中国药学杂志

No.	t_R /min	Formula	Molecular ion	MS (m/z)	δ /×10^-6	MS/MS (m/z)	Identification	Source
1²⁾	1.44	C₅H₁₁NO₂	[M+H]⁺	118.086 4	1.2	102.054 1, 58.066 2	Betaine^[18]	F\D\B\L\Q\JL\JX\W
2²⁾	1.52	C₇H₇NO₂	[M+H]⁺	138.054 9	-0.4	94.066 5	Trigonelline^[19]	F\\JL\JX\W
3²⁾	1.53	C₁₂H₂₂O₁₁	[M-H]^-	341.109 8	2.5	179.060 2, 119.039 3, 89.028 3, 59.015 5	Sucrose^[20]	B\JL\JX
4²⁾	1.64	C₆H₁₁NO₂	[M+H]⁺	130.086 0	-2.0	84.085 1, 56.051 7	L-Pipecolic acid^[19]	-
5²⁾	2.43	C₆H₅NO₂	[M+H]⁺	124.039 2	-0.8	106.028 1, 80.050 3	Nicotinic acid^[21]	-
6²⁾	3.44	C₇H₁₁NO₅	[M+H]⁺	190.070 7	-1.6	130.048 8, 84.045 0	N-Acetylglutamate^[19]	-
7²⁾	5.98	C₆H₆O₃	[M+H]⁺	127.038 7	-2.1	109.027 7, 81.034 6	5-Hydroxymethylfurfural^[21]	-
8¹⁾	6.03	C₇H₆O₅	[M+H]⁺	171.028 5	-1.8	153.018 9, 125.022 7, 109.028 1, 107.012 8	Gallic acid^[21]	B\JL
9²⁾	6.28	C₁₀H₁₃N₅O₅	[M+H]⁺	284.099 5	2.0	152.055 8, 135.028 8, 110.033 6	Guanosine^[22]	-
10²⁾	8.80	C₁₁H₁₅NO₂	[M+H]⁺	194.117 4	-0.8	177.089 6, 145.063 8, 117.069 1	Heliamine	F\Q
11²⁾	10.12	C₁₁H₁₂O₇	[M-H]^-	255.052 0	3.8	179.035 8, 165.056 6, 72.993 6	Piscidic acid^[23]	L\JL
12²⁾	10.31	C₂₂H₂₇NO₈	[M+H]⁺	434.181 2	0.6	272.127 3, 255.100 5, 237.089 2, 107.049 1	Higenamine glucoside^[20]	Q
13³⁾	11.03	C₂₂H₂₅NO₈	[M+H]⁺	432.165 2	-0.2	270.110 9, 235.072 5, 107.049 0	Dehydrohigenamine glucoside	Q
14²⁾	11.05	C₂₆H₃₅NO₁₀	[M+H]⁺	522.233 5	0.2	285.112 2, 271.097 1, 254.094 0, 243.101 8	Cephatonine glucoside^[20]	Q
15¹⁾	12.40	C₁₆H₁₈O₉	[M-H]^-	353.088 1	0.8	191.056 3, 179.035 1, 173.045 4, 135.045 5	Chlorogenic acid^[21]	F\L\Q\W
16²⁾	12.55	C₂₅H₃₄NO₈⁺	[M]⁺	476.227 2	-1.5	314.174 9, 269.117 8, 107.049 2, 58.066 1	Magnocurarine4'-O-glucopyranoside/Isomer^[20]	F\Q
17²⁾	13.79	C₁₆H₁₇NO₃	[M+H]⁺	272.128 2	0.3	255.100 7, 161.058 6, 143.048 3, 107.049 1	Higenamine^[20]	F\L\Q
18²⁾	13.88	C₂₃H₂₉NO₈	[M+H]⁺	448.195 5	-2.4	314.142 9, 286.141 6, 269.115 0, 107.048 6	Coclaurine glucoside^[20]	Q
19²⁾	14.04	C₂₄H₃₁NO₉	[M+H]⁺	478.206 9	-0.5	316.152 9, 285.111 2, 192.101 6, 177.077 5	3'-Hydroxy-N-methyl coclaurine glucoside^[20]	Q
20³⁾	14.34	C₁₆H₁₅NO₃	[M+H]⁺	270.112 5	0.1	252.100 6, 235.067 3, 207.078 9, 107.048 4	Dehydrohigenamine	Q
21¹⁾	14.66	C₁₉H₂₃NO₄	[M+H]⁺	330.169 5	-1.5	239.070 4, 223.074 0, 207.045 1, 181.063 9	Sinomenine^[20]	Q
22²⁾	14.84	C₁₆H₁₈O₈	[M-H]^-	337.092 6	-0.9	191.054 0, 163.039 8, 119.050 2	3-O-Coumaroylquinic acid^[24]	F\L
23²⁾	15.38	C₁₇H₂₂O₁₂	[M-H]^-	417.104 4	1.3	285.061 4, 241.071 2, 152.011 8, 108.021 6	5-O-(β-Apiosyl-(1→2)-O-β-xylopyranosyl) gentisic acid^[25]	JL\W
24¹⁾	15.80	C₁₆H₁₈O₉	[M-H]^-	353.087 7	-0.3	191.056 7	Neochlorogenic acid^[21]	F\L\Q\W
25²⁾	16.00	C₁₈H₂₁NO₄	[M+H]⁺	316.154 6	0.8	285.113 8, 192.101 5, 175.075 4, 123.043 7	3'-Hydroxy-N-methylcoclaurine^[20]	F\Q
26¹⁾	16.40	C₈H₈O₄	[M-H]^-	167.035 4	2.5	152.011 3, 108.021 7	Vanillic acid^[26]	F\D\B\L\Q\W
27²⁾	16.47	C₂₅H₃₄NO₈⁺	[M]⁺	476.227 4	-1.0	314.173 8, 269.116 6, 107.049 4, 58.066 0	Magnocurarine-4'-O-glucopyranoside/Isomer^[20]	Q
28¹⁾	16.63	C₁₆H₁₈O₉	[M-H]^-	353.087 8	0.0	191.056 0, 179.034 6, 173.045 0, 135.045 1	Cryptochlorogenic acid^[24]	F\L\Q\W
29²⁾	16.95	C₂₆H₃₁NO₁₀	[M+H]⁺	518.201 6	-0.9	356.147 7, 338.137 2, 206.080 3, 188.070 1	2', 4',10'-Trimethoxy-5,8-dihydro-6H-isoquinolino [3,2-a]isoquinoline-3,11-diolglucoside^[27]	F\L
30²⁾	17.24	C₂₀H₂₄NO₄⁺	[M]⁺	342.170 1	0.3	192.101 6, 177.077 9, 151.074 8	Cyclanoline^[28]	F\L
31¹⁾	17.82	C₉H₁₀O₅	[M-H]^-	197.045 5	3.3	182.022 4, 166.998 4	Syringic acid^[26]	F\D\B\L\Q\JL\JX\W
32¹⁾	17.84	C₂₀H₂₄NO₄⁺	[M]⁺	342.170 2	0.6	192.101 5, 177.077 5, 149.083 4, 120.076 4	Phellodendrine^[29]	F\L
33²⁾	17.93	C₁₇H₁₉NO₃	[M+H]⁺	286.144 2	1.5	255.100 7, 237.090 2, 143.048 7, 107.049 3	Coclaurine^[20]	F\Q\L
34²⁾	18.20	C₁₈H₁₉NO₃	[M+H]⁺	298.143 8	0.1	269.116 2, 238.097 8, 192.101 7, 161.083 0	Stepharine^[20]	F\Q
35¹⁾	18.69	C₂₁H₂₀O₉	[M+H]⁺	417.118 4	0.9	399.102 9, 363.082 2, 297.075 1	Puerarin^[30]	Q
36²⁾	18.74	C₂₀H₂₆NO₄⁺	[M]⁺	344.185 4	-0.7	299.127 3, 175.074 7, 137.059 1, 58.066 2	Tembetarine^[20]	F\L
37¹⁾	19.04	C₂₀H₂₄NO₄⁺	[M]⁺	342.169 7	-0.8	297.110 1, 282.086 8, 265.083 9	Magnoflorine^[20]	F\L\Q
38²⁾	20.36	C₁₉H₂₃NO₄	[M+H]⁺	330.170 7	2.2	239.071 7, 209.058 5, 181.063 9	Isosinomenine^[28]	Q
39²⁾	20.62	C₁₇H₂₀O₉	[M-H]^-	367.103 3	-0.4	191.056 4, 134.037 2	3-O-Feruloylquinic acid^[24]	F\L
40²⁾	21.04	C₂₀H₂₄NO₄⁺	[M]⁺	342.170 2	0.6	297.111 0, 265.084 7, 237.089 9, 58.066 0	Laurifoline^[20]	F\L\Q
41²⁾	21.42	C₁₉H₂₄NO₃⁺	[M]⁺	314.175 3	0.7	269.116 7, 143.048 9, 107.049 3, 58.066 1	Magnocurarine/Isomer^[20]	F\L\Q
42²⁾	21.51	C₂₁H₂₇NO₄	[M+H]⁺	358.201 2	-0.2	313.141 7, 189.090 1, 137.059 1, 58.066 1	N-Methylpalaudinium^[31]	F\L\Q
43¹⁾	21.60	C₉H₈O₃	[M+H]⁺	165.054 6	-0.1	147.052 4, 119.048 2, 91.056 9	4-Hydroxycinnamic acid	F\L\Q\W
44¹⁾	22.41	C₉H₆O₃	[M+H]⁺	163.039 3	2.0	119.048 1, 107.048 3	Umbelliferone^[32]	F\L\W
45²⁾	22.43	C₃₄H₄₆O₁₈	[M-H]^-	741.262 0	1.2	579.209 6, 417.155 2	Syringaresionl-di-O-β-D-glucopyranoside^[17]	L\Q
46²⁾	23.13	C₂₁H₂₆NO₄⁺	[M]⁺	356.186 2	1.6	311.125 8, 296.102 5	N-Methyl isocorydine/N-Methyl corydine^[20]	F\L\Q
47²⁾	23.25	C₁₅H₁₇NO₃	[M+H]⁺	260.128 7	2.2	242.116 8, 188.070 0, 176.069 9, 134.059 9	Psi-Ribalinine/Ribalinine^[33]	F\L
48²⁾	24.07	C₂₇H₃₀O₁₅	[M-H]^-	593.151 9	1.2	446.086 1, 301.035 5, 299.020 3, 271.024 0	Quercetin-3,7-O-α-L-dirhamnopyranoside^[34]	JL
49³⁾	24.11	C₂₀H₂₆NO₃⁺	[M]⁺	328.191 2	1.5	251.105 6, 223.109 8, 143.048 5, 58.066 1	4'-Methoxymagnocurarine	F\L\Q
50²⁾	25.41	C₁₉H₁₇NO₄	[M+H]⁺	324.124 0	3.0	309.099 1, 294.075 2, 281.105 7	Stepharanine^[20]	Q
51¹⁾	25.87	C₂₀H₂₄O₉	[M+H]⁺	409.149 1	-0.5	247.095 5, 229.083 6	Nodakenin^[35]	F
52²⁾	26.19	C₃₃H₄₄O₁₇	[M-H]^-	711.250 9	0.5	387.138 8	Medioresinol-di-O-β-D-glucopyranoside^[17]	Q
53¹⁾	27.21	C₂₅H₂₄O₁₂	[M-H]^-	515.118 2	-2.5	353.087 2, 191.056 9, 179.036 0, 135.045 7	3,4-Dicaffeoylquinic acid^[24]	F\B\Q\JX
54²⁾	28.30	C₁₅H₁₇NO₃	[M+H]⁺	260.128 6	1.8	242.116 9, 188.070 2, 176.069 7, 134.059 3	Psi-Ribalinine/Ribalinine^[33]	F\L
55¹⁾	28.89	C₂₈H₃₄O₁₅	[M-H]^-	609.182 9	0.7	301.073 2, 286.049 0, 257.082 1, 151.003 8	Hesperidin^[14]	F\L
56²⁾	28.95	C₂₁H₂₃NO₅	[M+H]⁺	370.165 1	0.5	352.153 3, 290.093 6, 189.078 0, 188.070 1	Allocryptopine^[33]	F\L
57²⁾	29.38	C₁₁H₁₀O₄	[M+H]⁺	207.064 9	-1.4	179.067 4, 151.074 2, 107.048 6, 91.056 3	5,7-Dimethoxycoumarin^[14]	F\L\Q
58²⁾	29.60	C₂₀H₂₀NO₄⁺	[M]⁺	338.138 8	0.3	323.114 9, 322.106 5, 308.090 9, 294.111 7	Columbamine isomer^[20]	F\L\Q
59¹⁾	29.84	C₂₀H₁₈NO₄⁺	[M]⁺	336.123 4	1.1	320.091 5, 308.125 0, 292.095 8	Epiberberine^[36]	Q
60¹⁾	30.03	C₁₉H₁₆NO₄⁺	[M]⁺	322.107 6	0.7	307.083 1, 279.089 5	Berberrubine^[36]	F\L
61¹⁾	30.17	C₂₀H₂₀NO₄⁺	[M]⁺	338.138 5	-0.5	323.114 0, 322.105 9, 308.092 5, 294.111 3	Columbamine^[20]	F\L\Q
62²⁾	30.75	C₁₇H₉NO₃	[M+H]⁺	276.065 8	1.0	248.069 3, 218.058 9, 190.063 5	Liriodenine^[33]	F\L
63¹⁾	31.64	C₂₂H₂₂O₉	[M+H]⁺	431.133 8	0.3	269.079 4	Ononin^[30]	JX
64²⁾	32.37	C₁₄H₁₄O₄	[M+H]⁺	247.096 8	1.3	229.084 5, 175.038 6, 147.043 8	Marmesin^[32]	F\W
65²⁾	32.44	C₂₀H₁₅NO₄	[M+H]⁺	334.107 5	0.3	319.082 3, 304.060 2, 291.087 1, 276.064 5	Nornitidine^[37]	F\L
66²⁾	32.57	C₁₃H₁₁NO₄	[M+H]⁺	246.076 2	0.5	231.051 5, 216.028 4, 188.033 2, 160.038 9	Haplopine^[14]	F\L
67²⁾	32.62	C₂₀H₁₅NO₄	[M+H]⁺	334.107 5	0.6	319.082 2, 304.059 1, 291.088 0, 276.064 4	Norchelerythrine^[14]	F\L
68²⁾	33.39	C₁₈H₁₉NO₄	[M+H]⁺	314.139 2	1.6	177.054 4, 145.028 1, 117.033 1	Feruloyltyramine^[20]	Q
69¹⁾	33.46	C₁₅H₁₀O₄	[M+H]⁺	255.065 5	1.2	199.076 7, 137.024 4	Daidzein^[30]	JX
70²⁾	33.74	C₂₀H₁₄NO₄⁺	[M]⁺	332.092 3	1.7	317.069 4, 304.099 3, 302.081 3, 274.087 2	Sanguinarine^[38]	F\L
71¹⁾	33.76	C₂₁H₂₂NO₄⁺	[M]⁺	352.155 0	1.9	336.121 3, 322.105 2, 308.127 1, 294.113 0	Palmatine^[36]	Q
72²⁾	33.85	C₁₆H₂₀O₆	[M+H]⁺	309.133 8	1.7	235.059 6, 219.064 9, 205.049 3, 177.053 8	Mexoticin/Toddalolactone^[14]	F
73¹⁾	34.07	C₁₅H₁₂O₄	[M-H]^-	255.066 9	2.4	135.008 6	Liquiritigenin^[39]	JX
74²⁾	34.27	C₁₅H₁₂O₆	[M-H]^-	287.056 2	0.3	151.003 7, 135.044 6, 107.013 4	Eriodictyol	JX
75²⁾	34.28	C₁₉H₂₁NO₅	[M+H]⁺	344.148 8	-1.3	177.054 2, 149.059 7, 145.028 1, 117.032 8	N-trans-Feruloyl-3-O-methyldopamine^[40]	Q
76¹⁾	34.31	C₂₀H₁₈NO₄⁺	[M]⁺	336.123 8	2.3	321.096 8, 320.092 2, 306.075 2, 292.095 9, 278.079 3	Berberine^[36]	F\L\Q
77²⁾	34.96	C₁₁H₁₁NO₂	[M+H]⁺	190.086 6	1.8	175.065 3, 158.062 6, 147.069 1, 118.066 0	4-Methoxy-1-methyl-2-quinolone^[14]	F\L
78²⁾	35.30	C₂₂H₂₆O₈	[M-H]^-	417.154 6	-2.1	402.133 1, 387.111 6, 359.112 5, 181.050 9	Syringaresinol^[17]	F\L\Q
79¹⁾	35.68	C₁₆H₁₂O₅	[M+H]⁺	285.076 0	0.9	253.051 2, 225.054 9, 137.023 2	Calycosin^[30]	JX
80¹⁾	35.73	C₂₁H₁₈NO₄⁺	[M]⁺	348.123 3	0.8	332.089 8, 318.074 7, 304.095 3	Nitidine^[11]	F\L
81¹⁾	35.89	C₁₅H₁₀O₇	[M-H]^-	301.035 3	-0.3	273.033 3, 255.026 1, 178.998 2, 151.002 7	Quercetin^[10]	JL\JX
82²⁾	36.50	C₁₂H₉NO₃	[M+H]⁺	216.064 9	-2.9	201.042 8, 183.031 1, 173.045 6, 155.034 1	Robustine^[14]	F
83²⁾	36.76	C₁₇H₁₄O₆	[M+H]⁺	315.086 9	1.9	300.065 0, 167.032 6	Odoratin^[41]	JX
84¹⁾	37.28	C₂₁H₁₈NO₄⁺	[M]⁺	348.123 2	0.5	332.089 3, 318.073 8, 304.095 0	Chelerythrine^[14]	F\L
85²⁾	37.37	C₂₂H₂₆O₈	[M-H]^-	417.155 0	-1.2	387.115 0, 166.025 2	Syringaresinol^[17]	Q
86¹⁾	37.76	C₁₁H₆O₃	[M+H]⁺	187.039 1	0.7	159.043 2, 143.048 7, 131.049 1, 115.054 1	Psoralen^[16]	Q
87¹⁾	39.00	C₁₄H₁₃NO₄	[M+H]⁺	260.091 9	0.6	245.066 9, 227.056 4, 216.064 2, 199.061 8	Skimmianine^[14]	F\L
88²⁾	39.55	C₁₅H₁₂O₅	[M-H]^-	271.061 8	2.2	135.045 3, 135.008 7, 117.033 5, 107.049 1	3',4',7-Trihydroxyflavanone^[41]	JX
89²⁾	40.06	C₁₃H₁₁NO₃	[M+H]⁺	230.081 5	1.4	215.056 8, 200.033 4, 186.054 0, 172.038 8	γ-Fagarine^[14]	F\B\L\W
90¹⁾	41.15	C₁₆H₁₄O₆	[M-H]^-	301.072 0	0.8	286.047 0, 151.003 1	Hesperetin^[39]	F\L
91²⁾	41.17	C₁₆H₁₂O₆	[M-H]^-	299.056 1	0.0	284.033 2, 227.033 5, 133.029 5, 107.014 3	Diosmetin^[42]	F
92¹⁾	42.35	C₁₂H₉NO₂	[M+H]⁺	200.070 9	1.5	185.046 8, 129.057 0,102.046 0	Dictamnine^[14]	F\L
93¹⁾	42.83	C₁₂H₈O₄	[M+H]⁺	217.049 8	1.2	202.025 2, 174.030 2, 146.035 5, 118.040 7	Bergapten^[14]	W
94¹⁾	43.30	C₁₅H₁₂O₄	[M+H]⁺	257.080 8	-0.1	239.069 3, 147.043 4, 137.023 2, 119.048 8	Isoliquiritigenin^[39]	JX
95¹⁾	43.57	C₁₆H₁₂O₄	[M+H]⁺	269.081 1	1.0	254.056 4, 237.053 9, 226.061 4,213.091 3, 197.059 3,181.062 8, 137.022 0, 118.041 6, 107.047 9	Formononetin^[30]	JX
96²⁾	44.02	C₂₁H₁₉NO₆	[M+H]⁺	382.128 4	-0.3	364.116 3, 349.094 6, 339.105 4, 292.070 4	Isoarnottianamide^[33]	F\L
97²⁾	44.62	C₂₀H₂₀O₇	[M+H]⁺	373.128 2	0.1	357.098 0, 343.081 5, 153.017 7	Pentamethoxyflavone^[43]	JL
98²⁾	45.11	C₂₀H₂₀O₇	[M+H]⁺	373.128 4	0.6	357.095 3, 343.080 6	Pentamethoxyflavone^[43]	JL
99²⁾	46.03	C₂₁H₂₂O₈	[M+H]⁺	403.139 6	2.1	373.089 8, 359.112 3	5,6,7,3',4',5'-Hexamethoxyflavone^[44]	JL
100²⁾	46.37	C₁₉H₁₆O₇	[M+H]⁺	357.097 0	0.3	342.072 3, 327.047 2, 313.068 6, 153.017 9	5,7,5'-Trimethoxy-3',4'-methylenedioxy- flavone^[45]	JL
101²⁾	46.92	C₁₅H₁₄O₄	[M+H]⁺	259.096 7	0.8	243.067 2, 229.054 5, 201.051 6	Luvangetin^[14]	F\L
102²⁾	47.20	C₂₁H₁₉NO₆	[M+H]⁺	382.128 8	0.7	364.126 1, 354.137 6, 339.112 6, 292.071 9	Arnottianamide^[33]	F\L
103²⁾	47.30	C₂₀H₁₇NO₅	[M+H]⁺	352.118 2	0.7	337.092 9, 322.069 5, 308.088 3, 294.073 6	Oxyberberine^[46]	Q
104²⁾	47.30	C₂₀H₁₈O₈	[M+H]⁺	387.107 7	0.7	371.074 9, 357.058 4, 343.081 1	5,6,7,5'-Tetramethoxy-3',4'-methylenedioxy flavone^[44]	JL
105²⁾	48.61	C₁₅H₁₅NO₂	[M+H]⁺	242.117 7	0.6	200.070 6, 188.070 9, 172.076 7, 144.080 5	N-Methylflindersine^[14]	F\L
106²⁾	49.38	C₂₁H₁₇NO₅	[M+H]⁺	364.118 3	1.0	349.093 4, 334.069 6, 320.089 6, 306.075 6	Oxychelerythrine^[14]	F\L
107¹⁾	51.06	C₂₀H₁₈O₆	[M+H]⁺	355.118 0	1.1	337.106 5, 319.098 2, 289.078 7, 135.044 0	Sesamin	D
108²⁾	51.18	C7₅H₁₀O₅	[M-H]^-	269.045 7	0.6	241.050 5, 225.055 6	Emodin^[21]	F
109²⁾	52.42	C₂₃H₂₁NO₆	[M+H]⁺	408.144 6	1.1	348.121 2, 333.098 2, 332.089 0, 318.074 4	6-Propoxychelerythrine^[38]	F\L
110²⁾	52.80	C₂₂H₂₁NO₅	[M+H]⁺	380.149 7	1.2	362.137 5, 347.114 5, 334.106 0, 319.085 5	6-Hydroxyl-10-methoxysanguinarine^[38]	F\L
111²⁾	54.51	C₁₆H₁₈O₄	[M+H]⁺	275.127 9	0.4	245.080 9, 217.050 0, 205.048 9	7-Methyl ether heteropeucenin	F\D\B\L\Q\JL\JX\W
112²⁾	54.54	C₂₀H₁₅NO₄	[M+H]⁺	334.107 5	0.3	319.082 1, 304.060 5	Norchelerythrine^[14]	F\L
113²⁾	55.86	C₂₁H₁₉NO₄	[M+H]⁺	350.138 7	0.0	335.113 7, 334.105 9, 318.098 4, 304.094 5	Dihydrochelerythrine^[14]	F\L

No.	t_R /min	Formula	Molecular ion	MS (m/z)	δ /×10^-6	MS/MS (m/z)	Identification	Source
1²⁾	1.44	C₅H₁₁NO₂	[M+H]⁺	118.086 4	1.2	102.054 1, 58.066 2	Betaine^[18]	F\D\B\L\Q\JL\JX\W
2²⁾	1.52	C₇H₇NO₂	[M+H]⁺	138.054 9	-0.4	94.066 5	Trigonelline^[19]	F\\JL\JX\W
3²⁾	1.53	C₁₂H₂₂O₁₁	[M-H]^-	341.109 8	2.5	179.060 2, 119.039 3, 89.028 3, 59.015 5	Sucrose^[20]	B\JL\JX
4²⁾	1.64	C₆H₁₁NO₂	[M+H]⁺	130.086 0	-2.0	84.085 1, 56.051 7	L-Pipecolic acid^[19]	-
5²⁾	2.43	C₆H₅NO₂	[M+H]⁺	124.039 2	-0.8	106.028 1, 80.050 3	Nicotinic acid^[21]	-
6²⁾	3.44	C₇H₁₁NO₅	[M+H]⁺	190.070 7	-1.6	130.048 8, 84.045 0	N-Acetylglutamate^[19]	-
7²⁾	5.98	C₆H₆O₃	[M+H]⁺	127.038 7	-2.1	109.027 7, 81.034 6	5-Hydroxymethylfurfural^[21]	-
8¹⁾	6.03	C₇H₆O₅	[M+H]⁺	171.028 5	-1.8	153.018 9, 125.022 7, 109.028 1, 107.012 8	Gallic acid^[21]	B\JL
9²⁾	6.28	C₁₀H₁₃N₅O₅	[M+H]⁺	284.099 5	2.0	152.055 8, 135.028 8, 110.033 6	Guanosine^[22]	-
10²⁾	8.80	C₁₁H₁₅NO₂	[M+H]⁺	194.117 4	-0.8	177.089 6, 145.063 8, 117.069 1	Heliamine	F\Q
11²⁾	10.12	C₁₁H₁₂O₇	[M-H]^-	255.052 0	3.8	179.035 8, 165.056 6, 72.993 6	Piscidic acid^[23]	L\JL
12²⁾	10.31	C₂₂H₂₇NO₈	[M+H]⁺	434.181 2	0.6	272.127 3, 255.100 5, 237.089 2, 107.049 1	Higenamine glucoside^[20]	Q
13³⁾	11.03	C₂₂H₂₅NO₈	[M+H]⁺	432.165 2	-0.2	270.110 9, 235.072 5, 107.049 0	Dehydrohigenamine glucoside	Q
14²⁾	11.05	C₂₆H₃₅NO₁₀	[M+H]⁺	522.233 5	0.2	285.112 2, 271.097 1, 254.094 0, 243.101 8	Cephatonine glucoside^[20]	Q
15¹⁾	12.40	C₁₆H₁₈O₉	[M-H]^-	353.088 1	0.8	191.056 3, 179.035 1, 173.045 4, 135.045 5	Chlorogenic acid^[21]	F\L\Q\W
16²⁾	12.55	C₂₅H₃₄NO₈⁺	[M]⁺	476.227 2	-1.5	314.174 9, 269.117 8, 107.049 2, 58.066 1	Magnocurarine4'-O-glucopyranoside/Isomer^[20]	F\Q
17²⁾	13.79	C₁₆H₁₇NO₃	[M+H]⁺	272.128 2	0.3	255.100 7, 161.058 6, 143.048 3, 107.049 1	Higenamine^[20]	F\L\Q
18²⁾	13.88	C₂₃H₂₉NO₈	[M+H]⁺	448.195 5	-2.4	314.142 9, 286.141 6, 269.115 0, 107.048 6	Coclaurine glucoside^[20]	Q
19²⁾	14.04	C₂₄H₃₁NO₉	[M+H]⁺	478.206 9	-0.5	316.152 9, 285.111 2, 192.101 6, 177.077 5	3'-Hydroxy-N-methyl coclaurine glucoside^[20]	Q
20³⁾	14.34	C₁₆H₁₅NO₃	[M+H]⁺	270.112 5	0.1	252.100 6, 235.067 3, 207.078 9, 107.048 4	Dehydrohigenamine	Q
21¹⁾	14.66	C₁₉H₂₃NO₄	[M+H]⁺	330.169 5	-1.5	239.070 4, 223.074 0, 207.045 1, 181.063 9	Sinomenine^[20]	Q
22²⁾	14.84	C₁₆H₁₈O₈	[M-H]^-	337.092 6	-0.9	191.054 0, 163.039 8, 119.050 2	3-O-Coumaroylquinic acid^[24]	F\L
23²⁾	15.38	C₁₇H₂₂O₁₂	[M-H]^-	417.104 4	1.3	285.061 4, 241.071 2, 152.011 8, 108.021 6	5-O-(β-Apiosyl-(1→2)-O-β-xylopyranosyl) gentisic acid^[25]	JL\W
24¹⁾	15.80	C₁₆H₁₈O₉	[M-H]^-	353.087 7	-0.3	191.056 7	Neochlorogenic acid^[21]	F\L\Q\W
25²⁾	16.00	C₁₈H₂₁NO₄	[M+H]⁺	316.154 6	0.8	285.113 8, 192.101 5, 175.075 4, 123.043 7	3'-Hydroxy-N-methylcoclaurine^[20]	F\Q
26¹⁾	16.40	C₈H₈O₄	[M-H]^-	167.035 4	2.5	152.011 3, 108.021 7	Vanillic acid^[26]	F\D\B\L\Q\W
27²⁾	16.47	C₂₅H₃₄NO₈⁺	[M]⁺	476.227 4	-1.0	314.173 8, 269.116 6, 107.049 4, 58.066 0	Magnocurarine-4'-O-glucopyranoside/Isomer^[20]	Q
28¹⁾	16.63	C₁₆H₁₈O₉	[M-H]^-	353.087 8	0.0	191.056 0, 179.034 6, 173.045 0, 135.045 1	Cryptochlorogenic acid^[24]	F\L\Q\W
29²⁾	16.95	C₂₆H₃₁NO₁₀	[M+H]⁺	518.201 6	-0.9	356.147 7, 338.137 2, 206.080 3, 188.070 1	2', 4',10'-Trimethoxy-5,8-dihydro-6H-isoquinolino [3,2-a]isoquinoline-3,11-diolglucoside^[27]	F\L
30²⁾	17.24	C₂₀H₂₄NO₄⁺	[M]⁺	342.170 1	0.3	192.101 6, 177.077 9, 151.074 8	Cyclanoline^[28]	F\L
31¹⁾	17.82	C₉H₁₀O₅	[M-H]^-	197.045 5	3.3	182.022 4, 166.998 4	Syringic acid^[26]	F\D\B\L\Q\JL\JX\W
32¹⁾	17.84	C₂₀H₂₄NO₄⁺	[M]⁺	342.170 2	0.6	192.101 5, 177.077 5, 149.083 4, 120.076 4	Phellodendrine^[29]	F\L
33²⁾	17.93	C₁₇H₁₉NO₃	[M+H]⁺	286.144 2	1.5	255.100 7, 237.090 2, 143.048 7, 107.049 3	Coclaurine^[20]	F\Q\L
34²⁾	18.20	C₁₈H₁₉NO₃	[M+H]⁺	298.143 8	0.1	269.116 2, 238.097 8, 192.101 7, 161.083 0	Stepharine^[20]	F\Q
35¹⁾	18.69	C₂₁H₂₀O₉	[M+H]⁺	417.118 4	0.9	399.102 9, 363.082 2, 297.075 1	Puerarin^[30]	Q
36²⁾	18.74	C₂₀H₂₆NO₄⁺	[M]⁺	344.185 4	-0.7	299.127 3, 175.074 7, 137.059 1, 58.066 2	Tembetarine^[20]	F\L
37¹⁾	19.04	C₂₀H₂₄NO₄⁺	[M]⁺	342.169 7	-0.8	297.110 1, 282.086 8, 265.083 9	Magnoflorine^[20]	F\L\Q
38²⁾	20.36	C₁₉H₂₃NO₄	[M+H]⁺	330.170 7	2.2	239.071 7, 209.058 5, 181.063 9	Isosinomenine^[28]	Q
39²⁾	20.62	C₁₇H₂₀O₉	[M-H]^-	367.103 3	-0.4	191.056 4, 134.037 2	3-O-Feruloylquinic acid^[24]	F\L
40²⁾	21.04	C₂₀H₂₄NO₄⁺	[M]⁺	342.170 2	0.6	297.111 0, 265.084 7, 237.089 9, 58.066 0	Laurifoline^[20]	F\L\Q
41²⁾	21.42	C₁₉H₂₄NO₃⁺	[M]⁺	314.175 3	0.7	269.116 7, 143.048 9, 107.049 3, 58.066 1	Magnocurarine/Isomer^[20]	F\L\Q
42²⁾	21.51	C₂₁H₂₇NO₄	[M+H]⁺	358.201 2	-0.2	313.141 7, 189.090 1, 137.059 1, 58.066 1	N-Methylpalaudinium^[31]	F\L\Q
43¹⁾	21.60	C₉H₈O₃	[M+H]⁺	165.054 6	-0.1	147.052 4, 119.048 2, 91.056 9	4-Hydroxycinnamic acid	F\L\Q\W
44¹⁾	22.41	C₉H₆O₃	[M+H]⁺	163.039 3	2.0	119.048 1, 107.048 3	Umbelliferone^[32]	F\L\W
45²⁾	22.43	C₃₄H₄₆O₁₈	[M-H]^-	741.262 0	1.2	579.209 6, 417.155 2	Syringaresionl-di-O-β-D-glucopyranoside^[17]	L\Q
46²⁾	23.13	C₂₁H₂₆NO₄⁺	[M]⁺	356.186 2	1.6	311.125 8, 296.102 5	N-Methyl isocorydine/N-Methyl corydine^[20]	F\L\Q
47²⁾	23.25	C₁₅H₁₇NO₃	[M+H]⁺	260.128 7	2.2	242.116 8, 188.070 0, 176.069 9, 134.059 9	Psi-Ribalinine/Ribalinine^[33]	F\L
48²⁾	24.07	C₂₇H₃₀O₁₅	[M-H]^-	593.151 9	1.2	446.086 1, 301.035 5, 299.020 3, 271.024 0	Quercetin-3,7-O-α-L-dirhamnopyranoside^[34]	JL
49³⁾	24.11	C₂₀H₂₆NO₃⁺	[M]⁺	328.191 2	1.5	251.105 6, 223.109 8, 143.048 5, 58.066 1	4'-Methoxymagnocurarine	F\L\Q
50²⁾	25.41	C₁₉H₁₇NO₄	[M+H]⁺	324.124 0	3.0	309.099 1, 294.075 2, 281.105 7	Stepharanine^[20]	Q
51¹⁾	25.87	C₂₀H₂₄O₉	[M+H]⁺	409.149 1	-0.5	247.095 5, 229.083 6	Nodakenin^[35]	F
52²⁾	26.19	C₃₃H₄₄O₁₇	[M-H]^-	711.250 9	0.5	387.138 8	Medioresinol-di-O-β-D-glucopyranoside^[17]	Q
53¹⁾	27.21	C₂₅H₂₄O₁₂	[M-H]^-	515.118 2	-2.5	353.087 2, 191.056 9, 179.036 0, 135.045 7	3,4-Dicaffeoylquinic acid^[24]	F\B\Q\JX
54²⁾	28.30	C₁₅H₁₇NO₃	[M+H]⁺	260.128 6	1.8	242.116 9, 188.070 2, 176.069 7, 134.059 3	Psi-Ribalinine/Ribalinine^[33]	F\L
55¹⁾	28.89	C₂₈H₃₄O₁₅	[M-H]^-	609.182 9	0.7	301.073 2, 286.049 0, 257.082 1, 151.003 8	Hesperidin^[14]	F\L
56²⁾	28.95	C₂₁H₂₃NO₅	[M+H]⁺	370.165 1	0.5	352.153 3, 290.093 6, 189.078 0, 188.070 1	Allocryptopine^[33]	F\L
57²⁾	29.38	C₁₁H₁₀O₄	[M+H]⁺	207.064 9	-1.4	179.067 4, 151.074 2, 107.048 6, 91.056 3	5,7-Dimethoxycoumarin^[14]	F\L\Q
58²⁾	29.60	C₂₀H₂₀NO₄⁺	[M]⁺	338.138 8	0.3	323.114 9, 322.106 5, 308.090 9, 294.111 7	Columbamine isomer^[20]	F\L\Q
59¹⁾	29.84	C₂₀H₁₈NO₄⁺	[M]⁺	336.123 4	1.1	320.091 5, 308.125 0, 292.095 8	Epiberberine^[36]	Q
60¹⁾	30.03	C₁₉H₁₆NO₄⁺	[M]⁺	322.107 6	0.7	307.083 1, 279.089 5	Berberrubine^[36]	F\L
61¹⁾	30.17	C₂₀H₂₀NO₄⁺	[M]⁺	338.138 5	-0.5	323.114 0, 322.105 9, 308.092 5, 294.111 3	Columbamine^[20]	F\L\Q
62²⁾	30.75	C₁₇H₉NO₃	[M+H]⁺	276.065 8	1.0	248.069 3, 218.058 9, 190.063 5	Liriodenine^[33]	F\L
63¹⁾	31.64	C₂₂H₂₂O₉	[M+H]⁺	431.133 8	0.3	269.079 4	Ononin^[30]	JX
64²⁾	32.37	C₁₄H₁₄O₄	[M+H]⁺	247.096 8	1.3	229.084 5, 175.038 6, 147.043 8	Marmesin^[32]	F\W
65²⁾	32.44	C₂₀H₁₅NO₄	[M+H]⁺	334.107 5	0.3	319.082 3, 304.060 2, 291.087 1, 276.064 5	Nornitidine^[37]	F\L
66²⁾	32.57	C₁₃H₁₁NO₄	[M+H]⁺	246.076 2	0.5	231.051 5, 216.028 4, 188.033 2, 160.038 9	Haplopine^[14]	F\L
67²⁾	32.62	C₂₀H₁₅NO₄	[M+H]⁺	334.107 5	0.6	319.082 2, 304.059 1, 291.088 0, 276.064 4	Norchelerythrine^[14]	F\L
68²⁾	33.39	C₁₈H₁₉NO₄	[M+H]⁺	314.139 2	1.6	177.054 4, 145.028 1, 117.033 1	Feruloyltyramine^[20]	Q
69¹⁾	33.46	C₁₅H₁₀O₄	[M+H]⁺	255.065 5	1.2	199.076 7, 137.024 4	Daidzein^[30]	JX
70²⁾	33.74	C₂₀H₁₄NO₄⁺	[M]⁺	332.092 3	1.7	317.069 4, 304.099 3, 302.081 3, 274.087 2	Sanguinarine^[38]	F\L
71¹⁾	33.76	C₂₁H₂₂NO₄⁺	[M]⁺	352.155 0	1.9	336.121 3, 322.105 2, 308.127 1, 294.113 0	Palmatine^[36]	Q
72²⁾	33.85	C₁₆H₂₀O₆	[M+H]⁺	309.133 8	1.7	235.059 6, 219.064 9, 205.049 3, 177.053 8	Mexoticin/Toddalolactone^[14]	F
73¹⁾	34.07	C₁₅H₁₂O₄	[M-H]^-	255.066 9	2.4	135.008 6	Liquiritigenin^[39]	JX
74²⁾	34.27	C₁₅H₁₂O₆	[M-H]^-	287.056 2	0.3	151.003 7, 135.044 6, 107.013 4	Eriodictyol	JX
75²⁾	34.28	C₁₉H₂₁NO₅	[M+H]⁺	344.148 8	-1.3	177.054 2, 149.059 7, 145.028 1, 117.032 8	N-trans-Feruloyl-3-O-methyldopamine^[40]	Q
76¹⁾	34.31	C₂₀H₁₈NO₄⁺	[M]⁺	336.123 8	2.3	321.096 8, 320.092 2, 306.075 2, 292.095 9, 278.079 3	Berberine^[36]	F\L\Q
77²⁾	34.96	C₁₁H₁₁NO₂	[M+H]⁺	190.086 6	1.8	175.065 3, 158.062 6, 147.069 1, 118.066 0	4-Methoxy-1-methyl-2-quinolone^[14]	F\L
78²⁾	35.30	C₂₂H₂₆O₈	[M-H]^-	417.154 6	-2.1	402.133 1, 387.111 6, 359.112 5, 181.050 9	Syringaresinol^[17]	F\L\Q
79¹⁾	35.68	C₁₆H₁₂O₅	[M+H]⁺	285.076 0	0.9	253.051 2, 225.054 9, 137.023 2	Calycosin^[30]	JX
80¹⁾	35.73	C₂₁H₁₈NO₄⁺	[M]⁺	348.123 3	0.8	332.089 8, 318.074 7, 304.095 3	Nitidine^[11]	F\L
81¹⁾	35.89	C₁₅H₁₀O₇	[M-H]^-	301.035 3	-0.3	273.033 3, 255.026 1, 178.998 2, 151.002 7	Quercetin^[10]	JL\JX
82²⁾	36.50	C₁₂H₉NO₃	[M+H]⁺	216.064 9	-2.9	201.042 8, 183.031 1, 173.045 6, 155.034 1	Robustine^[14]	F
83²⁾	36.76	C₁₇H₁₄O₆	[M+H]⁺	315.086 9	1.9	300.065 0, 167.032 6	Odoratin^[41]	JX
84¹⁾	37.28	C₂₁H₁₈NO₄⁺	[M]⁺	348.123 2	0.5	332.089 3, 318.073 8, 304.095 0	Chelerythrine^[14]	F\L
85²⁾	37.37	C₂₂H₂₆O₈	[M-H]^-	417.155 0	-1.2	387.115 0, 166.025 2	Syringaresinol^[17]	Q
86¹⁾	37.76	C₁₁H₆O₃	[M+H]⁺	187.039 1	0.7	159.043 2, 143.048 7, 131.049 1, 115.054 1	Psoralen^[16]	Q
87¹⁾	39.00	C₁₄H₁₃NO₄	[M+H]⁺	260.091 9	0.6	245.066 9, 227.056 4, 216.064 2, 199.061 8	Skimmianine^[14]	F\L
88²⁾	39.55	C₁₅H₁₂O₅	[M-H]^-	271.061 8	2.2	135.045 3, 135.008 7, 117.033 5, 107.049 1	3',4',7-Trihydroxyflavanone^[41]	JX
89²⁾	40.06	C₁₃H₁₁NO₃	[M+H]⁺	230.081 5	1.4	215.056 8, 200.033 4, 186.054 0, 172.038 8	γ-Fagarine^[14]	F\B\L\W
90¹⁾	41.15	C₁₆H₁₄O₆	[M-H]^-	301.072 0	0.8	286.047 0, 151.003 1	Hesperetin^[39]	F\L
91²⁾	41.17	C₁₆H₁₂O₆	[M-H]^-	299.056 1	0.0	284.033 2, 227.033 5, 133.029 5, 107.014 3	Diosmetin^[42]	F
92¹⁾	42.35	C₁₂H₉NO₂	[M+H]⁺	200.070 9	1.5	185.046 8, 129.057 0,102.046 0	Dictamnine^[14]	F\L
93¹⁾	42.83	C₁₂H₈O₄	[M+H]⁺	217.049 8	1.2	202.025 2, 174.030 2, 146.035 5, 118.040 7	Bergapten^[14]	W
94¹⁾	43.30	C₁₅H₁₂O₄	[M+H]⁺	257.080 8	-0.1	239.069 3, 147.043 4, 137.023 2, 119.048 8	Isoliquiritigenin^[39]	JX
95¹⁾	43.57	C₁₆H₁₂O₄	[M+H]⁺	269.081 1	1.0	254.056 4, 237.053 9, 226.061 4,213.091 3, 197.059 3,181.062 8, 137.022 0, 118.041 6, 107.047 9	Formononetin^[30]	JX
96²⁾	44.02	C₂₁H₁₉NO₆	[M+H]⁺	382.128 4	-0.3	364.116 3, 349.094 6, 339.105 4, 292.070 4	Isoarnottianamide^[33]	F\L
97²⁾	44.62	C₂₀H₂₀O₇	[M+H]⁺	373.128 2	0.1	357.098 0, 343.081 5, 153.017 7	Pentamethoxyflavone^[43]	JL
98²⁾	45.11	C₂₀H₂₀O₇	[M+H]⁺	373.128 4	0.6	357.095 3, 343.080 6	Pentamethoxyflavone^[43]	JL
99²⁾	46.03	C₂₁H₂₂O₈	[M+H]⁺	403.139 6	2.1	373.089 8, 359.112 3	5,6,7,3',4',5'-Hexamethoxyflavone^[44]	JL
100²⁾	46.37	C₁₉H₁₆O₇	[M+H]⁺	357.097 0	0.3	342.072 3, 327.047 2, 313.068 6, 153.017 9	5,7,5'-Trimethoxy-3',4'-methylenedioxy- flavone^[45]	JL
101²⁾	46.92	C₁₅H₁₄O₄	[M+H]⁺	259.096 7	0.8	243.067 2, 229.054 5, 201.051 6	Luvangetin^[14]	F\L
102²⁾	47.20	C₂₁H₁₉NO₆	[M+H]⁺	382.128 8	0.7	364.126 1, 354.137 6, 339.112 6, 292.071 9	Arnottianamide^[33]	F\L
103²⁾	47.30	C₂₀H₁₇NO₅	[M+H]⁺	352.118 2	0.7	337.092 9, 322.069 5, 308.088 3, 294.073 6	Oxyberberine^[46]	Q
104²⁾	47.30	C₂₀H₁₈O₈	[M+H]⁺	387.107 7	0.7	371.074 9, 357.058 4, 343.081 1	5,6,7,5'-Tetramethoxy-3',4'-methylenedioxy flavone^[44]	JL
105²⁾	48.61	C₁₅H₁₅NO₂	[M+H]⁺	242.117 7	0.6	200.070 6, 188.070 9, 172.076 7, 144.080 5	N-Methylflindersine^[14]	F\L
106²⁾	49.38	C₂₁H₁₇NO₅	[M+H]⁺	364.118 3	1.0	349.093 4, 334.069 6, 320.089 6, 306.075 6	Oxychelerythrine^[14]	F\L
107¹⁾	51.06	C₂₀H₁₈O₆	[M+H]⁺	355.118 0	1.1	337.106 5, 319.098 2, 289.078 7, 135.044 0	Sesamin	D
108²⁾	51.18	C7₅H₁₀O₅	[M-H]^-	269.045 7	0.6	241.050 5, 225.055 6	Emodin^[21]	F
109²⁾	52.42	C₂₃H₂₁NO₆	[M+H]⁺	408.144 6	1.1	348.121 2, 333.098 2, 332.089 0, 318.074 4	6-Propoxychelerythrine^[38]	F\L
110²⁾	52.80	C₂₂H₂₁NO₅	[M+H]⁺	380.149 7	1.2	362.137 5, 347.114 5, 334.106 0, 319.085 5	6-Hydroxyl-10-methoxysanguinarine^[38]	F\L
111²⁾	54.51	C₁₆H₁₈O₄	[M+H]⁺	275.127 9	0.4	245.080 9, 217.050 0, 205.048 9	7-Methyl ether heteropeucenin	F\D\B\L\Q\JL\JX\W
112²⁾	54.54	C₂₀H₁₅NO₄	[M+H]⁺	334.107 5	0.3	319.082 1, 304.060 5	Norchelerythrine^[14]	F\L
113²⁾	55.86	C₂₁H₁₉NO₄	[M+H]⁺	350.138 7	0.0	335.113 7, 334.105 9, 318.098 4, 304.094 5	Dihydrochelerythrine^[14]	F\L

基于LC-MS/MS分析壮药龙钻通痹颗粒的化学成分

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程硕涵 ¹ , 雷小英 ¹ , 康雯 ¹ , 姚兰 ¹ , 张航 ¹ , 张青槐 ² , 庞宇舟 ² , 周文斌 ¹^,³^,^* , 再帕尔·阿不力孜 ¹^,³

中国药学杂志 | 论著 2024,59(9): 818-826

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中国药学杂志 | 论著 2024, 59(9): 818-826

基于LC-MS/MS分析壮药龙钻通痹颗粒的化学成分

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程硕涵¹, 雷小英¹, 康雯¹, 姚兰¹, 张航¹, 张青槐², 庞宇舟², 周文斌¹^,³^,^*, 再帕尔·阿不力孜¹^,³

作者信息

¹ 中央民族大学药学院,民族医药教育部重点实验室,北京 100081

² 广西中医药大学, 南宁 530001

³ 中央民族大学生命与环境科学学院, 质谱成像与代谢组学国家民委重点实验室, 北京 100081

程硕涵,女,博士研究生研究方向:中药质谱分析

通讯作者:

*周文斌,男,副教授,硕士生导师研究方向:中药分析 Tel:(010)68939942

Analysis of Chemical Constituents of Zhuang Medicine Longzuan Tongbi Granules by LC-MS/MS

Shuohan CHENG¹, Xiaoying LEI¹, Wen KANG¹, Lan YAO¹, Hang ZHANG¹, Qinghuai ZHANG², Yuzhou PANG², Wenbin ZHOU¹^,³^,^*, Abliz ZEPER¹^,³

Affiliations

¹ Key Laboratory of Ethnomedicine, Ministry of Education, School of Pharmacy, Minzu University of China, Beijing 100081, China

² Guangxi University of Chinese Medicine, Nanning 530001, China

³ Key Laboratory of Mass Spectrometry Imaging and Metabonomics, National Ethnic Affairs Commission, Ministry of Education, College of Life and Environmental Sciences, Minzu University of China, Beijing 100081, China

出版时间: 2024-05-08 doi: 10.11669/cpj.2024.09.007

文章导航

摘要

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目的采用液相色谱-串联质谱联用(LC-MS/MS)技术分析壮药经典方剂龙钻通痹颗粒的化学成分。方法使用ACQUITY UPLC HSS T3色谱柱(2.1 mm×100 mm, 1.8 μm)及体积分数0.1%甲酸水(A)-0.1%甲酸乙腈(B)流动相系统对供试品溶液进行梯度洗脱,而后在正负离子模式下采集MS/MS数据。结果通过高分辨质谱数据解析、对照品及数据库比对,同时参考文献已报道的化合物裂解规律,共鉴定出113个化合物,包括生物碱类64个、黄酮类20个、有机酸类12个、香豆素类8个、木脂素类5个及其他类4个,并对其中的109个次生代谢产物进行归属识别。结论龙钻通痹颗粒物质基础丰富,以生物碱类成分为代表,且飞龙掌血为其重要“主药”,以上可为此方剂的药效机制研究与临床合理使用提供科学依据。

关键词

龙钻通痹颗粒 / 壮药 / 生物碱 / 黄酮 / 液相色谱-串联质谱联用 / 质谱裂解规律

Abstract

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OBJECTIVE To analyze the chemical components of Longzuan Tongbi Granules, a classical prescription of Zhuang medicine by liquid chromatography-tandem mass spectrometry (LC-MS/MS). METHODS The MS/MS data were collected in positive and negative ion mode after gradient elution of the test solution using an ACQUITY UPLC HSS T3 column (2.1 mm×100 mm, 1.8 μm) and a mobile phase system consisting of 0.1% formic acid water (A)-0.1% formic acid acetonitrile (B). RESULTS A total of 113 compounds, including 64 alkaloids, 20 flavonoids, 12 organic acids, 8 coumarins, 5 lignans and 4 others, were identified by high-resolution mass spectrometry data analysis, reference substance and database comparison, while referring to the mass fragmentation patterns of relevant components reported in the literature, and of which 109 secondary metabolites were attributed for recognition. CONCLUSION The material basis of Longzuan Tongbi Granules is rich, represented by alkaloids, and Toddalia asiatica is the important “main drug”. This information can provide a scientific basis for the pharmacodynamic mechanism study and rational clinical use of this formula.

Key words

Longzuan Tongbi Granule / Zhuang medicine / alkaloid / flavonoid / LC-MS/MS / mass fragmentation pattern

引用本文

程硕涵, 雷小英, 康雯, 姚兰, 张航, 张青槐, 庞宇舟, 周文斌, 再帕尔·阿不力孜. 基于LC-MS/MS分析壮药龙钻通痹颗粒的化学成分. 中国药学杂志, 2024 , 59 (9) : 818 -826 . DOI: 10.11669/cpj.2024.09.007

Shuohan CHENG, Xiaoying LEI, Wen KANG, Lan YAO, Hang ZHANG, Qinghuai ZHANG, Yuzhou PANG, Wenbin ZHOU, Abliz ZEPER. Analysis of Chemical Constituents of Zhuang Medicine Longzuan Tongbi Granules by LC-MS/MS[J]. Chinese Pharmaceutical Journal, 2024 , 59 (9) : 818 -826 . DOI: 10.11669/cpj.2024.09.007

正文

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龙钻通痹颗粒是壮药治疗类风湿性关节炎(rheumatoid arthritis, RA)的经典方剂。该方剂由主药:飞龙掌血、大钻;帮药:八角枫、两面针、青风藤、九龙藤;公药:鸡血藤、五指毛桃;以5∶10∶1∶5∶10∶10∶10∶10比例组成,具有祛风除湿、通痹止痛的作用^[1]。临床实践表明,该方能明显降低RA患者的血沉,临床治疗有效率可达85.0%,并且可明显改善患者的晨僵、关节疼痛等症状^[2]。目前,内服龙钻通痹颗粒、壮医热敏探穴针刺疗法、壮医发旺食疗方三者结合已形成治疗RA的壮医立体综合疗法。一项多中心随机对照研究^[3]结果表明,相较于单纯的西药治疗,该方法联合西药治疗能够显著改善RA 患者的类风湿因子、C反应蛋白、血沉水平,显著降低晨僵时间、改善壮医证候评分状况,临床有效率高达94%,不良反应发生率低,值得在临床上推广应用。研究表明^[4-5],该制剂化学成分复杂且结构类型多样,如方剂中飞龙掌血主要含有生物碱、香豆素、黄酮和甾体类成分,大钻主要含有木脂素、挥发油、三萜和生物碱类成分,八角枫主要含有生物碱、酚苷类成分,两面针主要含有生物碱和香豆素类成分,青风藤主要含有生物碱类成分,九龙藤、鸡血藤均富含黄酮类成分,五指毛桃主要含有氨基酸、糖类、甾类和香豆素类成分。近年来,国内主要针对该方剂抗炎、抗风湿药理作用^[6-7]和质量控制^[8-10]方面进行了研究,但关于复方中全成分的研究较少,从龙钻通痹颗粒中报道的化学成分仅25个^[9-11],相较于组方药材的物质基础研究明显滞后,制约了其药效物质基础和作用机制的深入研究。因此,本研究系统总结了龙钻通痹颗粒组方8味药材已报道化学成分,构建了包括2 063条化合物信息的数据库,可作为龙钻通痹颗粒全成分表征的参考。液相色谱-串联质谱联用(LC-MS/MS)技术在中医药物质基础研究中应用广泛,采用液相色谱配合四级杆-飞行时间串联质谱(LC-Q/TOF-MS)可以同时发挥分离效率和扫描速度的优势,获得待测物的高分辨MS及MS/MS信息,实现复杂成分的快速识别^[12-13],特别在痕量成分的检测和鉴定中可弥补传统方法的不足。因此,本研究拟采用LC-Q/TOF-MS技术,通过高分辨质谱数据解析、对照品比对、结合龙钻通痹颗粒组方中各单味药化学成分数据库及PubChem在线数据库比对,开展龙钻通痹颗粒化学成分系统分析,了解其物质组成,为后续的药效物质基础发现和作用机制研究提供科学依据。

1 材料与方法

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1.1 仪器

ExionLC^TM液相色谱仪、TripleTOF^TM 6600型质谱仪(美国SCIEX公司);ACOUITY UPLC HSS T3色谱柱(2.1 mm×100 mm,1.8 μm,Waters 公司);Shim-pack GVP-ODS(2 mm×5 mm,5 μm,日本岛津);X6型超声仪(美国Ultrasonic Generator公司);XP205型分析天平(瑞士Mettler Toledo公司);3-18KS型冷冻离心机(美国Sigma公司)。

1.2 药物与试剂

对照品青藤碱(批号PCS-181128)、橙皮苷(批号PCS-180903)、毛蕊异黄酮(批号PCS-190420)、氯化两面针碱(批号PCS-181119)、槲皮素(批号PCS-181023)、白屈菜红碱(批号PCS-190407)、佛手柑内酯(批号PCS-190320)、芝麻素(批号PCS-181013)、木兰花碱(批号PCS-180903)(北京世纪奥科生物技术有限公司);香草酸(批号17120503)、丁香酸(批号17031705)(成都康邦生物科技有限公司);小檗红碱(批号MUST-20060701)、新绿原酸(批号MUST-20031002)、异绿原酸(批号MUST-20042403)(成都曼思特生物科技有限公司);甘草素(批号4280)、异甘草素(批号1891)(上海诗丹德标准技术服务有限公司);对香豆酸(批号 Y30A11C112277)、7-羟基香豆素(批号 A04A6L1)、紫花前胡苷(批号 W07A10Z94862)、表小檗碱(批号 F26O10X95974)、非洲防己碱(批号 Y21O11W128337)、掌叶防己碱(批号 W27S9Z71290)、茵芋碱(批号 P14M11L110695)、小檗碱(批号 M06M10K87560)、补骨脂素(批号 Z24A11B12220)、刺芒柄花苷(批号 M02A11S120167)、芒柄花黄素(批号 H06S9Z69494)、橙皮素(批号 C03F6Y1)、大豆苷元(批号 C06N6Y5504)、葛根素(批号 S02M9B54875)(上海源叶生物科技有限公司);黄柏碱(批号111895-201805)、没食子酸(批号110831-201906)、绿原酸(批号110753-201817)、白鲜碱(批号111654-200602)(中国食品药品检定研究院);3,4-二-O-咖啡酰奎宁酸(批号13d-12-5,美国Cato Research Chemicals Inc.)。所有对照品质量分数均大于90%。乙腈、甲醇、甲酸均为质谱级;水为娃哈哈纯净水。

龙钻通痹颗粒由广西中医药大学附属药厂生产(批号 20180501)。其制备工艺为:飞龙掌血5份、大钻10份、八角枫1份、两面针5份、青风藤10份、九龙藤10份、鸡血藤10份、五指毛桃根10份,加10倍水加热回流煎煮2次,每次1 h,滤过,滤液合并,60~70 ℃减压浓缩至55 ℃相对密度为1.15~1.20的清膏,加体积分数90%乙醇使含醇量为60%,室温静置12 h,滤过回收乙醇,浓缩至相对密度为1.30~1.35的稠膏,加入适量辅料,混匀,制成颗粒剂。飞龙掌血(F)为芸香科植物飞龙掌血[Toddalia asiatica (L.) Lam.]的干燥根;大钻(D)为木兰科植物厚叶五味子[Kadsura coccinea (Lem.) A.C.Smith]的干燥根;八角枫(B)为八角枫科植物八角枫[Alangium chinense (Lour.) Harms]的干燥根及须根;两面针(L)为芸香科植物两面针[Zanthoxylum nitidum (Roxb.) DC.]的干燥根;青风藤(Q)为防己科植物青藤[Sinomenium acutum (Thunb.) Rehd.et Wils]的干燥藤茎;九龙藤(JL)为豆科植物龙须藤[Bauhinia championii (Benth.)Benth.]的干燥藤茎;鸡血藤(JX)为豆科植物密花豆(Spatholobus suberectus Dunn)的干燥藤茎;五指毛桃(W)为桑科植物粗叶榕(Ficus hirta Vahl)的干燥根,均由广西中医药大学提供,由广西中医药大学韦松基教授鉴定。

1.3 样品制备

各单味药供试品溶液的制备:分别取各单味药药材适量,粉碎,取粉末约10 g,精密称定,置圆底烧瓶中,加入100 mL水,回流提取2次,每次1 h,滤过,合并滤液,取滤液2 mL于离心管中,在12 000 r·min^-1的转速下离心10 min,经0.22 μm针头滤器过滤,取续滤液,即得。龙钻通痹颗粒供试品溶液的制备:取龙钻通痹颗粒,粉碎,取粉末约0.5 g,精密称定,置具塞锥形瓶中,加入5 mL 体积分数70%甲醇溶液,超声30 min,取提取液2 mL于离心管在12 000 r·min^-1的转速下离心10 min,经0.22 μm针头滤器过滤,取续滤液,即得。对照品溶液的制备:称各对照品2~5 mg,分别溶于甲醇制得1 mg·mL^-1的贮备液。分别吸取上述贮备液制备混合对照品溶液,用甲醇稀释至1 μg·mL^-1,取混合对照品溶液2 mL于离心管在12 000 r·min^-1的转速下离心10 min,经0.22 μm针头滤器过滤,取续滤液,即得。

1.4 色谱条件

ACQUITY UPLC HSS T3色谱柱(2.1 mm×100 mm,1.8 μm),Shim-pack Column Holder, Shim-pack GVP-ODS(2 mm×5 mm, 5 μm);柱温30 ℃;流速0.2 mL·min^-1;进样量2 μL;以水(含体积分数0.1%甲酸,A)和乙腈(含体积分数0.1%甲酸,B)为流动相,梯度洗脱(0~8 min,2%~8%B;8~10 min,8%~10%B;10~35 min,10%~30%B;35~40 min,30%~40%B;40~50 min,40%~60%B;50~60 min,60%~95%B;60~75 min,95%B)。

1.5 质谱条件

选用电喷雾离子源,采用TOF MS-IDA-PI模式分别采集正负离子模式下的数据,参数设置如下:喷雾电压+5 500 V/-4 500 V、离子源温500 ℃/450 ℃、喷雾气344.74 kPa、辅助加热气344.74 kPa、气帘气275.79 kPa、解簇电压100 V;TOF MS扫描范围m/z 100~1 000;设置动态背景扣除,选取10个响应最强的离子进行MS/MS扫描;PI扫描范围m/z 50~1 000、碰撞能量±(40±20) eV。

1.6 数据处理

通过高分辨MS及MS/MS数据分析,结合对照品、数据库比对以及文献报道的化合物质谱裂解规律进行化合物解析。

本研究比对的数据库主要包括自建库和PubChem在线数据库。自建库中包括基于CNKI、PubMed等文献库检索总结的龙钻通痹颗粒组方各单味药化学成分名称及分子式信息,共2 063条。包含飞龙掌血信息337条、大钻信息337条、八角枫信息103条、青风藤信息322条、两面针信息382条、九龙藤信息151条、鸡血藤信息228条、五指毛桃信息203条,用于辅助化合物鉴定。

2 结果

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2.1 化合物鉴定结果

LC-Q/TOF-MS采集到的基峰离子流色谱图见图1,按“1.6”项下数据处理方法,共分析和鉴定出113个化合物,其中35个经对照品指认,结果见表1,主要包括生物碱类、黄酮类和有机酸类等,其中4个为初生代谢产物,109个为次生代谢产物。

2.2 代表性化合物结构解析过程

2.2.1 生物碱类

本研究共分析和鉴定出64个生物碱类化合物,由于N原子中心被取代情况不同,在正离子检测模式下可检测两种类型的分子离子峰,如小檗碱类为[M]⁺型,呋喃喹啉类为[M+H]⁺型。以化合物76(t_R=34.31 min)为例,阐述小檗碱类化合物的质谱裂解途径。正离子模式下,其分子离子峰为m/z 336.123 8 [M]⁺,推测其分子式为C₂₀H₁₈NO₄⁺。MS/MS谱(图2A)中可见m/z 321.096 8[M-CH₃]^+·、m/z 320.092 2 [M-CH₃-H]⁺、m/z 306.075 2 [M-2CH₃]⁺、m/z 292.095 9 [M-CH₃-H-CO]⁺、m/z 278.079 3 [M-2CH₃-CO]⁺,经对照品比对鉴定为小檗碱,推测其可能的质谱裂解途径见图2B。以化合物92(t_R=42.35 min)为例,阐述呋喃喹啉类化合物的质谱裂解途径。正离子模式下,其分子离子峰为m/z 200.070 9 [M+H]⁺,推测其分子组成为C₁₂H₉NO₂。其MS/MS谱(图3A)中可见分子离子丢失CH₃·产生的子离子m/z 185.046 8 [M+H-CH₃]^+·(基峰)、中性丢失HCN的现象(m/z 129.057 0→m/z 102.046 0),推测其为呋喃喹啉类化合物,与相关文献[14]报道一致,经对照品比对鉴定为白鲜碱,推测其可能的质谱裂解途径见图3B。

2.2.2 黄酮类

本研究共分析和鉴定出20个黄酮类化合物,主要为异黄酮类化合物。研究表明,正离子检测模式下可获得更多的异黄酮类化合物的裂解信息,其母核主要表现为C环裂解和B环脱落,可产生^1,3A⁺、^1,3B⁺、B⁺等。以化合物95(t_R=43.57 min)为例,阐述异黄酮类化合物的质谱裂解途径。正离子模式下,其分子离子峰为m/z 269.081 1[M+H]⁺,推测其分子式为C₁₆H₁₂O₄。其MS/MS谱(图4A)中可见m/z 254.056 4 [M+H-CH₃]^+·、^1,3A⁺(m/z 137.022 0)、^1,3B⁺-CH₃(m/z 118.041 6)、B⁺(m/z 107.047 9)离子,推测其为异黄酮类化合物,经对照品比对鉴定为芒柄花黄素,推测其可能的质谱裂解途径见图4B。

2.2.3 有机酸类

本研究共分析和鉴定12个有机酸类化合物,主要为咖啡酰奎宁酸类化合物。该类化合物在负离子模式下有明显的裂解特征,母核的α裂解和β裂解分别产生m/z 179[M-H-C₇H₁₀O₅]^-和m/z 191 [M-H-C₉H₆O₃]^-,而后分别发生CO₂、H₂O中性丢失,可产生子离子m/z 135、m/z 173。文献报道,绿原酸和新绿原酸通过α裂解可产生基峰m/z 191;隐绿原酸MS/MS谱中可见高丰度的m/z 173;子离子m/z 179的相对丰度排序为绿原酸>新绿原酸^[15]。化合物15(t_R=12.40 min)、24(t_R=15.80 min)、28(t_R=16.63 min)的高分辨质量数接近,推测得到的分子式均为C₁₆H₁₈O₉,它们的MS/MS谱见图5,可见化合物15、24的基峰均为m/z 191,且化合物15子离子m/z 179的相对丰度更大,推测化合物15为绿原酸、化合物24为新绿原酸。化合物28可产生与化合物15相似的子离子,其MS/MS谱中可见丰度较高的m/z 173 [M-H-C₉H₆O₃-H₂O]^-,推测其为隐绿原酸,经对照品比对化合物15、24、28分别鉴定为绿原酸、新绿原酸、隐绿原酸。

2.2.4 其他类

除上述成分外,本研究还分析鉴定了少量香豆素类、木脂素类等化合物,均通过与文献或标准品比对鉴定,以下举例说明这些化合物的鉴定过程。正离子模式下,化合物86(t_R=37.76 min)的分子离子峰为m/z 187.039 1 [M+H]⁺,推测其分子式为C₁₁H₆O₃。其高分辨MS/MS谱中可见m/z 159.043 2 [M+H-CO]⁺、m/z 143.048 7 [M+H-CO₂]⁺、m/z 131.049 1 [M+H-2CO]⁺、m/z 115.054 1 [M+H-CO₂-CO]⁺,结合相关文献推测其为补骨脂素^[16],并经对照品比对鉴定。负离子模式下,化合物78(t_R=35.30 min)的分子离子峰为m/z 417.154 6 [M-H]^-,预测其分子式为C₂₂H₂₆O₈。其高分辨MS/MS谱中可见分子离子丢失CH₃·和CO产生的子离子m/z 402.133 1 [M-H-CH₃]^-·、m/z 387.111 6 [M-H-2CH₃]^-、m/z 359.112 5[M-H-2CH₃-CO]^-,并发现基峰m/z 181.050 9 [M-H-C₁₃H₁₆O₄]^-也出现连续丢失CH₃·和CO的现象,结合相关文献推测其为丁香树脂酚^[17],并经对照品比对鉴定。

2.2.5 化学成分归属

植物的次生代谢产物往往反应其基源特征,且多有独特、显著的生理活性。因此,根据来源及化合物类型对分析鉴定到的109个次生代谢产物进行归属分析(图6),结果直观表明龙钻通痹颗粒所含化学成分复杂,覆盖了生物碱、黄酮、有机酸、香豆素及木脂素等多类功能次生代谢产物。结合方剂配伍比例分析发现主药飞龙掌血在处方中的质量占比为5/61,但有66个成分检出(含41个特有成分),主要为生物碱类、有机酸类、香豆素类、黄酮类成分,对龙钻通痹颗粒的化学物质组成的贡献度最大。帮药两面针(质量占比为5/61)、青风藤(质量占比为10/61)对方剂化学物质组成的贡献度次之,分别有57个、46(含19个特有成分)个成分检出。相比之下,本次实验仅识别出5个与另一主药大钻(质量占比为10/61)相关联的成分,推测与此颗粒剂的水提醇沉制备工艺及各类成分离子化的竞争抑制有关,将在后续研究工作中进一步探讨。

3 讨论

收起

本研究基于LC-Q/TOF-MS共分析和鉴定了113个化合物,包括生物碱类64个、黄酮类20个、有机酸类12个、香豆素类8个、木脂素类5个、其他类4个,进一步掌握了龙钻通痹颗粒的物质基础,对109个次生代谢产物的归属分析结果表明,方剂代表性化合物为生物碱类成分。此外,综合各单味药的药材质量占比、化合物检出数目结果可见飞龙掌血对方剂的化学物质组成的贡献度最大,为龙钻通痹颗粒中,飞龙掌血药材作为其“主药”提供了重要佐证。综上,本研究结果丰富了龙钻通痹颗粒的物质基础研究并为其配伍合理性提供了依据,可为后续的药效物质基础发现和作用机制研究提供有力支撑。

基金

收起

国家重点研发计划中医药现代化研究重点专项资助(2017YFC1704000)

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2024年第59卷第9期

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文章信息

doi: 10.11669/cpj.2024.09.007

接收时间：2023-12-13
首发时间：2025-11-25
出版时间：2024-05-08

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收稿日期：2023-12-13

基金

国家重点研发计划中医药现代化研究重点专项资助(2017YFC1704000)

作者信息

¹ 中央民族大学药学院,民族医药教育部重点实验室,北京 100081

² 广西中医药大学, 南宁 530001

³ 中央民族大学生命与环境科学学院, 质谱成像与代谢组学国家民委重点实验室, 北京 100081

通讯作者:

*周文斌,男,副教授,硕士生导师研究方向:中药分析 Tel:(010)68939942

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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	Formula	Molecular ion	MS (m/z)	δ /×10^-6	MS/MS (m/z)	Identification	Source
1²⁾	1.44	C₅H₁₁NO₂	[M+H]⁺	118.086 4	1.2	102.054 1, 58.066 2	Betaine^[18]	F\D\B\L\Q\JL\JX\W
2²⁾	1.52	C₇H₇NO₂	[M+H]⁺	138.054 9	-0.4	94.066 5	Trigonelline^[19]	F\\JL\JX\W
3²⁾	1.53	C₁₂H₂₂O₁₁	[M-H]^-	341.109 8	2.5	179.060 2, 119.039 3, 89.028 3, 59.015 5	Sucrose^[20]	B\JL\JX
4²⁾	1.64	C₆H₁₁NO₂	[M+H]⁺	130.086 0	-2.0	84.085 1, 56.051 7	L-Pipecolic acid^[19]	-
5²⁾	2.43	C₆H₅NO₂	[M+H]⁺	124.039 2	-0.8	106.028 1, 80.050 3	Nicotinic acid^[21]	-
6²⁾	3.44	C₇H₁₁NO₅	[M+H]⁺	190.070 7	-1.6	130.048 8, 84.045 0	N-Acetylglutamate^[19]	-
7²⁾	5.98	C₆H₆O₃	[M+H]⁺	127.038 7	-2.1	109.027 7, 81.034 6	5-Hydroxymethylfurfural^[21]	-
8¹⁾	6.03	C₇H₆O₅	[M+H]⁺	171.028 5	-1.8	153.018 9, 125.022 7, 109.028 1, 107.012 8	Gallic acid^[21]	B\JL
9²⁾	6.28	C₁₀H₁₃N₅O₅	[M+H]⁺	284.099 5	2.0	152.055 8, 135.028 8, 110.033 6	Guanosine^[22]	-
10²⁾	8.80	C₁₁H₁₅NO₂	[M+H]⁺	194.117 4	-0.8	177.089 6, 145.063 8, 117.069 1	Heliamine	F\Q
11²⁾	10.12	C₁₁H₁₂O₇	[M-H]^-	255.052 0	3.8	179.035 8, 165.056 6, 72.993 6	Piscidic acid^[23]	L\JL
12²⁾	10.31	C₂₂H₂₇NO₈	[M+H]⁺	434.181 2	0.6	272.127 3, 255.100 5, 237.089 2, 107.049 1	Higenamine glucoside^[20]	Q
13³⁾	11.03	C₂₂H₂₅NO₈	[M+H]⁺	432.165 2	-0.2	270.110 9, 235.072 5, 107.049 0	Dehydrohigenamine glucoside	Q
14²⁾	11.05	C₂₆H₃₅NO₁₀	[M+H]⁺	522.233 5	0.2	285.112 2, 271.097 1, 254.094 0, 243.101 8	Cephatonine glucoside^[20]	Q
15¹⁾	12.40	C₁₆H₁₈O₉	[M-H]^-	353.088 1	0.8	191.056 3, 179.035 1, 173.045 4, 135.045 5	Chlorogenic acid^[21]	F\L\Q\W
16²⁾	12.55	C₂₅H₃₄NO₈⁺	[M]⁺	476.227 2	-1.5	314.174 9, 269.117 8, 107.049 2, 58.066 1	Magnocurarine4'-O-glucopyranoside/Isomer^[20]	F\Q
17²⁾	13.79	C₁₆H₁₇NO₃	[M+H]⁺	272.128 2	0.3	255.100 7, 161.058 6, 143.048 3, 107.049 1	Higenamine^[20]	F\L\Q
18²⁾	13.88	C₂₃H₂₉NO₈	[M+H]⁺	448.195 5	-2.4	314.142 9, 286.141 6, 269.115 0, 107.048 6	Coclaurine glucoside^[20]	Q
19²⁾	14.04	C₂₄H₃₁NO₉	[M+H]⁺	478.206 9	-0.5	316.152 9, 285.111 2, 192.101 6, 177.077 5	3'-Hydroxy-N-methyl coclaurine glucoside^[20]	Q
20³⁾	14.34	C₁₆H₁₅NO₃	[M+H]⁺	270.112 5	0.1	252.100 6, 235.067 3, 207.078 9, 107.048 4	Dehydrohigenamine	Q
21¹⁾	14.66	C₁₉H₂₃NO₄	[M+H]⁺	330.169 5	-1.5	239.070 4, 223.074 0, 207.045 1, 181.063 9	Sinomenine^[20]	Q
22²⁾	14.84	C₁₆H₁₈O₈	[M-H]^-	337.092 6	-0.9	191.054 0, 163.039 8, 119.050 2	3-O-Coumaroylquinic acid^[24]	F\L
23²⁾	15.38	C₁₇H₂₂O₁₂	[M-H]^-	417.104 4	1.3	285.061 4, 241.071 2, 152.011 8, 108.021 6	5-O-(β-Apiosyl-(1→2)-O-β-xylopyranosyl) gentisic acid^[25]	JL\W
24¹⁾	15.80	C₁₆H₁₈O₉	[M-H]^-	353.087 7	-0.3	191.056 7	Neochlorogenic acid^[21]	F\L\Q\W
25²⁾	16.00	C₁₈H₂₁NO₄	[M+H]⁺	316.154 6	0.8	285.113 8, 192.101 5, 175.075 4, 123.043 7	3'-Hydroxy-N-methylcoclaurine^[20]	F\Q
26¹⁾	16.40	C₈H₈O₄	[M-H]^-	167.035 4	2.5	152.011 3, 108.021 7	Vanillic acid^[26]	F\D\B\L\Q\W
27²⁾	16.47	C₂₅H₃₄NO₈⁺	[M]⁺	476.227 4	-1.0	314.173 8, 269.116 6, 107.049 4, 58.066 0	Magnocurarine-4'-O-glucopyranoside/Isomer^[20]	Q
28¹⁾	16.63	C₁₆H₁₈O₉	[M-H]^-	353.087 8	0.0	191.056 0, 179.034 6, 173.045 0, 135.045 1	Cryptochlorogenic acid^[24]	F\L\Q\W
29²⁾	16.95	C₂₆H₃₁NO₁₀	[M+H]⁺	518.201 6	-0.9	356.147 7, 338.137 2, 206.080 3, 188.070 1	2', 4',10'-Trimethoxy-5,8-dihydro-6H-isoquinolino [3,2-a]isoquinoline-3,11-diolglucoside^[27]	F\L
30²⁾	17.24	C₂₀H₂₄NO₄⁺	[M]⁺	342.170 1	0.3	192.101 6, 177.077 9, 151.074 8	Cyclanoline^[28]	F\L
31¹⁾	17.82	C₉H₁₀O₅	[M-H]^-	197.045 5	3.3	182.022 4, 166.998 4	Syringic acid^[26]	F\D\B\L\Q\JL\JX\W
32¹⁾	17.84	C₂₀H₂₄NO₄⁺	[M]⁺	342.170 2	0.6	192.101 5, 177.077 5, 149.083 4, 120.076 4	Phellodendrine^[29]	F\L
33²⁾	17.93	C₁₇H₁₉NO₃	[M+H]⁺	286.144 2	1.5	255.100 7, 237.090 2, 143.048 7, 107.049 3	Coclaurine^[20]	F\Q\L
34²⁾	18.20	C₁₈H₁₉NO₃	[M+H]⁺	298.143 8	0.1	269.116 2, 238.097 8, 192.101 7, 161.083 0	Stepharine^[20]	F\Q
35¹⁾	18.69	C₂₁H₂₀O₉	[M+H]⁺	417.118 4	0.9	399.102 9, 363.082 2, 297.075 1	Puerarin^[30]	Q
36²⁾	18.74	C₂₀H₂₆NO₄⁺	[M]⁺	344.185 4	-0.7	299.127 3, 175.074 7, 137.059 1, 58.066 2	Tembetarine^[20]	F\L
37¹⁾	19.04	C₂₀H₂₄NO₄⁺	[M]⁺	342.169 7	-0.8	297.110 1, 282.086 8, 265.083 9	Magnoflorine^[20]	F\L\Q
38²⁾	20.36	C₁₉H₂₃NO₄	[M+H]⁺	330.170 7	2.2	239.071 7, 209.058 5, 181.063 9	Isosinomenine^[28]	Q
39²⁾	20.62	C₁₇H₂₀O₉	[M-H]^-	367.103 3	-0.4	191.056 4, 134.037 2	3-O-Feruloylquinic acid^[24]	F\L
40²⁾	21.04	C₂₀H₂₄NO₄⁺	[M]⁺	342.170 2	0.6	297.111 0, 265.084 7, 237.089 9, 58.066 0	Laurifoline^[20]	F\L\Q
41²⁾	21.42	C₁₉H₂₄NO₃⁺	[M]⁺	314.175 3	0.7	269.116 7, 143.048 9, 107.049 3, 58.066 1	Magnocurarine/Isomer^[20]	F\L\Q
42²⁾	21.51	C₂₁H₂₇NO₄	[M+H]⁺	358.201 2	-0.2	313.141 7, 189.090 1, 137.059 1, 58.066 1	N-Methylpalaudinium^[31]	F\L\Q
43¹⁾	21.60	C₉H₈O₃	[M+H]⁺	165.054 6	-0.1	147.052 4, 119.048 2, 91.056 9	4-Hydroxycinnamic acid	F\L\Q\W
44¹⁾	22.41	C₉H₆O₃	[M+H]⁺	163.039 3	2.0	119.048 1, 107.048 3	Umbelliferone^[32]	F\L\W
45²⁾	22.43	C₃₄H₄₆O₁₈	[M-H]^-	741.262 0	1.2	579.209 6, 417.155 2	Syringaresionl-di-O-β-D-glucopyranoside^[17]	L\Q
46²⁾	23.13	C₂₁H₂₆NO₄⁺	[M]⁺	356.186 2	1.6	311.125 8, 296.102 5	N-Methyl isocorydine/N-Methyl corydine^[20]	F\L\Q
47²⁾	23.25	C₁₅H₁₇NO₃	[M+H]⁺	260.128 7	2.2	242.116 8, 188.070 0, 176.069 9, 134.059 9	Psi-Ribalinine/Ribalinine^[33]	F\L
48²⁾	24.07	C₂₇H₃₀O₁₅	[M-H]^-	593.151 9	1.2	446.086 1, 301.035 5, 299.020 3, 271.024 0	Quercetin-3,7-O-α-L-dirhamnopyranoside^[34]	JL
49³⁾	24.11	C₂₀H₂₆NO₃⁺	[M]⁺	328.191 2	1.5	251.105 6, 223.109 8, 143.048 5, 58.066 1	4'-Methoxymagnocurarine	F\L\Q
50²⁾	25.41	C₁₉H₁₇NO₄	[M+H]⁺	324.124 0	3.0	309.099 1, 294.075 2, 281.105 7	Stepharanine^[20]	Q
51¹⁾	25.87	C₂₀H₂₄O₉	[M+H]⁺	409.149 1	-0.5	247.095 5, 229.083 6	Nodakenin^[35]	F
52²⁾	26.19	C₃₃H₄₄O₁₇	[M-H]^-	711.250 9	0.5	387.138 8	Medioresinol-di-O-β-D-glucopyranoside^[17]	Q
53¹⁾	27.21	C₂₅H₂₄O₁₂	[M-H]^-	515.118 2	-2.5	353.087 2, 191.056 9, 179.036 0, 135.045 7	3,4-Dicaffeoylquinic acid^[24]	F\B\Q\JX
54²⁾	28.30	C₁₅H₁₇NO₃	[M+H]⁺	260.128 6	1.8	242.116 9, 188.070 2, 176.069 7, 134.059 3	Psi-Ribalinine/Ribalinine^[33]	F\L
55¹⁾	28.89	C₂₈H₃₄O₁₅	[M-H]^-	609.182 9	0.7	301.073 2, 286.049 0, 257.082 1, 151.003 8	Hesperidin^[14]	F\L
56²⁾	28.95	C₂₁H₂₃NO₅	[M+H]⁺	370.165 1	0.5	352.153 3, 290.093 6, 189.078 0, 188.070 1	Allocryptopine^[33]	F\L
57²⁾	29.38	C₁₁H₁₀O₄	[M+H]⁺	207.064 9	-1.4	179.067 4, 151.074 2, 107.048 6, 91.056 3	5,7-Dimethoxycoumarin^[14]	F\L\Q
58²⁾	29.60	C₂₀H₂₀NO₄⁺	[M]⁺	338.138 8	0.3	323.114 9, 322.106 5, 308.090 9, 294.111 7	Columbamine isomer^[20]	F\L\Q
59¹⁾	29.84	C₂₀H₁₈NO₄⁺	[M]⁺	336.123 4	1.1	320.091 5, 308.125 0, 292.095 8	Epiberberine^[36]	Q
60¹⁾	30.03	C₁₉H₁₆NO₄⁺	[M]⁺	322.107 6	0.7	307.083 1, 279.089 5	Berberrubine^[36]	F\L
61¹⁾	30.17	C₂₀H₂₀NO₄⁺	[M]⁺	338.138 5	-0.5	323.114 0, 322.105 9, 308.092 5, 294.111 3	Columbamine^[20]	F\L\Q
62²⁾	30.75	C₁₇H₉NO₃	[M+H]⁺	276.065 8	1.0	248.069 3, 218.058 9, 190.063 5	Liriodenine^[33]	F\L
63¹⁾	31.64	C₂₂H₂₂O₉	[M+H]⁺	431.133 8	0.3	269.079 4	Ononin^[30]	JX
64²⁾	32.37	C₁₄H₁₄O₄	[M+H]⁺	247.096 8	1.3	229.084 5, 175.038 6, 147.043 8	Marmesin^[32]	F\W
65²⁾	32.44	C₂₀H₁₅NO₄	[M+H]⁺	334.107 5	0.3	319.082 3, 304.060 2, 291.087 1, 276.064 5	Nornitidine^[37]	F\L
66²⁾	32.57	C₁₃H₁₁NO₄	[M+H]⁺	246.076 2	0.5	231.051 5, 216.028 4, 188.033 2, 160.038 9	Haplopine^[14]	F\L
67²⁾	32.62	C₂₀H₁₅NO₄	[M+H]⁺	334.107 5	0.6	319.082 2, 304.059 1, 291.088 0, 276.064 4	Norchelerythrine^[14]	F\L
68²⁾	33.39	C₁₈H₁₉NO₄	[M+H]⁺	314.139 2	1.6	177.054 4, 145.028 1, 117.033 1	Feruloyltyramine^[20]	Q
69¹⁾	33.46	C₁₅H₁₀O₄	[M+H]⁺	255.065 5	1.2	199.076 7, 137.024 4	Daidzein^[30]	JX
70²⁾	33.74	C₂₀H₁₄NO₄⁺	[M]⁺	332.092 3	1.7	317.069 4, 304.099 3, 302.081 3, 274.087 2	Sanguinarine^[38]	F\L
71¹⁾	33.76	C₂₁H₂₂NO₄⁺	[M]⁺	352.155 0	1.9	336.121 3, 322.105 2, 308.127 1, 294.113 0	Palmatine^[36]	Q
72²⁾	33.85	C₁₆H₂₀O₆	[M+H]⁺	309.133 8	1.7	235.059 6, 219.064 9, 205.049 3, 177.053 8	Mexoticin/Toddalolactone^[14]	F
73¹⁾	34.07	C₁₅H₁₂O₄	[M-H]^-	255.066 9	2.4	135.008 6	Liquiritigenin^[39]	JX
74²⁾	34.27	C₁₅H₁₂O₆	[M-H]^-	287.056 2	0.3	151.003 7, 135.044 6, 107.013 4	Eriodictyol	JX
75²⁾	34.28	C₁₉H₂₁NO₅	[M+H]⁺	344.148 8	-1.3	177.054 2, 149.059 7, 145.028 1, 117.032 8	N-trans-Feruloyl-3-O-methyldopamine^[40]	Q
76¹⁾	34.31	C₂₀H₁₈NO₄⁺	[M]⁺	336.123 8	2.3	321.096 8, 320.092 2, 306.075 2, 292.095 9, 278.079 3	Berberine^[36]	F\L\Q
77²⁾	34.96	C₁₁H₁₁NO₂	[M+H]⁺	190.086 6	1.8	175.065 3, 158.062 6, 147.069 1, 118.066 0	4-Methoxy-1-methyl-2-quinolone^[14]	F\L
78²⁾	35.30	C₂₂H₂₆O₈	[M-H]^-	417.154 6	-2.1	402.133 1, 387.111 6, 359.112 5, 181.050 9	Syringaresinol^[17]	F\L\Q
79¹⁾	35.68	C₁₆H₁₂O₅	[M+H]⁺	285.076 0	0.9	253.051 2, 225.054 9, 137.023 2	Calycosin^[30]	JX
80¹⁾	35.73	C₂₁H₁₈NO₄⁺	[M]⁺	348.123 3	0.8	332.089 8, 318.074 7, 304.095 3	Nitidine^[11]	F\L
81¹⁾	35.89	C₁₅H₁₀O₇	[M-H]^-	301.035 3	-0.3	273.033 3, 255.026 1, 178.998 2, 151.002 7	Quercetin^[10]	JL\JX
82²⁾	36.50	C₁₂H₉NO₃	[M+H]⁺	216.064 9	-2.9	201.042 8, 183.031 1, 173.045 6, 155.034 1	Robustine^[14]	F
83²⁾	36.76	C₁₇H₁₄O₆	[M+H]⁺	315.086 9	1.9	300.065 0, 167.032 6	Odoratin^[41]	JX
84¹⁾	37.28	C₂₁H₁₈NO₄⁺	[M]⁺	348.123 2	0.5	332.089 3, 318.073 8, 304.095 0	Chelerythrine^[14]	F\L
85²⁾	37.37	C₂₂H₂₆O₈	[M-H]^-	417.155 0	-1.2	387.115 0, 166.025 2	Syringaresinol^[17]	Q
86¹⁾	37.76	C₁₁H₆O₃	[M+H]⁺	187.039 1	0.7	159.043 2, 143.048 7, 131.049 1, 115.054 1	Psoralen^[16]	Q
87¹⁾	39.00	C₁₄H₁₃NO₄	[M+H]⁺	260.091 9	0.6	245.066 9, 227.056 4, 216.064 2, 199.061 8	Skimmianine^[14]	F\L
88²⁾	39.55	C₁₅H₁₂O₅	[M-H]^-	271.061 8	2.2	135.045 3, 135.008 7, 117.033 5, 107.049 1	3',4',7-Trihydroxyflavanone^[41]	JX
89²⁾	40.06	C₁₃H₁₁NO₃	[M+H]⁺	230.081 5	1.4	215.056 8, 200.033 4, 186.054 0, 172.038 8	γ-Fagarine^[14]	F\B\L\W
90¹⁾	41.15	C₁₆H₁₄O₆	[M-H]^-	301.072 0	0.8	286.047 0, 151.003 1	Hesperetin^[39]	F\L
91²⁾	41.17	C₁₆H₁₂O₆	[M-H]^-	299.056 1	0.0	284.033 2, 227.033 5, 133.029 5, 107.014 3	Diosmetin^[42]	F
92¹⁾	42.35	C₁₂H₉NO₂	[M+H]⁺	200.070 9	1.5	185.046 8, 129.057 0,102.046 0	Dictamnine^[14]	F\L
93¹⁾	42.83	C₁₂H₈O₄	[M+H]⁺	217.049 8	1.2	202.025 2, 174.030 2, 146.035 5, 118.040 7	Bergapten^[14]	W
94¹⁾	43.30	C₁₅H₁₂O₄	[M+H]⁺	257.080 8	-0.1	239.069 3, 147.043 4, 137.023 2, 119.048 8	Isoliquiritigenin^[39]	JX
95¹⁾	43.57	C₁₆H₁₂O₄	[M+H]⁺	269.081 1	1.0	254.056 4, 237.053 9, 226.061 4,213.091 3, 197.059 3,181.062 8, 137.022 0, 118.041 6, 107.047 9	Formononetin^[30]	JX
96²⁾	44.02	C₂₁H₁₉NO₆	[M+H]⁺	382.128 4	-0.3	364.116 3, 349.094 6, 339.105 4, 292.070 4	Isoarnottianamide^[33]	F\L
97²⁾	44.62	C₂₀H₂₀O₇	[M+H]⁺	373.128 2	0.1	357.098 0, 343.081 5, 153.017 7	Pentamethoxyflavone^[43]	JL
98²⁾	45.11	C₂₀H₂₀O₇	[M+H]⁺	373.128 4	0.6	357.095 3, 343.080 6	Pentamethoxyflavone^[43]	JL
99²⁾	46.03	C₂₁H₂₂O₈	[M+H]⁺	403.139 6	2.1	373.089 8, 359.112 3	5,6,7,3',4',5'-Hexamethoxyflavone^[44]	JL
100²⁾	46.37	C₁₉H₁₆O₇	[M+H]⁺	357.097 0	0.3	342.072 3, 327.047 2, 313.068 6, 153.017 9	5,7,5'-Trimethoxy-3',4'-methylenedioxy- flavone^[45]	JL
101²⁾	46.92	C₁₅H₁₄O₄	[M+H]⁺	259.096 7	0.8	243.067 2, 229.054 5, 201.051 6	Luvangetin^[14]	F\L
102²⁾	47.20	C₂₁H₁₉NO₆	[M+H]⁺	382.128 8	0.7	364.126 1, 354.137 6, 339.112 6, 292.071 9	Arnottianamide^[33]	F\L
103²⁾	47.30	C₂₀H₁₇NO₅	[M+H]⁺	352.118 2	0.7	337.092 9, 322.069 5, 308.088 3, 294.073 6	Oxyberberine^[46]	Q
104²⁾	47.30	C₂₀H₁₈O₈	[M+H]⁺	387.107 7	0.7	371.074 9, 357.058 4, 343.081 1	5,6,7,5'-Tetramethoxy-3',4'-methylenedioxy flavone^[44]	JL
105²⁾	48.61	C₁₅H₁₅NO₂	[M+H]⁺	242.117 7	0.6	200.070 6, 188.070 9, 172.076 7, 144.080 5	N-Methylflindersine^[14]	F\L
106²⁾	49.38	C₂₁H₁₇NO₅	[M+H]⁺	364.118 3	1.0	349.093 4, 334.069 6, 320.089 6, 306.075 6	Oxychelerythrine^[14]	F\L
107¹⁾	51.06	C₂₀H₁₈O₆	[M+H]⁺	355.118 0	1.1	337.106 5, 319.098 2, 289.078 7, 135.044 0	Sesamin	D
108²⁾	51.18	C7₅H₁₀O₅	[M-H]^-	269.045 7	0.6	241.050 5, 225.055 6	Emodin^[21]	F
109²⁾	52.42	C₂₃H₂₁NO₆	[M+H]⁺	408.144 6	1.1	348.121 2, 333.098 2, 332.089 0, 318.074 4	6-Propoxychelerythrine^[38]	F\L
110²⁾	52.80	C₂₂H₂₁NO₅	[M+H]⁺	380.149 7	1.2	362.137 5, 347.114 5, 334.106 0, 319.085 5	6-Hydroxyl-10-methoxysanguinarine^[38]	F\L
111²⁾	54.51	C₁₆H₁₈O₄	[M+H]⁺	275.127 9	0.4	245.080 9, 217.050 0, 205.048 9	7-Methyl ether heteropeucenin	F\D\B\L\Q\JL\JX\W
112²⁾	54.54	C₂₀H₁₅NO₄	[M+H]⁺	334.107 5	0.3	319.082 1, 304.060 5	Norchelerythrine^[14]	F\L
113²⁾	55.86	C₂₁H₁₉NO₄	[M+H]⁺	350.138 7	0.0	335.113 7, 334.105 9, 318.098 4, 304.094 5	Dihydrochelerythrine^[14]	F\L

No.

t_R
/min

Formula

Molecular
ion

MS
(m/z)

δ
/×10^-6

MS/MS
(m/z)

Identification

Source

1²⁾

1.44

C₅H₁₁NO₂

[M+H]⁺

118.086 4

1.2

102.054 1, 58.066 2

Betaine^[18]

F\D\B\L\Q\JL\JX\W

2²⁾

1.52

C₇H₇NO₂

[M+H]⁺

138.054 9

-0.4

94.066 5

Trigonelline^[19]

F\\JL\JX\W

3²⁾

1.53

C₁₂H₂₂O₁₁

[M-H]^-

341.109 8

2.5

179.060 2, 119.039 3, 89.028 3, 59.015 5

Sucrose^[20]

B\JL\JX

4²⁾

1.64

C₆H₁₁NO₂

[M+H]⁺

130.086 0

-2.0

84.085 1, 56.051 7

L-Pipecolic acid^[19]

5²⁾

2.43

C₆H₅NO₂

[M+H]⁺

124.039 2

-0.8

106.028 1, 80.050 3

Nicotinic acid^[21]

6²⁾

3.44

C₇H₁₁NO₅

[M+H]⁺

190.070 7

-1.6

130.048 8, 84.045 0

N-Acetylglutamate^[19]

7²⁾

5.98

C₆H₆O₃

[M+H]⁺

127.038 7

-2.1

109.027 7, 81.034 6

5-Hydroxymethylfurfural^[21]

8¹⁾

6.03

C₇H₆O₅

[M+H]⁺

171.028 5

-1.8

153.018 9, 125.022 7, 109.028 1, 107.012 8

Gallic acid^[21]

B\JL

9²⁾

6.28

C₁₀H₁₃N₅O₅

[M+H]⁺

284.099 5

2.0

152.055 8, 135.028 8, 110.033 6

Guanosine^[22]

10²⁾

8.80

C₁₁H₁₅NO₂

[M+H]⁺

194.117 4

-0.8

177.089 6, 145.063 8, 117.069 1

Heliamine

F\Q

11²⁾

10.12

C₁₁H₁₂O₇

[M-H]^-

255.052 0

3.8

179.035 8, 165.056 6, 72.993 6

Piscidic acid^[23]

L\JL

12²⁾

10.31

C₂₂H₂₇NO₈

[M+H]⁺

434.181 2

0.6

272.127 3, 255.100 5, 237.089 2, 107.049 1

Higenamine glucoside^[20]

13³⁾

11.03

C₂₂H₂₅NO₈

[M+H]⁺

432.165 2

-0.2

270.110 9, 235.072 5, 107.049 0

Dehydrohigenamine glucoside

14²⁾

11.05

C₂₆H₃₅NO₁₀

[M+H]⁺

522.233 5

0.2

285.112 2, 271.097 1, 254.094 0, 243.101 8

Cephatonine glucoside^[20]

15¹⁾

12.40

C₁₆H₁₈O₉

[M-H]^-

353.088 1

0.8

191.056 3, 179.035 1, 173.045 4, 135.045 5

Chlorogenic acid^[21]

F\L\Q\W

16²⁾

12.55

C₂₅H₃₄NO₈⁺

[M]⁺

476.227 2

-1.5

314.174 9, 269.117 8, 107.049 2, 58.066 1

Magnocurarine4'-O-glucopyranoside/Isomer^[20]

F\Q

17²⁾

13.79

C₁₆H₁₇NO₃

[M+H]⁺

272.128 2

0.3

255.100 7, 161.058 6, 143.048 3, 107.049 1

Higenamine^[20]

F\L\Q

18²⁾

13.88

C₂₃H₂₉NO₈

[M+H]⁺

448.195 5

-2.4

314.142 9, 286.141 6, 269.115 0, 107.048 6

Coclaurine glucoside^[20]

19²⁾

14.04

C₂₄H₃₁NO₉

[M+H]⁺

478.206 9

-0.5

316.152 9, 285.111 2, 192.101 6, 177.077 5

3'-Hydroxy-N-methyl coclaurine glucoside^[20]

20³⁾

14.34

C₁₆H₁₅NO₃

[M+H]⁺

270.112 5

0.1

252.100 6, 235.067 3, 207.078 9, 107.048 4

Dehydrohigenamine

21¹⁾

14.66

C₁₉H₂₃NO₄

[M+H]⁺

330.169 5

-1.5

239.070 4, 223.074 0, 207.045 1, 181.063 9

Sinomenine^[20]

22²⁾

14.84

C₁₆H₁₈O₈

[M-H]^-

337.092 6

-0.9

191.054 0, 163.039 8, 119.050 2

3-O-Coumaroylquinic acid^[24]

F\L

23²⁾

15.38

C₁₇H₂₂O₁₂

[M-H]^-

417.104 4

1.3

285.061 4, 241.071 2, 152.011 8, 108.021 6

5-O-(β-Apiosyl-(1→2)-O-β-xylopyranosyl)
gentisic acid^[25]

JL\W

24¹⁾

15.80

C₁₆H₁₈O₉

[M-H]^-

353.087 7

-0.3

191.056 7

Neochlorogenic acid^[21]

F\L\Q\W

25²⁾

16.00

C₁₈H₂₁NO₄

[M+H]⁺

316.154 6

0.8

285.113 8, 192.101 5, 175.075 4, 123.043 7

3'-Hydroxy-N-methylcoclaurine^[20]

F\Q

26¹⁾

16.40

C₈H₈O₄

[M-H]^-

167.035 4

2.5

152.011 3, 108.021 7

Vanillic acid^[26]

F\D\B\L\Q\W

27²⁾

16.47

C₂₅H₃₄NO₈⁺

[M]⁺

476.227 4

-1.0

314.173 8, 269.116 6, 107.049 4, 58.066 0

Magnocurarine-4'-O-glucopyranoside/Isomer^[20]

28¹⁾

16.63

C₁₆H₁₈O₉

[M-H]^-

353.087 8

0.0

191.056 0, 179.034 6, 173.045 0, 135.045 1

Cryptochlorogenic acid^[24]

F\L\Q\W

29²⁾

16.95

C₂₆H₃₁NO₁₀

[M+H]⁺

518.201 6

-0.9

356.147 7, 338.137 2, 206.080 3, 188.070 1

2', 4',10'-Trimethoxy-5,8-dihydro-6H-isoquinolino
[3,2-a]isoquinoline-3,11-diolglucoside^[27]

F\L

30²⁾

17.24

C₂₀H₂₄NO₄⁺

[M]⁺

342.170 1

0.3

192.101 6, 177.077 9, 151.074 8

Cyclanoline^[28]

F\L

31¹⁾

17.82

C₉H₁₀O₅

[M-H]^-

197.045 5

3.3

182.022 4, 166.998 4

Syringic acid^[26]

F\D\B\L\Q\JL\JX\W

32¹⁾

17.84

C₂₀H₂₄NO₄⁺

[M]⁺

342.170 2

0.6

192.101 5, 177.077 5, 149.083 4, 120.076 4

Phellodendrine^[29]

F\L

33²⁾

17.93

C₁₇H₁₉NO₃

[M+H]⁺

286.144 2

1.5

255.100 7, 237.090 2, 143.048 7, 107.049 3

Coclaurine^[20]

F\Q\L

34²⁾

18.20

C₁₈H₁₉NO₃

[M+H]⁺

298.143 8

0.1

269.116 2, 238.097 8, 192.101 7, 161.083 0

Stepharine^[20]

F\Q

35¹⁾

18.69

C₂₁H₂₀O₉

[M+H]⁺

417.118 4

0.9

399.102 9, 363.082 2, 297.075 1

Puerarin^[30]

36²⁾

18.74

C₂₀H₂₆NO₄⁺

[M]⁺

344.185 4

-0.7

299.127 3, 175.074 7, 137.059 1, 58.066 2

Tembetarine^[20]

F\L

37¹⁾

19.04

C₂₀H₂₄NO₄⁺

[M]⁺

342.169 7

-0.8

297.110 1, 282.086 8, 265.083 9

Magnoflorine^[20]

F\L\Q

38²⁾

20.36

C₁₉H₂₃NO₄

[M+H]⁺

330.170 7

2.2

239.071 7, 209.058 5, 181.063 9

Isosinomenine^[28]

39²⁾

20.62

C₁₇H₂₀O₉

[M-H]^-

367.103 3

-0.4

191.056 4, 134.037 2

3-O-Feruloylquinic acid^[24]

F\L

40²⁾

21.04

C₂₀H₂₄NO₄⁺

[M]⁺

342.170 2

0.6

297.111 0, 265.084 7, 237.089 9, 58.066 0

Laurifoline^[20]

F\L\Q

41²⁾

21.42

C₁₉H₂₄NO₃⁺

[M]⁺

314.175 3

0.7

269.116 7, 143.048 9, 107.049 3, 58.066 1

Magnocurarine/Isomer^[20]

F\L\Q

42²⁾

21.51

C₂₁H₂₇NO₄

[M+H]⁺

358.201 2

-0.2

313.141 7, 189.090 1, 137.059 1, 58.066 1

N-Methylpalaudinium^[31]

F\L\Q

43¹⁾

21.60

C₉H₈O₃

[M+H]⁺

165.054 6

-0.1

147.052 4, 119.048 2, 91.056 9

4-Hydroxycinnamic acid

F\L\Q\W

44¹⁾

22.41

C₉H₆O₃

[M+H]⁺

163.039 3

2.0

119.048 1, 107.048 3

Umbelliferone^[32]

F\L\W

45²⁾

22.43

C₃₄H₄₆O₁₈

[M-H]^-

741.262 0

1.2

579.209 6, 417.155 2

Syringaresionl-di-O-β-D-glucopyranoside^[17]

L\Q

46²⁾

23.13

C₂₁H₂₆NO₄⁺

[M]⁺

356.186 2

1.6

311.125 8, 296.102 5

N-Methyl isocorydine/N-Methyl corydine^[20]

F\L\Q

47²⁾

23.25

C₁₅H₁₇NO₃

[M+H]⁺

260.128 7

2.2

242.116 8, 188.070 0, 176.069 9, 134.059 9

Psi-Ribalinine/Ribalinine^[33]

F\L

48²⁾

24.07

C₂₇H₃₀O₁₅

[M-H]^-

593.151 9

1.2

446.086 1, 301.035 5, 299.020 3, 271.024 0

Quercetin-3,7-O-α-L-dirhamnopyranoside^[34]

49³⁾

24.11

C₂₀H₂₆NO₃⁺

[M]⁺

328.191 2

1.5

251.105 6, 223.109 8, 143.048 5, 58.066 1

4'-Methoxymagnocurarine

F\L\Q

50²⁾

25.41

C₁₉H₁₇NO₄

[M+H]⁺

324.124 0

3.0

309.099 1, 294.075 2, 281.105 7

Stepharanine^[20]

51¹⁾

25.87

C₂₀H₂₄O₉

[M+H]⁺

409.149 1

-0.5

247.095 5, 229.083 6

Nodakenin^[35]

52²⁾

26.19

C₃₃H₄₄O₁₇

[M-H]^-

711.250 9

0.5

387.138 8

Medioresinol-di-O-β-D-glucopyranoside^[17]

53¹⁾

27.21

C₂₅H₂₄O₁₂

[M-H]^-

515.118 2

-2.5

353.087 2, 191.056 9, 179.036 0, 135.045 7

3,4-Dicaffeoylquinic acid^[24]

F\B\Q\JX

54²⁾

28.30

C₁₅H₁₇NO₃

[M+H]⁺

260.128 6

1.8

242.116 9, 188.070 2, 176.069 7, 134.059 3

Psi-Ribalinine/Ribalinine^[33]

F\L

55¹⁾

28.89

C₂₈H₃₄O₁₅

[M-H]^-

609.182 9

0.7

301.073 2, 286.049 0, 257.082 1, 151.003 8

Hesperidin^[14]

F\L

56²⁾

28.95

C₂₁H₂₃NO₅

[M+H]⁺

370.165 1

0.5

352.153 3, 290.093 6, 189.078 0, 188.070 1

Allocryptopine^[33]

F\L

57²⁾

29.38

C₁₁H₁₀O₄

[M+H]⁺

207.064 9

-1.4

179.067 4, 151.074 2, 107.048 6, 91.056 3

5,7-Dimethoxycoumarin^[14]

F\L\Q

58²⁾

29.60

C₂₀H₂₀NO₄⁺

[M]⁺

338.138 8

0.3

323.114 9, 322.106 5, 308.090 9, 294.111 7

Columbamine isomer^[20]

F\L\Q

59¹⁾

29.84

C₂₀H₁₈NO₄⁺

[M]⁺

336.123 4

1.1

320.091 5, 308.125 0, 292.095 8

Epiberberine^[36]

60¹⁾

30.03

C₁₉H₁₆NO₄⁺

[M]⁺

322.107 6

0.7

307.083 1, 279.089 5

Berberrubine^[36]

F\L

61¹⁾

30.17

C₂₀H₂₀NO₄⁺

[M]⁺

338.138 5

-0.5

323.114 0, 322.105 9, 308.092 5, 294.111 3

Columbamine^[20]

F\L\Q

62²⁾

30.75

C₁₇H₉NO₃

[M+H]⁺

276.065 8

1.0

248.069 3, 218.058 9, 190.063 5

Liriodenine^[33]

F\L

63¹⁾

31.64

C₂₂H₂₂O₉

[M+H]⁺

431.133 8

0.3

269.079 4

Ononin^[30]

64²⁾

32.37

C₁₄H₁₄O₄

[M+H]⁺

247.096 8

1.3

229.084 5, 175.038 6, 147.043 8

Marmesin^[32]

F\W

65²⁾

32.44

C₂₀H₁₅NO₄

[M+H]⁺

334.107 5

0.3

319.082 3, 304.060 2, 291.087 1, 276.064 5

Nornitidine^[37]

F\L

66²⁾

32.57

C₁₃H₁₁NO₄

[M+H]⁺

246.076 2

0.5

231.051 5, 216.028 4, 188.033 2, 160.038 9

Haplopine^[14]

F\L

67²⁾

32.62

C₂₀H₁₅NO₄

[M+H]⁺

334.107 5

0.6

319.082 2, 304.059 1, 291.088 0, 276.064 4

Norchelerythrine^[14]

F\L

68²⁾

33.39

C₁₈H₁₉NO₄

[M+H]⁺

314.139 2

1.6

177.054 4, 145.028 1, 117.033 1

Feruloyltyramine^[20]

69¹⁾

33.46

C₁₅H₁₀O₄

[M+H]⁺

255.065 5

1.2

199.076 7, 137.024 4

Daidzein^[30]

70²⁾

33.74

C₂₀H₁₄NO₄⁺

[M]⁺

332.092 3

1.7

317.069 4, 304.099 3, 302.081 3, 274.087 2

Sanguinarine^[38]

F\L

71¹⁾

33.76

C₂₁H₂₂NO₄⁺

[M]⁺

352.155 0

1.9

336.121 3, 322.105 2, 308.127 1, 294.113 0

Palmatine^[36]

72²⁾

33.85

C₁₆H₂₀O₆

[M+H]⁺

309.133 8

1.7

235.059 6, 219.064 9, 205.049 3, 177.053 8

Mexoticin/Toddalolactone^[14]

73¹⁾

34.07

C₁₅H₁₂O₄

[M-H]^-

255.066 9

2.4

135.008 6

Liquiritigenin^[39]

74²⁾

34.27

C₁₅H₁₂O₆

[M-H]^-

287.056 2

0.3

151.003 7, 135.044 6, 107.013 4

Eriodictyol

75²⁾

34.28

C₁₉H₂₁NO₅

[M+H]⁺

344.148 8

-1.3

177.054 2, 149.059 7, 145.028 1, 117.032 8

N-trans-Feruloyl-3-O-methyldopamine^[40]

76¹⁾

34.31

C₂₀H₁₈NO₄⁺

[M]⁺

336.123 8

2.3

321.096 8, 320.092 2, 306.075 2, 292.095 9,
278.079 3

Berberine^[36]

F\L\Q

77²⁾

34.96

C₁₁H₁₁NO₂

[M+H]⁺

190.086 6

1.8

175.065 3, 158.062 6, 147.069 1, 118.066 0

4-Methoxy-1-methyl-2-quinolone^[14]

F\L

78²⁾

35.30

C₂₂H₂₆O₈

[M-H]^-

417.154 6

-2.1

402.133 1, 387.111 6, 359.112 5, 181.050 9

Syringaresinol^[17]

F\L\Q

79¹⁾

35.68

C₁₆H₁₂O₅

[M+H]⁺

285.076 0

0.9

253.051 2, 225.054 9, 137.023 2

Calycosin^[30]

80¹⁾

35.73

C₂₁H₁₈NO₄⁺

[M]⁺

348.123 3

0.8

332.089 8, 318.074 7, 304.095 3

Nitidine^[11]

F\L

81¹⁾

35.89

C₁₅H₁₀O₇

[M-H]^-

301.035 3

-0.3

273.033 3, 255.026 1, 178.998 2, 151.002 7

Quercetin^[10]

JL\JX

82²⁾

36.50

C₁₂H₉NO₃

[M+H]⁺

216.064 9

-2.9

201.042 8, 183.031 1, 173.045 6, 155.034 1

Robustine^[14]

83²⁾

36.76

C₁₇H₁₄O₆

[M+H]⁺

315.086 9

1.9

300.065 0, 167.032 6

Odoratin^[41]

84¹⁾

37.28

C₂₁H₁₈NO₄⁺

[M]⁺

348.123 2

0.5

332.089 3, 318.073 8, 304.095 0

Chelerythrine^[14]

F\L

85²⁾

37.37

C₂₂H₂₆O₈

[M-H]^-

417.155 0

-1.2

387.115 0, 166.025 2

Syringaresinol^[17]

86¹⁾

37.76

C₁₁H₆O₃

[M+H]⁺

187.039 1

0.7

159.043 2, 143.048 7, 131.049 1, 115.054 1

Psoralen^[16]

87¹⁾

39.00

C₁₄H₁₃NO₄

[M+H]⁺

260.091 9

0.6

245.066 9, 227.056 4, 216.064 2, 199.061 8

Skimmianine^[14]

F\L

88²⁾

39.55

C₁₅H₁₂O₅

[M-H]^-

271.061 8

2.2

135.045 3, 135.008 7, 117.033 5, 107.049 1

3',4',7-Trihydroxyflavanone^[41]

89²⁾

40.06

C₁₃H₁₁NO₃

[M+H]⁺

230.081 5

1.4

215.056 8, 200.033 4, 186.054 0, 172.038 8

γ-Fagarine^[14]

F\B\L\W

90¹⁾

41.15

C₁₆H₁₄O₆

[M-H]^-

301.072 0

0.8

286.047 0, 151.003 1

Hesperetin^[39]

F\L

91²⁾

41.17

C₁₆H₁₂O₆

[M-H]^-

299.056 1

0.0

284.033 2, 227.033 5, 133.029 5, 107.014 3

Diosmetin^[42]

92¹⁾

42.35

C₁₂H₉NO₂

[M+H]⁺

200.070 9

1.5

185.046 8, 129.057 0,102.046 0

Dictamnine^[14]

F\L

93¹⁾

42.83

C₁₂H₈O₄

[M+H]⁺

217.049 8

1.2

202.025 2, 174.030 2, 146.035 5, 118.040 7

Bergapten^[14]

94¹⁾

43.30

C₁₅H₁₂O₄

[M+H]⁺

257.080 8

-0.1

239.069 3, 147.043 4, 137.023 2, 119.048 8

Isoliquiritigenin^[39]

95¹⁾

43.57

C₁₆H₁₂O₄

[M+H]⁺

269.081 1

1.0

254.056 4, 237.053 9, 226.061 4,213.091 3,
197.059 3,181.062 8, 137.022 0, 118.041 6,
107.047 9

Formononetin^[30]

96²⁾

44.02

C₂₁H₁₉NO₆

[M+H]⁺

382.128 4

-0.3

364.116 3, 349.094 6, 339.105 4, 292.070 4

Isoarnottianamide^[33]

F\L

97²⁾

44.62

C₂₀H₂₀O₇

[M+H]⁺

373.128 2

0.1

357.098 0, 343.081 5, 153.017 7

Pentamethoxyflavone^[43]

98²⁾

45.11

C₂₀H₂₀O₇

[M+H]⁺

373.128 4

0.6

357.095 3, 343.080 6

Pentamethoxyflavone^[43]

99²⁾

46.03

C₂₁H₂₂O₈

[M+H]⁺

403.139 6

2.1

373.089 8, 359.112 3

5,6,7,3',4',5'-Hexamethoxyflavone^[44]

100²⁾

46.37

C₁₉H₁₆O₇

[M+H]⁺

357.097 0

0.3

342.072 3, 327.047 2, 313.068 6, 153.017 9

5,7,5'-Trimethoxy-3',4'-methylenedioxy-
flavone^[45]

101²⁾

46.92

C₁₅H₁₄O₄

[M+H]⁺

259.096 7

0.8

243.067 2, 229.054 5, 201.051 6

Luvangetin^[14]

F\L

102²⁾

47.20

C₂₁H₁₉NO₆

[M+H]⁺

382.128 8

0.7

364.126 1, 354.137 6, 339.112 6, 292.071 9

Arnottianamide^[33]

F\L

103²⁾

47.30

C₂₀H₁₇NO₅

[M+H]⁺

352.118 2

0.7

337.092 9, 322.069 5, 308.088 3, 294.073 6

Oxyberberine^[46]

104²⁾

47.30

C₂₀H₁₈O₈

[M+H]⁺

387.107 7

0.7

371.074 9, 357.058 4, 343.081 1

5,6,7,5'-Tetramethoxy-3',4'-methylenedioxy
flavone^[44]

105²⁾

48.61

C₁₅H₁₅NO₂

[M+H]⁺

242.117 7

0.6

200.070 6, 188.070 9, 172.076 7, 144.080 5

N-Methylflindersine^[14]

F\L

106²⁾

49.38

C₂₁H₁₇NO₅

[M+H]⁺

364.118 3

1.0

349.093 4, 334.069 6, 320.089 6, 306.075 6

Oxychelerythrine^[14]

F\L

107¹⁾

51.06

C₂₀H₁₈O₆

[M+H]⁺

355.118 0

1.1

337.106 5, 319.098 2, 289.078 7, 135.044 0

Sesamin

108²⁾

51.18

C7₅H₁₀O₅

[M-H]^-

269.045 7

0.6

241.050 5, 225.055 6

Emodin^[21]

109²⁾

52.42

C₂₃H₂₁NO₆

[M+H]⁺

408.144 6

1.1

348.121 2, 333.098 2, 332.089 0, 318.074 4

6-Propoxychelerythrine^[38]

F\L

110²⁾

52.80

C₂₂H₂₁NO₅

[M+H]⁺

380.149 7

1.2

362.137 5, 347.114 5, 334.106 0, 319.085 5

6-Hydroxyl-10-methoxysanguinarine^[38]

F\L

111²⁾

54.51

C₁₆H₁₈O₄

[M+H]⁺

275.127 9

0.4

245.080 9, 217.050 0, 205.048 9

7-Methyl ether heteropeucenin

F\D\B\L\Q\JL\JX\W

112²⁾

54.54

C₂₀H₁₅NO₄

[M+H]⁺

334.107 5

0.3

319.082 1, 304.060 5

Norchelerythrine^[14]

F\L

113²⁾

55.86

C₂₁H₁₉NO₄

[M+H]⁺

350.138 7

0.0

335.113 7, 334.105 9, 318.098 4, 304.094 5

Dihydrochelerythrine^[14]

F\L