述。成分60的准分子离子峰为m/z 567.172 1 [M-H]^-, 推测其分子式为C₂₆H₃₂O₁₄, 二级质谱图观察到其一系列碎片离子405.119 2 [M-H-162]^-、243.066 0 [M-H-162-162]^-、225.055 2 [M-H-162-162]^-, 中性丢失依次为162、162、18, 提示其依次丢失2分子Glc和1分子H₂O。经文献^[39]对照确认其为桑皮苷A, 并根据二级质谱信息推测其裂解途径(图6), 并总结该类成分的诊断离子有m/z 243、225。

成分60在分子网络簇(图2B)中与附近准分子离子峰为m/z 1 135.343 7的成分62的二级质谱图有相同碎片离子m/z 567、405、243, 且分子簇显示两者具有结构相似性, 提示其为芪类成分。根据其二级碎片信息, 其碎片离子与成分60基本相同, 由于未在文献和数据库中找到该成分, 初步鉴定其为桑皮苷A二聚体。

2.4　生物碱类成分解析

泻白散中的生物碱成分来源于地骨皮, 主要为酚酰胺类生物碱。本文通过对比自建数据库和查阅相关文献, 结合分子网络簇分析, 从泻白散汤剂中鉴定出42个生物碱类成分。

以成分43和成分32为例对泻白散中生物碱成分分裂途径进行阐述。成分43的准分子离子峰为m/z 531.317 1 [M+H]⁺, 推测其分子式为C₂₈H₄₂N₄O₆, 在正离子模式下其二级质谱图观察到其一系列碎片离子367.269 7 [M+H-C₉H₈O₃]⁺、293.185 5 [M+H-C₉H₈O₃-C₃H₁₀N₂]⁺、222.112 0 [M+H-C₉H₈O₃-C₃H₁₀N₂-C₄H₉N]⁺、165.054 4 [M+H-C₁₉H₃₄N₄O₅]⁺。经文献^[40]对照确认其为地骨皮甲素, 根据二级质谱信息推测其裂解途径(图7A、B)。成分32的准分子离子峰为m/z 251.139 0 [M+H]⁺, 推测其分子式为C₁₃H₁₈N₂O₃, 在正离子模式下其二级质谱图观察到其一系列碎片离子234.111 9 [M+H-NH₃]⁺、192.101 0 [M+H-NH₃-C₃H₆]⁺、89.107 7 [M+H-C₉H₆O₃]⁺。经文献^[41]对照确认其为咖啡酰丁二胺, 根据二级质谱信息推测其裂解途径(图7C、D), 并总结该类成分的诊断离子有m/z 293、222。

成分45的准分子离子峰为m/z 531.317 3 [M+H]⁺, 推测其分子式为C₂₈H₄₂N₄O₆, 其碎片离子m/z 293、222、165, 和成分43相似, 推断成分45和43互为同分异构体。结合文献^[41]以及保留时间, 推断成分45为地骨皮乙素。

成分43在分子网络簇(图2C)中与附近准分子离子峰为m/z 474.259 7的成分73的二级质谱图有相同碎片离子m/z 293、222, 且分子簇显示两者具有结构相似性, 提示其为酚酰胺类成分, 推测其分子式为C₂₅H₃₅N₃O₆, 二级质谱图观察到其一系列碎片离子310.261 1 [M+H-C₉H₁₀O₃]⁺、293.185 9 [M+H-C₉H₁₀O₃-NH₃]⁺、222.112 2 [M+H-C₉H₁₀O₃-NH₃-C₄H₉N]⁺。经文献^[41]对照, 推断该成分为N¹, N¹⁰-双(二氢咖啡酰基)亚精胺。

讨论

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泻白散作为一首治疗小儿肺热咳喘的经典名方, 受到了研究者及企业的广泛关注, 但是其药效物质基础尚未被完全阐明。目前, 已有研究对桑白皮、地骨皮及甘草单味药材的化学成分进行了初步表征, 主要成分为黄酮类、芪类、生物碱类和有机酸类。泻白散复方制剂的化学组成亦有文献报道。Zhang等^[42]考察了引入甘草、粳米对泻白散物质基础的影响, 并通过比对文献数据以及CD软件中数据库共鉴定了158个成分, 其中黄酮类30个、生物碱类10个、皂苷类15个、有机酸类50个、其他类53个。Xu等^[3]通过比对Pubchem、TCMSP、BioTree中药数据库以及文献报道成分首次报道了在泻白散中鉴定了162个成分, 其中黄酮类40个、生物碱类21个、皂苷类成分4个、芪类5个、有机酸类45个, 其他类47个, 但是缺失关键二级碎片信息。上述两个报道中的鉴定结果中1/3为中药中广泛存在的有机酸, 1/3为其他类成分, 而对泻白散中特征成分/关键活性成分鉴定数目少。Peng等^[5]同样结合上述在线数据库鉴定了108个成分, 基于更多碎片信息其鉴定结果的准确性有所提升, 但鉴定成分的数量较少。上述研究结果, 由于鉴定方法单一, 鉴定结果缺乏不同方法之间的验证, 准确性不明; 鉴定结果中泻白散的关键活性成分鉴定较少且未有新成分的发现。

本研究联合运用多点筛查MDF技术和MN技术, 在Pubchem、Chemspider等权威数据库的基础上结合CD软件中的mzCloud和mzVault数据库, 依据已报道文献数据自建实验室成分数据库, 为复方成分质谱数据的全面解析提供了技术保证和全面的数据库。mzCloud和mzVault数据库包含了丰富且准确的二级碎片离子信息, 自建数据库收纳了文献报道的复方所有药味的化学成分的质谱信息, 扩大数据库的基础上也为该复方成分的鉴定提供了特征性数据库, 便于提高鉴定结果的数量和准确性。多点筛查MDF技术进一步构建了黄酮类、芪类两大类成分的质量亏损过滤窗口, 提高了复方中黄酮类和芪类特征成分的鉴定数量和准确性。MN分析技术在泻白散样品中识别出复方中主要成分群, 包括黄酮类、生物碱类、皂苷类、芪类四大类成分分子簇。上述三种方法鉴定的结果可以相互佐证, 不仅大大提高鉴定结果的准确性, 而且实现了对该复方化学成分的系统、快速与全面表征。

采用上述方法本研究共鉴定出185个化学成分, 包括黄酮类54个、生物碱类42个、皂苷类17个、芪类16个、有机酸34个、苯丙素类15个和其他类7个。其中, 139个成分通过数据库与文献比对确认, 46个成分为首次在泻白散复方中报道, 包括18个潜在新成分。在鉴定策略方面, 通过多点筛查MDF技术鉴定了50个成分, 通过MN分析技术鉴定了74个成分, 通过两种技术同时挖掘出14个成分。在化学成分类型方面, 大幅提升了对泻白散主要成分的鉴定数量, 如生物碱类和芪类等泻白散中活性成分的数量比已有文献^{[3, 5]}报道提升了一倍以上, 增加了苯丙素类成分的鉴定, 且多方法结合有效改善了鉴定结果的准确性。

泻白散具有止咳平喘、清泻肺热的功效, 其作用主要源于君药桑白皮、臣药地骨皮及佐使药甘草中所含的多种活性成分, 包括黄酮类、生物碱类、皂苷类以及芪类成分。其中, 黄酮类成分作为该方中最重要的活性大类之一, 主要源自甘草和桑白皮, 表现出显著的抗炎与抗氧化作用。例如, 桑白皮中的桑辛素能够通过调控NF-κB/TGF-β信号通路有效抑制炎症反应^[43]; 而甘草所含的甘草苷则具有减轻细胞损伤^[44]及缓解氧化应激的作用^[45]。生物碱类成分主要来源于地骨皮, 其代表性成分地骨皮甲素显示出广泛的抗炎效果, 其作用机制与抑制NF-κB通路、减少促炎因子生成密切相关^[46]。皂苷类成分则以甘草中的甘草酸为代表, 不仅展现出抗病毒活性, 尤其在冠状病毒感染治疗中备受关注^[47], 还表现出一定的肝脏保护作用^[48]。此外, 桑白皮所含芪类成分亦具有重要药理价值, 例如桑皮苷A可通过抑制氧化应激进而缓解气道炎症^[49]。本研究基于质谱分析鉴定出的上述特征化学成分, 不仅与泻白散的传统功效高度契合, 也为深入揭示其药理作用机制提供了可靠的科学依据。

本研究首次将多点筛查MDF与GNPS分子网络联用, 实现了对泻白散中多类成分的系统挖掘与交叉验证, 尤其是对关键活性成分的鉴定, 提高了鉴定效率和鉴定结果的准确性。MDF可以对采集的高分辨质谱数据进行处理和识别, 从复杂背景中筛选结构类似物, 具备独特的技术优势。然而, 传统MDF方法仅以单一母体化学成分为模板, 质量亏损窗口设置宽泛, 易导致筛选偏差及较多假阳性结果。本研究采用多点筛查质量亏损过滤策略, 选取多个代表性化学成分为模板, 分类进行筛选。该方法^{[3, 5, 8]}无需依赖裂解规律总结即可识别多个衍生物, 显著去除假阳性信号, 提高筛选效率, 尤其适用于黄酮类成分的挖掘。并进一步引入MN分析技术, 该策略在处理复杂MS/MS数据方面具有明显优势, 可有效过滤冗余信息, 降低数据解析的盲目性, 并借助GNPS数据库实现已知成分的匹配与未知同类物的快速定位, 显著提升了质谱数据解析效率、结构鉴定准确性及新成分发现潜力。两种方法协同互补, 增强了潜在成分的挖掘广度与鉴定结果的可信度。尽管MDF和MN能高效处理质谱数据, 但其应用仍存在一定局限性。MDF窗口内难以完全避免假阳性, 需辅以人工甄别; 且该方法对于结构变异较大的类别(如本研究中的酚酰胺类生物碱、芪类), 因质量亏损差异显著, 应用效果受限。MN技术对质谱数据的质量高度敏感, 需要低背景噪音、电离能量适中的质谱数据。

质谱分析中的化合物鉴定准确性是本研究关注的核心。本研究构建的全面鉴定流程阐明, 高分辨的原始数据是提升鉴定准确性的基石, 通过优化质谱采集参数并有效降低基质效应, 可为后续分析奠定可靠基础。构建的数据库要尽可能全面, 涵盖目前报道的所有可能成分。在数据解析阶段, 需综合运用多维数据分析策略, 从不同维度交叉验证, 方能确保鉴定结果的可信度。综上所述, 本研究对泻白散的化学成分进行了整体、全面的鉴定, 为后续的药效研究提供了坚实的实验数据基础。

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2026年第61卷第4期

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doi: 10.16438/j.0513-4870.2025-1318

接收时间：2025-11-08
首发时间：2026-09-21
出版时间：2026-04-12

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收稿日期：2025-11-08
修回日期：2026-01-05

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¹中国中医科学院, 中药研究所, 北京 100700

²山东中医药大学, 山东济南 250355

³首都医科大学附属北京地坛医院药学部, 北京 100015

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代云桃, E-mail: ytdai@icmm.ac.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	Identification	Formula	Ion mode	Observed (m/z)	Error (×10^-6)	Fragment	Structure class	Origin
1	1.12	Histamine	C₅H₉N₃	[M+H]⁺	112.087 3	3.09	95.060 8, 83.060 9, 68.049 2	g	D
2	1.12	1-Deoxynojirimycin	C₆H₁₃NO₄	[M+H]⁺	164.091 8	0.46	146.081 0, 128.070 2, 68.049 1	b	S
3	1.15	Arginine	C₆H₁₄N₄O₂	[M-H]^-	173.104 4	-0.59	156.076 5, 131.081 1, 114.054 5	c	S/D/G
4	1.16	Valinol	C₅H₁₃NO	[M+H]⁺	104.107 2	2.2	87.084 5, 71.029 9, 60.081 6	b	S/G
5^△	1.24	Xylonic acid	C₅H₁₀O₆	[M-H]^-	165.039 1	-1.54	147.028 5, 129.017 9, 87.007 1, 75.007 0	c	S/D/G
6	1.26	Sugar acid	C₆H₁₀O₈	[M-H]^-	209.030 3	1.9	191.018 8, 133.012 8, 129.017 9, 85.027 8	c	S/D/G
7	1.27	Quinic acid	C₇H₁₂O₆	[M-H]^-	191.056 1	0.92	173.044 3, 127.038 6, 111.007 2, 85.027 8	c	S/D
8	1.34	Betaine	C₅H₁₁NO₂	[M+H]⁺	118.086 4	0.97	94.365 8, 72.081 5, 59.073 7, 58.065 8	b	S/D/G
9	1.86	Malic acid	C₄H₆O₅	[M-H]^-	133.013 1	-0.52	115.002 1, 89.022 8, 73.002 2	c	S/D/G
10^*	1.98	Adenine	C₅H₅N₅	[M+H]⁺	136.061 6	-1.61	119.035 3, 109.064 9, 100.274 0	g	S/D/G
11	1.99	Guanine	C₅H₅N₅O	[M+H]⁺	152.056 5	-1.42	135.033 0, 134.033 3, 110.035 0	g	S/D/G
12	1.99	Malic acid isomer	C₄H₆O₅	[M-H]^-	133.012 6	-3.53	115.002 1, 89.022 8, 72.991 4	c	S/D/G
13^△	1.99	Dehydroascorbic acid	C₆H₆O₆	[M-H]^-	173.009 2	-1.88	111.007 2, 85.028 7, 67.017 2	c	S/D/G
14^△	2.01	2-Acetamidoacrylic acid	C₅H₇NO₃	[M+H]⁺	130.049 5	2.45	112.087 1, 84.044 8, 70.065 7	c	S/D/G
15	2.02	Citric acid	C₆H₈O₇	[M-H]^-	191.018 9	1.21	173.088 1, 129.017 9, 111.007 2, 87.007 1	c	S/D/G
16	2.03	Stachydrine	C₇H₁₃NO₂	[M+H]⁺	144.101 9	-0.38	126.091 4, 98.096 8, 84.061 2, 70.062 5	b	G
17	2.07	Uridine	C₉H₁₂N₂O₆	[M-H]^-	243.062 3	3.24	200.055 8, 152.034 0, 110.023 2, 82.028 3	g	S/D/G
18	2.17	Suberic acid	C₈H₁₄O₄	[M-H]^-	173.081 9	0.46	129.017 9, 111.007 2, 85.027 8, 72.991 5	c	S/D
19	2.17	N-Acetyl-L-glutamic acid	C₇H₁₁NO₅	[M-H]^-	188.056 4	1.36	170.044 8, 144.065 3, 128.033 9, 102.054 5	c	S/D
20	2.27	Adenosine	C₁₀H₁₃N₅O₄	[M+H]⁺	268.104 0	-1.46	206.107 8, 152.648 5, 136.061 7	g	S/D/G
21	2.41	δ-Ribosyl-1,4-lactone	C₅H₈O₅	[M-H]^-	147.028 6	-1.5	129.018 0, 102.947 2, 87.007 1, 59.012 2	c	S/D/G
22	2.49	4-Hydroxyphenethylamine	C₈H₁₁NO	[M+H]⁺	138.091 3	-0.66	121.064 9, 111.007 9, 93.070 3	b	D
23	2.49	Isoleucine	C₆H₁₃NO₂	[M+H]⁺	132.101 9	-0.04	113.963 8, 86.096 9, 69.070 5	c	D/G
24	2.55	Guanosine	C₁₀H₁₃N₅O₅	[M-H]^-	282.084 4	4.59	178.900 8, 152.040 8, 126.029 4	g	S/D/G
25	2.56	Trigonelline	C₇H₇NO₂	[M+H]⁺	138.055 4	3.37	110.060 2, 94.056 3, 68.997 8	b	S/G
26	4.12	Cytisine	C₁₁H₁₄N₂O	[M+H]⁺	191.117 8	-0.57	162.090 8, 122.060 0, 105.963 0	b	D
27	5.08	Protocatechuic acid 4-O-β-glucoside	C₁₃H₁₆O₉	[M-H]^-	315.072 5	4.79	152.010 1, 125.256 2, 109.027 9	c	S/D/G
28^*	6.15	Vanillic acid 4-β-D-glucoside	C₁₄H₁₈O₉	[M-H]^-	329.088 0	1.27	167.033 8, 152.010 3, 123.043 7	c	S/D/G
29	6.98	Catechol	C₆H₆O₂	[M-H]^-	109.028 0	-3.62	108.020 4, 79.029 0, 67.029 1	c	S/D/G
30	7.02	Protocatechuic acid	C₇H₆O₄	[M-H]^-	153.019 3	-1.08	135.044 1, 109.028 0, 91.017 3	c	S/D/G
31^△	7.29	Daphneside	C₂₁H₂₆O₁₄	[M-H]^-	501.125 5	3.33	381.082 7, 219.029 3, 191.034 1	d	S/G
32^*	7.64	Caffeoylputrescine	C₁₃H₁₈N₂O₃	[M+H]⁺	251.139 0	-0.56	234.111 7, 163.038 6, 145.028 1, 89.107 7	b	D
33	7.95	Syringic acid glucoside	C₁₅H₂₀O₁₀	[M-H]^-	359.099 0	4.73	197.044 8, 182.022 1, 138.030 9	c	D
34^△*	8.57	Mulberroside A+Glc	C₃₃H₄₄O₂₁	[M-H]^-	775.231 3	2.13	729.225 3, 567.172 0, 405.119 1, 243.009 0	e	S
35^*	8.59	Oxyresveratrol-6-O-D-glucopyranosyl-D-glucopyranoside isomer	C₃₂H₄₂O₁₉	[M-H]^-	729.225 9	3.07	567.172 6, 405.112 5, 243.066 1, 225.055 2	e	S
36^*	8.78	Neochlorogenic acid	C₁₆H₁₈O₉	[M-H]^-	353.088 1	1.18	191.055 3, 179.034 0, 135.043 8	d	S
37	8.87	Indole-3-acrylic acid	C₁₁H₉NO₂	[M+H]⁺	188.070 4	-1.3	170.059 7, 146.059 8, 118.065 2, 88.022 0	b	S/D/G
38	9.01	Tryptophan	C₁₁H₁₂N₂O₂	[M-H]^-	203.082 6	2.15	186.055 2, 159.091 6, 116.049 1	c	D
39	9.4	8-Hydroxyquinoline	C₉H₇NO	[M+H]⁺	146.059 9	-1.24	128.950 7, 118.065 3, 99.044 4	b	D/G
40	10.13	Salicylic acid	C₇H₆O₃	[M-H]^-	137.023 1	-1.9	119.012 6, 93.033 3, 65.038 0	c	S/D/G
41	10.54	2-Isopropylmalic acid	C₇H₁₂O₅	[M-H]^-	175.061 2	0.4	146.959 9, 115.038 6, 85.064 3	c	G
42^△*	10.85	Unknown	C₃₂H₅₀N₇O₁₀	[M+H]⁺	693.369 1	-0.16	657.343 4, 474.257 4, 293.185 8, 222.112 1	b	D
43^*	11.	Kukoamine A	C₂₈H₄₂N₄O₆	[M+H]⁺	531.317 1	-0.45	293.185 6, 222.112 1, 165.054 5, 123.043 9	b	D
44	11.13	Phenyllactic acid	C₉H₁₀O₃	[M-H]^-	165.054 6	-0.43	121.064 5, 93.033 0, 59.012 2	d	S/D/G
45^*	11.14	Kukoamine B	C₂₈H₄₂N₄O₆	[M+H]⁺	531.317 3	-0.57	293.185 5, 222.122 0, 165.054 5, 123.043 9	b	D
46	11.2	6-Methylquinoline	C₁₀H₉N	[M+H]⁺	144.080 6	-1.14	117.065 4, 98.331 1, 84.081 2	b	D
47	11.28	Esculin	C₁₅H₁₆O₉	[M-H]^-	339.071 8	2.22	249.040 5, 219.029 3, 191.034 2	d	S
48^*	11.98	Caffeoylagmatine	C₁₄H₂₀N₄O₃	[M+H]⁺	293.160 4	-0.45	276.134 7, 163.038 7, 131.092 5, 114.102 7	b	D
49^*	12.62	Feruloylputrescine	C₁₄H₂₀N₂O₃	[M+H]⁺	265.154 3	-0.34	177.054 4, 163.039 5, 145.028 3, 89.107 8	b	D
50	12.94	7-Hydroxycoumarin	C₉H₆O₃	[M+H]⁺	163.038 7	-0.24	145.028 3, 135.044 1, 119.033 9, 104.049 4	d	S/G
51	12.98	Dihydrocaffeic acid	C₉H₁₀O₄	[M-H]^-	181.050 6	0.63	163.038 9, 137.059 4, 121.027 9, 109.028 0, 93.069 3	c	G
52^*	13.15	N¹-Caffeoyl-N¹⁰-dihydro caffeoylspermine	C₂₈H₄₀N₄O₆	[M+H]⁺	529.301 9	-0.34	511.471 6, 367.271 4, 293.186 5, 220.096 5, 163.038 7	b	D
53^*	13.21	Chlorogenic acid	C₁₆H₁₈O₉	[M-H]^-	353.087 8	3.34	191.055 2, 179.034 0, 161.023 2	d	S
54^*	13.31	N¹-Caffeoyl-N¹⁴-dihydro caffeoylspermine	C₂₈H₄₀N₄O₆	[M+H]⁺	529.301 9	-0.18	511.472 2, 458.227 0, 367.270 0, 293.184 7, 220.096 5, 163.038 7	b	D
55^△	13.36	Sinapic acid glucuronide	C₁₇H₂₀O₁₁	[M-H]^-	399.093 0	2.16	221.702 8, 192.037 4	d	S/G
56^△*	13.45	Multiflorin A	C₂₉H₃₂O₁₆	[M-H]^-	635.156 6	-4.04	567.171 9, 405.120 3, 243.066 0, 225.056 1	a	S
57^*	13.48	N⁵-3-Acetyldihydrocaffeoyl-N¹⁰-dihydrocaffeoylspermine	C₂₈H₄₀N₄O₆	[M+H]⁺	529.301 9	-0.12	291.170 1, 220.096 7, 163.038 8, 147.069 4	b	D
58^△*	13.55	Mulberroside A +2H₂O	C₂₆H₃₆O₁₆	[M-H]^-	603.146 4	1.23	567.172 3, 405.119 3, 243.066 1	e	S
59^△*	13.57	Leiocarposide	C₂₇H₃₄O₁₆	[M-H]^-	613.176 7	0.39	567.172 2, 405.119 4, 243.066 1, 225.055 4	e	S
60^*	13.61	Mulberroside A	C₂₆H₃₂O₁₄	[M-H]^-	567.172 4	2.69	405.119 3, 243.006 1, 225.055 3, 199.075 7	e	S
61^*	13.63	Glucosyl-3-O-β-D-apiosyl-(1→6)-O-β-D-glucoside	C₃₁H₄₀O₁₈	[M-H]^-	699.216 1	3.1	537.159 9, 405.119 2, 243.066 1, 225.055 4	e	S
62^△*	13.67	Mulberroside A dimer	C₅₂H₆₄O₂₈	[M-H]^-	1 135.343 7	-4.58	567.172 1, 405.119 1, 243.066 0, 225.055 1	e	S
63^△*	14.1	L-Leucyl-L-tyrosine	C₁₅H₂₂N₂O₄	[M+H]⁺	295.164 8	-0.4	207.065 0, 175.038 8, 147.039 9, 119.049 3	b	D
64^△	14.29	Capsaicin	C₁₃H₂₇N₈O₃	[M+H]⁺	344.228 3	1.11	327.200 9, 283.174 7, 177.112 0, 133.086 0, 89.068 2	b	D
65^*	14.49	Cryptochlorogenic acid	C₁₆H₁₈O₉	[M-H]^-	353.087 9	3.34	191.055 3, 179.034 0, 161.023 4, 135.043 8	d	S
66	14.61	4-Hydroxybenzaldehyde	C₇H₆O₂	[M-H]^-	121.028 0	-3.11	108.020 1, 93.020 9, 69.985 5	g	S/G
67	14.71	N¹-Dihydrocaffeoyl-N⁵ dihydroferuoylspermine	C₂₉H₄₄N₄O₆	[M+H]⁺	545.330 0	-0.35	307.200 9, 293.185 2, 236.127 8, 222.112 2, 179.070 7, 137.059 7	b	D
68	14.79	Scopoletin	C₁₀H₈O₄	[M+H]⁺	193.049 4	-0.75	178.027 5, 165.054 4, 149.059 3, 133.028 4, 127.298 6	d	D
69	14.95	α-Rhamnosyl-(1→6)-O-β-D-glucoside	C₂₁H₂₆O₁₃	[M-H]^-	485.130 1	1.31	363.248 8, 293.088 3, 191.034 2, 176.010 4	d	S
70^*	15.02	Oxyresveratrol-6-O-D-glucopyranosyl-D-glucopyranoside	C₃₂H₄₂O₁₉	[M-H]^-	729.227 2	4.9	567.171 8, 243.066 1, 225.055 1	e	S
71^△*	15.13	Hydroxyprolyl-tryptophan	C₁₆H₁₉N₃O₄	[M+H]⁺	318.144 4	-1.42	207.065 1, 175.038 7, 147.043 4	b	D
72^#	15.37	Quercetin-3-O-sophoroside	C₂₇H₃₀O₁₇	[M-H]^-	625.141 2	1.99	463.088 4, 299.020 1, 151.002 4, 125.002 9	a	S
73^*	16.92	N¹,N¹⁰-Bis(dihydrocaffeoyl)spermidine	C₂₅H₃₅N₃O₆	[M+H]⁺	474.259 7	-0.16	293.185 9, 222.112 2, 165.054 5, 123.044 1	b	D
74^#	17.67	Glucoliquiritin apioside	C₃₂H₄₀O₁₈	[M-H]^-	711.214 7	2.21	711.216 5, 549.160 5, 255.065 8, 153.018 5, 135.008 6, 119.048 7	a	G
75	17.8	3-p-Coumaroylquinic acid	C₁₆H₁₈O₈	[M-H]^-	337.092 4	1.74	191.055 2, 163.038 7, 119.048 8, 93.033 0	c	S
76^△#*	17.88	Hydroxysafflor yellow A	C₂₇H₃₂O₁₆	[M-H]^-	611.162 0	2.17	565.156 3, 403.103 4, 241.050 3, 197.060 2	a	S
77^#*	17.93	Glabranin	C₂₀H₂₀O₄	[M-H]^-	323.125 4	-2.36	257.678 3, 203.081 4, 189.066 0, 175.086 9	a	G
78	18.46	Riboflavin	C₁₇H₂₀N₄O₆	[M+H]⁺	377.145 1	-1.2	359.134 3, 243.087 4, 172.086 8	b	D
79	18.93	N⁵-Dihydrocaffeoyl-N¹⁰ caffeoylspermidine	C₂₅H₃₃N₃O₆	[M+H]⁺	472.243 8	-0.41	455.214 8, 310.212 0, 293.185 4, 236.127 6, 220.096 5, 163.038 7	b	D
80^△*	19.02	Unknown	C₂₇H₄₀N₇O₆	[M+H]⁺	559.311 5	0.42	321.179 8, 293.185 5, 222.122 0, 165.054 6, 123.044 2	b	D
81	19.18	Magnoflorine	C₂₀H₂₃NO₄	[M+H]⁺	342.168 8	-3.58	297.110 6, 265.084 5, 237.090 6, 183.521 0, 177.054 2, 115.076 2	b	D
82	19.34	Esculetin	C₉H₆O₄	[M-H]^-	177.018 2	-0.01	149.023 3, 133.028 1, 105.032 9, 89.038 1	d	S/G
83	19.83	Vicenin-2	C₂₇H₃₀O₁₅	[M-H]^-	593.151 1	1.73	473.104 7, 383.075 9, 353.066 7, 325.073 0, 297.076 6	a	G
84^△*	19.93	Unknown	C₂₆H₁₈O₇	[M-H]^-	441.094 3	-5.78	405.119 3, 243.066 1, 225.056 2, 199.076 3, 175.074 9	e	S
85^△*	19.97	Catechin-7-O-β-D-glucopyranoside	C₂₁H₂₄O₁₁	[M-H]^-	451.124 8	1.3	405.119 3, 243.066 1, 225.055 2, 199.075 8, 175.075 5, 157.064 7	e	S
86^△*	19.98	6"-O-Acetylgenistin	C₂₃H₂₂O₁₁	[M-H]^-	473.106 1	-1.7	405.119 3, 243.066 2, 225.055 6, 175.075 3	e	S
87^*	20.01	2,3,5,4′-Tetrahydroxy stilbene-2-Ο-β-D-glucoside isomer	C₂₀H₂₂O₉	[M-H]^-	405.119 1	2.79	243.066 1, 225.055 2, 199.075 7, 175.075 3, 157.064 5	e	S/G
88^△*	20.22	Acremonidin D	C₃₃H₂₈O₁₄	[M-H]^-	647.139 4	-0.2	449.109 3, 287.057 6, 161.023 4, 125.023 0	a	S
89^*	20.24	N¹-3-Acetyldihydrocaffeoyl-N¹⁰-dihydrocaffeoyl spermine	C₃₀H₄₄N₄O₇	[M+H]⁺	573.327 7	-1.01	475.269 6, 335.196 6, 293.184 1, 222.112 2, 208.681 9, 165.054 3	b	D
90^△*	20.44	Unknown	C₂₈H₃₄O₁₈	[M-H]^-	657.167 8	1.65	611.162 0, 449.109 1, 287.056 2, 125.023 0	a	S
91	20.77	N-Acetyl-L-phenylalanine	C₁₁H₁₃NO₃	[M-H]^-	206.082 3	2.23	192.005 5, 164.070 5, 147.043 8, 118.991 6, 91.053 7	c	D
92^△#	21.05	Diosmetin-7-O-glucoside	C₂₂H₂₂O₁₁	[M-H]^-	461.329 1	0.92	415.161 4, 299.057 2, 191.055 3, 149.099 3, 131.033 7, 89.022 8	a	S
93^△*	21.28	Unknown	C₂₈H₃₄O₁₈	[M-H]^-	657.168 2	2.11	611.162 8, 449.109 2, 287.056 2, 161.023 3, 125.023 1	a	S
94^△#*	21.45	Unknown	C₃₂H₄₀O₂₀	[M-H]^-	743.202 6	-0.38	700.649 8, 449.111 5, 405.341 5, 287.056 7, 161.023 2, 125.022 9	a	S
95^△*	21.48	Plantagoside	C₂₁H₂₂O₁₂	[M-H]^-	465.103 7	0.92	303.105 8, 151.002 8, 125.023 0	a	S
96^*	21.73	2,3,5,4′-Tetrahydroxy stilbene-2-Ο-β-D-glucoside	C₂₀H₂₂O₉	[M-H]^-	405.119 1	2.79	243.066 1, 225.055 2, 199.075 8, 175.075 4, 159.044 0	e	S/G
97^△#	21.94	Unknown	C₂₁H₂₉O₁₄	[M-H]^-	504.147 3	3.89	412.140 9, 301.831 4, 192.067 1, 165.054 8	a	S
98^#	22.18	Daidzin	C₂₁H₂₀O₉	[M+H]⁺	417.117 8	-0.5	255.064 8, 237.054 6, 199.074 3, 149.717 5	a	G
99^△*	22.96	N-Acetyl-1-O-benzyl-α-muramyl-α-aminoisobutyryl-D-isoglutamine benzyl ester	C₃₄H₄₆N₄O₁₁	[M+H]⁺	687.322 5	0.3	449.191 0, 293.185 9, 222.121 6, 165.054 1	b	D
100^*	22.98	Hyperoside	C₂₁H₂₀O₁₂	[M-H]^-	463.088 5	3.08	301.033 5, 273.040 3, 255.030 0, 151.002 4, 125.002 9	a	S
101^#	23.44	Schaftoside	C₂₆H₂₈O₁₄	[M-H]^-	563.140 8	2.38	473.106 1, 443.098 0, 383.077 7, 353.066 4, 325.071 8, 297.076 7	a	G
102	23.5	Isoscopoletin	C₁₀H₈O₄	[M+H]⁺	193.049 4	-0.15	178.025 0, 165.054 7, 149.056 9, 137.059 7, 133.024 8	d	D
103	24.21	Ferulic acid	C₁₀H₁₀O₄	[M-H]^-	193.050 0	2.51	178.026 1, 149.059 5, 134.036 0	c	S/D/G
104^#	25.35	Tetrahydroxychalcone 4′-O-glucoside	C₂₁H₂₂O₁₀	[M-H]^-	433.113 6	-1.	271.061 0, 151.003 6, 135.008 7, 119.050 2	a	G
105^*	25.75	Isoliquiritin	C₂₁H₂₂O₉	[M-H]^-	417.118 5	-1.45	255.065 5, 148.016 4, 135.008 6, 119.050 1	a	G
106^△#*	25.85	Unknown	C₂₀H₂₂O₁₂	[M-H]^-	453.095 4	-7.35	417.119 3, 255.066 7, 153.018 1, 135.007 6, 119.048 6	a	G
107	26.08	Dihydro-N-caffeoyltyramine	C₁₇H₁₉NO₄	[M+H]⁺	302.138 4	-0.29	165.054 3, 143.572 4, 138.091 3, 121.064 9	b	D
108^*	26.17	Isoliquiritin apioside	C₂₆H₃₀O₁₃	[M-H]^-	549.160 3	-1.95	429.104 2, 297.077 5, 255.065 7, 135.008 5, 119.050 0	a	G
109^△#*	26.17	Eriocitrin isomer	C₂₇H₃₂O₁₅	[M-H]^-	595.167 2	1.49	255.066 1, 135.007 6, 119.049 0	a	S
110^△*	26.2	Unknown	C₂₅H₃₀O₁₆	[M-H]^-	585.135 9	-6.16	429.102 8, 255.066 3, 135.007 5	a	G
111^*	26.38	N¹,N⁵-Bis(dihydroferuloyl)spermidine	C₂₇H₃₉N₃O₆	[M+H]⁺	502.291 2	0.04	388.415 9, 250.142 4, 236.127 8, 179.070 5, 137.059 7	b	D
112^#*	26.47	Liquiritin	C₂₁H₂₂O₉	[M-H]^-	417.119 3	3.28	255.066 2, 163.018 0, 148.015 0, 135.007 4, 119.048 7	a	G
113^△#	26.54	Tetrahydroxychalcone 4′-O-glucoside isomer	C₂₁H₂₂O₁₀	[M-H]^-	433.113 9	2.3	271.061 3, 151.002 4, 135.008 7, 119.050 3	a	S
114^#*	26.68	Naringenin-7-O-glucoside	C₂₁H₂₂O₁₀	[M-H]^-	433.114 2	3.02	271.061 5, 151.002 4, 119.048 7	a	G
115^*	26.74	N¹,N⁵,N¹⁰-tris(di hydrocaffeoyl) spermine	C₃₇H₅₀N₄O₉	[M+H]⁺	695.363 3	-2.5	678.344 1, 457.234 3, 293.185 9, 222.112 3	b	D
116^△*	26.75	Liquiritin apioside	C₂₆H₃₀O₁₃	[M-H]^-	549.161 3	2.02	417.119 3, 255.066 1, 153.018 0, 135.007 3, 119.048 6, 91.017 3	a	G
117^△*	26.79	Unknown	C₂₅H₃₀O₁₆	[M-H]^-	585.138 9	-0.49	549.161 8, 429.102 8, 255.066 3, 153.017 7, 135.007 5	a	G
118^#	27.19	Dihydromorin	C₁₅H₁₂O₇	[M-H]^-	303.052 2	7.66	275.056 3, 177.018 2, 125.023 0	a	S
119^#*	27.76	Eriodictyol-7-O-glucoside	C₂₁H₂₂O₁₁	[M-H]^-	449.109 9	4.57	287.056 7, 269.136 8, 197.059 8, 125.022 9	a	S
120^#	27.89	6′′-O-Acetylliquiritin isomer	C₂₃H₂₄O₁₀	[M-H]^-	459.130 0	3.04	339.087 5, 255.044 6, 153.010 3	a	G
121^△*	27.97	Unknown	C₃₄H₄₆N₄O₈	[M+H]⁺	639.338 6	-0.35	621.330 1, 293.185 9, 222.112 2	b	D
122	28.79	Oxyresveratrol	C₁₄H₁₂O₄	[M-H]^-	243.066 1	3.76	225.055 1, 199.075 8, 175.075 3	e	S
123^#	28.91	6′′-O-Acetylliquiritin isomer	C₂₃H₂₄O₁₀	[M-H]^-	459.129 3	1.16	339.087 4, 263.056 7, 255.045 2, 153.010 0	a	G
124^#	29.13	Naringenin chalcone	C₁₅H₁₂O₅	[M-H]^-	271.061 4	4.91	151.002 3, 140.975 4, 119.048 9	a	G
125	29.14	Mulberroside F	C₂₆H₃₀O₁₄	[M-H]^-	565.156 2	1.78	433.112 0, 335.243 8, 271.061 4, 227.071 2, 151.002 4, 119.048 7	e	S
126^*	29.21	trans-N-Caffeoyltyramine	C₁₇H₁₇NO₄	[M+H]⁺	300.122 8	-0.78	163.038 7, 121.064 9, 89.060 1	b	D
127	29.23	Azelaic acid	C₉H₁₆O₄	[M-H]^-	187.096 5	-0.03	169.085 7, 143.106 5, 125.095 7	c	S/D/G
128^△#	29.25	Tetrahydroxychalcone 4′-O-glucoside isomer	C₂₁H₂₂O₁₀	[M-H]^-	433.113 1	0.41	271.061 4, 151.002 4, 135.008 7, 119.050 4	a	S
129^*	29.77	Lyciumin A	C₄₂H₅₁N₉O₁₂	[M+H]⁺	874.372 6	-0.5	856.363 7, 486.198 1, 468.187 6, 136.075 7	b	D
130^#	29.78	Eriodictyol	C₁₅H₁₂O₆	[M-H]^-	287.056 1	3.85	259.061 4, 243.067 2, 151.002 3, 125.022 9	a	S
131^△	29.9	4-Oxododecanedioic acid	C₁₂H₂₀O₅	[M-H]^-	243.123 8	2.88	225.112 8, 207.102 2, 181.122 5, 146.959 9	c	S/D/G
132	30.04	7-O-β-D-Apiosyl-3-O-p-coumaroylkaempferol	C₂₇H₃₀O₁₃	[M-H]^-	561.161 6	2.41	309.076 8, 267.066 4, 252.042 8	d	G
133^△*	30.17	Eriodictyol isomer	C₂₇H₃₂O₁₅	[M-H]^-	595.167 6	1.85	351.069 3, 255.066 2, 135.007 4, 119.048 8, 91.017 2	a	S
134^△#	30.47	Isoformononetin	C₁₆H₁₂O₄	[M-H]^-	269.080 4	-1.69	254.055 9, 237.054 2, 213.091 2, 119.041 4	a	S
135^*	30.9	Neoisoliquiritin	C₂₁H₂₂O₉	[M-H]^-	417.111 9	-4.7	255.066 2, 153.019 1, 148.015 4, 135.007 1, 119.048 7	a	G
136^#	30.92	Liquiritin B	C₃₅H₃₆O₁₅	[M-H]^-	695.198 8	2.51	531.152 5, 255.066 3, 119.048 8, 72.991 5	a	G
137	30.94	N-p-trans-Coumaroyltyramine	C₁₇H₁₇NO₃	[M+H]⁺	284.128 1	0.07	239.149 7, 147.043 9, 121.064 8, 119.049 2	b	D
138^#	31.08	Liquiritin A	C₃₆H₃₈O₁₆	[M-H]^-	725.210 0	3.24	531.152 7, 255.066 0, 193.049 5, 135.007 5	a	G
139^#	31.25	Morin	C₁₅H₁₀O₇	[M-H]^-	301.035 6	4.42	273.042 0, 229.050 2, 151.002 4, 125.023 0	a	S
140^*	31.34	Feruloyltyramine	C₁₈H₁₉NO₄	[M+H]⁺	314.138 5	-0.52	292.079 3, 177.054 4, 145.028 3, 117.033 6	b	D
141^△*	31.41	Baicalin	C₂₁H₁₈O₁₁	[M-H]^-	445.077 0	3.46	269.045 8, 235.303 8, 175.023 9, 113.022 9	a	S
142	31.43	Lyciumin B	C₄₄H₅₂N₁₀O₁₁	[M+H]⁺	897.388 7	-0.34	689.307 3, 486.198 0, 468.187 5, 159.091 5	b	D
143^*	31.62	N-Feruloyl-3-methoxy tyramine	C₁₉H₂₁NO₅	[M+H]⁺	344.148 7	-1.74	177.054 4, 145.028 4, 117.033 6	b	D
144^△#	31.62	Licorice saponin J2 isomer	C₄₂H₆₄O₁₆	[M-H]^-	823.413 2	2.61	671.079 0, 351.057 4, 193.034 9, 113.002 9	f	G
145^#	31.65	4′,7-Dihydroxyflavanone	C₁₅H₁₂O₄	[M-H]^-	255.062 5	-7.28	219.845 1, 153.018 1, 135.007 2, 119.004 2	a	G
146^△#	31.71	24-Hydroxy-licorice saponin A3	C₄₈H₇₂O₂₂	[M-H]^-	999.445 6	2.41	837.388 9, 377.540 1, 351.056 2, 193.034 4, 113.022 9	f	G
147^#	31.8	Liquiritigenin	C₁₅H₁₂O₄	[M-H]^-	255.065 0	4.57	219.844 9, 153.018 1, 135.007 2, 119.004 8	a	G
148^△*	31.85	Chrysin-7-O-β-D-glucuronide	C₂₁H₁₈O₁₀	[M-H]^-	429.082 1	4.5	253.050 6, 175.023 9, 113.022 9	a	S
149	31.86	Sebacic acid	C₁₀H₁₈O₄	[M-H]^-	201.113 2	1.76	183.101 7, 139.111 5, 111.080 1	c	S/D
150^△*	31.91	Diosmetin-7-glucuronide	C₂₂H₂₀O₁₂	[M-H]^-	475.087 6	2.49	299.056 5, 284.032 9, 217.056 7, 113.022 6	a	S
151	31.99	7-Hydroxy-1-(3,4-dihydroxyphenyl)-N²,N³-bis(4-hydroxyphenethyl)-6,8-dimethoxy-1,2-dihydronaphthalene-2,3-dicarboxamide	C₃₆H₃₆N₂O₉	[M+H]⁺	641.245 3	-6.33	504.163 9, 476.167 8, 339.086 8	b	D
152	32.07	Lyciumin C	C₄₉H₅₇N₉O₁₂	[M+H]⁺	964.419 9	-0.09	593.273 4, 576.246 5, 389.181 5, 257.128 1, 188.070 4	b	D
153^△*	32.1	3,7-Bis(2-hydroxyethyl) icaritin	C₂₅H₂₈O₈	[M-H]^-	455.170 9	0.83	371.217 2, 213.221 2, 153.349 6, 125.022 9	a	S
154^△#	32.4	22-Hydroxy-licorice saponin G2	C₄₂H₆₂O₁₈	[M-H]^-	853.387 2	2.3	351.056 6, 193.034 6, 175.024 5, 113.022 8	f	G
155^*	32.53	Licorice saponin A3	C₄₈H₇₂O₂₁	[M-H]^-	983.450 5	2.3	821.398 5, 645.365 0, 469.335 2, 351.056 9, 193.034 5, 113.022 9	f	G
156^△*	32.94	Rhaglycyrrhizin	C₄₈H₇₂O₂₀	[M-H]^-	969.461 1	-0.15	601.403 5, 351.056 9, 193.034 9, 113.022 9	f	G
157^#*	33.25	Licorice saponin G2 isomer	C₄₂H₆₂O₁₇	[M-H]^-	837.391 8	1.74	485.330 3, 351.056 9, 235.046 4, 193.034 3, 113.022 9	f	G
158^*	33.26	Glycyrrhetinic acid	C₃₀H₄₆O₄	[M+H]⁺	471.346 4	-0.95	453.335 7, 317.210 8, 135.116 7	f	G
159	33.28	Glabrolide	C₃₀H₄₄O₄	[M+H]⁺	469.330 6	-1.29	451.319 3, 405.315 1, 243.137 3, 175.147 9	d	G
160	33.39	(11E,15Z)-9,10,13-Trihydroxy-11,15-octadecadienoic acid	C₁₈H₃₂O₅	[M-H]^-	327.218 0	4.15	309.207 6, 211.133 3, 171.101 6, 85.027 9	c	S/D
161^△#	33.48	Licorice saponin J2 isomer	C₄₂H₆₄O₁₆	[M-H]^-	823.411 2	0.16	759.278 1, 351.056 9, 193.034 7, 113.022 9	f	G
162^#*	33.68	Naringenin	C₁₅H₁₂O₅	[M-H]^-	271.061 5	5.02	225.222 1, 177.018 1, 151.00 24, 119.048 6	a	G
163^△	33.77	Hedione	C₁₃H₂₂O₃	[M-H]^-	225.149 6	3.24	207.138 5, 181.159 0, 167.106 8, 125.095 7	c	S/D/G
164^#*	34.25	Licorice saponin G2 isomer	C₄₂H₆₂O₁₇	[M-H]^-	837.392 5	1.09	351.057 1, 193.034 6, 175.024 1, 113.022 9	f	G
165^#*	34.81	Licorice saponin G2 isomer	C₄₂H₆₂O₁₇	[M-H]^-	837.391 5	1.45	351.056 6, 193.034 3, 175.023 1, 113.022 9	f	G
166^#*	34.9	Glycyrrhizic acid	C₄₂H₆₂O₁₆	[M-H]^-	821.397 6	2.71	645.365 8, 351.057 1, 193.034 6, 174.023 8, 113.022 9	f	G
167^*	34.95	Oleaside E	C₄₂H₆₄O₁₇	[M-H]^-	839.409 2	3.2	351.057 3, 193.034 6, 175.024 0, 113.023 0	f	G
168^#	35.12	Licorice saponin H2	C₄₂H₆₂O₁₆	[M-H]^-	821.397 5	2.52	351.057 1, 193.034 6, 175.023 7, 113.022 9	f	G
169^#*	35.16	Isoliquiritigenin	C₁₅H₁₂O₄	[M-H]^-	255.065 0	3.56	219.845 2, 153.018 1, 135.007 4, 119.004 9, 91.017 3	a	G
170^△#	35.47	Licorice saponin B2 isomer	C₄₂H₆₄O₁₅	[M-H]^-	807.416 1	3.16	351.057 1, 193.034 4, 175.023 7, 113.022 9	f	G
171^#*	35.48	Formononetin	C₁₆H₁₂O₄	[M+H]⁺	269.080 3	-1.8	254.057 3, 237.054 7, 213.090 7, 154.026 0	a	G
172^△#	35.96	Licorice saponin K2	C₄₂H₆₂O₁₆	[M-H]^-	821.397 6	2.23	643.293 9, 351.057 1, 193.034 7, 175.023 9, 113.023 0	f	G
173^△#*	36.33	Kushenol L	C₂₅H₂₈O₇	[M-H]^-	439.177 1	1.93	151.005 2, 125.023 0, 92.089 7	a	S
174^△#	36.44	Kuwanon G	C₂₅H₂₆O₇	[M-H]^-	437.161 4	4.42	401.187 3, 174.185 5, 152.994 9, 125.022 9	a	S
175^△#	36.46	Licorice saponin C2	C₄₂H₆₂O₁₅	[M-H]^-	805.401 2	0.75	573.278 4, 351.057 1, 295.579 1, 193.034 7, 113.022 9	f	G
176^△#	36.6	Licorice saponin B2 isomer	C₄₂H₆₄O₁₅	[M-H]^-	807.415 9	-0.25	351.057 2, 193.034 0, 175.023 9, 113.023 1	f	G
177^#*	36.86	Glycycoumarin	C₂₁H₂₀O₆	[M-H]^-	367.118 5	0.89	297.040 3, 139.038 8	a	G
178^#	36.93	Ononin	C₂₂H₂₂O₉	[M-H]^-	429.113 0	-3.2	361.163 4, 293.176 5, 236.105 2, 221.154 1	a	G
179	36.97	3,5-Di-tert-butylcatechol	C₁₄H₂₂O₂	[M-H]^-	221.154 7	2.28	205.071 6, 177.039 4, 135.969 8, 91.952 1	c	S/D/G
180	37.06	(±)9-HpODE	C₁₈H₃₂O₄	[M-H]^-	311.222 8	4.	293.176 2, 267.196 8, 223.170 0, 99.007 2	c	S/D/G
181	37.85	Morusin P	C₁₉H₁₈O₅	[M-H]^-	325.104 3	-2.74	249.131 9, 235.248 0, 193.506 0	e	S
182^△#	38.25	Cyclomorusin	C₂₅H₂₄O₆	[M+H]⁺	421.164 2	-0.67	365.101 7, 347.090 8, 311.054 7, 137.291 7	a	S
183	38.63	Glycycoumarin isomer	C₂₁H₂₀O₆	[M-H]^-	367.118 4	2.41	313.071 0, 263.538 2, 139.038 8, 111.810 5	d	G
184	39.15	Oleic acid	C₁₈H₃₄O₂	[M-H]^-	281.248 6	4.74	192.471 9, 152.055 1, 134.683 8, 95.195 3	c	S/D/G
185	39.25	Stearic acid	C₁₈H₃₆O₂	[M-H]^-	283.264 3	4.85	167.095 3, 139.668 7, 66.418 6	c	S/D/G

No.

t_R/min

Identification

Formula

Ion mode

Observed
(m/z)

Error
(×10^-6)

Fragment

Structure class

Origin

1.12

Histamine

C₅H₉N₃

[M+H]⁺

112.087 3

3.09

95.060 8, 83.060 9, 68.049 2

1.12

1-Deoxynojirimycin

C₆H₁₃NO₄

[M+H]⁺

164.091 8

0.46

146.081 0, 128.070 2, 68.049 1

1.15

Arginine

C₆H₁₄N₄O₂

[M-H]^-

173.104 4

-0.59

156.076 5, 131.081 1, 114.054 5

S/D/G

1.16

Valinol

C₅H₁₃NO

[M+H]⁺

104.107 2

2.2

87.084 5, 71.029 9, 60.081 6

S/G

5^△

1.24

Xylonic acid

C₅H₁₀O₆

[M-H]^-

165.039 1

-1.54

147.028 5, 129.017 9, 87.007 1, 75.007 0

S/D/G

1.26

Sugar acid

C₆H₁₀O₈

[M-H]^-

209.030 3

1.9

191.018 8, 133.012 8, 129.017 9, 85.027 8

S/D/G

1.27

Quinic acid

C₇H₁₂O₆

[M-H]^-

191.056 1

0.92

173.044 3, 127.038 6, 111.007 2, 85.027 8

S/D

1.34

Betaine

C₅H₁₁NO₂

[M+H]⁺

118.086 4

0.97

94.365 8, 72.081 5, 59.073 7, 58.065 8

S/D/G

1.86

Malic acid

C₄H₆O₅

[M-H]^-

133.013 1

-0.52

115.002 1, 89.022 8, 73.002 2

S/D/G

10^*

1.98

Adenine

C₅H₅N₅

[M+H]⁺

136.061 6

-1.61

119.035 3, 109.064 9, 100.274 0

S/D/G

1.99

Guanine

C₅H₅N₅O

[M+H]⁺

152.056 5

-1.42

135.033 0, 134.033 3, 110.035 0

S/D/G

1.99

Malic acid isomer

C₄H₆O₅

[M-H]^-

133.012 6

-3.53

115.002 1, 89.022 8, 72.991 4

S/D/G

13^△

1.99

Dehydroascorbic acid

C₆H₆O₆

[M-H]^-

173.009 2

-1.88

111.007 2, 85.028 7, 67.017 2

S/D/G

14^△

2.01

2-Acetamidoacrylic acid

C₅H₇NO₃

[M+H]⁺

130.049 5

2.45

112.087 1, 84.044 8, 70.065 7

S/D/G

2.02

Citric acid

C₆H₈O₇

[M-H]^-

191.018 9

1.21

173.088 1, 129.017 9, 111.007 2, 87.007 1

S/D/G

2.03

Stachydrine

C₇H₁₃NO₂

[M+H]⁺

144.101 9

-0.38

126.091 4, 98.096 8, 84.061 2, 70.062 5

2.07

Uridine

C₉H₁₂N₂O₆

[M-H]^-

243.062 3

3.24

200.055 8, 152.034 0, 110.023 2, 82.028 3

S/D/G

2.17

Suberic acid

C₈H₁₄O₄

[M-H]^-

173.081 9

0.46

129.017 9, 111.007 2, 85.027 8, 72.991 5

S/D

2.17

N-Acetyl-L-glutamic acid

C₇H₁₁NO₅

[M-H]^-

188.056 4

1.36

170.044 8, 144.065 3, 128.033 9, 102.054 5

S/D

2.27

Adenosine

C₁₀H₁₃N₅O₄

[M+H]⁺

268.104 0

-1.46

206.107 8, 152.648 5, 136.061 7

S/D/G

2.41

δ-Ribosyl-1,4-lactone

C₅H₈O₅

[M-H]^-

147.028 6

-1.5

129.018 0, 102.947 2, 87.007 1, 59.012 2

S/D/G

2.49

4-Hydroxyphenethylamine

C₈H₁₁NO

[M+H]⁺

138.091 3

-0.66

121.064 9, 111.007 9, 93.070 3

2.49

Isoleucine

C₆H₁₃NO₂

[M+H]⁺

132.101 9

-0.04

113.963 8, 86.096 9, 69.070 5

D/G

2.55

Guanosine

C₁₀H₁₃N₅O₅

[M-H]^-

282.084 4

4.59

178.900 8, 152.040 8, 126.029 4

S/D/G

2.56

Trigonelline

C₇H₇NO₂

[M+H]⁺

138.055 4

3.37

110.060 2, 94.056 3, 68.997 8

S/G

4.12

Cytisine

C₁₁H₁₄N₂O

[M+H]⁺

191.117 8

-0.57

162.090 8, 122.060 0, 105.963 0

5.08

Protocatechuic acid 4-O-β-glucoside

C₁₃H₁₆O₉

[M-H]^-

315.072 5

4.79

152.010 1, 125.256 2, 109.027 9

S/D/G

28^*

6.15

Vanillic acid 4-β-D-glucoside

C₁₄H₁₈O₉

[M-H]^-

329.088 0

1.27

167.033 8, 152.010 3, 123.043 7

S/D/G

6.98

Catechol

C₆H₆O₂

[M-H]^-

109.028 0

-3.62

108.020 4, 79.029 0, 67.029 1

S/D/G

7.02

Protocatechuic acid

C₇H₆O₄

[M-H]^-

153.019 3

-1.08

135.044 1, 109.028 0, 91.017 3

S/D/G

31^△

7.29

Daphneside

C₂₁H₂₆O₁₄

[M-H]^-

501.125 5

3.33

381.082 7, 219.029 3, 191.034 1

S/G

32^*

7.64

Caffeoylputrescine

C₁₃H₁₈N₂O₃

[M+H]⁺

251.139 0

-0.56

234.111 7, 163.038 6, 145.028 1, 89.107 7

7.95

Syringic acid glucoside

C₁₅H₂₀O₁₀

[M-H]^-

359.099 0

4.73

197.044 8, 182.022 1, 138.030 9

34^△*

8.57

Mulberroside A+Glc

C₃₃H₄₄O₂₁

[M-H]^-

775.231 3

2.13

729.225 3, 567.172 0, 405.119 1, 243.009 0

35^*

8.59

Oxyresveratrol-6-O-D-glucopyranosyl-D-glucopyranoside isomer

C₃₂H₄₂O₁₉

[M-H]^-

729.225 9

3.07

567.172 6, 405.112 5, 243.066 1, 225.055 2

36^*

8.78

Neochlorogenic acid

C₁₆H₁₈O₉

[M-H]^-

353.088 1

1.18

191.055 3, 179.034 0, 135.043 8

8.87

Indole-3-acrylic acid

C₁₁H₉NO₂

[M+H]⁺

188.070 4

-1.3

170.059 7, 146.059 8, 118.065 2, 88.022 0

S/D/G

9.01

Tryptophan

C₁₁H₁₂N₂O₂

[M-H]^-

203.082 6

2.15

186.055 2, 159.091 6, 116.049 1

9.4

8-Hydroxyquinoline

C₉H₇NO

[M+H]⁺

146.059 9

-1.24

128.950 7, 118.065 3, 99.044 4

D/G

10.13

Salicylic acid

C₇H₆O₃

[M-H]^-

137.023 1

-1.9

119.012 6, 93.033 3, 65.038 0

S/D/G

10.54

2-Isopropylmalic acid

C₇H₁₂O₅

[M-H]^-

175.061 2

0.4

146.959 9, 115.038 6, 85.064 3

42^△*

10.85

Unknown

C₃₂H₅₀N₇O₁₀

[M+H]⁺

693.369 1

-0.16

657.343 4, 474.257 4, 293.185 8, 222.112 1

43^*

11.

Kukoamine A

C₂₈H₄₂N₄O₆

[M+H]⁺

531.317 1

-0.45

293.185 6, 222.112 1, 165.054 5, 123.043 9

11.13

Phenyllactic acid

C₉H₁₀O₃

[M-H]^-

165.054 6

-0.43

121.064 5, 93.033 0, 59.012 2

S/D/G

45^*

11.14

Kukoamine B

C₂₈H₄₂N₄O₆

[M+H]⁺

531.317 3

-0.57

293.185 5, 222.122 0, 165.054 5, 123.043 9

11.2

6-Methylquinoline

C₁₀H₉N

[M+H]⁺

144.080 6

-1.14

117.065 4, 98.331 1, 84.081 2

11.28

Esculin

C₁₅H₁₆O₉

[M-H]^-

339.071 8

2.22

249.040 5, 219.029 3, 191.034 2

48^*

11.98

Caffeoylagmatine

C₁₄H₂₀N₄O₃

[M+H]⁺

293.160 4

-0.45

276.134 7, 163.038 7, 131.092 5, 114.102 7

49^*

12.62

Feruloylputrescine

C₁₄H₂₀N₂O₃

[M+H]⁺

265.154 3

-0.34

177.054 4, 163.039 5, 145.028 3, 89.107 8

12.94

7-Hydroxycoumarin

C₉H₆O₃

[M+H]⁺

163.038 7

-0.24

145.028 3, 135.044 1, 119.033 9, 104.049 4

S/G

12.98

Dihydrocaffeic acid

C₉H₁₀O₄

[M-H]^-

181.050 6

0.63

163.038 9, 137.059 4, 121.027 9, 109.028 0, 93.069 3

52^*

13.15

N¹-Caffeoyl-N¹⁰-dihydro caffeoylspermine

C₂₈H₄₀N₄O₆

[M+H]⁺

529.301 9

-0.34

511.471 6, 367.271 4, 293.186 5, 220.096 5, 163.038 7

53^*

13.21

Chlorogenic acid

C₁₆H₁₈O₉

[M-H]^-

353.087 8

3.34

191.055 2, 179.034 0, 161.023 2

54^*

13.31

N¹-Caffeoyl-N¹⁴-dihydro caffeoylspermine

C₂₈H₄₀N₄O₆

[M+H]⁺

529.301 9

-0.18

511.472 2, 458.227 0, 367.270 0, 293.184 7, 220.096 5, 163.038 7

55^△

13.36

Sinapic acid glucuronide

C₁₇H₂₀O₁₁

[M-H]^-

399.093 0

2.16

221.702 8, 192.037 4

S/G

56^△*

13.45

Multiflorin A

C₂₉H₃₂O₁₆

[M-H]^-

635.156 6

-4.04

567.171 9, 405.120 3, 243.066 0, 225.056 1

57^*

13.48

N⁵-3-Acetyldihydrocaffeoyl-N¹⁰-dihydrocaffeoylspermine

C₂₈H₄₀N₄O₆

[M+H]⁺

529.301 9

-0.12

291.170 1, 220.096 7, 163.038 8, 147.069 4

58^△*

13.55

Mulberroside A +2H₂O

C₂₆H₃₆O₁₆

[M-H]^-

603.146 4

1.23

567.172 3, 405.119 3, 243.066 1

59^△*

13.57

Leiocarposide

C₂₇H₃₄O₁₆

[M-H]^-

613.176 7

0.39

567.172 2, 405.119 4, 243.066 1, 225.055 4

60^*

13.61

Mulberroside A

C₂₆H₃₂O₁₄

[M-H]^-

567.172 4

2.69

405.119 3, 243.006 1, 225.055 3, 199.075 7

61^*

13.63

Glucosyl-3-O-β-D-apiosyl-(1→6)-O-β-D-glucoside

C₃₁H₄₀O₁₈

[M-H]^-

699.216 1

3.1

537.159 9, 405.119 2, 243.066 1, 225.055 4

62^△*

13.67

Mulberroside A dimer

C₅₂H₆₄O₂₈

[M-H]^-

1 135.343 7

-4.58

567.172 1, 405.119 1, 243.066 0, 225.055 1

63^△*

14.1

L-Leucyl-L-tyrosine

C₁₅H₂₂N₂O₄

[M+H]⁺

295.164 8

-0.4

207.065 0, 175.038 8, 147.039 9, 119.049 3

64^△

14.29

Capsaicin

C₁₃H₂₇N₈O₃

[M+H]⁺

344.228 3

1.11

327.200 9, 283.174 7, 177.112 0, 133.086 0, 89.068 2

65^*

14.49

Cryptochlorogenic acid

C₁₆H₁₈O₉

[M-H]^-

353.087 9

3.34

191.055 3, 179.034 0, 161.023 4, 135.043 8

14.61

4-Hydroxybenzaldehyde

C₇H₆O₂

[M-H]^-

121.028 0

-3.11

108.020 1, 93.020 9, 69.985 5

S/G

14.71

N¹-Dihydrocaffeoyl-N⁵ dihydroferuoylspermine

C₂₉H₄₄N₄O₆

[M+H]⁺

545.330 0

-0.35

307.200 9, 293.185 2, 236.127 8, 222.112 2, 179.070 7, 137.059 7

14.79

Scopoletin

C₁₀H₈O₄

[M+H]⁺

193.049 4

-0.75

178.027 5, 165.054 4, 149.059 3, 133.028 4, 127.298 6

14.95

α-Rhamnosyl-(1→6)-O-β-D-glucoside

C₂₁H₂₆O₁₃

[M-H]^-

485.130 1

1.31

363.248 8, 293.088 3, 191.034 2, 176.010 4

70^*

15.02

Oxyresveratrol-6-O-D-glucopyranosyl-D-glucopyranoside

C₃₂H₄₂O₁₉

[M-H]^-

729.227 2

4.9

567.171 8, 243.066 1, 225.055 1

71^△*

15.13

Hydroxyprolyl-tryptophan

C₁₆H₁₉N₃O₄

[M+H]⁺

318.144 4

-1.42

207.065 1, 175.038 7, 147.043 4

72^#

15.37

Quercetin-3-O-sophoroside

C₂₇H₃₀O₁₇

[M-H]^-

625.141 2

1.99

463.088 4, 299.020 1, 151.002 4, 125.002 9

73^*

16.92

N¹,N¹⁰-Bis(dihydrocaffeoyl)spermidine

C₂₅H₃₅N₃O₆

[M+H]⁺

474.259 7

-0.16

293.185 9, 222.112 2, 165.054 5, 123.044 1

74^#

17.67

Glucoliquiritin apioside

C₃₂H₄₀O₁₈

[M-H]^-

711.214 7

2.21

711.216 5, 549.160 5, 255.065 8, 153.018 5, 135.008 6, 119.048 7

17.8

3-p-Coumaroylquinic acid

C₁₆H₁₈O₈

[M-H]^-

337.092 4

1.74

191.055 2, 163.038 7, 119.048 8, 93.033 0

76^△#*

17.88

Hydroxysafflor yellow A

C₂₇H₃₂O₁₆

[M-H]^-

611.162 0

2.17

565.156 3, 403.103 4, 241.050 3, 197.060 2

77^#*

17.93

Glabranin

C₂₀H₂₀O₄

[M-H]^-

323.125 4

-2.36

257.678 3, 203.081 4, 189.066 0, 175.086 9

18.46

Riboflavin

C₁₇H₂₀N₄O₆

[M+H]⁺

377.145 1

-1.2

359.134 3, 243.087 4, 172.086 8

18.93

N⁵-Dihydrocaffeoyl-N¹⁰ caffeoylspermidine

C₂₅H₃₃N₃O₆

[M+H]⁺

472.243 8

-0.41

455.214 8, 310.212 0, 293.185 4, 236.127 6, 220.096 5, 163.038 7

80^△*

19.02

Unknown

C₂₇H₄₀N₇O₆

[M+H]⁺

559.311 5

0.42

321.179 8, 293.185 5, 222.122 0, 165.054 6, 123.044 2

19.18

Magnoflorine

C₂₀H₂₃NO₄

[M+H]⁺

342.168 8

-3.58

297.110 6, 265.084 5, 237.090 6, 183.521 0, 177.054 2, 115.076 2

19.34

Esculetin

C₉H₆O₄

[M-H]^-

177.018 2

-0.01

149.023 3, 133.028 1, 105.032 9, 89.038 1

S/G

19.83

Vicenin-2

C₂₇H₃₀O₁₅

[M-H]^-

593.151 1

1.73

473.104 7, 383.075 9, 353.066 7, 325.073 0, 297.076 6

84^△*

19.93

Unknown

C₂₆H₁₈O₇

[M-H]^-

441.094 3

-5.78

405.119 3, 243.066 1, 225.056 2, 199.076 3, 175.074 9

85^△*

19.97

Catechin-7-O-β-D-glucopyranoside

C₂₁H₂₄O₁₁

[M-H]^-

451.124 8

1.3

405.119 3, 243.066 1, 225.055 2, 199.075 8, 175.075 5, 157.064 7

86^△*

19.98

6"-O-Acetylgenistin

C₂₃H₂₂O₁₁

[M-H]^-

473.106 1

-1.7

405.119 3, 243.066 2, 225.055 6, 175.075 3

87^*

20.01

2,3,5,4′-Tetrahydroxy stilbene-2-Ο-β-D-glucoside isomer

C₂₀H₂₂O₉

[M-H]^-

405.119 1

2.79

243.066 1, 225.055 2, 199.075 7, 175.075 3, 157.064 5

S/G

88^△*

20.22

Acremonidin D

C₃₃H₂₈O₁₄

[M-H]^-

647.139 4

-0.2

449.109 3, 287.057 6, 161.023 4, 125.023 0

89^*

20.24

N¹-3-Acetyldihydrocaffeoyl-N¹⁰-dihydrocaffeoyl spermine

C₃₀H₄₄N₄O₇

[M+H]⁺

573.327 7

-1.01

475.269 6, 335.196 6, 293.184 1, 222.112 2, 208.681 9, 165.054 3

90^△*

20.44

Unknown

C₂₈H₃₄O₁₈

[M-H]^-

657.167 8

1.65

611.162 0, 449.109 1, 287.056 2, 125.023 0

20.77

N-Acetyl-L-phenylalanine

C₁₁H₁₃NO₃

[M-H]^-

206.082 3

2.23

192.005 5, 164.070 5, 147.043 8, 118.991 6, 91.053 7

92^△#

21.05

Diosmetin-7-O-glucoside

C₂₂H₂₂O₁₁

[M-H]^-

461.329 1

0.92

415.161 4, 299.057 2, 191.055 3, 149.099 3, 131.033 7, 89.022 8

93^△*

21.28

Unknown

C₂₈H₃₄O₁₈

[M-H]^-

657.168 2

2.11

611.162 8, 449.109 2, 287.056 2, 161.023 3, 125.023 1

94^△#*

21.45

Unknown

C₃₂H₄₀O₂₀

[M-H]^-

743.202 6

-0.38

700.649 8, 449.111 5, 405.341 5, 287.056 7, 161.023 2, 125.022 9

95^△*

21.48

Plantagoside

C₂₁H₂₂O₁₂

[M-H]^-

465.103 7

0.92

303.105 8, 151.002 8, 125.023 0

96^*

21.73

2,3,5,4′-Tetrahydroxy stilbene-2-Ο-β-D-glucoside

C₂₀H₂₂O₉

[M-H]^-

405.119 1

2.79

243.066 1, 225.055 2, 199.075 8, 175.075 4, 159.044 0

S/G

97^△#

21.94

Unknown

C₂₁H₂₉O₁₄

[M-H]^-

504.147 3

3.89

412.140 9, 301.831 4, 192.067 1, 165.054 8

98^#

22.18

Daidzin

C₂₁H₂₀O₉

[M+H]⁺

417.117 8

-0.5

255.064 8, 237.054 6, 199.074 3, 149.717 5

99^△*

22.96

N-Acetyl-1-O-benzyl-α-muramyl-α-aminoisobutyryl-D-isoglutamine benzyl ester

C₃₄H₄₆N₄O₁₁

[M+H]⁺

687.322 5

0.3

449.191 0, 293.185 9, 222.121 6, 165.054 1

100^*

22.98

Hyperoside

C₂₁H₂₀O₁₂

[M-H]^-

463.088 5

3.08

301.033 5, 273.040 3, 255.030 0, 151.002 4, 125.002 9

101^#

23.44

Schaftoside

C₂₆H₂₈O₁₄

[M-H]^-

563.140 8

2.38

473.106 1, 443.098 0, 383.077 7, 353.066 4, 325.071 8, 297.076 7

102

23.5

Isoscopoletin

C₁₀H₈O₄

[M+H]⁺

193.049 4

-0.15

178.025 0, 165.054 7, 149.056 9, 137.059 7, 133.024 8

103

24.21

Ferulic acid

C₁₀H₁₀O₄

[M-H]^-

193.050 0

2.51

178.026 1, 149.059 5, 134.036 0

S/D/G

104^#

25.35

Tetrahydroxychalcone 4′-O-glucoside

C₂₁H₂₂O₁₀

[M-H]^-

433.113 6

-1.

271.061 0, 151.003 6, 135.008 7, 119.050 2

105^*

25.75

Isoliquiritin

C₂₁H₂₂O₉

[M-H]^-

417.118 5

-1.45

255.065 5, 148.016 4, 135.008 6, 119.050 1

106^△#*

25.85

Unknown

C₂₀H₂₂O₁₂

[M-H]^-

453.095 4

-7.35

417.119 3, 255.066 7, 153.018 1, 135.007 6, 119.048 6

107

26.08

Dihydro-N-caffeoyltyramine

C₁₇H₁₉NO₄

[M+H]⁺

302.138 4

-0.29

165.054 3, 143.572 4, 138.091 3, 121.064 9

108^*

26.17

Isoliquiritin apioside

C₂₆H₃₀O₁₃

[M-H]^-

549.160 3

-1.95

429.104 2, 297.077 5, 255.065 7, 135.008 5, 119.050 0

109^△#*

26.17

Eriocitrin isomer

C₂₇H₃₂O₁₅

[M-H]^-

595.167 2

1.49

255.066 1, 135.007 6, 119.049 0

110^△*

26.2

Unknown

C₂₅H₃₀O₁₆

[M-H]^-

585.135 9

-6.16

429.102 8, 255.066 3, 135.007 5

111^*

26.38

N¹,N⁵-Bis(dihydroferuloyl)spermidine

C₂₇H₃₉N₃O₆

[M+H]⁺

502.291 2

0.04

388.415 9, 250.142 4, 236.127 8, 179.070 5, 137.059 7

112^#*

26.47

Liquiritin

C₂₁H₂₂O₉

[M-H]^-

417.119 3

3.28

255.066 2, 163.018 0, 148.015 0, 135.007 4, 119.048 7

113^△#

26.54

Tetrahydroxychalcone 4′-O-glucoside isomer

C₂₁H₂₂O₁₀

[M-H]^-

433.113 9

2.3

271.061 3, 151.002 4, 135.008 7, 119.050 3

114^#*

26.68

Naringenin-7-O-glucoside

C₂₁H₂₂O₁₀

[M-H]^-

433.114 2

3.02

271.061 5, 151.002 4, 119.048 7

115^*

26.74

N¹,N⁵,N¹⁰-tris(di hydrocaffeoyl) spermine

C₃₇H₅₀N₄O₉

[M+H]⁺

695.363 3

-2.5

678.344 1, 457.234 3, 293.185 9, 222.112 3

116^△*

26.75

Liquiritin apioside

C₂₆H₃₀O₁₃

[M-H]^-

549.161 3

2.02

417.119 3, 255.066 1, 153.018 0, 135.007 3, 119.048 6, 91.017 3

117^△*

26.79

Unknown

C₂₅H₃₀O₁₆

[M-H]^-

585.138 9

-0.49

549.161 8, 429.102 8, 255.066 3, 153.017 7, 135.007 5

118^#

27.19

Dihydromorin

C₁₅H₁₂O₇

[M-H]^-

303.052 2

7.66

275.056 3, 177.018 2, 125.023 0

119^#*

27.76

Eriodictyol-7-O-glucoside

C₂₁H₂₂O₁₁

[M-H]^-

449.109 9

4.57

287.056 7, 269.136 8, 197.059 8, 125.022 9

120^#

27.89

6′′-O-Acetylliquiritin isomer

C₂₃H₂₄O₁₀

[M-H]^-

459.130 0

3.04

339.087 5, 255.044 6, 153.010 3

121^△*

27.97

Unknown

C₃₄H₄₆N₄O₈

[M+H]⁺

639.338 6

-0.35

621.330 1, 293.185 9, 222.112 2

122

28.79

Oxyresveratrol

C₁₄H₁₂O₄

[M-H]^-

243.066 1

3.76

225.055 1, 199.075 8, 175.075 3

123^#

28.91

6′′-O-Acetylliquiritin isomer

C₂₃H₂₄O₁₀

[M-H]^-

459.129 3

1.16

339.087 4, 263.056 7, 255.045 2, 153.010 0

124^#

29.13

Naringenin chalcone

C₁₅H₁₂O₅

[M-H]^-

271.061 4

4.91

151.002 3, 140.975 4, 119.048 9

125

29.14

Mulberroside F

C₂₆H₃₀O₁₄

[M-H]^-

565.156 2

1.78

433.112 0, 335.243 8, 271.061 4, 227.071 2, 151.002 4, 119.048 7

126^*

29.21

trans-N-Caffeoyltyramine

C₁₇H₁₇NO₄

[M+H]⁺

300.122 8

-0.78

163.038 7, 121.064 9, 89.060 1

127

29.23

Azelaic acid

C₉H₁₆O₄

[M-H]^-

187.096 5

-0.03

169.085 7, 143.106 5, 125.095 7

S/D/G

128^△#

29.25

Tetrahydroxychalcone 4′-O-glucoside isomer

C₂₁H₂₂O₁₀

[M-H]^-

433.113 1

0.41

271.061 4, 151.002 4, 135.008 7, 119.050 4

129^*

29.77

Lyciumin A

C₄₂H₅₁N₉O₁₂

[M+H]⁺

874.372 6

-0.5

856.363 7, 486.198 1, 468.187 6, 136.075 7

130^#

29.78

Eriodictyol

C₁₅H₁₂O₆

[M-H]^-

287.056 1

3.85

259.061 4, 243.067 2, 151.002 3, 125.022 9

131^△

29.9

4-Oxododecanedioic acid

C₁₂H₂₀O₅

[M-H]^-

243.123 8

2.88

225.112 8, 207.102 2, 181.122 5, 146.959 9

S/D/G

132

30.04

7-O-β-D-Apiosyl-3-O-p-coumaroylkaempferol

C₂₇H₃₀O₁₃

[M-H]^-

561.161 6

2.41

309.076 8, 267.066 4, 252.042 8

133^△*

30.17

Eriodictyol isomer

C₂₇H₃₂O₁₅

[M-H]^-

595.167 6

1.85

351.069 3, 255.066 2, 135.007 4, 119.048 8, 91.017 2

134^△#

30.47

Isoformononetin

C₁₆H₁₂O₄

[M-H]^-

269.080 4

-1.69

254.055 9, 237.054 2, 213.091 2, 119.041 4

135^*

30.9

Neoisoliquiritin

C₂₁H₂₂O₉

[M-H]^-

417.111 9

-4.7

255.066 2, 153.019 1, 148.015 4, 135.007 1, 119.048 7

136^#

30.92

Liquiritin B

C₃₅H₃₆O₁₅

[M-H]^-

695.198 8

2.51

531.152 5, 255.066 3, 119.048 8, 72.991 5

137

30.94

N-p-trans-Coumaroyltyramine

C₁₇H₁₇NO₃

[M+H]⁺

284.128 1

0.07

239.149 7, 147.043 9, 121.064 8, 119.049 2

138^#

31.08

Liquiritin A

C₃₆H₃₈O₁₆

[M-H]^-

725.210 0

3.24

531.152 7, 255.066 0, 193.049 5, 135.007 5

139^#

31.25

Morin

C₁₅H₁₀O₇

[M-H]^-

301.035 6

4.42

273.042 0, 229.050 2, 151.002 4, 125.023 0

140^*

31.34

Feruloyltyramine

C₁₈H₁₉NO₄

[M+H]⁺

314.138 5

-0.52

292.079 3, 177.054 4, 145.028 3, 117.033 6

141^△*

31.41

Baicalin

C₂₁H₁₈O₁₁

[M-H]^-

445.077 0

3.46

269.045 8, 235.303 8, 175.023 9, 113.022 9

142

31.43

Lyciumin B

C₄₄H₅₂N₁₀O₁₁

[M+H]⁺

897.388 7

-0.34

689.307 3, 486.198 0, 468.187 5, 159.091 5

143^*

31.62

N-Feruloyl-3-methoxy tyramine

C₁₉H₂₁NO₅

[M+H]⁺

344.148 7

-1.74

177.054 4, 145.028 4, 117.033 6

144^△#

31.62

Licorice saponin J2 isomer

C₄₂H₆₄O₁₆

[M-H]^-

823.413 2

2.61

671.079 0, 351.057 4, 193.034 9, 113.002 9

145^#

31.65

4′,7-Dihydroxyflavanone

C₁₅H₁₂O₄

[M-H]^-

255.062 5

-7.28

219.845 1, 153.018 1, 135.007 2, 119.004 2

146^△#

31.71

24-Hydroxy-licorice saponin A3

C₄₈H₇₂O₂₂

[M-H]^-

999.445 6

2.41

837.388 9, 377.540 1, 351.056 2, 193.034 4, 113.022 9

147^#

31.8

Liquiritigenin

C₁₅H₁₂O₄

[M-H]^-

255.065 0

4.57

219.844 9, 153.018 1, 135.007 2, 119.004 8

148^△*

31.85

Chrysin-7-O-β-D-glucuronide

C₂₁H₁₈O₁₀

[M-H]^-

429.082 1

4.5

253.050 6, 175.023 9, 113.022 9

149

31.86

Sebacic acid

C₁₀H₁₈O₄

[M-H]^-

201.113 2

1.76

183.101 7, 139.111 5, 111.080 1

S/D

150^△*

31.91

Diosmetin-7-glucuronide

C₂₂H₂₀O₁₂

[M-H]^-

475.087 6

2.49

299.056 5, 284.032 9, 217.056 7, 113.022 6

151

31.99

7-Hydroxy-1-(3,4-dihydroxyphenyl)-N²,N³-bis(4-hydroxyphenethyl)-6,8-dimethoxy-1,2-dihydronaphthalene-2,3-dicarboxamide

C₃₆H₃₆N₂O₉

[M+H]⁺

641.245 3

-6.33

504.163 9, 476.167 8, 339.086 8

152

32.07

Lyciumin C

C₄₉H₅₇N₉O₁₂

[M+H]⁺

964.419 9

-0.09

593.273 4, 576.246 5, 389.181 5, 257.128 1, 188.070 4

153^△*

32.1

3,7-Bis(2-hydroxyethyl) icaritin

C₂₅H₂₈O₈

[M-H]^-

455.170 9

0.83

371.217 2, 213.221 2, 153.349 6, 125.022 9

154^△#

32.4

22-Hydroxy-licorice saponin G2

C₄₂H₆₂O₁₈

[M-H]^-

853.387 2

2.3

351.056 6, 193.034 6, 175.024 5, 113.022 8

155^*

32.53

Licorice saponin A3

C₄₈H₇₂O₂₁

[M-H]^-

983.450 5

2.3

821.398 5, 645.365 0, 469.335 2, 351.056 9, 193.034 5, 113.022 9

156^△*

32.94

Rhaglycyrrhizin

C₄₈H₇₂O₂₀

[M-H]^-

969.461 1

-0.15

601.403 5, 351.056 9, 193.034 9, 113.022 9

157^#*

33.25

Licorice saponin G2 isomer

C₄₂H₆₂O₁₇

[M-H]^-

837.391 8

1.74

485.330 3, 351.056 9, 235.046 4, 193.034 3, 113.022 9

158^*

33.26

Glycyrrhetinic acid

C₃₀H₄₆O₄

[M+H]⁺

471.346 4

-0.95

453.335 7, 317.210 8, 135.116 7

159

33.28

Glabrolide

C₃₀H₄₄O₄

[M+H]⁺

469.330 6

-1.29

451.319 3, 405.315 1, 243.137 3, 175.147 9

160

33.39

(11E,15Z)-9,10,13-Trihydroxy-11,15-octadecadienoic acid

C₁₈H₃₂O₅

[M-H]^-

327.218 0

4.15

309.207 6, 211.133 3, 171.101 6, 85.027 9

S/D

161^△#

33.48

Licorice saponin J2 isomer

C₄₂H₆₄O₁₆

[M-H]^-

823.411 2

0.16

759.278 1, 351.056 9, 193.034 7, 113.022 9

162^#*

33.68

Naringenin

C₁₅H₁₂O₅

[M-H]^-

271.061 5

5.02

225.222 1, 177.018 1, 151.00 24, 119.048 6

163^△

33.77

Hedione

C₁₃H₂₂O₃

[M-H]^-

225.149 6

3.24

207.138 5, 181.159 0, 167.106 8, 125.095 7

S/D/G

164^#*

34.25

Licorice saponin G2 isomer

C₄₂H₆₂O₁₇

[M-H]^-

837.392 5

1.09

351.057 1, 193.034 6, 175.024 1, 113.022 9

165^#*

34.81

Licorice saponin G2 isomer

C₄₂H₆₂O₁₇

[M-H]^-

837.391 5

1.45

351.056 6, 193.034 3, 175.023 1, 113.022 9

166^#*

34.9

Glycyrrhizic acid

C₄₂H₆₂O₁₆

[M-H]^-

821.397 6

2.71

645.365 8, 351.057 1, 193.034 6, 174.023 8, 113.022 9

167^*

34.95

Oleaside E

C₄₂H₆₄O₁₇

[M-H]^-

839.409 2

3.2

351.057 3, 193.034 6, 175.024 0, 113.023 0

168^#

35.12

Licorice saponin H2

C₄₂H₆₂O₁₆

[M-H]^-

821.397 5

2.52

351.057 1, 193.034 6, 175.023 7, 113.022 9

169^#*

35.16

Isoliquiritigenin

C₁₅H₁₂O₄

[M-H]^-

255.065 0

3.56

219.845 2, 153.018 1, 135.007 4, 119.004 9, 91.017 3

170^△#

35.47

Licorice saponin B2 isomer

C₄₂H₆₄O₁₅

[M-H]^-

807.416 1

3.16

351.057 1, 193.034 4, 175.023 7, 113.022 9

171^#*

35.48

Formononetin

C₁₆H₁₂O₄

[M+H]⁺

269.080 3

-1.8

254.057 3, 237.054 7, 213.090 7, 154.026 0

172^△#

35.96

Licorice saponin K2

C₄₂H₆₂O₁₆

[M-H]^-

821.397 6

2.23

643.293 9, 351.057 1, 193.034 7, 175.023 9, 113.023 0

173^△#*

36.33

Kushenol L

C₂₅H₂₈O₇

[M-H]^-

439.177 1

1.93

151.005 2, 125.023 0, 92.089 7

174^△#

36.44

Kuwanon G

C₂₅H₂₆O₇

[M-H]^-

437.161 4

4.42

401.187 3, 174.185 5, 152.994 9, 125.022 9

175^△#

36.46

Licorice saponin C2

C₄₂H₆₂O₁₅

[M-H]^-

805.401 2

0.75

573.278 4, 351.057 1, 295.579 1, 193.034 7, 113.022 9

176^△#

36.6

Licorice saponin B2 isomer

C₄₂H₆₄O₁₅

[M-H]^-

807.415 9

-0.25

351.057 2, 193.034 0, 175.023 9, 113.023 1

177^#*

36.86

Glycycoumarin

C₂₁H₂₀O₆

[M-H]^-

367.118 5

0.89

297.040 3, 139.038 8

178^#

36.93

Ononin

C₂₂H₂₂O₉

[M-H]^-

429.113 0

-3.2

361.163 4, 293.176 5, 236.105 2, 221.154 1

179

36.97

3,5-Di-tert-butylcatechol

C₁₄H₂₂O₂

[M-H]^-

221.154 7

2.28

205.071 6, 177.039 4, 135.969 8, 91.952 1

S/D/G

180

37.06

(±)9-HpODE

C₁₈H₃₂O₄

[M-H]^-

311.222 8

293.176 2, 267.196 8, 223.170 0, 99.007 2

S/D/G

181

37.85

Morusin P

C₁₉H₁₈O₅

[M-H]^-

325.104 3

-2.74

249.131 9, 235.248 0, 193.506 0

182^△#

38.25

Cyclomorusin

C₂₅H₂₄O₆

[M+H]⁺

421.164 2

-0.67

365.101 7, 347.090 8, 311.054 7, 137.291 7

183

38.63

Glycycoumarin isomer

C₂₁H₂₀O₆

[M-H]^-

367.118 4

2.41

313.071 0, 263.538 2, 139.038 8, 111.810 5

184

39.15

Oleic acid

C₁₈H₃₄O₂

[M-H]^-

281.248 6

4.74

192.471 9, 152.055 1, 134.683 8, 95.195 3

S/D/G

185

39.25

Stearic acid

C₁₈H₃₆O₂

[M-H]^-

283.264 3

4.85

167.095 3, 139.668 7, 66.418 6

S/D/G