药学学报

Type	t_R/min	Formula	[M+H]⁺/[M-H]^-	Fragment ions	Identification
Peptides	P1	4.13	C₂₅H₃₂ClN₅O₈	566.201 2	566.199 9 [+]	-2.3	548.189 5, 318.085 5, 232.096 9, 106.065 1	Astin L^[17]
P2	4.52	C₂₅H₃₅N₅O₇	518.260 9	518.259 8 [+]	-2.1	490.264 9, 286.139 8, 171.112 7, 106.065 1	Asterinin F^[18]
P3	5.35	C₂₅H₃₂ClN₅O₇	550.206 3	550.205 8 [+]	-0.9	532.192 7, 302.089 9, 215.058 0, 106.065 0	Astin H^[19]
P4	5.58	C₂₅H₃₅N₅O₆	502.266 0	502.264 9 [+]	-2.3	474.267 9, 270.143 7, 183.111 7, 106.065 0	Astin G^[19]
P5	6.11	C₂₅H₃₂ClN₅O₇	550.206 3	550.205 4 [+]	-1.7	522.209 8, 447.142 2, 300.074 1, 106.065 0	Astin E^[19]
P6	6.21	C₂₅H₃₄ClN₅O₇	552.222 0	552.219 7 [+]	-4.1	524.225 7, 449.159 2, 320.100 7, 106.065 0	Astin I^[19]
P7	6.88	C₂₅H₃₄ClN₅O₆	536.227 0	536.226 3 [+]	-1.4	508.231 4, 451.174 3, 304.106 0, 106.065 4	Astin F^[19]
P8	7.21	C₂₅H₃₂ClN₅O₆	534.211 4	543.211 0 [+]	-0.8	506.215 2, 449.157 9, 106.065 1	Astin D^[19]
P9	7.27	C₂₅H₃₃N₅O₈	532.240 2	532.239 2 [+]	-1.8	514.226 7, 338.169 9, 235.105 8, 106.065 3	Asterinin A^[20]
P10	7.33	C₂₅H₃₃Cl₂N₅O₈	602.177 9	602.176 3 [+]	-3.0	584.165 1, 336.057 1, 232.097 3, 106.064 4	Astin K^[17]
P11	7.58	C₂₆H₃₅N₅O₈	546.255 8	546.254 0 [+]	-3.4	528.244 7, 350.170 7, 235.107 8, 106.065 0	Asterinin C^[20]
P12	7.84	C₂₅H₃₃Cl₂N₅O₇	586.183 0	586.181 4 [+]	-2.6	558.183 6, 336.049 7, 106.065 2, 58.065 0	Astin A^[19]
P13	7.87	C₂₅H₃₃Cl₂N₅O₇	586.183 0	586.182 9 [+]	-0.1	558.183 1, 130.049 1, 106.065 5, 60.044 2	Astin B^[19]
P14	8.19	C₂₅H₃₃N₅O₇	516.2453	516.243 9 [+]	-2.7	498.232 9, 338.170 0, 235.106 6, 106.065 3	Astin J^[21]
P15	8.25	C₂₅H₃₃N₅O₈	546.255 8	546.254 6 [+]	-2.3	528.245 8, 352.186 4, 235.107 6, 106.065 0	Asterinin B^[20]
P16^*	8.46	C₂₅H₃₃Cl₂N₅O₆	570.188 1	570.187 3 [+]	-1.4	485.133 3, 338.066 5, 251.034 1, 106.064 9	Astin C
P17	8.53	C₂₆H₃₃Cl₂N₅O₇	600.198 6	600.198 2 [+]	-0.7	582.193 5, 501.132 8, 336.051 5, 106.065 2	Astin P^[17]
P18	11.07	C₂₇H₃₅Cl₂N₅O₇	612.198 6	612.197 2 [+]	-2.3	548.202 3, 467.124 2, 380.077 5, 106.065 3	Astin O^[17]
Organic acids	O1	0.61	C₄H₆O₄	117.019 3	117.019 3 [-]	0.1	99.008 8, 71.031 8	Succinic acid
O2	0.75	C₆H₁₀O₄	145.050 6	145.050 7 [-]	0.4	127.039 4, 109.037 7, 71.031 5	2, 2-Dimethylsuccinic acid
O3^*	0.81	C₆H₆O₃	127.039 0	127.039 0 [+]	0.2	109.028 8, 81.034 6, 53.041 4	Pyrogallic acid
O4^*	1.30	C₇H₆O₄	155.033 9	155.033 7 [+]	-1.0	93.032 7, 65.040 1	Protocatechuate
O5	2.04	C₇H₆O₃	139.039 0	139.038 7 [+]	-2.2	121.027 8, 95.049 1, 77.038 9, 65.040 2	4-Hydroxybenzoic acid
O6^*	2.57	C₁₆H₁₈O₉	353.087 8	353.087 5 [-]	-1.0	191.055 6, 93.035 8	Chlorogenic acid
O7	2.70	C₈H₈O₄	169.049 5	169.049 1 [+]	-2.8	151.038 2, 125.058 6, 65.040 4	Vanillic acid
O8^*	2.80	C₉H₈O₄	181.049 5	181.049 1 [+]	-2.3	163.038 7, 135.034 4, 117.033 4, 89.038 7	Caffeic acid
O9	2.85	C₁₆H₁₈O₉	353.087 8	353.087 2 [-]	-1.7	191.055 6, 173.045 0, 93.035 9	Cryptochlorogenic acid^[22]
O10	3.87	C₂₅H₂₄O₁₂	515.119 5	515.118 5 [-]	-1.9	353.086 6, 335.076 4, 191.055 6, 179.034 6	3, 4-Dicaffeoylquinic acid^[23]
O11^*	4.71	C₁₀H₁₀O₄	195.065 2	195.064 8 [+]	-2.0	177.054 4, 145.028 0, 117.032 9, 89.038 4	Ferulic acid
O12^*	5.09	C₇H₆O₂	123.044 1	123.043 6 [+]	-3.4	105.032 9, 77.039 8	Benzoic acid
O13	5.23	C₁₆H₁₈O₉	353.087 8	353.087 5 [-]	-1.0	191.055 6, 179.035 0, 135.044 9	1, 5-caffeoylquinic acid^[22]
O14^*	5.33	C₁₀H₁₀O₄	195.065 2	195.065 0 [+]	-0.7	177.053 8, 149.058 7, 117.032 5, 89.038 4	Isoferulic acid
O15	5.95	C₂₅H₂₄O₁₂	515.119 5	515.118 9 [-]	-1.2	353.086 9, 335.077 2, 191.056 2, 179.034 7	4, 5-Dicaffeoylquinic acid^[23]
O16^*	6.27	C₂₅H₂₄O₁₂	515.119 5	515.118 6 [-]	-1.9	353.086 0, 335.076 0, 191.055 6, 179.033 4	cynarin
O17^*	6.33	C₁₀H₁₀O₄	195.065 2	195.065 4 [+]	1.0	163.039 4, 145.028 4, 117.033 5, 89.039 7	Methyl caffeate
O18	6.99	C₂₅H₂₄O₁₂	515.119 5	515.118 3 [-]	-2.3	353.086 5, 335.076 1, 191.055 6, 161.023 4	3, 5-Dicaffeoylquinic acid^[23]
O19^*	9.05	C₉H₁₀O₃	167.070 3	167.070 0 [+]	-1.5	149.059 0, 121.064 2, 91.054 5, 77.039 4	Paeonol
O20	21.97	C₂₇H₄₄O₄	433.331 2	433.329 8 [+]	-3.4	181.049 7, 163.039 1	Octadecyl caffeate
O21	22.84	C₂₂H₄₄O₂	339.326 9	339.326 3 [-]	-1.6	321.315 5, 293.066 5	n-Docosanoic acid
O22	24.29	C₃₁H₅₂O₄	489.393 8	489.391 8 [+]	-4.2	181.049 2, 163.039 2	Docosyl caffeate
Flavonoids	F1^*	3.63	C₁₅H₁₂O₈	321.060 5	321.060 8 [+]	0.5	303.049 8, 275.054 6, 247.059 7, 153.017 4	Dihydromyricetin
F2^*	4.73	C₂₆H₂₈O₁₄	563.140 6	563.140 2 [-]	-0.8	545.130 8, 473.107 4, 443.096 9, 353.065 0	Schaftoside
F3^*	4.79	C₂₆H₂₈O₁₄	563.140 6	563.140 0 [-]	-1.0	503.118 6, 473.108 4, 443.097 4, 383.076 0	Isoschaftoside
F4	5.19	C₂₁H₂₀O₉	417.118 0	417.118 1 [+]	0.1	271.060 3, 243.065 7, 197.059 9, 153.018 2	Apigenin-5-rhamnoside
F5^*	5.25	C₂₁H₂₀O₁₂	463.088 2	463.088 9 [-]	1.2	317.029 6, 151.023 0	Myrictrin
F6^*	5.38	C₂₁H₂₀O₁₂	465.102 8	465.102 2 [+]	-0.9	303.050 3, 287.055 8, 121.028 0	Hyperoside
F7^*	5.47	C₂₇H₃₀O₁₆	609.146 0	609.146 0 [-]	-0.1	463.189 8, 301.038 9	Rutin
F8^*	5.61	C₂₁H₂₀O₁₂	465.102 8	465.102 1 [+]	-1.3	303.050 4, 287.054 5, 121.028 9	Isoquercitrin
F9^*	5.64	C₂₁H₂₀O₁₁	449.107 8	449.108 6 [+]	1.7	287.055 9, 153.017 5	Luteolin-7-galacturonide
F10^*	5.75	C₂₁H₂₀O₁₀	433.112 9	433.112 5 [+]	-0.9	271.059 2, 215.068 8	Genistin
F11	6.08	C₂₈H₃₂O₁₆	625.176 3	625.176 4 [+]	0.1	317.066 1, 285.043 4, 153.017 6	Isorhamnetin-3-O- neohespeidoside
F12^*	6.42	C₂₁H₂₀O₁₁	449.107 8	449.106 9 [+]	-2.0	303.050 4, 287.055 0, 121.028 4	Quercitrin
F13^*	6.56	C₂₁H₂₀O₁₁	449.107 8	449.107 2 [+]	-1.5	287.054 5, 153.017 2	Kaempferol-7-O-β-D- glucopyranoside
F14	6.62	C₂₂H₂₂O₁₂	478.393 4	478.391 9 [+]	-3.6	317.065 6, 285.043 4, 153.017 6	Isorhamnetin-3-O-glucoside
F15^*	6.68	C₁₅H₁₀O₈	319.044 8	319.044 9 [+]	0.2	301.034 1, 273.038 7, 245.043 6, 153.017 4	Myricetin
F16^*	6.95	C₂₈H₁₄O₁₅	611.197 0	611.196 2 [+]	-1.5	303.086 7, 263.055 3, 177.055 2	Hesperidin
F17^*	7.66	C₁₅H₁₂O₄	257.080 8	257.080 9 [+]	0.2	239.069 4, 211.074 7, 147.044 2, 137.023 3	Liquiritigenin
F18^*	7.72	C₂₁H₁₈O₁₁	447.092 2	447.091 2 [+]	-2.2	271.059 6, 253.049 5, 123.007 4	Baicalin
F19^*	7.97	C₁₅H₁₀O₆	287.055 0	287.054 9 [+]	-0.6	269.043 8, 185.059 0, 153.017 9	Luteolin
F20^*	8.15	C₁₅H₁₀O₇	303.049 9	303.050 0 [+]	0.2	285.038 6, 257.045 7, 229.049 4, 153.018 0	Quercetin
F21	8.46	C₂₇H₃₀O₁₅	595.165 8	595.168 6 [+]	4.9	287.054 7, 153.017 3	Biorobin^[24]
F22^*	8.86	C₁₅H₁₂O₅	273.075 8	273.075 5 [+]	-0.9	153.018 0, 147.043 6, 119.049 0	Naringenin
F23^*	8.95	C₁₅H₁₀O₅	271.060 1	271.059 9 [+]	-0.9	253.050 1, 215.070 4, 153.018 2, 91.055 0	Genistein
F24^*	9.01	C₁₅H₁₀O₅	271.060 1	271.060 0 [+]	-0.4	253.050 3, 243.065 7, 197.059 9, 153.018 2	Apigenin
F25^*	9.16	C₁₅H₁₀O₆	287.055 0	287.055 2 [+]	0.8	269.043 4, 153.017 3, 121.027 8	Kaempferol
F26^*	9.37	C₁₆H₁₂O₆	301.070 7	301.070 9 [+]	0.9	286.047 9, 258.053 0, 229.050 2	Diosmetin
F27^*	9.45	C₁₆H₁₂O₇	317.065 6	317.065 8 [+]	0.8	299.060 7, 289.067 8, 229.049 4, 153.018 2	Isorhamnetin
F28^*	9.61	C₁₅H₁₀O₃₅	271.060 1	271.060 0 [+]	-0.4	253.049 7, 169.012 8, 123.007 4	Baicalein
F29^*	10.95	C₁₆H₁₂O₅	285.075 8	285.076 0 [+]	0.8	252.042 6, 179.049 6	Wogonin
F30^*	11.20	C₁₆H₁₂O₅	285.075 8	285.076 0 [+]	0.8	270.053 0, 242.057 6, 153.018 0	Acacetin
F31^*	11.33	C₁₆H₁₂O₅	285.075 8	285.075 7 [+]	-0.1	270.050 8, 242.056 0, 167.033 0, 124.015 1	Genkwanin
Monoterpenes	MP1	8.23	C₂₁H₃₆O₁₀	449.238 1	449.237 2 [+]	-2.1	317.195 7, 133.049 8	Shionoside A
MP2	8.34	C₂₂H₃₈O₁₀	463.253 8	463.252 8 [+]	-2.2	317.196 3, 147.065 4	Shionoside B
Diterpenes	DP1	7.05	C₂₀H₂₀O₆	357.133 3	357.133 0 [+]	-0.8	339.122 4, 207.064 4, 189.053 5, 137.059 2	A^a^[28]
DP2	9.76	C₄₂H₆₆O₁₆	825.427 8	825.431 0 [-]	3.9	779.430 3	Smithoside B^[28]
DP3	10.07	C₂₀H₃₂O₆	367.212 6	367.211 4 [-]	-3.2	329.235 6, 206.019 8, 171.102 1, 146.967 1	Lingulatusin^[26]
DP4	12.91	C₂₀H₃₂O₄	337.237 3	337.237 4 [+]	0.1	319.230 9	B^b^[27]
DP5	21.29	C₂₆H₄₄O₅	435.311 6	435.309 6 [-]	-4.7	367.323 7, 321.316 1	Glycoside 1^[28]
Triterpenens	TP1	9.28	C₃₀H₄₈O₅	489.357 5	489.356 5 [+]	-1.9	471.345 5, 453.336 6, 201.164 4, 187.148 7	C^c
TP2	9.35	C₄₁H₆₆O₁₄	783.452 5	783.450 5 [+]	-2.6	489.357 3, 453.336 3, 407.331 3, 259.081 5	D^d^[29]
TP3	9.43	C₆₇H₁₀₈O₃₄	1 455.664 9	1 455.663 7 [-]	-0.8	1 323.618 7, 673.228 8	Astersaponin A^[30]
TP4	9.61	C₆₂H₁₀₀O₃₄	1 323.622 7	1 323.621 8 [-]	-0.6	541.178 8, 337.117 0	Astersaponin E^[30]
TP5	10.32	C₆₂H₁₀₀O₂₉	1 307.627 8	1 307.627 7 [-]	-0.1	1 175.588 9, 541.179 0	Astersaponin F^[30]
TP6	10.41	C₅₇H₉₂O₂₅	1 175.585 5	1 175.584 8 [-]	-0.6	953.530 8, 765.447 1, 633.412 4, 471.358 3	Asterlingulatoside D
TP7	10.46	C₅₂H₈₄O₂₁	1 043.542 3	1 043.542 5 [-]	-0.7	997.541 0, 765.456 8, 633.415 3, 471.336 2	Asterlingulatoside C
TP8	10.53	C₅₃H₈₆O₂₃	1 089.548 7	1 089.548 2 [-]	-0.5	953.514 5, 807.456 6, 765.445 4, 633.403 3	Bellidiastroside C2
TP9	10.71	C₅₃H₈₆O₂₂	1 073.553 8	1 073.553 7 [-]	-0.1	937.522 6, 617.405 5	Bellidiastroside B1^[31]
TP10	10.85	C₄₂H₆₈O₁₅	811.448 6	811.447 7 [-]	-1.0	765.448 7	Asterbatanoside B
TP11	10.94	C₅₆H₉₀O₂₅	1 161.569 8	1 161.569 3 [-]	-0.5	673.226 3, 601.197 8, 487.341 1, 281.085 2	Asterbatanoside F^[31]
TP12	11.01	C₅₃H₈₆O₂₂	1 073.553 8	1 073.553 9 [-]	0.1	937.522 6, 749.455 1	Bellidiastrodise B3^[31]
TP13	11.37	C₅₇H₉₀O₂₇	1 205.559 7	1 205.559 2 [-]	-0.4	131.034 3	Ageratoside B2^[31]
TP14	12.47	C₄₂H₆₈O₁₅	811.448 6	811.448 1 [-]	-0.6	765.448 5	Asterbatanoside C^[31]
TP15	13.58	C₄₇H₇₆O₁₇	911.501 0	911.499 9 [-]	-1.2	865.458 2	Asterlingulatoside B
TP16	13.89	C₄₁H₆₆O₁₃	765.443 1	765.441 2 [-]	-2.4	719.440 8	Asterlingulatoside A
TP17^*	14.06	C₃₀H₄₈O₄	471.348 0	471.348 2 [-]	0.5	327.525 4, 242.835 4	23-Hydroxybetulinic acid^[31]
TP18	16.32	C₃₀H₄₈O₄	471.348 0	471.348 1 [-]	0.3	407.333 2	Echinocystic acid
TP19	16.59	C₂₆H₄₂O₃	403.320 7	403.319 6 [+]	-2.7	385.310 0, 367.298 8, 203.179 4, 121.100 8	Astershionone A^[32]
TP20^*	17.01	C₃₀H₄₈O₃	455.353 1	455.354 9 [-]	4.0	409.381 9, 302.969 8, 258.499 2, 81.122 8	Betulinic acid
TP21	17.07	C₂₇H₄₂O₂	399.325 8	399.324 5 [+]	-3.2	381.316 3, 363.303 2, 217.195 0, 191.177 4	Astershionone F^[32]
TP22	17.41	C₂₇H₄₄O₃	417.336 3	417.335 1 [+]	-2.9	399.324 8, 381.315 5, 217.195 1, 191.178 6	Astershionone C^[32]
TP23^*	17.57	C₃₀H₄₈O₃	457.367 6	457.367 3 [+]	-0.7	439.355 3, 411.362 1, 217.192 9, 191.177 9	Oleanic acid
TP24	17.77	C₃₀H₅₀O₂	443.388 4	443.387 1 [+]	-2.8	425.377 2, 407.365 3, 217.195 1, 191.178 0	Friedelan-3-ol
TP25	18.28	C₃₀H₅₀O₂	443.388 4	443.386 8 [+]	-3.5	425.376 4, 407.365 9, 217.194 9, 191.178 9	Astertarone B^[37]
TP26^*	18.94	C₃₀H₅₀O	429.409 1	429.409 2 [+]	0.2	411.312 3, 338.347 1, 191.178 9	epi-Friedellanol^[31]
TP27	19.20	C₂₉H₄₆O₂	427.357 1	427.356 [+]	-2.6	409.346 9, 391.334 1, 287.200 9, 191.178 8	Astershionone B^[32]
TP28	19.39	C₃₀H₅₀O	427.393 4	427.392 0 [+]	-3.3	409.381 7, 217.195 0, 191.179 4	beta-Amyrin^[31]
TP29	19.79	C₃₀H₄₈O₂	441.372 7	441.372 3 [+]	-1.0	423.362 2, 405.348 5, 191.178 7	E^e^[31]
TP30	20.01	C₃₀H₄₈O	425.377 8	425.376 8 [+]	-2.4	407.366 0, 217.194 6, 191.179 1	Taraxerone^{[33, 34]}
TP31	20.22	C₃₀H₅₀O₂	443.388 4	443.387 1 [+]	-2.9	425.380 1, 407.367 7, 217.194 8, 191.179 0	Astatarone G
TP32^*	20.96	C₃₀H₅₀O₂	443.388 4	443.387 4 [+]	-2.2	425.379 7, 413.379 7, 217.194 9, 191.179 4	Betulin
TP33	21.81	C₃₀H₅₀O	427.393 4	427.391 9 [+]	-3.6	409.383 3, 341.321 2, 191.179 1	Taraxasterol^[36]
TP34	23.74	C₃₀H₅₀O	427.393 4	427.392 9 [+]	-2.4	409.379 9, 217.195 1, 191.178 2	Astertarone A^[35]
TP35^*	23.87	C₃₀H₅₀O	427.393 4	427.393 1 [+]	-0.9	409.386 1, 331.298 3, 217.194 4, 191.179 4	Friedelin
TP36^*	24.72	C₃₀H₅₀O	427.393 4	427.393 2 [+]	-0.6	409.382 8, 217.194 3, 191.178 9	Shionone
Coumarin	C1^*	2.00	C₁₅H₁₆O₉	341.086 7	341.087 0 [+]	0.9	179.034 2, 151.038 4, 105.034 6	Esculin
C2^*	2.68	C₉H₆O₄	179.033 9	179.033 9 [+]	-0.1	151.038 7, 133.028 6, 123.044 1, 105.034 0	Esculetin
C3^*	3.71	C₁₀H₈O₅	209.044 4	209.044 5 [+]	0.3	181.048 8, 163.038 7, 149.023 2, 121.028 4	Fraxetin
C4^*	4.23	C₁₀H₈O₄	193.049 5	193.049 4 [+]	-0.3	178.026 1, 150.031 0, 133.028 2, 122.036 1	Isoscopoletin
C5^*	4.39	C₉H₆O₃	163.039 0	163.038 7 [+]	-1.9	119.049 4, 107.049 2, 91.054 6, 77.039 5	7-Hydroxyeoumarin
C6^*	4.60	C₁₀H₈O₄	193.049 5	193.049 4 [+]	-0.3	178.026 3, 137.059 9, 133.028 6, 122.036 6	Scopoletin
C7^*	8.43	C₁₁H₆O₃	187.039 0	187.038 8 [+]	-0.8	143.049 5, 131.049 1, 115.054 6, 77.040 0	Psoralen
C8^*	8.93	C₁₂H₈O₄	217.049 5	217.049 7 [+]	0.8	202.026 0, 185.024 0, 174.031 2, 118.041 8	Xanthotoxin
C9^*	9.68	C₁₂H₈O₄	217.049 5	217.049 5 [+]	0.1	202.026 4, 174.030 7, 146.035 3, 118.040 6	Bergapten
Anthraquinones	AQ1^*	10.79	C₁₅H₈O₆	341.086 7	347.087 0 [-]	0.9	239.034 3, 211.039 3, 183.044 3	Rhein
AQ2	11.20	C₁₅H₁₂O₄	255.066 3	255.066 1 [-]	-0.9	227.072 2, 211.076 4, 183.079 7, 107.014 8	Emodin anthrone
AQ3^*	12.63	C₁₅H₁₀O₅	269.045 5	269.045 7 [-]	0.7	241.050 0, 225.055 1, 197.060 4, 181.065 8	Emodin
Steroids	S1	7.76	C₃₅H₅₈O₆	575.430 6	575.431 1 [+]	-2.3	413.377 1, 395.363 0, 255.208 1, 189.015 7	F^f^[31]
S2^*	18.81	C₂₉H₄₈O	413.377 8	413.376 2 [+]	-3.9	395.368 7, 255.208 4, 189.016 7, 109.065 3	α-Spinasterol
S3	24.25	C₂₉H₄₈O	413.377 8	413.376 5 [+]	-3.1	395.363 9, 109.064 6	Stigmasterol^[38]
Aldehydes	A1	1.46	C₆H₆O₃	127.039 0	127.038 8 [+]	-1.9	109.027 6, 53.040 5	5-Hydroxymethyl-2- furaldehyde
A2^*	1.93	C₇H₆O₃	139.039 0	139.038 8 [+]	-0.9	111.044 6, 93.034 1, 65.040 4	Benzaldehyde
A3^*	2.73	C₇H₆O₂	123.044 1	123.043 9 [+]	-1.3	95.049 3, 77.039 5, 67.055 7, 65.040 1	p-Hydroxybenzaldehyde

Type	t_R/min	Formula	[M+H]⁺/[M-H]^-	Fragment ions	Identification
Peptides	P1	4.13	C₂₅H₃₂ClN₅O₈	566.201 2	566.199 9 [+]	-2.3	548.189 5, 318.085 5, 232.096 9, 106.065 1	Astin L^[17]
P2	4.52	C₂₅H₃₅N₅O₇	518.260 9	518.259 8 [+]	-2.1	490.264 9, 286.139 8, 171.112 7, 106.065 1	Asterinin F^[18]
P3	5.35	C₂₅H₃₂ClN₅O₇	550.206 3	550.205 8 [+]	-0.9	532.192 7, 302.089 9, 215.058 0, 106.065 0	Astin H^[19]
P4	5.58	C₂₅H₃₅N₅O₆	502.266 0	502.264 9 [+]	-2.3	474.267 9, 270.143 7, 183.111 7, 106.065 0	Astin G^[19]
P5	6.11	C₂₅H₃₂ClN₅O₇	550.206 3	550.205 4 [+]	-1.7	522.209 8, 447.142 2, 300.074 1, 106.065 0	Astin E^[19]
P6	6.21	C₂₅H₃₄ClN₅O₇	552.222 0	552.219 7 [+]	-4.1	524.225 7, 449.159 2, 320.100 7, 106.065 0	Astin I^[19]
P7	6.88	C₂₅H₃₄ClN₅O₆	536.227 0	536.226 3 [+]	-1.4	508.231 4, 451.174 3, 304.106 0, 106.065 4	Astin F^[19]
P8	7.21	C₂₅H₃₂ClN₅O₆	534.211 4	543.211 0 [+]	-0.8	506.215 2, 449.157 9, 106.065 1	Astin D^[19]
P9	7.27	C₂₅H₃₃N₅O₈	532.240 2	532.239 2 [+]	-1.8	514.226 7, 338.169 9, 235.105 8, 106.065 3	Asterinin A^[20]
P10	7.33	C₂₅H₃₃Cl₂N₅O₈	602.177 9	602.176 3 [+]	-3.0	584.165 1, 336.057 1, 232.097 3, 106.064 4	Astin K^[17]
P11	7.58	C₂₆H₃₅N₅O₈	546.255 8	546.254 0 [+]	-3.4	528.244 7, 350.170 7, 235.107 8, 106.065 0	Asterinin C^[20]
P12	7.84	C₂₅H₃₃Cl₂N₅O₇	586.183 0	586.181 4 [+]	-2.6	558.183 6, 336.049 7, 106.065 2, 58.065 0	Astin A^[19]
P13	7.87	C₂₅H₃₃Cl₂N₅O₇	586.183 0	586.182 9 [+]	-0.1	558.183 1, 130.049 1, 106.065 5, 60.044 2	Astin B^[19]
P14	8.19	C₂₅H₃₃N₅O₇	516.2453	516.243 9 [+]	-2.7	498.232 9, 338.170 0, 235.106 6, 106.065 3	Astin J^[21]
P15	8.25	C₂₅H₃₃N₅O₈	546.255 8	546.254 6 [+]	-2.3	528.245 8, 352.186 4, 235.107 6, 106.065 0	Asterinin B^[20]
P16^*	8.46	C₂₅H₃₃Cl₂N₅O₆	570.188 1	570.187 3 [+]	-1.4	485.133 3, 338.066 5, 251.034 1, 106.064 9	Astin C
P17	8.53	C₂₆H₃₃Cl₂N₅O₇	600.198 6	600.198 2 [+]	-0.7	582.193 5, 501.132 8, 336.051 5, 106.065 2	Astin P^[17]
P18	11.07	C₂₇H₃₅Cl₂N₅O₇	612.198 6	612.197 2 [+]	-2.3	548.202 3, 467.124 2, 380.077 5, 106.065 3	Astin O^[17]
Organic acids	O1	0.61	C₄H₆O₄	117.019 3	117.019 3 [-]	0.1	99.008 8, 71.031 8	Succinic acid
O2	0.75	C₆H₁₀O₄	145.050 6	145.050 7 [-]	0.4	127.039 4, 109.037 7, 71.031 5	2, 2-Dimethylsuccinic acid
O3^*	0.81	C₆H₆O₃	127.039 0	127.039 0 [+]	0.2	109.028 8, 81.034 6, 53.041 4	Pyrogallic acid
O4^*	1.30	C₇H₆O₄	155.033 9	155.033 7 [+]	-1.0	93.032 7, 65.040 1	Protocatechuate
O5	2.04	C₇H₆O₃	139.039 0	139.038 7 [+]	-2.2	121.027 8, 95.049 1, 77.038 9, 65.040 2	4-Hydroxybenzoic acid
O6^*	2.57	C₁₆H₁₈O₉	353.087 8	353.087 5 [-]	-1.0	191.055 6, 93.035 8	Chlorogenic acid
O7	2.70	C₈H₈O₄	169.049 5	169.049 1 [+]	-2.8	151.038 2, 125.058 6, 65.040 4	Vanillic acid
O8^*	2.80	C₉H₈O₄	181.049 5	181.049 1 [+]	-2.3	163.038 7, 135.034 4, 117.033 4, 89.038 7	Caffeic acid
O9	2.85	C₁₆H₁₈O₉	353.087 8	353.087 2 [-]	-1.7	191.055 6, 173.045 0, 93.035 9	Cryptochlorogenic acid^[22]
O10	3.87	C₂₅H₂₄O₁₂	515.119 5	515.118 5 [-]	-1.9	353.086 6, 335.076 4, 191.055 6, 179.034 6	3, 4-Dicaffeoylquinic acid^[23]
O11^*	4.71	C₁₀H₁₀O₄	195.065 2	195.064 8 [+]	-2.0	177.054 4, 145.028 0, 117.032 9, 89.038 4	Ferulic acid
O12^*	5.09	C₇H₆O₂	123.044 1	123.043 6 [+]	-3.4	105.032 9, 77.039 8	Benzoic acid
O13	5.23	C₁₆H₁₈O₉	353.087 8	353.087 5 [-]	-1.0	191.055 6, 179.035 0, 135.044 9	1, 5-caffeoylquinic acid^[22]
O14^*	5.33	C₁₀H₁₀O₄	195.065 2	195.065 0 [+]	-0.7	177.053 8, 149.058 7, 117.032 5, 89.038 4	Isoferulic acid
O15	5.95	C₂₅H₂₄O₁₂	515.119 5	515.118 9 [-]	-1.2	353.086 9, 335.077 2, 191.056 2, 179.034 7	4, 5-Dicaffeoylquinic acid^[23]
O16^*	6.27	C₂₅H₂₄O₁₂	515.119 5	515.118 6 [-]	-1.9	353.086 0, 335.076 0, 191.055 6, 179.033 4	cynarin
O17^*	6.33	C₁₀H₁₀O₄	195.065 2	195.065 4 [+]	1.0	163.039 4, 145.028 4, 117.033 5, 89.039 7	Methyl caffeate
O18	6.99	C₂₅H₂₄O₁₂	515.119 5	515.118 3 [-]	-2.3	353.086 5, 335.076 1, 191.055 6, 161.023 4	3, 5-Dicaffeoylquinic acid^[23]
O19^*	9.05	C₉H₁₀O₃	167.070 3	167.070 0 [+]	-1.5	149.059 0, 121.064 2, 91.054 5, 77.039 4	Paeonol
O20	21.97	C₂₇H₄₄O₄	433.331 2	433.329 8 [+]	-3.4	181.049 7, 163.039 1	Octadecyl caffeate
O21	22.84	C₂₂H₄₄O₂	339.326 9	339.326 3 [-]	-1.6	321.315 5, 293.066 5	n-Docosanoic acid
O22	24.29	C₃₁H₅₂O₄	489.393 8	489.391 8 [+]	-4.2	181.049 2, 163.039 2	Docosyl caffeate
Flavonoids	F1^*	3.63	C₁₅H₁₂O₈	321.060 5	321.060 8 [+]	0.5	303.049 8, 275.054 6, 247.059 7, 153.017 4	Dihydromyricetin
F2^*	4.73	C₂₆H₂₈O₁₄	563.140 6	563.140 2 [-]	-0.8	545.130 8, 473.107 4, 443.096 9, 353.065 0	Schaftoside
F3^*	4.79	C₂₆H₂₈O₁₄	563.140 6	563.140 0 [-]	-1.0	503.118 6, 473.108 4, 443.097 4, 383.076 0	Isoschaftoside
F4	5.19	C₂₁H₂₀O₉	417.118 0	417.118 1 [+]	0.1	271.060 3, 243.065 7, 197.059 9, 153.018 2	Apigenin-5-rhamnoside
F5^*	5.25	C₂₁H₂₀O₁₂	463.088 2	463.088 9 [-]	1.2	317.029 6, 151.023 0	Myrictrin
F6^*	5.38	C₂₁H₂₀O₁₂	465.102 8	465.102 2 [+]	-0.9	303.050 3, 287.055 8, 121.028 0	Hyperoside
F7^*	5.47	C₂₇H₃₀O₁₆	609.146 0	609.146 0 [-]	-0.1	463.189 8, 301.038 9	Rutin
F8^*	5.61	C₂₁H₂₀O₁₂	465.102 8	465.102 1 [+]	-1.3	303.050 4, 287.054 5, 121.028 9	Isoquercitrin
F9^*	5.64	C₂₁H₂₀O₁₁	449.107 8	449.108 6 [+]	1.7	287.055 9, 153.017 5	Luteolin-7-galacturonide
F10^*	5.75	C₂₁H₂₀O₁₀	433.112 9	433.112 5 [+]	-0.9	271.059 2, 215.068 8	Genistin
F11	6.08	C₂₈H₃₂O₁₆	625.176 3	625.176 4 [+]	0.1	317.066 1, 285.043 4, 153.017 6	Isorhamnetin-3-O- neohespeidoside
F12^*	6.42	C₂₁H₂₀O₁₁	449.107 8	449.106 9 [+]	-2.0	303.050 4, 287.055 0, 121.028 4	Quercitrin
F13^*	6.56	C₂₁H₂₀O₁₁	449.107 8	449.107 2 [+]	-1.5	287.054 5, 153.017 2	Kaempferol-7-O-β-D- glucopyranoside
F14	6.62	C₂₂H₂₂O₁₂	478.393 4	478.391 9 [+]	-3.6	317.065 6, 285.043 4, 153.017 6	Isorhamnetin-3-O-glucoside
F15^*	6.68	C₁₅H₁₀O₈	319.044 8	319.044 9 [+]	0.2	301.034 1, 273.038 7, 245.043 6, 153.017 4	Myricetin
F16^*	6.95	C₂₈H₁₄O₁₅	611.197 0	611.196 2 [+]	-1.5	303.086 7, 263.055 3, 177.055 2	Hesperidin
F17^*	7.66	C₁₅H₁₂O₄	257.080 8	257.080 9 [+]	0.2	239.069 4, 211.074 7, 147.044 2, 137.023 3	Liquiritigenin
F18^*	7.72	C₂₁H₁₈O₁₁	447.092 2	447.091 2 [+]	-2.2	271.059 6, 253.049 5, 123.007 4	Baicalin
F19^*	7.97	C₁₅H₁₀O₆	287.055 0	287.054 9 [+]	-0.6	269.043 8, 185.059 0, 153.017 9	Luteolin
F20^*	8.15	C₁₅H₁₀O₇	303.049 9	303.050 0 [+]	0.2	285.038 6, 257.045 7, 229.049 4, 153.018 0	Quercetin
F21	8.46	C₂₇H₃₀O₁₅	595.165 8	595.168 6 [+]	4.9	287.054 7, 153.017 3	Biorobin^[24]
F22^*	8.86	C₁₅H₁₂O₅	273.075 8	273.075 5 [+]	-0.9	153.018 0, 147.043 6, 119.049 0	Naringenin
F23^*	8.95	C₁₅H₁₀O₅	271.060 1	271.059 9 [+]	-0.9	253.050 1, 215.070 4, 153.018 2, 91.055 0	Genistein
F24^*	9.01	C₁₅H₁₀O₅	271.060 1	271.060 0 [+]	-0.4	253.050 3, 243.065 7, 197.059 9, 153.018 2	Apigenin
F25^*	9.16	C₁₅H₁₀O₆	287.055 0	287.055 2 [+]	0.8	269.043 4, 153.017 3, 121.027 8	Kaempferol
F26^*	9.37	C₁₆H₁₂O₆	301.070 7	301.070 9 [+]	0.9	286.047 9, 258.053 0, 229.050 2	Diosmetin
F27^*	9.45	C₁₆H₁₂O₇	317.065 6	317.065 8 [+]	0.8	299.060 7, 289.067 8, 229.049 4, 153.018 2	Isorhamnetin
F28^*	9.61	C₁₅H₁₀O₃₅	271.060 1	271.060 0 [+]	-0.4	253.049 7, 169.012 8, 123.007 4	Baicalein
F29^*	10.95	C₁₆H₁₂O₅	285.075 8	285.076 0 [+]	0.8	252.042 6, 179.049 6	Wogonin
F30^*	11.20	C₁₆H₁₂O₅	285.075 8	285.076 0 [+]	0.8	270.053 0, 242.057 6, 153.018 0	Acacetin
F31^*	11.33	C₁₆H₁₂O₅	285.075 8	285.075 7 [+]	-0.1	270.050 8, 242.056 0, 167.033 0, 124.015 1	Genkwanin
Monoterpenes	MP1	8.23	C₂₁H₃₆O₁₀	449.238 1	449.237 2 [+]	-2.1	317.195 7, 133.049 8	Shionoside A
MP2	8.34	C₂₂H₃₈O₁₀	463.253 8	463.252 8 [+]	-2.2	317.196 3, 147.065 4	Shionoside B
Diterpenes	DP1	7.05	C₂₀H₂₀O₆	357.133 3	357.133 0 [+]	-0.8	339.122 4, 207.064 4, 189.053 5, 137.059 2	A^a^[28]
DP2	9.76	C₄₂H₆₆O₁₆	825.427 8	825.431 0 [-]	3.9	779.430 3	Smithoside B^[28]
DP3	10.07	C₂₀H₃₂O₆	367.212 6	367.211 4 [-]	-3.2	329.235 6, 206.019 8, 171.102 1, 146.967 1	Lingulatusin^[26]
DP4	12.91	C₂₀H₃₂O₄	337.237 3	337.237 4 [+]	0.1	319.230 9	B^b^[27]
DP5	21.29	C₂₆H₄₄O₅	435.311 6	435.309 6 [-]	-4.7	367.323 7, 321.316 1	Glycoside 1^[28]
Triterpenens	TP1	9.28	C₃₀H₄₈O₅	489.357 5	489.356 5 [+]	-1.9	471.345 5, 453.336 6, 201.164 4, 187.148 7	C^c
TP2	9.35	C₄₁H₆₆O₁₄	783.452 5	783.450 5 [+]	-2.6	489.357 3, 453.336 3, 407.331 3, 259.081 5	D^d^[29]
TP3	9.43	C₆₇H₁₀₈O₃₄	1 455.664 9	1 455.663 7 [-]	-0.8	1 323.618 7, 673.228 8	Astersaponin A^[30]
TP4	9.61	C₆₂H₁₀₀O₃₄	1 323.622 7	1 323.621 8 [-]	-0.6	541.178 8, 337.117 0	Astersaponin E^[30]
TP5	10.32	C₆₂H₁₀₀O₂₉	1 307.627 8	1 307.627 7 [-]	-0.1	1 175.588 9, 541.179 0	Astersaponin F^[30]
TP6	10.41	C₅₇H₉₂O₂₅	1 175.585 5	1 175.584 8 [-]	-0.6	953.530 8, 765.447 1, 633.412 4, 471.358 3	Asterlingulatoside D
TP7	10.46	C₅₂H₈₄O₂₁	1 043.542 3	1 043.542 5 [-]	-0.7	997.541 0, 765.456 8, 633.415 3, 471.336 2	Asterlingulatoside C
TP8	10.53	C₅₃H₈₆O₂₃	1 089.548 7	1 089.548 2 [-]	-0.5	953.514 5, 807.456 6, 765.445 4, 633.403 3	Bellidiastroside C2
TP9	10.71	C₅₃H₈₆O₂₂	1 073.553 8	1 073.553 7 [-]	-0.1	937.522 6, 617.405 5	Bellidiastroside B1^[31]
TP10	10.85	C₄₂H₆₈O₁₅	811.448 6	811.447 7 [-]	-1.0	765.448 7	Asterbatanoside B
TP11	10.94	C₅₆H₉₀O₂₅	1 161.569 8	1 161.569 3 [-]	-0.5	673.226 3, 601.197 8, 487.341 1, 281.085 2	Asterbatanoside F^[31]
TP12	11.01	C₅₃H₈₆O₂₂	1 073.553 8	1 073.553 9 [-]	0.1	937.522 6, 749.455 1	Bellidiastrodise B3^[31]
TP13	11.37	C₅₇H₉₀O₂₇	1 205.559 7	1 205.559 2 [-]	-0.4	131.034 3	Ageratoside B2^[31]
TP14	12.47	C₄₂H₆₈O₁₅	811.448 6	811.448 1 [-]	-0.6	765.448 5	Asterbatanoside C^[31]
TP15	13.58	C₄₇H₇₆O₁₇	911.501 0	911.499 9 [-]	-1.2	865.458 2	Asterlingulatoside B
TP16	13.89	C₄₁H₆₆O₁₃	765.443 1	765.441 2 [-]	-2.4	719.440 8	Asterlingulatoside A
TP17^*	14.06	C₃₀H₄₈O₄	471.348 0	471.348 2 [-]	0.5	327.525 4, 242.835 4	23-Hydroxybetulinic acid^[31]
TP18	16.32	C₃₀H₄₈O₄	471.348 0	471.348 1 [-]	0.3	407.333 2	Echinocystic acid
TP19	16.59	C₂₆H₄₂O₃	403.320 7	403.319 6 [+]	-2.7	385.310 0, 367.298 8, 203.179 4, 121.100 8	Astershionone A^[32]
TP20^*	17.01	C₃₀H₄₈O₃	455.353 1	455.354 9 [-]	4.0	409.381 9, 302.969 8, 258.499 2, 81.122 8	Betulinic acid
TP21	17.07	C₂₇H₄₂O₂	399.325 8	399.324 5 [+]	-3.2	381.316 3, 363.303 2, 217.195 0, 191.177 4	Astershionone F^[32]
TP22	17.41	C₂₇H₄₄O₃	417.336 3	417.335 1 [+]	-2.9	399.324 8, 381.315 5, 217.195 1, 191.178 6	Astershionone C^[32]
TP23^*	17.57	C₃₀H₄₈O₃	457.367 6	457.367 3 [+]	-0.7	439.355 3, 411.362 1, 217.192 9, 191.177 9	Oleanic acid
TP24	17.77	C₃₀H₅₀O₂	443.388 4	443.387 1 [+]	-2.8	425.377 2, 407.365 3, 217.195 1, 191.178 0	Friedelan-3-ol
TP25	18.28	C₃₀H₅₀O₂	443.388 4	443.386 8 [+]	-3.5	425.376 4, 407.365 9, 217.194 9, 191.178 9	Astertarone B^[37]
TP26^*	18.94	C₃₀H₅₀O	429.409 1	429.409 2 [+]	0.2	411.312 3, 338.347 1, 191.178 9	epi-Friedellanol^[31]
TP27	19.20	C₂₉H₄₆O₂	427.357 1	427.356 [+]	-2.6	409.346 9, 391.334 1, 287.200 9, 191.178 8	Astershionone B^[32]
TP28	19.39	C₃₀H₅₀O	427.393 4	427.392 0 [+]	-3.3	409.381 7, 217.195 0, 191.179 4	beta-Amyrin^[31]
TP29	19.79	C₃₀H₄₈O₂	441.372 7	441.372 3 [+]	-1.0	423.362 2, 405.348 5, 191.178 7	E^e^[31]
TP30	20.01	C₃₀H₄₈O	425.377 8	425.376 8 [+]	-2.4	407.366 0, 217.194 6, 191.179 1	Taraxerone^{[33, 34]}
TP31	20.22	C₃₀H₅₀O₂	443.388 4	443.387 1 [+]	-2.9	425.380 1, 407.367 7, 217.194 8, 191.179 0	Astatarone G
TP32^*	20.96	C₃₀H₅₀O₂	443.388 4	443.387 4 [+]	-2.2	425.379 7, 413.379 7, 217.194 9, 191.179 4	Betulin
TP33	21.81	C₃₀H₅₀O	427.393 4	427.391 9 [+]	-3.6	409.383 3, 341.321 2, 191.179 1	Taraxasterol^[36]
TP34	23.74	C₃₀H₅₀O	427.393 4	427.392 9 [+]	-2.4	409.379 9, 217.195 1, 191.178 2	Astertarone A^[35]
TP35^*	23.87	C₃₀H₅₀O	427.393 4	427.393 1 [+]	-0.9	409.386 1, 331.298 3, 217.194 4, 191.179 4	Friedelin
TP36^*	24.72	C₃₀H₅₀O	427.393 4	427.393 2 [+]	-0.6	409.382 8, 217.194 3, 191.178 9	Shionone
Coumarin	C1^*	2.00	C₁₅H₁₆O₉	341.086 7	341.087 0 [+]	0.9	179.034 2, 151.038 4, 105.034 6	Esculin
C2^*	2.68	C₉H₆O₄	179.033 9	179.033 9 [+]	-0.1	151.038 7, 133.028 6, 123.044 1, 105.034 0	Esculetin
C3^*	3.71	C₁₀H₈O₅	209.044 4	209.044 5 [+]	0.3	181.048 8, 163.038 7, 149.023 2, 121.028 4	Fraxetin
C4^*	4.23	C₁₀H₈O₄	193.049 5	193.049 4 [+]	-0.3	178.026 1, 150.031 0, 133.028 2, 122.036 1	Isoscopoletin
C5^*	4.39	C₉H₆O₃	163.039 0	163.038 7 [+]	-1.9	119.049 4, 107.049 2, 91.054 6, 77.039 5	7-Hydroxyeoumarin
C6^*	4.60	C₁₀H₈O₄	193.049 5	193.049 4 [+]	-0.3	178.026 3, 137.059 9, 133.028 6, 122.036 6	Scopoletin
C7^*	8.43	C₁₁H₆O₃	187.039 0	187.038 8 [+]	-0.8	143.049 5, 131.049 1, 115.054 6, 77.040 0	Psoralen
C8^*	8.93	C₁₂H₈O₄	217.049 5	217.049 7 [+]	0.8	202.026 0, 185.024 0, 174.031 2, 118.041 8	Xanthotoxin
C9^*	9.68	C₁₂H₈O₄	217.049 5	217.049 5 [+]	0.1	202.026 4, 174.030 7, 146.035 3, 118.040 6	Bergapten
Anthraquinones	AQ1^*	10.79	C₁₅H₈O₆	341.086 7	347.087 0 [-]	0.9	239.034 3, 211.039 3, 183.044 3	Rhein
AQ2	11.20	C₁₅H₁₂O₄	255.066 3	255.066 1 [-]	-0.9	227.072 2, 211.076 4, 183.079 7, 107.014 8	Emodin anthrone
AQ3^*	12.63	C₁₅H₁₀O₅	269.045 5	269.045 7 [-]	0.7	241.050 0, 225.055 1, 197.060 4, 181.065 8	Emodin
Steroids	S1	7.76	C₃₅H₅₈O₆	575.430 6	575.431 1 [+]	-2.3	413.377 1, 395.363 0, 255.208 1, 189.015 7	F^f^[31]
S2^*	18.81	C₂₉H₄₈O	413.377 8	413.376 2 [+]	-3.9	395.368 7, 255.208 4, 189.016 7, 109.065 3	α-Spinasterol
S3	24.25	C₂₉H₄₈O	413.377 8	413.376 5 [+]	-3.1	395.363 9, 109.064 6	Stigmasterol^[38]
Aldehydes	A1	1.46	C₆H₆O₃	127.039 0	127.038 8 [+]	-1.9	109.027 6, 53.040 5	5-Hydroxymethyl-2- furaldehyde
A2^*	1.93	C₇H₆O₃	139.039 0	139.038 8 [+]	-0.9	111.044 6, 93.034 1, 65.040 4	Benzaldehyde
A3^*	2.73	C₇H₆O₂	123.044 1	123.043 9 [+]	-1.3	95.049 3, 77.039 5, 67.055 7, 65.040 1	p-Hydroxybenzaldehyde

基于UHPLC-Q-TOF-MS/MS的紫菀药材全成分解析

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陈奕君 ¹^,² , 吴浩 ¹ , 魏紫奕 ¹ , 陈炼明 ¹ , 董姣姣 ¹ , 刘洁 ³ , 贾志鑫 ³ , 肖红斌 ¹^,²^,^*

药学学报 | 研究论文 2019,54(9): 1645-1654

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药学学报 | 研究论文 2019, 54(9): 1645-1654

基于UHPLC-Q-TOF-MS/MS的紫菀药材全成分解析

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陈奕君¹^,², 吴浩¹, 魏紫奕¹, 陈炼明¹, 董姣姣¹, 刘洁³, 贾志鑫³, 肖红斌¹^,²^,^*

作者信息

1.北京中医药大学中药学院, 北京 100029

2.北京中医药大学北京市方剂与证候研究重点实验室, 北京 100029

3.北京中医药大学北京中医药研究院, 北京 100029

通讯作者:

*肖红斌, Tel:86-10-64286490, E-mail:hbxiao69@163.com

Identification of chemical constituents in Aster tataricus by UHPLC-Q-TOF-MS

Yi-jun CHEN¹^,², Hao WU¹, Zi-yi WEI¹, Lian-ming CHEN¹, Jiao-jiao DONG¹, Jie LIU³, Zhi-xin JIA³, Hong-bin XIAO¹^,²^,^*

Affiliations

1. School of Chinese Materia Medica, Beijing University of Chinese Medicine, Beijing 100029, China

2. Beijing Key Laboratory of Syndrome Prescription Basic Research, Beijing University of Chinese Medicine, Beijing 100029, China

3. Beijing Research Institute of Chinese Medicine, Beijing University of Chinese Medicine, Beijing 100029, China

出版时间: 2019-09-12 doi: 10.16438/j.0513-4870.2019-0214

文章导航

摘要

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紫菀是临床常用的润肺祛痰止咳药，对于呼吸系统疾病的疗效显著。为全面阐明紫菀的化学成分组成，本研究采用超高效液相色谱-四级杆飞行时间串联质谱联用技术（UHPLC-Q-TOF-MS/MS），建立了一种组合的数据采集及相应的数据挖掘策略。从紫菀中共鉴定了132个化学成分，包括43个萜类、31个黄酮类、22个有机酸类、18个肽类、9个香豆素类、3个甾体类、3个蒽醌类及3个醛类化合物。其中，有59个成分通过与对照品进行比对而确认。本研究不仅可以为紫菀成分的全面解析提供可靠的数据支撑，同时也可以为其他中药及中药复方的药效物质发现提供高效的数据采集及挖掘策略。

关键词

紫菀 / UHPLC-Q-TOF-MS/MS / 数据采集及挖掘 / 全成分解析

Abstract

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The root of Aster tataricus L. f. (RA) has been widely used in the clinic for moistening lung, dispelling phlegm and relieving cough because of its significant therapeutic effects on respiratory diseases. In this study, a systematic data acquisition and mining strategy was established aimed at solving the complexity of the traditional Chinese medicine using ultra high performance liquid chromatography coupled with quadruple time of flight mass spectrometry (UHPLC-Q-TOF-MS). A total of 132 chemical constituents, including 43 terpenes, 31 flavonoids, 22 organic acids, 18 peptides, 9 coumarins, 3 steroids, 3 anthraquinones and 3 aldehydes were identified or tentatively characterized, among which 59 components were confirmed by comparison with the standard references. Meanwhile, the accurate mass measurements of the identified components were all with ±5 ppm error. Therefore, this work provided not only reliable data supports for the comprehensive analysis of the chemical constituents in RA, but also provided an efficient data acquisition and mining strategy to profile the chemical constituents for other traditional Chinese medicine complex system.

Key words

Aster tataricus / UHPLC-Q-TOF-MS/MS / data acquisition and mining / comprehensive components analysis

引用本文

陈奕君, 吴浩, 魏紫奕, 陈炼明, 董姣姣, 刘洁, 贾志鑫, 肖红斌. 基于UHPLC-Q-TOF-MS/MS的紫菀药材全成分解析. 药学学报, 2019 , 54 (9) : 1645 -1654 . DOI: 10.16438/j.0513-4870.2019-0214

Yi-jun CHEN, Hao WU, Zi-yi WEI, Lian-ming CHEN, Jiao-jiao DONG, Jie LIU, Zhi-xin JIA, Hong-bin XIAO. Identification of chemical constituents in Aster tataricus by UHPLC-Q-TOF-MS[J]. Acta Pharmaceutica Sinica, 2019 , 54 (9) : 1645 -1654 . DOI: 10.16438/j.0513-4870.2019-0214

正文

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紫菀为菊科(Compositae)多年生草本植物紫菀(Aster tataricus L. f.)的干燥根及根茎, 性辛、苦, 温, 归肺经, 具有润肺下气, 消痰止咳的功效, 临床常用于治疗痰多咳喘、新久咳嗽、劳嗽咳血等症^[1]。现代药理研究结果表明, 紫菀的药理功效十分广泛, 除传统的祛痰、止咳、平喘活性外^[2-4], 紫菀提取物还可以显著的缓解由脂多糖所诱导的小鼠急性肺损伤^[5]; 并可以通过控制糖尿病大鼠的血糖浓度及抑制血液中炎症因子的表达, 缓解糖尿病视网膜病变^[6]; 不仅如此, 紫菀多糖还可以显著的诱导胃癌细胞SGC-7901的凋亡等^[7]。

众所周知, 中药所包含的化学成分是中药发挥药效的物质基础, 且与药理活性密切相关。越来越多的学者逐渐认识到, 中药药效的发挥并不只是简单地依靠其中的某一种化学成分, 而是由多种成分协同作用所产生的效果^[8]。因此建立系统的数据采集及相应的数据挖掘策略, 用于紫菀药材成分的全面表征, 对于系统阐释紫菀的药效物质基础及作用机制具有十分重要的意义。

超高效液相色谱-四级杆飞行时间串联质谱(UHPLC-Q-TOF-MS/MS)联用技术因其强大高效的成分解析能力, 常用于复杂体系成分解析^[9]。在本研究中根据数据依赖性采集和数据非依赖性采集的互补性, 利用UHPLC-Q-TOF-MS/MS联用技术, 建立了一种组合的数据采集及相应的数据挖掘策略, 并用于紫菀中化学成分的高效分离及鉴定。

材料与方法

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仪器与试剂 Agilent 1290超高效液相色谱仪和Agilent 6550离子漏斗四级杆飞行时间串联质谱仪(型号: G6550A, 美国Agilent公司); Milli-Q超纯水制备仪(美国Millipore公司); 乙腈和甲醇(LC/MS级, 美国Fisher公司), 甲酸(LC/MS级, 美国Sigma公司), 其他试剂均为分析纯(北京华威锐科化工有限公司)。紫菀(Aster tataricus L. f.)购自北京同仁堂, 由北京中医药大学王学勇教授鉴定, 药材样本陈列于北京中医药大学中药分析与转化研究中心, 样本编号No.CMAT-AT-201604, 对照品购自中国食品药品检定研究院、成都瑞芬思生物科技有限公司及实验室自制(纯度≥98%)。

供试品溶液的制备 以2015版《中国药典》中紫菀样品的提取方法为依据:取紫菀样品粉末约1 g, 过3号筛, 精密称定, 置具塞锥形瓶中, 精密加入甲醇20 mL, 称定重量, 40 ℃温浸1 h后, 超声处理(功率250 W, 40 kHz) 1 h, 取出, 放冷, 再次称定重量, 并用甲醇补足失重, 摇匀, 过滤。重述上述操作, 合并两次续滤液, 离心(10 000 r·min^-1) 10 min, 取上清液, N₂吹干, 用50%甲醇溶液1 mL复溶, 过0.22 μm滤膜, 即得。

超高液相色谱条件 样品的分离采用Acquity UPLC HSS T3柱(100 mm×2.1 mm, 1.8 μm, Waters), 柱温箱设定为30 ℃, 检测波长设定为220、254、275、315和360 nm; 流动相由0.1%甲酸水(A)和乙腈(B)组成, 梯度洗脱: 0 min, 95% A; 1 min, 95% A; 5 min, 85% A; 15 min, 60% A; 20 min, 25% A; 25 min, 5% A, 进样体积为2 μL, 流速为0.4 mL·min^-1。

质谱条件 电喷雾离子源(ESI), 扫描范围m/z为50~1 500, 正负离子模式检测, 毛细管电压分别为4 kV (ESI⁺)和3.5 kV (ESI^-), 干燥气温度230 ℃, 干燥气流速15 L·min^-1, 鞘气温度300 ℃, 鞘气流速12 L·min^-1, 雾化气压力50 psig, 碰撞能量10~40 eV, 采样频率0.25 s。

样品分析流程 分别利用数据依赖性和数据非依赖性采集方法, 获取每个样品的高分辨质谱数据。同时, 为了提高检测的灵敏度, 减少碎片离子的遗漏, 采用碰撞能量传播(collision energy spread, CES)的方法, 在数据依赖性采集模式下CES的设置为0 (数据非依赖性采集模式下为15 eV), 当碰撞能量分别为10、20和40 eV时, 可以得到一个不断增强的产物离子色谱图。在数据依赖性采集模式下, 每一次全扫描中, 5个响应最强的离子(响应值大于10 000 counts), 被用于做TOF扫描及相应的产物离子扫描。

数据后处理及分析策略 ①靶向成分的发现。首先, 利用Personal Compound Database Library (PCDL) Manager软件(Agilent Technologies, USA, Version B.07.00)构建紫菀属成分数据库, 数据库中共包含273个紫菀属植物化学成分及其相关信息; 然后, 进一步利用该软件构建对照品成分数据库, 用于收集各对照品在不同碰撞能量下(10/20/40 eV)的高分辨率的特征离子碎片信息; 为确保测定的准确性, 同时还建立了适用于每个对照品的色谱检测方法。②非靶向成分发现。首先, 通过在线数据库对化合物进行实时监测; 然后, 利用MassHunter软件(Agilent Technologies, USA)峰发现集成算法, 生成化合物母离子的提取色谱图(Extracted Ion Chromatograms, EIC), 并对化合物进行识别; 最后, 将MS/MS谱图用于数据库检索, 与数据库匹配的化合物将进一步利用软件中的靶向二级质谱信息(Target MS/MS)进行核查, 以确认待核查化合物的名称及结构。③基于靶向的非靶向成分发现。以紫菀中4种具有代表性的化合物(芹菜素、异鼠李素、山柰酚和α-菠菜甾醇)作为次生代谢产物的模板, 结合Agilent Masshunter Metabolite ID软件, 通过推导其产生的碎片离子, 反向寻找模板衍生化合物, 并进行化合物的鉴定或表征。④化合物的辅助鉴定。关键产物离子(key product ions, KPIs)可用于化合物的快速检测和识别^{[10, 11]}。本研究中主要包含4类化合物的KPIs, 分别为:肽类(106.064 9 m/z, positive, astin C), 酚酸类(191.055 6 m/z, negative, 4-caffeoylquinic acid), 黄酮类(153.018 0 m/z, Positive, 山柰酚)及三萜类(191.178 9 m/z, positive, 紫菀酮)。此外, 在研究的过程中还借助ChemBioDraw Ultra 14.0软件中的一个重要参数Clog P值, 用于预测化合物的同分异构体^{[12, 13]}。

结果与讨论

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利用上述的全成分采集和挖掘策略, 共有132个化学成分, 包括18个肽类、22个有机酸类、31个黄酮类、43个萜类、9个香豆素类、3个甾体类、3个蒽醌类及3个醛类, 被鉴定或初步表征(图 1和表 1)。在这132个化合物中, 有120个化合物的质谱数据可以通过数据依赖性采集方法获得(占92%), 而所有的132个化合物的质谱数据都可通过数据非依赖性采集方法获得。对于某些化合物(如某些多肽和糖苷), 在数据依赖性采集模式下可以观察到相应的二级碎片离子数据信息, 但是在数据非依赖性采集模式下则无法观察到。矩阵效应是可能导致数据非依赖性采集模式下二级数据采集失败的主要原因^[14]。同时, 所鉴定的化合物中, 有59个化合物通过与对照品的保留时间及质谱图进行比对而确认。所鉴定的化合物的误差范围均在±5 ppm以内。

1 肽类化合物

肽类是紫菀中的主要特征性化学成分。在本研究中, 正离子模式下共鉴定了18种肽类化合物, 其关键产物离子为m/z 106.064 9。同时, 在研究的过程中还发现, 该类化合物的二级质谱图信息中通常可以清楚地观察到H₂0或CO的丢失, 进而得到[M+H-H₂O]⁺或[M+H-CO]⁺的产物离子^{[15, 16]}。在化合物解析的过程中发现P5与P3是同分异构体; 借助Clog P值可将P5指认为astin E, 因为P5 (astin E)的Clog P值(1.521)比P3 (astin H)的Clog P值(1.468)更大, 进而保留时间也更长。其他化合物, 如asterin B和asterin C, astin A和astin B等同分异构体的判定方法与此类同。

2 有机酸类化合物

在本文中共鉴定了22种有机酸类化合物, 其中焦性没食子酸(O3)、原儿茶酸(O4)、绿原酸(O6)、咖啡酸(O8)、阿魏酸(O11)、苯甲酸(O12)、异阿魏酸(O14)、洋蓟素(O16)、咖啡酸甲酯(O17)和丹皮酚(O19)通过与对照品比对而确认。通过非靶向分析, 借助Chemspider在线数据库匹配, 进一步表征了琥珀酸(O1)、2, 2-二甲基琥珀酸(O2)、4-羟基苯甲酸(O5)和正十二烷酸(O21)。母离子为m/z 353.0878的化合物有3个, 其中通过与对照品比对可以确认绿原酸(O6), 对于另外两个化合物, 通过比对其DAD色谱图(波长315 nm), 色谱保留时间及二级碎片离子信息, 结合文献报道, 辅以Clog P值, 可得知另外两个化合物应分别为隐绿原酸(O9)和1-咖啡酰奎宁酸(O13)^[22]。洋蓟素(O16)及其同分异构体[3, 4-二咖啡酰奎宁酸(O10)、4, 5-二咖啡酰奎宁酸(O15)和3, 5-二咖啡酰奎宁酸(O18)]的鉴定方法同理^[23]。此外, 化合物O20和O22都具有m/z 181和m/z 163的特征碎片离子, 这种碎片离子经常在咖啡酸和咖啡酸酯中出现, 借助PCDL manager数据库初步确定O20和O22分别为十八烷基咖啡酸和二十二酯咖啡酸。

3 黄酮类化合物

在本文中共有31种黄酮类成分被鉴定或初步表征, 其关键产物离子为m/z 153.018 3。通过与对照品的保留时间, 二级碎片离子信息进行比对, 共确认了其中的27个化合物。利用上述指定的次生代谢产物模板(芹菜素、异鼠李素和山柰酚), 结合Metabolite ID软件, 对模板化合物的糖基化的产物进行预测, 进一步表征了另外4种黄酮类化合物:芹菜素-5-异鼠李糖苷(F4)、异鼠李素-3-O-新橙皮苷(F11)、异鼠李素-3-O-葡萄糖苷(F14)和山柰酚-3-O-洋槐糖苷(F21)。为佐证所推断化合物的准确性, 可进一步利用多重质量亏损过滤(MMDF)技术对潜在代谢产物进行辅助筛选^[25]。例如:化合物F25的准分子离子峰为[M+H]⁺m/z 287.055 2 (0.8 ppm, C₁₅H₁₀O₅, kaempferol), 化合物F13的准分子离子峰为[M+H]⁺m/z 449.107 2 (-1.5 ppm, C₂₁H₂₀O₁₁), 化合物F13的分子质量比F25多162 Da, 利用MMDF筛选推测F13可能是F25的葡萄糖苷的结合物; 进一步观察其碎片离子峰的信息, 化合物F13与F25在断裂的过程中, 均产生了黄酮类化合物的特征碎片离子m/z 153.017 3, 由此可以判定, F13即为F25的葡萄糖苷代谢产物。

4 萜类化合物

萜类化合物是紫菀中最重要的指标性成分, 在本文中共鉴定了36个三萜、5个二萜及2个单萜, 其中三萜类化合物的关键产物离子为m/z 191.179 2。通过与对照品的保留时间及碎片离子信息比对, 明确了其中的7个成分, 分别为23-羟基白桦脂酸(TP17)、白桦脂酸(TP20)、齐墩果酸(TP23)、表木栓醇(TP26)、桦木醇(TP32)、木栓酮(TP35)、紫菀酮(TP36)。利用自建PCDL manager成分数据库结合文献比对, 除TP24、TP25、TP28、TP31、TP33和TP34之外, 其余的未知萜类化合物均被初步表征^[26-34]。观察发现TP28、TP33、TP34、TP35 (木栓酮)和TP36 (紫菀酮)具有相同的母离子及相似的二级碎片离子信息, 为同分异构体。他们在色谱柱中的保留时间T28最小, 紫菀酮最大。根据它们的二级碎片离子信息, 初步推测TP28、TP33、TP34可能分别为β-香树精、蒲公英甾醇和astertarone A^{[31, 35, 36]}。进一步对所推断化合物的Clog P值进行分析, 它们的Clog P值分别为10.144、10.663、10.675、10.745和10.825, 与它们在色谱柱的保留时间一致, 由此可知化合物的推断正确。同理TP24、TP25、TP31与TP32 (桦木醇)为同分异构体。通过查阅文献及数据库比对, 初步推测TP24、TP25和TP31分别为friedelan-3-ol、astertarone B和astatarone G^{[31, 37]}; 且4个化合物的Clog P值分别为8.087 (TP24)、8.375 (TP25)、10.332 (TP31)和10.479 (TP32), 与其在色谱中的出峰先后顺序一致。

5 其他化合物

除上述4种主要类型的化合物之外, 还从紫菀中鉴定或初步表征了18种其他类型的化合物, 其中包括9种香豆素类、3种蒽醌类、3种甾体类和3种醛类化合物。其中9种香豆素类成分(C1-C9)、2种蒽醌类化合物(AQ1、AQ3)、2种醛类化合物(A2、A3)和1种甾体类化合物(S2)通过与对照品比对而确认。利用PCDL manager进行快速识别, 并与文献比对, 可以判定化合物S3为豆甾醇^[38]。通过非靶向分析, 结合Chemspider在线数据进行比对, 进一步表征了AQ2和A1分别为大黄素蒽酮和5-羟甲基-2-糠醛。同时, 根据次生代谢产物模板(菠菜甾醇), 利用MetaboliteID软件进行非靶向离线数据分析, 将化合物S1初步表征为菠菜甾醇-3-O-D-葡萄糖苷。

结论

收起

本文首次利用超高效液相色谱-四级杆飞行时间串联质谱联用技术(UHPLC-Q-TOF-MS/MS)对紫菀的化学成分进行了全面、高效地解析, 在25 min内, 对紫菀中的132个化合物进行了鉴定或初步表征, 其中有59个化合物通过与对照品比对而确认。同时, 本文还对紫菀中的2种特征性化学成分(多肽及萜类)、2种高含量、高活性成分(酚酸及黄酮类)及其他4种类型的化合物(香豆素、蒽醌、甾体、醛类)的二级质谱裂解规律进行了归纳和总结。利用本文所建立的化合物分析策略, 不仅可以全面的了解紫菀药材的物质基础, 同时也可以为其他类型中药材或中药复方的成分解析提供有效的指导。

基金

收起

国家新药创制重大专项资助项目(2018ZX09201008-001)
国家自然科学基金资助项目(81774155)
国家自然科学基金资助项目(81803703)
中央高校基本科研业务费专项资金资助项目(2019-JYB-XJSJJ-011)

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2019年第54卷第9期

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doi: 10.16438/j.0513-4870.2019-0214

接收时间：2019-03-28
首发时间：2026-01-26
出版时间：2019-09-12

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收稿日期：2019-03-28
修回日期：2019-04-30

基金

国家新药创制重大专项资助项目(2018ZX09201008-001)

国家自然科学基金资助项目(81774155)

国家自然科学基金资助项目(81803703)

中央高校基本科研业务费专项资金资助项目(2019-JYB-XJSJJ-011)

作者信息

1.北京中医药大学中药学院, 北京 100029

2.北京中医药大学北京市方剂与证候研究重点实验室, 北京 100029

3.北京中医药大学北京中医药研究院, 北京 100029

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*肖红斌, Tel:86-10-64286490, E-mail:hbxiao69@163.com

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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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Type	t_R/min	Formula	[M+H]⁺/[M-H]^-	Fragment ions	Identification
Peptides	P1	4.13	C₂₅H₃₂ClN₅O₈	566.201 2	566.199 9 [+]	-2.3	548.189 5, 318.085 5, 232.096 9, 106.065 1	Astin L^[17]
P2	4.52	C₂₅H₃₅N₅O₇	518.260 9	518.259 8 [+]	-2.1	490.264 9, 286.139 8, 171.112 7, 106.065 1	Asterinin F^[18]
P3	5.35	C₂₅H₃₂ClN₅O₇	550.206 3	550.205 8 [+]	-0.9	532.192 7, 302.089 9, 215.058 0, 106.065 0	Astin H^[19]
P4	5.58	C₂₅H₃₅N₅O₆	502.266 0	502.264 9 [+]	-2.3	474.267 9, 270.143 7, 183.111 7, 106.065 0	Astin G^[19]
P5	6.11	C₂₅H₃₂ClN₅O₇	550.206 3	550.205 4 [+]	-1.7	522.209 8, 447.142 2, 300.074 1, 106.065 0	Astin E^[19]
P6	6.21	C₂₅H₃₄ClN₅O₇	552.222 0	552.219 7 [+]	-4.1	524.225 7, 449.159 2, 320.100 7, 106.065 0	Astin I^[19]
P7	6.88	C₂₅H₃₄ClN₅O₆	536.227 0	536.226 3 [+]	-1.4	508.231 4, 451.174 3, 304.106 0, 106.065 4	Astin F^[19]
P8	7.21	C₂₅H₃₂ClN₅O₆	534.211 4	543.211 0 [+]	-0.8	506.215 2, 449.157 9, 106.065 1	Astin D^[19]
P9	7.27	C₂₅H₃₃N₅O₈	532.240 2	532.239 2 [+]	-1.8	514.226 7, 338.169 9, 235.105 8, 106.065 3	Asterinin A^[20]
P10	7.33	C₂₅H₃₃Cl₂N₅O₈	602.177 9	602.176 3 [+]	-3.0	584.165 1, 336.057 1, 232.097 3, 106.064 4	Astin K^[17]
P11	7.58	C₂₆H₃₅N₅O₈	546.255 8	546.254 0 [+]	-3.4	528.244 7, 350.170 7, 235.107 8, 106.065 0	Asterinin C^[20]
P12	7.84	C₂₅H₃₃Cl₂N₅O₇	586.183 0	586.181 4 [+]	-2.6	558.183 6, 336.049 7, 106.065 2, 58.065 0	Astin A^[19]
P13	7.87	C₂₅H₃₃Cl₂N₅O₇	586.183 0	586.182 9 [+]	-0.1	558.183 1, 130.049 1, 106.065 5, 60.044 2	Astin B^[19]
P14	8.19	C₂₅H₃₃N₅O₇	516.2453	516.243 9 [+]	-2.7	498.232 9, 338.170 0, 235.106 6, 106.065 3	Astin J^[21]
P15	8.25	C₂₅H₃₃N₅O₈	546.255 8	546.254 6 [+]	-2.3	528.245 8, 352.186 4, 235.107 6, 106.065 0	Asterinin B^[20]
P16^*	8.46	C₂₅H₃₃Cl₂N₅O₆	570.188 1	570.187 3 [+]	-1.4	485.133 3, 338.066 5, 251.034 1, 106.064 9	Astin C
P17	8.53	C₂₆H₃₃Cl₂N₅O₇	600.198 6	600.198 2 [+]	-0.7	582.193 5, 501.132 8, 336.051 5, 106.065 2	Astin P^[17]
P18	11.07	C₂₇H₃₅Cl₂N₅O₇	612.198 6	612.197 2 [+]	-2.3	548.202 3, 467.124 2, 380.077 5, 106.065 3	Astin O^[17]
Organic acids	O1	0.61	C₄H₆O₄	117.019 3	117.019 3 [-]	0.1	99.008 8, 71.031 8	Succinic acid
O2	0.75	C₆H₁₀O₄	145.050 6	145.050 7 [-]	0.4	127.039 4, 109.037 7, 71.031 5	2, 2-Dimethylsuccinic acid
O3^*	0.81	C₆H₆O₃	127.039 0	127.039 0 [+]	0.2	109.028 8, 81.034 6, 53.041 4	Pyrogallic acid
O4^*	1.30	C₇H₆O₄	155.033 9	155.033 7 [+]	-1.0	93.032 7, 65.040 1	Protocatechuate
O5	2.04	C₇H₆O₃	139.039 0	139.038 7 [+]	-2.2	121.027 8, 95.049 1, 77.038 9, 65.040 2	4-Hydroxybenzoic acid
O6^*	2.57	C₁₆H₁₈O₉	353.087 8	353.087 5 [-]	-1.0	191.055 6, 93.035 8	Chlorogenic acid
O7	2.70	C₈H₈O₄	169.049 5	169.049 1 [+]	-2.8	151.038 2, 125.058 6, 65.040 4	Vanillic acid
O8^*	2.80	C₉H₈O₄	181.049 5	181.049 1 [+]	-2.3	163.038 7, 135.034 4, 117.033 4, 89.038 7	Caffeic acid
O9	2.85	C₁₆H₁₈O₉	353.087 8	353.087 2 [-]	-1.7	191.055 6, 173.045 0, 93.035 9	Cryptochlorogenic acid^[22]
O10	3.87	C₂₅H₂₄O₁₂	515.119 5	515.118 5 [-]	-1.9	353.086 6, 335.076 4, 191.055 6, 179.034 6	3, 4-Dicaffeoylquinic acid^[23]
O11^*	4.71	C₁₀H₁₀O₄	195.065 2	195.064 8 [+]	-2.0	177.054 4, 145.028 0, 117.032 9, 89.038 4	Ferulic acid
O12^*	5.09	C₇H₆O₂	123.044 1	123.043 6 [+]	-3.4	105.032 9, 77.039 8	Benzoic acid
O13	5.23	C₁₆H₁₈O₉	353.087 8	353.087 5 [-]	-1.0	191.055 6, 179.035 0, 135.044 9	1, 5-caffeoylquinic acid^[22]
O14^*	5.33	C₁₀H₁₀O₄	195.065 2	195.065 0 [+]	-0.7	177.053 8, 149.058 7, 117.032 5, 89.038 4	Isoferulic acid
O15	5.95	C₂₅H₂₄O₁₂	515.119 5	515.118 9 [-]	-1.2	353.086 9, 335.077 2, 191.056 2, 179.034 7	4, 5-Dicaffeoylquinic acid^[23]
O16^*	6.27	C₂₅H₂₄O₁₂	515.119 5	515.118 6 [-]	-1.9	353.086 0, 335.076 0, 191.055 6, 179.033 4	cynarin
O17^*	6.33	C₁₀H₁₀O₄	195.065 2	195.065 4 [+]	1.0	163.039 4, 145.028 4, 117.033 5, 89.039 7	Methyl caffeate
O18	6.99	C₂₅H₂₄O₁₂	515.119 5	515.118 3 [-]	-2.3	353.086 5, 335.076 1, 191.055 6, 161.023 4	3, 5-Dicaffeoylquinic acid^[23]
O19^*	9.05	C₉H₁₀O₃	167.070 3	167.070 0 [+]	-1.5	149.059 0, 121.064 2, 91.054 5, 77.039 4	Paeonol
O20	21.97	C₂₇H₄₄O₄	433.331 2	433.329 8 [+]	-3.4	181.049 7, 163.039 1	Octadecyl caffeate
O21	22.84	C₂₂H₄₄O₂	339.326 9	339.326 3 [-]	-1.6	321.315 5, 293.066 5	n-Docosanoic acid
O22	24.29	C₃₁H₅₂O₄	489.393 8	489.391 8 [+]	-4.2	181.049 2, 163.039 2	Docosyl caffeate
Flavonoids	F1^*	3.63	C₁₅H₁₂O₈	321.060 5	321.060 8 [+]	0.5	303.049 8, 275.054 6, 247.059 7, 153.017 4	Dihydromyricetin
F2^*	4.73	C₂₆H₂₈O₁₄	563.140 6	563.140 2 [-]	-0.8	545.130 8, 473.107 4, 443.096 9, 353.065 0	Schaftoside
F3^*	4.79	C₂₆H₂₈O₁₄	563.140 6	563.140 0 [-]	-1.0	503.118 6, 473.108 4, 443.097 4, 383.076 0	Isoschaftoside
F4	5.19	C₂₁H₂₀O₉	417.118 0	417.118 1 [+]	0.1	271.060 3, 243.065 7, 197.059 9, 153.018 2	Apigenin-5-rhamnoside
F5^*	5.25	C₂₁H₂₀O₁₂	463.088 2	463.088 9 [-]	1.2	317.029 6, 151.023 0	Myrictrin
F6^*	5.38	C₂₁H₂₀O₁₂	465.102 8	465.102 2 [+]	-0.9	303.050 3, 287.055 8, 121.028 0	Hyperoside
F7^*	5.47	C₂₇H₃₀O₁₆	609.146 0	609.146 0 [-]	-0.1	463.189 8, 301.038 9	Rutin
F8^*	5.61	C₂₁H₂₀O₁₂	465.102 8	465.102 1 [+]	-1.3	303.050 4, 287.054 5, 121.028 9	Isoquercitrin
F9^*	5.64	C₂₁H₂₀O₁₁	449.107 8	449.108 6 [+]	1.7	287.055 9, 153.017 5	Luteolin-7-galacturonide
F10^*	5.75	C₂₁H₂₀O₁₀	433.112 9	433.112 5 [+]	-0.9	271.059 2, 215.068 8	Genistin
F11	6.08	C₂₈H₃₂O₁₆	625.176 3	625.176 4 [+]	0.1	317.066 1, 285.043 4, 153.017 6	Isorhamnetin-3-O- neohespeidoside
F12^*	6.42	C₂₁H₂₀O₁₁	449.107 8	449.106 9 [+]	-2.0	303.050 4, 287.055 0, 121.028 4	Quercitrin
F13^*	6.56	C₂₁H₂₀O₁₁	449.107 8	449.107 2 [+]	-1.5	287.054 5, 153.017 2	Kaempferol-7-O-β-D- glucopyranoside
F14	6.62	C₂₂H₂₂O₁₂	478.393 4	478.391 9 [+]	-3.6	317.065 6, 285.043 4, 153.017 6	Isorhamnetin-3-O-glucoside
F15^*	6.68	C₁₅H₁₀O₈	319.044 8	319.044 9 [+]	0.2	301.034 1, 273.038 7, 245.043 6, 153.017 4	Myricetin
F16^*	6.95	C₂₈H₁₄O₁₅	611.197 0	611.196 2 [+]	-1.5	303.086 7, 263.055 3, 177.055 2	Hesperidin
F17^*	7.66	C₁₅H₁₂O₄	257.080 8	257.080 9 [+]	0.2	239.069 4, 211.074 7, 147.044 2, 137.023 3	Liquiritigenin
F18^*	7.72	C₂₁H₁₈O₁₁	447.092 2	447.091 2 [+]	-2.2	271.059 6, 253.049 5, 123.007 4	Baicalin
F19^*	7.97	C₁₅H₁₀O₆	287.055 0	287.054 9 [+]	-0.6	269.043 8, 185.059 0, 153.017 9	Luteolin
F20^*	8.15	C₁₅H₁₀O₇	303.049 9	303.050 0 [+]	0.2	285.038 6, 257.045 7, 229.049 4, 153.018 0	Quercetin
F21	8.46	C₂₇H₃₀O₁₅	595.165 8	595.168 6 [+]	4.9	287.054 7, 153.017 3	Biorobin^[24]
F22^*	8.86	C₁₅H₁₂O₅	273.075 8	273.075 5 [+]	-0.9	153.018 0, 147.043 6, 119.049 0	Naringenin
F23^*	8.95	C₁₅H₁₀O₅	271.060 1	271.059 9 [+]	-0.9	253.050 1, 215.070 4, 153.018 2, 91.055 0	Genistein
F24^*	9.01	C₁₅H₁₀O₅	271.060 1	271.060 0 [+]	-0.4	253.050 3, 243.065 7, 197.059 9, 153.018 2	Apigenin
F25^*	9.16	C₁₅H₁₀O₆	287.055 0	287.055 2 [+]	0.8	269.043 4, 153.017 3, 121.027 8	Kaempferol
F26^*	9.37	C₁₆H₁₂O₆	301.070 7	301.070 9 [+]	0.9	286.047 9, 258.053 0, 229.050 2	Diosmetin
F27^*	9.45	C₁₆H₁₂O₇	317.065 6	317.065 8 [+]	0.8	299.060 7, 289.067 8, 229.049 4, 153.018 2	Isorhamnetin
F28^*	9.61	C₁₅H₁₀O₃₅	271.060 1	271.060 0 [+]	-0.4	253.049 7, 169.012 8, 123.007 4	Baicalein
F29^*	10.95	C₁₆H₁₂O₅	285.075 8	285.076 0 [+]	0.8	252.042 6, 179.049 6	Wogonin
F30^*	11.20	C₁₆H₁₂O₅	285.075 8	285.076 0 [+]	0.8	270.053 0, 242.057 6, 153.018 0	Acacetin
F31^*	11.33	C₁₆H₁₂O₅	285.075 8	285.075 7 [+]	-0.1	270.050 8, 242.056 0, 167.033 0, 124.015 1	Genkwanin
Monoterpenes	MP1	8.23	C₂₁H₃₆O₁₀	449.238 1	449.237 2 [+]	-2.1	317.195 7, 133.049 8	Shionoside A
MP2	8.34	C₂₂H₃₈O₁₀	463.253 8	463.252 8 [+]	-2.2	317.196 3, 147.065 4	Shionoside B
Diterpenes	DP1	7.05	C₂₀H₂₀O₆	357.133 3	357.133 0 [+]	-0.8	339.122 4, 207.064 4, 189.053 5, 137.059 2	A^a^[28]
DP2	9.76	C₄₂H₆₆O₁₆	825.427 8	825.431 0 [-]	3.9	779.430 3	Smithoside B^[28]
DP3	10.07	C₂₀H₃₂O₆	367.212 6	367.211 4 [-]	-3.2	329.235 6, 206.019 8, 171.102 1, 146.967 1	Lingulatusin^[26]
DP4	12.91	C₂₀H₃₂O₄	337.237 3	337.237 4 [+]	0.1	319.230 9	B^b^[27]
DP5	21.29	C₂₆H₄₄O₅	435.311 6	435.309 6 [-]	-4.7	367.323 7, 321.316 1	Glycoside 1^[28]
Triterpenens	TP1	9.28	C₃₀H₄₈O₅	489.357 5	489.356 5 [+]	-1.9	471.345 5, 453.336 6, 201.164 4, 187.148 7	C^c
TP2	9.35	C₄₁H₆₆O₁₄	783.452 5	783.450 5 [+]	-2.6	489.357 3, 453.336 3, 407.331 3, 259.081 5	D^d^[29]
TP3	9.43	C₆₇H₁₀₈O₃₄	1 455.664 9	1 455.663 7 [-]	-0.8	1 323.618 7, 673.228 8	Astersaponin A^[30]
TP4	9.61	C₆₂H₁₀₀O₃₄	1 323.622 7	1 323.621 8 [-]	-0.6	541.178 8, 337.117 0	Astersaponin E^[30]
TP5	10.32	C₆₂H₁₀₀O₂₉	1 307.627 8	1 307.627 7 [-]	-0.1	1 175.588 9, 541.179 0	Astersaponin F^[30]
TP6	10.41	C₅₇H₉₂O₂₅	1 175.585 5	1 175.584 8 [-]	-0.6	953.530 8, 765.447 1, 633.412 4, 471.358 3	Asterlingulatoside D
TP7	10.46	C₅₂H₈₄O₂₁	1 043.542 3	1 043.542 5 [-]	-0.7	997.541 0, 765.456 8, 633.415 3, 471.336 2	Asterlingulatoside C
TP8	10.53	C₅₃H₈₆O₂₃	1 089.548 7	1 089.548 2 [-]	-0.5	953.514 5, 807.456 6, 765.445 4, 633.403 3	Bellidiastroside C2
TP9	10.71	C₅₃H₈₆O₂₂	1 073.553 8	1 073.553 7 [-]	-0.1	937.522 6, 617.405 5	Bellidiastroside B1^[31]
TP10	10.85	C₄₂H₆₈O₁₅	811.448 6	811.447 7 [-]	-1.0	765.448 7	Asterbatanoside B
TP11	10.94	C₅₆H₉₀O₂₅	1 161.569 8	1 161.569 3 [-]	-0.5	673.226 3, 601.197 8, 487.341 1, 281.085 2	Asterbatanoside F^[31]
TP12	11.01	C₅₃H₈₆O₂₂	1 073.553 8	1 073.553 9 [-]	0.1	937.522 6, 749.455 1	Bellidiastrodise B3^[31]
TP13	11.37	C₅₇H₉₀O₂₇	1 205.559 7	1 205.559 2 [-]	-0.4	131.034 3	Ageratoside B2^[31]
TP14	12.47	C₄₂H₆₈O₁₅	811.448 6	811.448 1 [-]	-0.6	765.448 5	Asterbatanoside C^[31]
TP15	13.58	C₄₇H₇₆O₁₇	911.501 0	911.499 9 [-]	-1.2	865.458 2	Asterlingulatoside B
TP16	13.89	C₄₁H₆₆O₁₃	765.443 1	765.441 2 [-]	-2.4	719.440 8	Asterlingulatoside A
TP17^*	14.06	C₃₀H₄₈O₄	471.348 0	471.348 2 [-]	0.5	327.525 4, 242.835 4	23-Hydroxybetulinic acid^[31]
TP18	16.32	C₃₀H₄₈O₄	471.348 0	471.348 1 [-]	0.3	407.333 2	Echinocystic acid
TP19	16.59	C₂₆H₄₂O₃	403.320 7	403.319 6 [+]	-2.7	385.310 0, 367.298 8, 203.179 4, 121.100 8	Astershionone A^[32]
TP20^*	17.01	C₃₀H₄₈O₃	455.353 1	455.354 9 [-]	4.0	409.381 9, 302.969 8, 258.499 2, 81.122 8	Betulinic acid
TP21	17.07	C₂₇H₄₂O₂	399.325 8	399.324 5 [+]	-3.2	381.316 3, 363.303 2, 217.195 0, 191.177 4	Astershionone F^[32]
TP22	17.41	C₂₇H₄₄O₃	417.336 3	417.335 1 [+]	-2.9	399.324 8, 381.315 5, 217.195 1, 191.178 6	Astershionone C^[32]
TP23^*	17.57	C₃₀H₄₈O₃	457.367 6	457.367 3 [+]	-0.7	439.355 3, 411.362 1, 217.192 9, 191.177 9	Oleanic acid
TP24	17.77	C₃₀H₅₀O₂	443.388 4	443.387 1 [+]	-2.8	425.377 2, 407.365 3, 217.195 1, 191.178 0	Friedelan-3-ol
TP25	18.28	C₃₀H₅₀O₂	443.388 4	443.386 8 [+]	-3.5	425.376 4, 407.365 9, 217.194 9, 191.178 9	Astertarone B^[37]
TP26^*	18.94	C₃₀H₅₀O	429.409 1	429.409 2 [+]	0.2	411.312 3, 338.347 1, 191.178 9	epi-Friedellanol^[31]
TP27	19.20	C₂₉H₄₆O₂	427.357 1	427.356 [+]	-2.6	409.346 9, 391.334 1, 287.200 9, 191.178 8	Astershionone B^[32]
TP28	19.39	C₃₀H₅₀O	427.393 4	427.392 0 [+]	-3.3	409.381 7, 217.195 0, 191.179 4	beta-Amyrin^[31]
TP29	19.79	C₃₀H₄₈O₂	441.372 7	441.372 3 [+]	-1.0	423.362 2, 405.348 5, 191.178 7	E^e^[31]
TP30	20.01	C₃₀H₄₈O	425.377 8	425.376 8 [+]	-2.4	407.366 0, 217.194 6, 191.179 1	Taraxerone^{[33, 34]}
TP31	20.22	C₃₀H₅₀O₂	443.388 4	443.387 1 [+]	-2.9	425.380 1, 407.367 7, 217.194 8, 191.179 0	Astatarone G
TP32^*	20.96	C₃₀H₅₀O₂	443.388 4	443.387 4 [+]	-2.2	425.379 7, 413.379 7, 217.194 9, 191.179 4	Betulin
TP33	21.81	C₃₀H₅₀O	427.393 4	427.391 9 [+]	-3.6	409.383 3, 341.321 2, 191.179 1	Taraxasterol^[36]
TP34	23.74	C₃₀H₅₀O	427.393 4	427.392 9 [+]	-2.4	409.379 9, 217.195 1, 191.178 2	Astertarone A^[35]
TP35^*	23.87	C₃₀H₅₀O	427.393 4	427.393 1 [+]	-0.9	409.386 1, 331.298 3, 217.194 4, 191.179 4	Friedelin
TP36^*	24.72	C₃₀H₅₀O	427.393 4	427.393 2 [+]	-0.6	409.382 8, 217.194 3, 191.178 9	Shionone
Coumarin	C1^*	2.00	C₁₅H₁₆O₉	341.086 7	341.087 0 [+]	0.9	179.034 2, 151.038 4, 105.034 6	Esculin
C2^*	2.68	C₉H₆O₄	179.033 9	179.033 9 [+]	-0.1	151.038 7, 133.028 6, 123.044 1, 105.034 0	Esculetin
C3^*	3.71	C₁₀H₈O₅	209.044 4	209.044 5 [+]	0.3	181.048 8, 163.038 7, 149.023 2, 121.028 4	Fraxetin
C4^*	4.23	C₁₀H₈O₄	193.049 5	193.049 4 [+]	-0.3	178.026 1, 150.031 0, 133.028 2, 122.036 1	Isoscopoletin
C5^*	4.39	C₉H₆O₃	163.039 0	163.038 7 [+]	-1.9	119.049 4, 107.049 2, 91.054 6, 77.039 5	7-Hydroxyeoumarin
C6^*	4.60	C₁₀H₈O₄	193.049 5	193.049 4 [+]	-0.3	178.026 3, 137.059 9, 133.028 6, 122.036 6	Scopoletin
C7^*	8.43	C₁₁H₆O₃	187.039 0	187.038 8 [+]	-0.8	143.049 5, 131.049 1, 115.054 6, 77.040 0	Psoralen
C8^*	8.93	C₁₂H₈O₄	217.049 5	217.049 7 [+]	0.8	202.026 0, 185.024 0, 174.031 2, 118.041 8	Xanthotoxin
C9^*	9.68	C₁₂H₈O₄	217.049 5	217.049 5 [+]	0.1	202.026 4, 174.030 7, 146.035 3, 118.040 6	Bergapten
Anthraquinones	AQ1^*	10.79	C₁₅H₈O₆	341.086 7	347.087 0 [-]	0.9	239.034 3, 211.039 3, 183.044 3	Rhein
AQ2	11.20	C₁₅H₁₂O₄	255.066 3	255.066 1 [-]	-0.9	227.072 2, 211.076 4, 183.079 7, 107.014 8	Emodin anthrone
AQ3^*	12.63	C₁₅H₁₀O₅	269.045 5	269.045 7 [-]	0.7	241.050 0, 225.055 1, 197.060 4, 181.065 8	Emodin
Steroids	S1	7.76	C₃₅H₅₈O₆	575.430 6	575.431 1 [+]	-2.3	413.377 1, 395.363 0, 255.208 1, 189.015 7	F^f^[31]
S2^*	18.81	C₂₉H₄₈O	413.377 8	413.376 2 [+]	-3.9	395.368 7, 255.208 4, 189.016 7, 109.065 3	α-Spinasterol
S3	24.25	C₂₉H₄₈O	413.377 8	413.376 5 [+]	-3.1	395.363 9, 109.064 6	Stigmasterol^[38]
Aldehydes	A1	1.46	C₆H₆O₃	127.039 0	127.038 8 [+]	-1.9	109.027 6, 53.040 5	5-Hydroxymethyl-2- furaldehyde
A2^*	1.93	C₇H₆O₃	139.039 0	139.038 8 [+]	-0.9	111.044 6, 93.034 1, 65.040 4	Benzaldehyde
A3^*	2.73	C₇H₆O₂	123.044 1	123.043 9 [+]	-1.3	95.049 3, 77.039 5, 67.055 7, 65.040 1	p-Hydroxybenzaldehyde

Type

t_R/min

Formula

[M+H]⁺/[M-H]^-

Fragment ions

Identification

Calculated mass

Experimental mass

Error
(ppm)

Peptides

4.13

C₂₅H₃₂ClN₅O₈

566.201 2

566.199 9 [+]

-2.3

548.189 5, 318.085 5, 232.096 9, 106.065 1

Astin L^[17]

4.52

C₂₅H₃₅N₅O₇

518.260 9

518.259 8 [+]

-2.1

490.264 9, 286.139 8, 171.112 7, 106.065 1

Asterinin F^[18]

5.35

C₂₅H₃₂ClN₅O₇

550.206 3

550.205 8 [+]

-0.9

532.192 7, 302.089 9, 215.058 0, 106.065 0

Astin H^[19]

5.58

C₂₅H₃₅N₅O₆

502.266 0

502.264 9 [+]

-2.3

474.267 9, 270.143 7, 183.111 7, 106.065 0

Astin G^[19]

6.11

C₂₅H₃₂ClN₅O₇

550.206 3

550.205 4 [+]

-1.7

522.209 8, 447.142 2, 300.074 1, 106.065 0

Astin E^[19]

6.21

C₂₅H₃₄ClN₅O₇

552.222 0

552.219 7 [+]

-4.1

524.225 7, 449.159 2, 320.100 7, 106.065 0

Astin I^[19]

6.88

C₂₅H₃₄ClN₅O₆

536.227 0

536.226 3 [+]

-1.4

508.231 4, 451.174 3, 304.106 0, 106.065 4

Astin F^[19]

7.21

C₂₅H₃₂ClN₅O₆

534.211 4

543.211 0 [+]

-0.8

506.215 2, 449.157 9, 106.065 1

Astin D^[19]

7.27

C₂₅H₃₃N₅O₈

532.240 2

532.239 2 [+]

-1.8

514.226 7, 338.169 9, 235.105 8, 106.065 3

Asterinin A^[20]

P10

7.33

C₂₅H₃₃Cl₂N₅O₈

602.177 9

602.176 3 [+]

-3.0

584.165 1, 336.057 1, 232.097 3, 106.064 4

Astin K^[17]

P11

7.58

C₂₆H₃₅N₅O₈

546.255 8

546.254 0 [+]

-3.4

528.244 7, 350.170 7, 235.107 8, 106.065 0

Asterinin C^[20]

P12

7.84

C₂₅H₃₃Cl₂N₅O₇

586.183 0

586.181 4 [+]

-2.6

558.183 6, 336.049 7, 106.065 2, 58.065 0

Astin A^[19]

P13

7.87

C₂₅H₃₃Cl₂N₅O₇

586.183 0

586.182 9 [+]

-0.1

558.183 1, 130.049 1, 106.065 5, 60.044 2

Astin B^[19]

P14

8.19

C₂₅H₃₃N₅O₇

516.2453

516.243 9 [+]

-2.7

498.232 9, 338.170 0, 235.106 6, 106.065 3

Astin J^[21]

P15

8.25

C₂₅H₃₃N₅O₈

546.255 8

546.254 6 [+]

-2.3

528.245 8, 352.186 4, 235.107 6, 106.065 0

Asterinin B^[20]

P16^*

8.46

C₂₅H₃₃Cl₂N₅O₆

570.188 1

570.187 3 [+]

-1.4

485.133 3, 338.066 5, 251.034 1, 106.064 9

Astin C

P17

8.53

C₂₆H₃₃Cl₂N₅O₇

600.198 6

600.198 2 [+]

-0.7

582.193 5, 501.132 8, 336.051 5, 106.065 2

Astin P^[17]

P18

11.07

C₂₇H₃₅Cl₂N₅O₇

612.198 6

612.197 2 [+]

-2.3

548.202 3, 467.124 2, 380.077 5, 106.065 3

Astin O^[17]

Organic acids

0.61

C₄H₆O₄

117.019 3

117.019 3 [-]

0.1

99.008 8, 71.031 8

Succinic acid

0.75

C₆H₁₀O₄

145.050 6

145.050 7 [-]

0.4

127.039 4, 109.037 7, 71.031 5

2, 2-Dimethylsuccinic acid

O3^*

0.81

C₆H₆O₃

127.039 0

127.039 0 [+]

0.2

109.028 8, 81.034 6, 53.041 4

Pyrogallic acid

O4^*

1.30

C₇H₆O₄

155.033 9

155.033 7 [+]

-1.0

93.032 7, 65.040 1

Protocatechuate

2.04

C₇H₆O₃

139.039 0

139.038 7 [+]

-2.2

121.027 8, 95.049 1, 77.038 9, 65.040 2

4-Hydroxybenzoic acid

O6^*

2.57

C₁₆H₁₈O₉

353.087 8

353.087 5 [-]

-1.0

191.055 6, 93.035 8

Chlorogenic acid

2.70

C₈H₈O₄

169.049 5

169.049 1 [+]

-2.8

151.038 2, 125.058 6, 65.040 4

Vanillic acid

O8^*

2.80

C₉H₈O₄

181.049 5

181.049 1 [+]

-2.3

163.038 7, 135.034 4, 117.033 4, 89.038 7

Caffeic acid

2.85

C₁₆H₁₈O₉

353.087 8

353.087 2 [-]

-1.7

191.055 6, 173.045 0, 93.035 9

Cryptochlorogenic acid^[22]

O10

3.87

C₂₅H₂₄O₁₂

515.119 5

515.118 5 [-]

-1.9

353.086 6, 335.076 4, 191.055 6, 179.034 6

3, 4-Dicaffeoylquinic acid^[23]

O11^*

4.71

C₁₀H₁₀O₄

195.065 2

195.064 8 [+]

-2.0

177.054 4, 145.028 0, 117.032 9, 89.038 4

Ferulic acid

O12^*

5.09

C₇H₆O₂

123.044 1

123.043 6 [+]

-3.4

105.032 9, 77.039 8

Benzoic acid

O13

5.23

C₁₆H₁₈O₉

353.087 8

353.087 5 [-]

-1.0

191.055 6, 179.035 0, 135.044 9

1, 5-caffeoylquinic acid^[22]

O14^*

5.33

C₁₀H₁₀O₄

195.065 2

195.065 0 [+]

-0.7

177.053 8, 149.058 7, 117.032 5, 89.038 4

Isoferulic acid

O15

5.95

C₂₅H₂₄O₁₂

515.119 5

515.118 9 [-]

-1.2

353.086 9, 335.077 2, 191.056 2, 179.034 7

4, 5-Dicaffeoylquinic acid^[23]

O16^*

6.27

C₂₅H₂₄O₁₂

515.119 5

515.118 6 [-]

-1.9

353.086 0, 335.076 0, 191.055 6, 179.033 4

cynarin

O17^*

6.33

C₁₀H₁₀O₄

195.065 2

195.065 4 [+]

1.0

163.039 4, 145.028 4, 117.033 5, 89.039 7

Methyl caffeate

O18

6.99

C₂₅H₂₄O₁₂

515.119 5

515.118 3 [-]

-2.3

353.086 5, 335.076 1, 191.055 6, 161.023 4

3, 5-Dicaffeoylquinic acid^[23]

O19^*

9.05

C₉H₁₀O₃

167.070 3

167.070 0 [+]

-1.5

149.059 0, 121.064 2, 91.054 5, 77.039 4

Paeonol

O20

21.97

C₂₇H₄₄O₄

433.331 2

433.329 8 [+]

-3.4

181.049 7, 163.039 1

Octadecyl caffeate

O21

22.84

C₂₂H₄₄O₂

339.326 9

339.326 3 [-]

-1.6

321.315 5, 293.066 5

n-Docosanoic acid

O22

24.29

C₃₁H₅₂O₄

489.393 8

489.391 8 [+]

-4.2

181.049 2, 163.039 2

Docosyl caffeate

Flavonoids

F1^*

3.63

C₁₅H₁₂O₈

321.060 5

321.060 8 [+]

0.5

303.049 8, 275.054 6, 247.059 7, 153.017 4

Dihydromyricetin

F2^*

4.73

C₂₆H₂₈O₁₄

563.140 6

563.140 2 [-]

-0.8

545.130 8, 473.107 4, 443.096 9, 353.065 0

Schaftoside

F3^*

4.79

C₂₆H₂₈O₁₄

563.140 6

563.140 0 [-]

-1.0

503.118 6, 473.108 4, 443.097 4, 383.076 0

Isoschaftoside

5.19

C₂₁H₂₀O₉

417.118 0

417.118 1 [+]

0.1

271.060 3, 243.065 7, 197.059 9, 153.018 2

Apigenin-5-rhamnoside

F5^*

5.25

C₂₁H₂₀O₁₂

463.088 2

463.088 9 [-]

1.2

317.029 6, 151.023 0

Myrictrin

F6^*

5.38

C₂₁H₂₀O₁₂

465.102 8

465.102 2 [+]

-0.9

303.050 3, 287.055 8, 121.028 0

Hyperoside

F7^*

5.47

C₂₇H₃₀O₁₆

609.146 0

609.146 0 [-]

-0.1

463.189 8, 301.038 9

Rutin

F8^*

5.61

C₂₁H₂₀O₁₂

465.102 8

465.102 1 [+]

-1.3

303.050 4, 287.054 5, 121.028 9

Isoquercitrin

F9^*

5.64

C₂₁H₂₀O₁₁

449.107 8

449.108 6 [+]

1.7

287.055 9, 153.017 5

Luteolin-7-galacturonide

F10^*

5.75

C₂₁H₂₀O₁₀

433.112 9

433.112 5 [+]

-0.9

271.059 2, 215.068 8

Genistin

F11

6.08

C₂₈H₃₂O₁₆

625.176 3

625.176 4 [+]

0.1

317.066 1, 285.043 4, 153.017 6

Isorhamnetin-3-O- neohespeidoside

F12^*

6.42

C₂₁H₂₀O₁₁

449.107 8

449.106 9 [+]

-2.0

303.050 4, 287.055 0, 121.028 4

Quercitrin

F13^*

6.56

C₂₁H₂₀O₁₁

449.107 8

449.107 2 [+]

-1.5

287.054 5, 153.017 2

Kaempferol-7-O-β-D- glucopyranoside

F14

6.62

C₂₂H₂₂O₁₂

478.393 4

478.391 9 [+]

-3.6

317.065 6, 285.043 4, 153.017 6

Isorhamnetin-3-O-glucoside

F15^*

6.68

C₁₅H₁₀O₈

319.044 8

319.044 9 [+]

0.2

301.034 1, 273.038 7, 245.043 6, 153.017 4

Myricetin

F16^*

6.95

C₂₈H₁₄O₁₅

611.197 0

611.196 2 [+]

-1.5

303.086 7, 263.055 3, 177.055 2

Hesperidin

F17^*

7.66

C₁₅H₁₂O₄

257.080 8

257.080 9 [+]

0.2

239.069 4, 211.074 7, 147.044 2, 137.023 3

Liquiritigenin

F18^*

7.72

C₂₁H₁₈O₁₁

447.092 2

447.091 2 [+]

-2.2

271.059 6, 253.049 5, 123.007 4

Baicalin

F19^*

7.97

C₁₅H₁₀O₆

287.055 0

287.054 9 [+]

-0.6

269.043 8, 185.059 0, 153.017 9

Luteolin

F20^*

8.15

C₁₅H₁₀O₇

303.049 9

303.050 0 [+]

0.2

285.038 6, 257.045 7, 229.049 4, 153.018 0

Quercetin

F21

8.46

C₂₇H₃₀O₁₅

595.165 8

595.168 6 [+]

4.9

287.054 7, 153.017 3

Biorobin^[24]

F22^*

8.86

C₁₅H₁₂O₅

273.075 8

273.075 5 [+]

-0.9

153.018 0, 147.043 6, 119.049 0

Naringenin

F23^*

8.95

C₁₅H₁₀O₅

271.060 1

271.059 9 [+]

-0.9

253.050 1, 215.070 4, 153.018 2, 91.055 0

Genistein

F24^*

9.01

C₁₅H₁₀O₅

271.060 1

271.060 0 [+]

-0.4

253.050 3, 243.065 7, 197.059 9, 153.018 2

Apigenin

F25^*

9.16

C₁₅H₁₀O₆

287.055 0

287.055 2 [+]

0.8

269.043 4, 153.017 3, 121.027 8

Kaempferol

F26^*

9.37

C₁₆H₁₂O₆

301.070 7

301.070 9 [+]

0.9

286.047 9, 258.053 0, 229.050 2

Diosmetin

F27^*

9.45

C₁₆H₁₂O₇

317.065 6

317.065 8 [+]

0.8

299.060 7, 289.067 8, 229.049 4, 153.018 2

Isorhamnetin

F28^*

9.61

C₁₅H₁₀O₃₅

271.060 1

271.060 0 [+]

-0.4

253.049 7, 169.012 8, 123.007 4

Baicalein

F29^*

10.95

C₁₆H₁₂O₅

285.075 8

285.076 0 [+]

0.8

252.042 6, 179.049 6

Wogonin

F30^*

11.20

C₁₆H₁₂O₅

285.075 8

285.076 0 [+]

0.8

270.053 0, 242.057 6, 153.018 0

Acacetin

F31^*

11.33

C₁₆H₁₂O₅

285.075 8

285.075 7 [+]

-0.1

270.050 8, 242.056 0, 167.033 0, 124.015 1

Genkwanin

Monoterpenes

MP1

8.23

C₂₁H₃₆O₁₀

449.238 1

449.237 2 [+]

-2.1

317.195 7, 133.049 8

Shionoside A

MP2

8.34

C₂₂H₃₈O₁₀

463.253 8

463.252 8 [+]

-2.2

317.196 3, 147.065 4

Shionoside B

Diterpenes

DP1

7.05

C₂₀H₂₀O₆

357.133 3

357.133 0 [+]

-0.8

339.122 4, 207.064 4, 189.053 5, 137.059 2

A^a^[28]

DP2

9.76

C₄₂H₆₆O₁₆

825.427 8

825.431 0 [-]

3.9

779.430 3

Smithoside B^[28]

DP3

10.07

C₂₀H₃₂O₆

367.212 6

367.211 4 [-]

-3.2

329.235 6, 206.019 8, 171.102 1, 146.967 1

Lingulatusin^[26]

DP4

12.91

C₂₀H₃₂O₄

337.237 3

337.237 4 [+]

0.1

319.230 9

B^b^[27]

DP5

21.29

C₂₆H₄₄O₅

435.311 6

435.309 6 [-]

-4.7

367.323 7, 321.316 1

Glycoside 1^[28]

Triterpenens

TP1

9.28

C₃₀H₄₈O₅

489.357 5

489.356 5 [+]

-1.9

471.345 5, 453.336 6, 201.164 4, 187.148 7

C^c

TP2

9.35

C₄₁H₆₆O₁₄

783.452 5

783.450 5 [+]

-2.6

489.357 3, 453.336 3, 407.331 3, 259.081 5

D^d^[29]

TP3

9.43

C₆₇H₁₀₈O₃₄

1 455.664 9

1 455.663 7 [-]

-0.8

1 323.618 7, 673.228 8

Astersaponin A^[30]

TP4

9.61

C₆₂H₁₀₀O₃₄

1 323.622 7

1 323.621 8 [-]

-0.6

541.178 8, 337.117 0

Astersaponin E^[30]

TP5

10.32

C₆₂H₁₀₀O₂₉

1 307.627 8

1 307.627 7 [-]

-0.1

1 175.588 9, 541.179 0

Astersaponin F^[30]

TP6

10.41

C₅₇H₉₂O₂₅

1 175.585 5

1 175.584 8 [-]

-0.6

953.530 8, 765.447 1, 633.412 4, 471.358 3

Asterlingulatoside D

TP7

10.46

C₅₂H₈₄O₂₁

1 043.542 3

1 043.542 5 [-]

-0.7

997.541 0, 765.456 8, 633.415 3, 471.336 2

Asterlingulatoside C

TP8

10.53

C₅₃H₈₆O₂₃

1 089.548 7

1 089.548 2 [-]

-0.5

953.514 5, 807.456 6, 765.445 4, 633.403 3

Bellidiastroside C2

TP9

10.71

C₅₃H₈₆O₂₂

1 073.553 8

1 073.553 7 [-]

-0.1

937.522 6, 617.405 5

Bellidiastroside B1^[31]

TP10

10.85

C₄₂H₆₈O₁₅

811.448 6

811.447 7 [-]

-1.0

765.448 7

Asterbatanoside B

TP11

10.94

C₅₆H₉₀O₂₅

1 161.569 8

1 161.569 3 [-]

-0.5

673.226 3, 601.197 8, 487.341 1, 281.085 2

Asterbatanoside F^[31]

TP12

11.01

C₅₃H₈₆O₂₂

1 073.553 8

1 073.553 9 [-]

0.1

937.522 6, 749.455 1

Bellidiastrodise B3^[31]

TP13

11.37

C₅₇H₉₀O₂₇

1 205.559 7

1 205.559 2 [-]

-0.4

131.034 3

Ageratoside B2^[31]

TP14

12.47

C₄₂H₆₈O₁₅

811.448 6

811.448 1 [-]

-0.6

765.448 5

Asterbatanoside C^[31]

TP15

13.58

C₄₇H₇₆O₁₇

911.501 0

911.499 9 [-]

-1.2

865.458 2

Asterlingulatoside B

TP16

13.89

C₄₁H₆₆O₁₃

765.443 1

765.441 2 [-]

-2.4

719.440 8

Asterlingulatoside A

TP17^*

14.06

C₃₀H₄₈O₄

471.348 0

471.348 2 [-]

0.5

327.525 4, 242.835 4

23-Hydroxybetulinic acid^[31]

TP18

16.32

C₃₀H₄₈O₄

471.348 0

471.348 1 [-]

0.3

407.333 2

Echinocystic acid

TP19

16.59

C₂₆H₄₂O₃

403.320 7

403.319 6 [+]

-2.7

385.310 0, 367.298 8, 203.179 4, 121.100 8

Astershionone A^[32]

TP20^*

17.01

C₃₀H₄₈O₃

455.353 1

455.354 9 [-]

4.0

409.381 9, 302.969 8, 258.499 2, 81.122 8

Betulinic acid

TP21

17.07

C₂₇H₄₂O₂

399.325 8

399.324 5 [+]

-3.2

381.316 3, 363.303 2, 217.195 0, 191.177 4

Astershionone F^[32]

TP22

17.41

C₂₇H₄₄O₃

417.336 3

417.335 1 [+]

-2.9

399.324 8, 381.315 5, 217.195 1, 191.178 6

Astershionone C^[32]

TP23^*

17.57

C₃₀H₄₈O₃

457.367 6

457.367 3 [+]

-0.7

439.355 3, 411.362 1, 217.192 9, 191.177 9

Oleanic acid

TP24

17.77

C₃₀H₅₀O₂

443.388 4

443.387 1 [+]

-2.8

425.377 2, 407.365 3, 217.195 1, 191.178 0

Friedelan-3-ol

TP25

18.28

C₃₀H₅₀O₂

443.388 4

443.386 8 [+]

-3.5

425.376 4, 407.365 9, 217.194 9, 191.178 9

Astertarone B^[37]

TP26^*

18.94

C₃₀H₅₀O

429.409 1

429.409 2 [+]

0.2

411.312 3, 338.347 1, 191.178 9

epi-Friedellanol^[31]

TP27

19.20

C₂₉H₄₆O₂

427.357 1

427.356 [+]

-2.6

409.346 9, 391.334 1, 287.200 9, 191.178 8

Astershionone B^[32]

TP28

19.39

C₃₀H₅₀O

427.393 4

427.392 0 [+]

-3.3

409.381 7, 217.195 0, 191.179 4

beta-Amyrin^[31]

TP29

19.79

C₃₀H₄₈O₂

441.372 7

441.372 3 [+]

-1.0

423.362 2, 405.348 5, 191.178 7

E^e^[31]

TP30

20.01

C₃₀H₄₈O

425.377 8

425.376 8 [+]

-2.4

407.366 0, 217.194 6, 191.179 1

Taraxerone^{[33, 34]}

TP31

20.22

C₃₀H₅₀O₂

443.388 4

443.387 1 [+]

-2.9

425.380 1, 407.367 7, 217.194 8, 191.179 0

Astatarone G

TP32^*

20.96

C₃₀H₅₀O₂

443.388 4

443.387 4 [+]

-2.2

425.379 7, 413.379 7, 217.194 9, 191.179 4

Betulin

TP33

21.81

C₃₀H₅₀O

427.393 4

427.391 9 [+]

-3.6

409.383 3, 341.321 2, 191.179 1

Taraxasterol^[36]

TP34

23.74

C₃₀H₅₀O

427.393 4

427.392 9 [+]

-2.4

409.379 9, 217.195 1, 191.178 2

Astertarone A^[35]

TP35^*

23.87

C₃₀H₅₀O

427.393 4

427.393 1 [+]

-0.9

409.386 1, 331.298 3, 217.194 4, 191.179 4

Friedelin

TP36^*

24.72

C₃₀H₅₀O

427.393 4

427.393 2 [+]

-0.6

409.382 8, 217.194 3, 191.178 9

Shionone

Coumarin

C1^*

2.00

C₁₅H₁₆O₉

341.086 7

341.087 0 [+]

0.9

179.034 2, 151.038 4, 105.034 6

Esculin

C2^*

2.68

C₉H₆O₄

179.033 9

179.033 9 [+]

-0.1

151.038 7, 133.028 6, 123.044 1, 105.034 0

Esculetin

C3^*

3.71

C₁₀H₈O₅

209.044 4

209.044 5 [+]

0.3

181.048 8, 163.038 7, 149.023 2, 121.028 4

Fraxetin

C4^*

4.23

C₁₀H₈O₄

193.049 5

193.049 4 [+]

-0.3

178.026 1, 150.031 0, 133.028 2, 122.036 1

Isoscopoletin

C5^*

4.39

C₉H₆O₃

163.039 0

163.038 7 [+]

-1.9

119.049 4, 107.049 2, 91.054 6, 77.039 5

7-Hydroxyeoumarin

C6^*

4.60

C₁₀H₈O₄

193.049 5

193.049 4 [+]

-0.3

178.026 3, 137.059 9, 133.028 6, 122.036 6

Scopoletin

C7^*

8.43

C₁₁H₆O₃

187.039 0

187.038 8 [+]

-0.8

143.049 5, 131.049 1, 115.054 6, 77.040 0

Psoralen

C8^*

8.93

C₁₂H₈O₄

217.049 5

217.049 7 [+]

0.8

202.026 0, 185.024 0, 174.031 2, 118.041 8

Xanthotoxin

C9^*

9.68

C₁₂H₈O₄

217.049 5

217.049 5 [+]

0.1

202.026 4, 174.030 7, 146.035 3, 118.040 6

Bergapten

Anthraquinones

AQ1^*

10.79

C₁₅H₈O₆

341.086 7

347.087 0 [-]

0.9

239.034 3, 211.039 3, 183.044 3

Rhein

AQ2

11.20

C₁₅H₁₂O₄

255.066 3

255.066 1 [-]

-0.9

227.072 2, 211.076 4, 183.079 7, 107.014 8

Emodin anthrone

AQ3^*

12.63

C₁₅H₁₀O₅

269.045 5

269.045 7 [-]

0.7

241.050 0, 225.055 1, 197.060 4, 181.065 8

Emodin

Steroids

7.76

C₃₅H₅₈O₆

575.430 6

575.431 1 [+]

-2.3

413.377 1, 395.363 0, 255.208 1, 189.015 7

F^f^[31]

S2^*

18.81

C₂₉H₄₈O

413.377 8

413.376 2 [+]

-3.9

395.368 7, 255.208 4, 189.016 7, 109.065 3

α-Spinasterol

24.25

C₂₉H₄₈O

413.377 8

413.376 5 [+]

-3.1

395.363 9, 109.064 6

Stigmasterol^[38]

Aldehydes

1.46

C₆H₆O₃

127.039 0

127.038 8 [+]

-1.9

109.027 6, 53.040 5

5-Hydroxymethyl-2- furaldehyde

A2^*

1.93

C₇H₆O₃

139.039 0

139.038 8 [+]

-0.9

111.044 6, 93.034 1, 65.040 4

Benzaldehyde

A3^*

2.73

C₇H₆O₂

123.044 1

123.043 9 [+]

-1.3

95.049 3, 77.039 5, 67.055 7, 65.040 1

p-Hydroxybenzaldehyde