药学学报

No.	t_R /min	Observed m/z	Adduct	Formula	Mass error /×10^-6	Observed CCS/Å²	Type	Fragment ion	Identification	HDMS^E	HDDDA
1	2.08	527.089 0	[M-H]^-	C₁₈H₂₄O₁₈	0.02	194.08	Glycoside	473.078 2, 421.103 7, 253.097 3, 165.079 1	4-Deoxy-β-L-threo-hex-4-enopyranuronosyl-(1- > 4)-α-D-galactopyranuronosyl-(1- > 4)-D-galactopyranuronic acid or isomer	√	√
2^*	3.41	153.018 2	[M-H]^-	C₇H₄O₄	-0.23	158.79	Organic acid	109.028 8	Protocatechuic acid	√
3	5.77	327.143 6	[M-H]^-	C₁₆H₂₄O₇	-4.12	188.05	Glycoside	272.088 9, 134.036 9	Thymoquinol 5-O-β-D-glucopyranoside or isomer	√
4	6.33	327.144 4	[M-H]^-	C₁₆H₂₄O₇	-1.49	185.24	Glycoside	161.024 1, 149.060 6	Thymoquinol 5-O-β-D-glucopyranoside or isomer	√
5	6.81	713.302 8	[M+H]⁺	C₃₄H₄₈O₁₆	1.85	173.65	Lignan	375.170 0, 165.066 0	1, 2, 13, 14-Tetramethoxydibenzo-cyclooctadiene 3, 12-O-β-D-diglucopyranoside or isomer	√
6^*	7.52	609.146 3	[M-H]^-	C₂₇H₃₀O₁₆	0.31	223.02	Flavonoid	301.033 9, 271.024 3, 255.028 7, 243.031 6, 227.031 9	Rutin	√	√
7	7.65	565.228 4	[M-H]^-	C₂₈H₃₈O₁₂	-1.20	237.91	Lignan	373.138 8	3, 7-Dihydroxy-1, 2, 13, 14-tetramethoxydibenzo-cyclooctadiene 12-O-β-D-glucopyranoside or isomer	√
8	7.85	463.087 9	[M-H]^-	C₂₁H₂₀O₁₂	-0.65	192.51	Glycoside	301.034 1, 271.022 8, 255.029 0, 243.027 4, 151.002 8	Hyperoside or isomer	√	√
9	8.48	473.202 4	[M-H]^-	C₂₂H₃₄O₁₁	-0.92	216.55	Glycoside	313.107 8, 271.024 5, 223.153 1	Schisandenoid A or isomer	√
10	8.93	565.229 6	[M-H]^-	C₂₈H₃₈O₁₂	0.94	229.49	Lignan	341.102 5, 326.078 0	3, 7-Dihydroxy-1, 2, 13, 14-tetramethoxydibenzo-cyclooctadiene 12-O-β-D-glucopyranoside or isomer	√	√
11	9.99	575.212 8	[M-H]^-	C₂₉H₃₆O₁₂	-1.09	209.75	Terpenoid	557.194 8, 497.185 7, 482.194 0, 453.192 7	Arisanlactone B or isomer	√	√
12	10.41	577.228 9	[M+H]⁺	C₂₉H₃₆O₁₂	1.60	213.53	Terpenoid	543.225 9, 485.213 1	Micradilactone A or isomer	√	√
13	10.42	561.232 9	[M+H]⁺	C₂₉H₃₆O₁₁	-0.18	211.64	Terpenoid	543.225 9, 507.203 3, 485.213 0	Schicagenin B or isomer	√
14	10.70	497.219 5	[M-H]^-	C₂₈H₃₄O₈	2.77	214.37	Lignan	387.136 9	Angeloylisogomisin O or isomer	√
15	10.89	559.218 7	[M-H]^-	C₂₉H₃₆O₁₁	0.30	209.42	Terpenoid	541.214 4, 465.152 1, 403.149 7, 383.145 1	Schindilactone C or isomer	√	√
16	11.14	561.233 2	[M+H]⁺	C₂₉H₃₆O₁₁	0.28	212.18	Terpenoid	543.219 3, 439.205 0, 425.176 4, 407.209 8	Schicagenin B or isomer	√	√
17	11.47	543.223 2	[M-H]^-	C₂₉H₃₆O₁₀	-0.70	222.66	Terpenoid	527.226 1, 473.247 7	Pre-schisanartanin N or isomer	√	√
18	11.51	527.226 2	[M+H]⁺	C₂₉H₃₄O₉	-2.49	206.62	Terpenoid	467.206 4, 419.185 0, 203.104 9, 185.094 6	Lancifodilactone D or isomer	√	√
19	11.63	549.232 7	[M+H]⁺	C₂₈H₃₆O₁₁	-0.62	216.71	Terpenoid	479.207 5, 387.179 5, 355.153 2	19(R)-Hydroxyl-wuweizidilactone H or isomer	√	√
20	11.75	559.218 5	[M-H]^-	C₂₉H₃₆O₁₁	-0.05	210.31	Terpenoid	469.222 6, 465.148 6, 413.197 5, 387.146 2, 347.157 5	Schicagenin B or isomer	√	√
21	11.82	543.223 5	[M-H]^-	C₂₉H₃₆O₁₀	-0.13	217.58	Terpenoid	463.211 7, 383.187 7, 365.196 6, 137.059 7	Pre-schisanartanin N or isomer	√	√
22	11.91	577.230 3	[M+H]⁺	C₂₉H₃₆O₁₂	4.10	215.81	Terpenoid	545.229 2, 525.181 0, 515.211 9, 495.204 6, 453.203 2	Arisanlactone B or isomer	√
23	12.09	559.218 3	[M-H]^-	C₂₉H₃₆O₁₁	-0.25	218.39	Terpenoid	497.217 5, 429.192 4	Schindilactone C	√	√
24	12.27	543.224 1	[M-H]^-	C₂₉H₃₆O₁₀	0.93	214.59	Terpenoid	483.135 8, 471.200 5, 463.208 3, 435.216 3	Pre-schisanartanin N or isomer	√	√
25	12.41	575.213 9	[M-H]^-	C₂₉H₃₆O₁₂	0.83	213.64	Terpenoid	515.191 9, 419.125 9, 413.161 4	Arisanlactone B or isomer	√	√
26	12.53	545.238 7	[M+H]⁺	C₂₉H₃₆O₁₀	1.05	211.05	Terpenoid	508.213 3, 451.215 6, 433.197 7, 391.175 5	Pre-schisanartanin N or isomer	√	√
27	12.84	527.227 5	[M+H]⁺	C₂₈H₃₆O₉	-1.50	209.72	Terpenoid	485.217 2, 453.222 8, 439.211 4, 423.221 8	Lancifodilactone D or isomer	√	√
28	13.17	561.233 2	[M+H]⁺	C₂₉H₃₆O₁₁	0.25	208.50	Terpenoid	527.222 3, 485.220 1, 467.207 1	Schindilactone C or isomer	√	√
29	13.42	515.228 6	[M-H]^-	C₂₈H₃₆O₉	-0.20	218.36	Terpenoid	437.203 4, 385.174 6	Wuweizidilactone N or isomer	√	√
30	13.70	417.192 1	[M+H]⁺	C₂₃H₂₈O₇	3.05	188.89	Lignan	385.169 1, 331.118 9, 315.080 0	Gomisin O or isomer	√	√
31	13.71	661.250 5	[M-H]^-	C₃₃H₄₂O₁₄	0.56	238.36	Terpenoid	369.137 8, 285.170 1	Schisandroside D or isomer	√
32	13.76	533.238 7	[M+H]⁺	C₂₈H₃₆O₁₀	1.03	213.75	Terpenoid	499.235 7, 479.204 3, 437.195 0	Wuweizidilactone H or isomer	√	√
33	13.88	369.168 8	[M+H]⁺	C₂₂H₂₄O₅	-2.31	181.98	Terpenoid	337.144 1, 323.130 5, 203.083 3	(8ξ, 14ξ)-17-Oxoestra-1, 3, 5(10), 9(11)-tetraene-3, 4-diyl diacetate or isomer	√	√
34	13.96	221.190 3	[M+H]⁺	C₁₅H₂₄O	1.26	150.76	Sesquiterpene	219.172 4, 189.125 6	α-Iso-cubebenol or isomer	√	√
35	14.13	545.239 2	[M+H]⁺	C₂₉H₃₆O₁₀	1.99	213.63	Terpenoid	485.217 6, 451.207 5, 433.203 2, 371.175 5	Pre-schisanartanin N or isomer	√	√
36	14.31	515.227 7	[M+H]⁺	C₂₈H₃₄O₉	0.19	210.80	Terpenoid	429.192 1, 401.196 0, 381.132 5	Wuweizidilactone O or isomer	√	√
37	14.41	545.238 1	[M+H]⁺	C₂₉H₃₆O₁₀	-0.08	207.63	Terpenoid	527.2327, 453.224 7, 437.230 9, 431.207 8	Pre-schisanartanin N or isomer	√	√
38^*	14.60	419.205 0	[M+H]⁺	C₂₃H₃₀O₇	-3.40	189.94	Lignan	401.196 1, 386.172 6, 333.127 9, 315.120 5	Gomisin H	√	√
39	14.76	529.243 3	[M+H]⁺	C₂₉H₃₆O₉	0.23	206.80	Terpenoid	509.215 7, 469.219 6, 449.196 5, 439.212 5, 421.201 3	Methyl acetoxyangolensate or isomer	√	√
40	14.84	517.244 1	[M+H]⁺	C₂₈H₃₆O₉	1.60	203.29	Terpenoid	499.233 5, 413.193 0, 343.117 4	Wuweizidilactone N or isomer	√	√
41	14.90	575.285 2	[M+H]⁺	C₃₁H₄₂O₁₀	0.21	221.29	Terpenoid	479.242 9, 437.232 3	Wuweizidilactone K or isomer	√	√
42	15.01	527.227 5	[M+H]⁺	C₂₉H₃₄O₉	-0.05	214.45	Terpenoid	509.222 2, 463.202 3, 449.193 9	Lancifodilactone D or isomer	√	√
43	15.06	417.191 1	[M+H]⁺	C₂₃H₂₈O₇	0.71	185.16	Lignan	386.173 4, 371.176 5	Gomisin O or isomer	√
44	15.09	557.202 5	[M-H]^-	C₃₁H₃₈O₁₀	-0.70	213.07	Terpenoid	513.214 2, 485.217 0, 481.150 8, 391.119 9, 365.139 1	Lancifodilactone N or isomer	√	√
45	15.28	387.179 9	[M+H]⁺	C₂₂H₂₆O₆	-0.86	188.43	Lignan	372.153 8, 356.161 8, 341.127 5, 300.096 5	(-)-Gomisin L or isomer	√	√
46	15.36	559.218 4	[M-H]^-	C₂₉H₃₆O₁₁	-0.08	209.30	Terpenoid	483.161 8, 457.191 1, 431.180 3, 413.195 2	Schindilactone C or isomer	√	√
47	15.61	545.237 9	[M+H]⁺	C₂₉H₃₆O₁₀	-0.43	216.79	Terpenoid	497.214 4, 463.212 4, 435.219 0, 391.181 7	Pre-schisanartanin N or isomer	√	√
48	15.77	527.228 2	[M-H]^-	C₂₉H₃₆O₉	-0.78	214.93	Terpenoid	497.218 2, 435.215 9, 407.183 7, 365.178 5	Wuweizidilactone L or isomer	√	√
49	15.98	515.229 6	[M-H]^-	C₂₈H₃₆O₉	1.75	211.39	Terpenoid	471.243 2, 411.182 1, 369.169 0	Wuweizidilactone N or isomer	√	√
50	16.03	415.211 7	[M+H]⁺	C₂₄H₃₀O₆	0.45	186.75	Terpenoid	385.194 5, 369.167 6, 353.170 6, 323.129 2, 165.064 3	Meprednisone acetate or isomer	√	√
51	16.09	527.229 0	[M+H]⁺	C₂₉H₃₄O₉	2.80	208.04	Terpenoid	483.236 5, 438.235 3, 423.211 6	Lancifodilactone D or isomer	√	√
52	16.26	529.242 9	[M+H]⁺	C₂₉H₃₆O₉	-0.50	210.27	Terpenoid	469.224 2, 451.213 5, 433.205 6	Methyl acetoxyangolensate or isomer	√	√
53	16.34	559.219 3	[M-H]^-	C₂₉H₃₆O₁₁	1.41	215.07	Terpenoid	499.195 6, 483.164 2, 457.187 5, 455.208 9, 399.179 4	Schicagenin B or isomer	√	√
54	16.52	527.228 6	[M+H]⁺	C₂₉H₃₄O₉	1.94	211.46	Terpenoid	483.205 1, 467.205 9, 455.240 1, 423.212 4	Lancifodilactone D or isomer	√	√
55	16.86	527.227 2	[M+H]⁺	C₂₉H₃₄O₉	-0.75	207.58	Terpenoid	473.209 3, 449.194 6	Lancifodilactone D or isomer	√	√
56	17.01	531.258 6	[M+H]⁺	C₂₉H₃₈O₉	-0.43	206.13	Terpenoid	513.242 4, 471.235 6, 435.219 0, 399.179 3	Pre-schisanartanin F or isomer	√	√
57	17.14	529.242 4	[M+H]⁺	C₂₉H₃₆O₉	-1.48	208.22	Terpenoid	453.218 2, 355.152 4, 299.090 2, 285.109 8	Pre-schisanartanin E or isomer	√
58^*	17.52	433.218 4	[M+H]⁺	C₂₄H₃₂O₇	-8.51	187.91	Lignan	415.211 0, 400.187 4, 374.165 8, 358.139 0, 361.161 2, 348.149 5	Schisandrol A	√	√
59	17.88	417.190 1	[M+H]⁺	C₂₃H₂₈O₇	-1.75	184.74	Lignan	373.165 0, 341.136 4, 329.100 7, 311.127 2	Gomisin O or isomer	√	√
60	18.10	615.280 7	[M+H]⁺	C₃₃H₄₂O₁₁	1.21	228.54	Terpenoid	597.274 6, 479.206 1, 437.197 5	Wuweizidilactone I or isomer	√
61	18.38	417.189 1	[M+H]⁺	C₂₃H₂₈O₇	-3.93	189.28	Lignan	370.180 1, 341.138 2, 331.106 9, 317.106 7	Gomisin O or isomer	√	√
62	18.45	657.290 4	[M+H]⁺	C₃₅H₄₄O₁₂	-0.25	236.73	Terpenoid	639.281 1, 479.205 5	Wuweizidilactone G or isomer	√	√
63	18.49	483.310 5	[M+H]⁺	C₃₀H₄₂O₅	0.00	210.35	Terpenoid	419.183 2, 377.119 9, 275.140 1, 151.053 0	Kadsuphilactone B or isomer
64^*	18.61	531.221 2	[M+H]⁺	C₂₈H₃₄O₁₀	-4.67	206.17	Lignan	401.159 1, 371.149 5, 357.132 9, 329.099 1	Gomisin D	√	√
65	18.69	481.293 8	[M+H]⁺	C₃₀H₄₀O₅	-2.18	206.91	Terpenoid	448.219 5, 417.284 9, 343.109 4	Schisanlactone C or isomer	√
66	18.90	341.137 2	[M+H]⁺	C₂₀H₂₀O₅	-3.27	172.62	Lignan	287.089 4, 219.100 2, 205.083 5, 122.036 1	D-Epigalbacin or isomer	√
67^*	18.93	389.194 8	[M+H]⁺	C₂₂H₂₈O₆	-2.83	180.02	Lignan	357.167 9, 325.141 9, 287.089 3, 227.068 9, 221.116 9	Gomisin J	√	√
68	19.16	587.250 3	[M-H]^-	C₂₉H₃₆O₉	0.90	229.45	Terpenoid	447.217 7, 403.225 6, 227.034 0	Pre-schisanartanin A or isomer	√	√
69	19.19	571.253 6	[M+H]⁺	C₃₁H₃₈O₁₀	-0.37	219.70	Terpenoid	511.233 5, 493.220 9, 469.222 3, 451.210 4	Wuweizidilactone M or isomer	√	√
70^*	19.42	399.179 5	[M-H₂O +H]⁺	C₂₃H₂₈O₇	-6.26	180.14	Lignan	369.167 8, 345.131 2, 329.100 7, 299.090 0, 285.074 0	Schisandrol B	√	√
71	19.57	589.264 9	[M-H]^-	C₃₁H₄₂O₁₁	-0.93	228.57	Terpenoid	467.241 6, 221.093 2	Pre-schisanartanin B or isomer	√	√
72	19.64	433.220 1	[M+H]⁺	C₂₄H₃₂O₇	-0.36	194.35	Lignan	415.211 1, 386.168 8, 339.121 8, 323.160 5	Schisandrin or isomer	√	√
73	19.83	401.158 3	[M+H]⁺	C₂₂H₂₄O₇	-2.95	182.28	Lignan	357.127 2, 341.101 3, 311.091 6, 299.089 2, 267.064 6	Methyl 2, 5-bis(3, 4-dimethoxyphenyl)-4, 5-dihydro-3-furancarboxylate or isomer	√	√
74	20.05	417.190 1	[M+H]⁺	C₂₃H₂₈O₇	-1.70	185.05	Lignan	401.196 4, 369.168 8, 339.121 8, 203.084 2	Gomisin O or isomer	√	√
75	20.23	387.180 5	[M-H]^-	C₂₂H₂₈O₆	-2.18	185.52	Lignan	341.139 1, 311.094 7, 275.066 7	Rubrisandrins A or isomer	√	√
76	20.59	531.222 6	[M-H]^-	C₂₈H₃₆O₁₀	-1.82	213.74	Terpenoid	401.159 1, 355.122 0, 341.098 3	Wuweizidilactone H or isomer	√	√
77	20.72	415.211 4	[M+H]⁺	C₂₄H₃₀O₆	-0.28	184.07	Terpenoid	385.195 3, 369.169 0, 353.174 9, 301.104 4	Meprednisone acetate or isomer	√	√
78	20.91	389.194 6	[M+H]⁺	C₂₂H₂₈O₆	-3.18	184.21	Lignan	374.164 0, 357.169 1, 341.135 9	Rubrisandrins A or isomer	√	√
79	21.17	515.227 2	[M+H]⁺	C₂₈H₃₄O₉	0.70	203.29	Terpenoid	469.223 6, 385.163 1, 355.153 2, 323.126 8	Wuweizidilactone O or isomer	√	√
80	21.34	389.194 0	[M+H]⁺	C₂₂H₂₈O₆	-4.72	183.08	Lignan	331.118 2, 235.074 2, 181.063 1	Rubrisandrins A or isomer	√	√
81	21.97	401.195 5	[M+H]⁺	C₂₃H₂₈O₆	-0.91	181.19	Lignan	370.177 4, 355.154 6, 323.127 2, 295.131 7, 165.066 0	Rubschisandrin or isomer	√	√
82^*	22.93	523.230 5	[M+Na]⁺	C₂₈H₃₆O₈	0.52	210.56	Lignan	431.205 9, 415.094 9, 356.160 5, 315.121 9, 267.099 7	Angeloylgomisin H	√
83^*	22.94	401.196 5	[M+H]⁺	C₂₃H₂₈O₆	-0.91	183.00	Lignan	386.170 0, 371.179 4, 356.160 5, 345.132 4, 221.093 4	Gomisin N	√	√
84	23.02	387.179 7	[M+H]⁺	C₂₂H₂₆O₆	-1.42	179.86	Lignan	372.157 5, 356.160 5, 327.121 1, 165.068 9	(-)-Gomisin L or isomer	√	√
85	23.49	415.174 1	[M+H]⁺	C₂₃H₂₆O₇	-2.49	180.88	Lignan	401.191 8, 355.145 0, 315.085 2, 181.063 8	Neoisostegane or isomer	√	√
86	24	433.212 4	[M+H]⁺	C₂₄H₃₂O₇	-1.23	189.16	Lignan	401.192 1, 387.180 9, 356.160 3, 341.137 6, 315.121 2	Schisandrin or isomer	√	√
87	24.03	341.136 8	[M+H]⁺	C₂₀H₂₀O₅	-4.60	168.22	Lignan	313.105 8, 285.110 3, 251.069 3, 165.068 2	Maceneolignan E or isomer	√	√
88	24.57	387.179 8	[M+H]⁺	C₂₄H₃₀O₇	-1.70	186.62	Lignan	372.155 6, 356.160 8, 341.136 9, 300.097 4, 165.068 7	(-)-Gomisin L or isomer	√	√
89^*	25.35	537.209 4	[M+H]⁺	C₃₀H₃₂O₉	-7.40	207.69	Lignan	416.176 6, 414.166 9, 371.149 2, 343.115 0, 285.073 8	Gomisin G	√
90	25.39	519.201 1	[M+H]⁺	C₃₀H₃₀O₈	-0.50	209.44	Lignan	415.173 9, 343.115 0, 219.079 6, 181.064 1	Schisanchinin A or isomer	√
91	25.70	483.309 8	[M+H]⁺	C₃₀H₄₂O₅	-1.49	207.08	Terpenoid	343.108 1, 253.129 1, 167.048 3	Henrischinin C or isomer	√
92	25.82	537.210 1	[M+H]⁺	C₃₀H₃₂O₉	-3.38	205.95	Lignan	416.176 4, 414.166 9, 371.148 5, 343.115 5, 312.098 5	Isomer of schisantherin A	√
93	26.42	403.210 7	[M+H]⁺	C₂₃H₃₀O₆	-2.03	185.97	Lignan	371.176 8, 341.137 3, 301.105 8, 287.090 5	Gomisin K2 or isomer	√	√
94	27.13	537.209 9	[M+H]⁺	C₃₀H₃₂O₉	-3.70	206.34	Lignan	416.177 0, 371.147 9, 343.115 1, 312.097 4	Isomer of schisantherin A	√	√
95	28.05	519.202 4	[M+H]⁺	C₃₀H₃₀O₈	1.94	207.95	Lignan	414.166 8, 398.170 6, 343.115 3, 285.073 8	Schisanchinin A or isomer	√
96^*	28.50	537.209 4	[M+H]⁺	C₃₀H₃₂O₉	-4.58	205.57	Lignan	416.179 5, 414.164 5, 371.148 3, 343.115 6, 312.098 2	Schisantherin A	√
97^*	28.51	553.184 3	[M+K]⁺	C₂₈H₃₄O₉	1.67	206.04	Lignan	416.179 4, 414.164 5, 371.148 3, 343.115 6	Schisantherin B	√
98^*	29.06	403.210 5	[M+H]⁺	C₂₃H₃₀O₆	-2.52	191.01	Lignan	357.167 8, 325.141 9, 301.106 7	Schisanhenol	√	√
99	31.15	415.210 4	[M+H]⁺	C₂₄H₃₀O₆	-2.69	188.75	Terpenoid	385.196 1, 369.168 5, 353.173 5, 323.126 9	Meprednisone acetate or isomer	√	√
100	32.12	415.210 5	[M+H]⁺	C₂₄H₃₀O₆	-2.45	187.92	Terpenoid	385.197 0, 369.168 6, 353.174 5, 323.126 6	Meprednisone acetate or isomer	√	√
101	35.48	399.178 4	[M+H]⁺	C₂₃H₂₆O₆	-4.56	184.94	Lignan	371.176 7, 301.105 7, 165.068 1	Allyl 2-O-benzoyl-3-O-benzyl-6-deoxy-α-L-mannopyranoside or isomer	√	√
102	37.35	417.226 3	[M+H]⁺	C₂₄H₃₂O₆	-2.08	190.55	Lignan	402.202 2, 387.179 2, 347.148 0, 301.105 9, 241.084 6	Schisandrin A or isomer	√	√
103	39.86	483.236 9	[M+H]⁺	C₂₈H₃₄O₇	-1.72	198.54	Terpenoid	453.216 1, 401.190 5, 323.124 4	Gedunin or isomer	√	√
104	40.26	401.194 5	[M+H]⁺	C₂₃H₂₈O₆	-3.41	186.38	Lignan	386.171 9, 331.114 8, 301.105 5, 285.075 3, 227.068 2	Schisandrin B or isomer	√	√
105	40.73	401.195 1	[M+H]⁺	C₂₃H₂₈O₆	-1.91	184.74	Lignan	386.171 0, 331.117 0, 301.103 7	Schisandrin B or isomer	√	√

No.

t_R /min

Observed m/z

Adduct

Formula

Mass error /×10^-6

Observed
CCS/Å²

Type

Fragment ion

Identification

HDMS^E

HDDDA

2.08

527.089 0

[M-H]^-

C₁₈H₂₄O₁₈

0.02

194.08

Glycoside

473.078 2, 421.103 7, 253.097 3, 165.079 1

4-Deoxy-β-L-threo-hex-4-enopyranuronosyl-(1- > 4)-α-D-galactopyranuronosyl-(1- > 4)-D-galactopyranuronic acid or isomer

√

2^*

3.41

153.018 2

[M-H]^-

C₇H₄O₄

-0.23

158.79

Organic acid

109.028 8

Protocatechuic acid

√

5.77

327.143 6

[M-H]^-

C₁₆H₂₄O₇

-4.12

188.05

Glycoside

272.088 9, 134.036 9

Thymoquinol 5-O-β-D-glucopyranoside or isomer

√

6.33

327.144 4

[M-H]^-

C₁₆H₂₄O₇

-1.49

185.24

Glycoside

161.024 1, 149.060 6

Thymoquinol 5-O-β-D-glucopyranoside or isomer

√

6.81

713.302 8

[M+H]⁺

C₃₄H₄₈O₁₆

1.85

173.65

Lignan

375.170 0, 165.066 0

1, 2, 13, 14-Tetramethoxydibenzo-cyclooctadiene 3, 12-O-β-D-diglucopyranoside or isomer

√

6^*

7.52

609.146 3

[M-H]^-

C₂₇H₃₀O₁₆

0.31

223.02

Flavonoid

301.033 9, 271.024 3, 255.028 7, 243.031 6, 227.031 9

Rutin

√

7.65

565.228 4

[M-H]^-

C₂₈H₃₈O₁₂

-1.20

237.91

Lignan

373.138 8

3, 7-Dihydroxy-1, 2, 13, 14-tetramethoxydibenzo-cyclooctadiene 12-O-β-D-glucopyranoside or isomer

√

7.85

463.087 9

[M-H]^-

C₂₁H₂₀O₁₂

-0.65

192.51

Glycoside

301.034 1, 271.022 8, 255.029 0, 243.027 4, 151.002 8

Hyperoside or isomer

√

8.48

473.202 4

[M-H]^-

C₂₂H₃₄O₁₁

-0.92

216.55

Glycoside

313.107 8, 271.024 5, 223.153 1

Schisandenoid A or isomer

√

8.93

565.229 6

[M-H]^-

C₂₈H₃₈O₁₂

0.94

229.49

Lignan

341.102 5, 326.078 0

3, 7-Dihydroxy-1, 2, 13, 14-tetramethoxydibenzo-cyclooctadiene 12-O-β-D-glucopyranoside or isomer

√

9.99

575.212 8

[M-H]^-

C₂₉H₃₆O₁₂

-1.09

209.75

Terpenoid

557.194 8, 497.185 7, 482.194 0, 453.192 7

Arisanlactone B or isomer

√

10.41

577.228 9

[M+H]⁺

C₂₉H₃₆O₁₂

1.60

213.53

Terpenoid

543.225 9, 485.213 1

Micradilactone A or isomer

√

10.42

561.232 9

[M+H]⁺

C₂₉H₃₆O₁₁

-0.18

211.64

Terpenoid

543.225 9, 507.203 3, 485.213 0

Schicagenin B or isomer

√

10.70

497.219 5

[M-H]^-

C₂₈H₃₄O₈

2.77

214.37

Lignan

387.136 9

Angeloylisogomisin O or isomer

√

10.89

559.218 7

[M-H]^-

C₂₉H₃₆O₁₁

0.30

209.42

Terpenoid

541.214 4, 465.152 1, 403.149 7, 383.145 1

Schindilactone C or isomer

√

11.14

561.233 2

[M+H]⁺

C₂₉H₃₆O₁₁

0.28

212.18

Terpenoid

543.219 3, 439.205 0, 425.176 4, 407.209 8

Schicagenin B or isomer

√

11.47

543.223 2

[M-H]^-

C₂₉H₃₆O₁₀

-0.70

222.66

Terpenoid

527.226 1, 473.247 7

Pre-schisanartanin N or isomer

√

11.51

527.226 2

[M+H]⁺

C₂₉H₃₄O₉

-2.49

206.62

Terpenoid

467.206 4, 419.185 0, 203.104 9, 185.094 6

Lancifodilactone D or isomer

√

11.63

549.232 7

[M+H]⁺

C₂₈H₃₆O₁₁

-0.62

216.71

Terpenoid

479.207 5, 387.179 5, 355.153 2

19(R)-Hydroxyl-wuweizidilactone H or isomer

√

11.75

559.218 5

[M-H]^-

C₂₉H₃₆O₁₁

-0.05

210.31

Terpenoid

469.222 6, 465.148 6, 413.197 5, 387.146 2, 347.157 5

Schicagenin B or isomer

√

11.82

543.223 5

[M-H]^-

C₂₉H₃₆O₁₀

-0.13

217.58

Terpenoid

463.211 7, 383.187 7, 365.196 6, 137.059 7

Pre-schisanartanin N or isomer

√

11.91

577.230 3

[M+H]⁺

C₂₉H₃₆O₁₂

4.10

215.81

Terpenoid

545.229 2, 525.181 0, 515.211 9, 495.204 6, 453.203 2

Arisanlactone B or isomer

√

12.09

559.218 3

[M-H]^-

C₂₉H₃₆O₁₁

-0.25

218.39

Terpenoid

497.217 5, 429.192 4

Schindilactone C

√

12.27

543.224 1

[M-H]^-

C₂₉H₃₆O₁₀

0.93

214.59

Terpenoid

483.135 8, 471.200 5, 463.208 3, 435.216 3

Pre-schisanartanin N or isomer

√

12.41

575.213 9

[M-H]^-

C₂₉H₃₆O₁₂

0.83

213.64

Terpenoid

515.191 9, 419.125 9, 413.161 4

Arisanlactone B or isomer

√

12.53

545.238 7

[M+H]⁺

C₂₉H₃₆O₁₀

1.05

211.05

Terpenoid

508.213 3, 451.215 6, 433.197 7, 391.175 5

Pre-schisanartanin N or isomer

√

12.84

527.227 5

[M+H]⁺

C₂₈H₃₆O₉

-1.50

209.72

Terpenoid

485.217 2, 453.222 8, 439.211 4, 423.221 8

Lancifodilactone D or isomer

√

13.17

561.233 2

[M+H]⁺

C₂₉H₃₆O₁₁

0.25

208.50

Terpenoid

527.222 3, 485.220 1, 467.207 1

Schindilactone C or isomer

√

13.42

515.228 6

[M-H]^-

C₂₈H₃₆O₉

-0.20

218.36

Terpenoid

437.203 4, 385.174 6

Wuweizidilactone N or isomer

√

13.70

417.192 1

[M+H]⁺

C₂₃H₂₈O₇

3.05

188.89

Lignan

385.169 1, 331.118 9, 315.080 0

Gomisin O or isomer

√

13.71

661.250 5

[M-H]^-

C₃₃H₄₂O₁₄

0.56

238.36

Terpenoid

369.137 8, 285.170 1

Schisandroside D or isomer

√

13.76

533.238 7

[M+H]⁺

C₂₈H₃₆O₁₀

1.03

213.75

Terpenoid

499.235 7, 479.204 3, 437.195 0

Wuweizidilactone H or isomer

√

13.88

369.168 8

[M+H]⁺

C₂₂H₂₄O₅

-2.31

181.98

Terpenoid

337.144 1, 323.130 5, 203.083 3

(8ξ, 14ξ)-17-Oxoestra-1, 3, 5(10), 9(11)-tetraene-3, 4-diyl diacetate or isomer

√

13.96

221.190 3

[M+H]⁺

C₁₅H₂₄O

1.26

150.76

Sesquiterpene

219.172 4, 189.125 6

α-Iso-cubebenol or isomer

√

14.13

545.239 2

[M+H]⁺

C₂₉H₃₆O₁₀

1.99

213.63

Terpenoid

485.217 6, 451.207 5, 433.203 2, 371.175 5

Pre-schisanartanin N or isomer

√

14.31

515.227 7

[M+H]⁺

C₂₈H₃₄O₉

0.19

210.80

Terpenoid

429.192 1, 401.196 0, 381.132 5

Wuweizidilactone O or isomer

√

14.41

545.238 1

[M+H]⁺

C₂₉H₃₆O₁₀

-0.08

207.63

Terpenoid

527.2327, 453.224 7, 437.230 9, 431.207 8

Pre-schisanartanin N or isomer

√

38^*

14.60

419.205 0

[M+H]⁺

C₂₃H₃₀O₇

-3.40

189.94

Lignan

401.196 1, 386.172 6, 333.127 9, 315.120 5

Gomisin H

√

14.76

529.243 3

[M+H]⁺

C₂₉H₃₆O₉

0.23

206.80

Terpenoid

509.215 7, 469.219 6, 449.196 5, 439.212 5, 421.201 3

Methyl acetoxyangolensate or isomer

√

14.84

517.244 1

[M+H]⁺

C₂₈H₃₆O₉

1.60

203.29

Terpenoid

499.233 5, 413.193 0, 343.117 4

Wuweizidilactone N or isomer

√

14.90

575.285 2

[M+H]⁺

C₃₁H₄₂O₁₀

0.21

221.29

Terpenoid

479.242 9, 437.232 3

Wuweizidilactone K or isomer

√

15.01

527.227 5

[M+H]⁺

C₂₉H₃₄O₉

-0.05

214.45

Terpenoid

509.222 2, 463.202 3, 449.193 9

Lancifodilactone D or isomer

√

15.06

417.191 1

[M+H]⁺

C₂₃H₂₈O₇

0.71

185.16

Lignan

386.173 4, 371.176 5

Gomisin O or isomer

√

15.09

557.202 5

[M-H]^-

C₃₁H₃₈O₁₀

-0.70

213.07

Terpenoid

513.214 2, 485.217 0, 481.150 8, 391.119 9, 365.139 1

Lancifodilactone N or isomer

√

15.28

387.179 9

[M+H]⁺

C₂₂H₂₆O₆

-0.86

188.43

Lignan

372.153 8, 356.161 8, 341.127 5, 300.096 5

(-)-Gomisin L or isomer

√

15.36

559.218 4

[M-H]^-

C₂₉H₃₆O₁₁

-0.08

209.30

Terpenoid

483.161 8, 457.191 1, 431.180 3, 413.195 2

Schindilactone C or isomer

√

15.61

545.237 9

[M+H]⁺

C₂₉H₃₆O₁₀

-0.43

216.79

Terpenoid

497.214 4, 463.212 4, 435.219 0, 391.181 7

Pre-schisanartanin N or isomer

√

15.77

527.228 2

[M-H]^-

C₂₉H₃₆O₉

-0.78

214.93

Terpenoid

497.218 2, 435.215 9, 407.183 7, 365.178 5

Wuweizidilactone L or isomer

√

15.98

515.229 6

[M-H]^-

C₂₈H₃₆O₉

1.75

211.39

Terpenoid

471.243 2, 411.182 1, 369.169 0

Wuweizidilactone N or isomer

√

16.03

415.211 7

[M+H]⁺

C₂₄H₃₀O₆

0.45

186.75

Terpenoid

385.194 5, 369.167 6, 353.170 6, 323.129 2, 165.064 3

Meprednisone acetate or isomer

√

16.09

527.229 0

[M+H]⁺

C₂₉H₃₄O₉

2.80

208.04

Terpenoid

483.236 5, 438.235 3, 423.211 6

Lancifodilactone D or isomer

√

16.26

529.242 9

[M+H]⁺

C₂₉H₃₆O₉

-0.50

210.27

Terpenoid

469.224 2, 451.213 5, 433.205 6

Methyl acetoxyangolensate or isomer

√

16.34

559.219 3

[M-H]^-

C₂₉H₃₆O₁₁

1.41

215.07

Terpenoid

499.195 6, 483.164 2, 457.187 5, 455.208 9, 399.179 4

Schicagenin B or isomer

√

16.52

527.228 6

[M+H]⁺

C₂₉H₃₄O₉

1.94

211.46

Terpenoid

483.205 1, 467.205 9, 455.240 1, 423.212 4

Lancifodilactone D or isomer

√

16.86

527.227 2

[M+H]⁺

C₂₉H₃₄O₉

-0.75

207.58

Terpenoid

473.209 3, 449.194 6

Lancifodilactone D or isomer

√

17.01

531.258 6

[M+H]⁺

C₂₉H₃₈O₉

-0.43

206.13

Terpenoid

513.242 4, 471.235 6, 435.219 0, 399.179 3

Pre-schisanartanin F or isomer

√

17.14

529.242 4

[M+H]⁺

C₂₉H₃₆O₉

-1.48

208.22

Terpenoid

453.218 2, 355.152 4, 299.090 2, 285.109 8

Pre-schisanartanin E or isomer

√

58^*

17.52

433.218 4

[M+H]⁺

C₂₄H₃₂O₇

-8.51

187.91

Lignan

415.211 0, 400.187 4, 374.165 8, 358.139 0, 361.161 2, 348.149 5

Schisandrol A

√

17.88

417.190 1

[M+H]⁺

C₂₃H₂₈O₇

-1.75

184.74

Lignan

373.165 0, 341.136 4, 329.100 7, 311.127 2

Gomisin O or isomer

√

18.10

615.280 7

[M+H]⁺

C₃₃H₄₂O₁₁

1.21

228.54

Terpenoid

597.274 6, 479.206 1, 437.197 5

Wuweizidilactone I or isomer

√

18.38

417.189 1

[M+H]⁺

C₂₃H₂₈O₇

-3.93

189.28

Lignan

370.180 1, 341.138 2, 331.106 9, 317.106 7

Gomisin O or isomer

√

18.45

657.290 4

[M+H]⁺

C₃₅H₄₄O₁₂

-0.25

236.73

Terpenoid

639.281 1, 479.205 5

Wuweizidilactone G or isomer

√

18.49

483.310 5

[M+H]⁺

C₃₀H₄₂O₅

0.00

210.35

Terpenoid

419.183 2, 377.119 9, 275.140 1, 151.053 0

Kadsuphilactone B or isomer

64^*

18.61

531.221 2

[M+H]⁺

C₂₈H₃₄O₁₀

-4.67

206.17

Lignan

401.159 1, 371.149 5, 357.132 9, 329.099 1

Gomisin D

√

18.69

481.293 8

[M+H]⁺

C₃₀H₄₀O₅

-2.18

206.91

Terpenoid

448.219 5, 417.284 9, 343.109 4

Schisanlactone C or isomer

√

18.90

341.137 2

[M+H]⁺

C₂₀H₂₀O₅

-3.27

172.62

Lignan

287.089 4, 219.100 2, 205.083 5, 122.036 1

D-Epigalbacin or isomer

√

67^*

18.93

389.194 8

[M+H]⁺

C₂₂H₂₈O₆

-2.83

180.02

Lignan

357.167 9, 325.141 9, 287.089 3, 227.068 9, 221.116 9

Gomisin J

√

19.16

587.250 3

[M-H]^-

C₂₉H₃₆O₉

0.90

229.45

Terpenoid

447.217 7, 403.225 6, 227.034 0

Pre-schisanartanin A or isomer

√

19.19

571.253 6

[M+H]⁺

C₃₁H₃₈O₁₀

-0.37

219.70

Terpenoid

511.233 5, 493.220 9, 469.222 3, 451.210 4

Wuweizidilactone M or isomer

√

70^*

19.42

399.179 5

[M-H₂O
+H]⁺

C₂₃H₂₈O₇

-6.26

180.14

Lignan

369.167 8, 345.131 2, 329.100 7, 299.090 0, 285.074 0

Schisandrol B

√

19.57

589.264 9

[M-H]^-

C₃₁H₄₂O₁₁

-0.93

228.57

Terpenoid

467.241 6, 221.093 2

Pre-schisanartanin B or isomer

√

19.64

433.220 1

[M+H]⁺

C₂₄H₃₂O₇

-0.36

194.35

Lignan

415.211 1, 386.168 8, 339.121 8, 323.160 5

Schisandrin or isomer

√

19.83

401.158 3

[M+H]⁺

C₂₂H₂₄O₇

-2.95

182.28

Lignan

357.127 2, 341.101 3, 311.091 6, 299.089 2, 267.064 6

Methyl 2, 5-bis(3, 4-dimethoxyphenyl)-4, 5-dihydro-3-furancarboxylate or isomer

√

20.05

417.190 1

[M+H]⁺

C₂₃H₂₈O₇

-1.70

185.05

Lignan

401.196 4, 369.168 8, 339.121 8, 203.084 2

Gomisin O or isomer

√

20.23

387.180 5

[M-H]^-

C₂₂H₂₈O₆

-2.18

185.52

Lignan

341.139 1, 311.094 7, 275.066 7

Rubrisandrins A or isomer

√

20.59

531.222 6

[M-H]^-

C₂₈H₃₆O₁₀

-1.82

213.74

Terpenoid

401.159 1, 355.122 0, 341.098 3

Wuweizidilactone H or isomer

√

20.72

415.211 4

[M+H]⁺

C₂₄H₃₀O₆

-0.28

184.07

Terpenoid

385.195 3, 369.169 0, 353.174 9, 301.104 4

Meprednisone acetate or isomer

√

20.91

389.194 6

[M+H]⁺

C₂₂H₂₈O₆

-3.18

184.21

Lignan

374.164 0, 357.169 1, 341.135 9

Rubrisandrins A or isomer

√

21.17

515.227 2

[M+H]⁺

C₂₈H₃₄O₉

0.70

203.29

Terpenoid

469.223 6, 385.163 1, 355.153 2, 323.126 8

Wuweizidilactone O or isomer

√

21.34

389.194 0

[M+H]⁺

C₂₂H₂₈O₆

-4.72

183.08

Lignan

331.118 2, 235.074 2, 181.063 1

Rubrisandrins A or isomer

√

21.97

401.195 5

[M+H]⁺

C₂₃H₂₈O₆

-0.91

181.19

Lignan

370.177 4, 355.154 6, 323.127 2, 295.131 7, 165.066 0

Rubschisandrin or isomer

√

82^*

22.93

523.230 5

[M+Na]⁺

C₂₈H₃₆O₈

0.52

210.56

Lignan

431.205 9, 415.094 9, 356.160 5, 315.121 9, 267.099 7

Angeloylgomisin H

√

83^*

22.94

401.196 5

[M+H]⁺

C₂₃H₂₈O₆

-0.91

183.00

Lignan

386.170 0, 371.179 4, 356.160 5, 345.132 4, 221.093 4

Gomisin N

√

23.02

387.179 7

[M+H]⁺

C₂₂H₂₆O₆

-1.42

179.86

Lignan

372.157 5, 356.160 5, 327.121 1, 165.068 9

(-)-Gomisin L or isomer

√

23.49

415.174 1

[M+H]⁺

C₂₃H₂₆O₇

-2.49

180.88

Lignan

401.191 8, 355.145 0, 315.085 2, 181.063 8

Neoisostegane or isomer

√

433.212 4

[M+H]⁺

C₂₄H₃₂O₇

-1.23

189.16

Lignan

401.192 1, 387.180 9, 356.160 3, 341.137 6, 315.121 2

Schisandrin or isomer

√

24.03

341.136 8

[M+H]⁺

C₂₀H₂₀O₅

-4.60

168.22

Lignan

313.105 8, 285.110 3, 251.069 3, 165.068 2

Maceneolignan E or isomer

√

24.57

387.179 8

[M+H]⁺

C₂₄H₃₀O₇

-1.70

186.62

Lignan

372.155 6, 356.160 8, 341.136 9, 300.097 4, 165.068 7

(-)-Gomisin L or isomer

√

89^*

25.35

537.209 4

[M+H]⁺

C₃₀H₃₂O₉

-7.40

207.69

Lignan

416.176 6, 414.166 9, 371.149 2, 343.115 0, 285.073 8

Gomisin G

√

25.39

519.201 1

[M+H]⁺

C₃₀H₃₀O₈

-0.50

209.44

Lignan

415.173 9, 343.115 0, 219.079 6, 181.064 1

Schisanchinin A or isomer

√

25.70

483.309 8

[M+H]⁺

C₃₀H₄₂O₅

-1.49

207.08

Terpenoid

343.108 1, 253.129 1, 167.048 3

Henrischinin C or isomer

√

25.82

537.210 1

[M+H]⁺

C₃₀H₃₂O₉

-3.38

205.95

Lignan

416.176 4, 414.166 9, 371.148 5, 343.115 5, 312.098 5

Isomer of schisantherin A

√

26.42

403.210 7

[M+H]⁺

C₂₃H₃₀O₆

-2.03

185.97

Lignan

371.176 8, 341.137 3, 301.105 8, 287.090 5

Gomisin K2 or isomer

√

27.13

537.209 9

[M+H]⁺

C₃₀H₃₂O₉

-3.70

206.34

Lignan

416.177 0, 371.147 9, 343.115 1, 312.097 4

Isomer of schisantherin A

√

28.05

519.202 4

[M+H]⁺

C₃₀H₃₀O₈

1.94

207.95

Lignan

414.166 8, 398.170 6, 343.115 3, 285.073 8

Schisanchinin A or isomer

√

96^*

28.50

537.209 4

[M+H]⁺

C₃₀H₃₂O₉

-4.58

205.57

Lignan

416.179 5, 414.164 5, 371.148 3, 343.115 6, 312.098 2

Schisantherin A

√

97^*

28.51

553.184 3

[M+K]⁺

C₂₈H₃₄O₉

1.67

206.04

Lignan

416.179 4, 414.164 5, 371.148 3, 343.115 6

Schisantherin B

√

98^*

29.06

403.210 5

[M+H]⁺

C₂₃H₃₀O₆

-2.52

191.01

Lignan

357.167 8, 325.141 9, 301.106 7

Schisanhenol

√

31.15

415.210 4

[M+H]⁺

C₂₄H₃₀O₆

-2.69

188.75

Terpenoid

385.196 1, 369.168 5, 353.173 5, 323.126 9

Meprednisone acetate or isomer

√

100

32.12

415.210 5

[M+H]⁺

C₂₄H₃₀O₆

-2.45

187.92

Terpenoid

385.197 0, 369.168 6, 353.174 5, 323.126 6

Meprednisone acetate or isomer

√

101

35.48

399.178 4

[M+H]⁺

C₂₃H₂₆O₆

-4.56

184.94

Lignan

371.176 7, 301.105 7, 165.068 1

Allyl 2-O-benzoyl-3-O-benzyl-6-deoxy-α-L-mannopyranoside or isomer

√

102

37.35

417.226 3

[M+H]⁺

C₂₄H₃₂O₆

-2.08

190.55

Lignan

402.202 2, 387.179 2, 347.148 0, 301.105 9, 241.084 6

Schisandrin A or isomer

√

103

39.86

483.236 9

[M+H]⁺

C₂₈H₃₄O₇

-1.72

198.54

Terpenoid

453.216 1, 401.190 5, 323.124 4

Gedunin or isomer

√

104

40.26

401.194 5

[M+H]⁺

C₂₃H₂₈O₆

-3.41

186.38

Lignan

386.171 9, 331.114 8, 301.105 5, 285.075 3, 227.068 2

Schisandrin B or isomer

√

105

40.73

401.195 1

[M+H]⁺

C₂₃H₂₈O₆

-1.91

184.74

Lignan

386.171 0, 331.117 0, 301.103 7

Schisandrin B or isomer

√

No.	t_R /min	Observed m/z	Adduct	Formula	Mass error /×10^-6	Observed CCS/Å²	Type	Fragment ion	Identification	HDMS^E	HDDDA
1	2.08	527.089 0	[M-H]^-	C₁₈H₂₄O₁₈	0.02	194.08	Glycoside	473.078 2, 421.103 7, 253.097 3, 165.079 1	4-Deoxy-β-L-threo-hex-4-enopyranuronosyl-(1- > 4)-α-D-galactopyranuronosyl-(1- > 4)-D-galactopyranuronic acid or isomer	√	√
2^*	3.41	153.018 2	[M-H]^-	C₇H₄O₄	-0.23	158.79	Organic acid	109.028 8	Protocatechuic acid	√
3	5.77	327.143 6	[M-H]^-	C₁₆H₂₄O₇	-4.12	188.05	Glycoside	272.088 9, 134.036 9	Thymoquinol 5-O-β-D-glucopyranoside or isomer	√
4	6.33	327.144 4	[M-H]^-	C₁₆H₂₄O₇	-1.49	185.24	Glycoside	161.024 1, 149.060 6	Thymoquinol 5-O-β-D-glucopyranoside or isomer	√
5	6.81	713.302 8	[M+H]⁺	C₃₄H₄₈O₁₆	1.85	173.65	Lignan	375.170 0, 165.066 0	1, 2, 13, 14-Tetramethoxydibenzo-cyclooctadiene 3, 12-O-β-D-diglucopyranoside or isomer	√
6^*	7.52	609.146 3	[M-H]^-	C₂₇H₃₀O₁₆	0.31	223.02	Flavonoid	301.033 9, 271.024 3, 255.028 7, 243.031 6, 227.031 9	Rutin	√	√
7	7.65	565.228 4	[M-H]^-	C₂₈H₃₈O₁₂	-1.20	237.91	Lignan	373.138 8	3, 7-Dihydroxy-1, 2, 13, 14-tetramethoxydibenzo-cyclooctadiene 12-O-β-D-glucopyranoside or isomer	√
8	7.85	463.087 9	[M-H]^-	C₂₁H₂₀O₁₂	-0.65	192.51	Glycoside	301.034 1, 271.022 8, 255.029 0, 243.027 4, 151.002 8	Hyperoside or isomer	√	√
9	8.48	473.202 4	[M-H]^-	C₂₂H₃₄O₁₁	-0.92	216.55	Glycoside	313.107 8, 271.024 5, 223.153 1	Schisandenoid A or isomer	√
10	8.93	565.229 6	[M-H]^-	C₂₈H₃₈O₁₂	0.94	229.49	Lignan	341.102 5, 326.078 0	3, 7-Dihydroxy-1, 2, 13, 14-tetramethoxydibenzo-cyclooctadiene 12-O-β-D-glucopyranoside or isomer	√	√
11	9.99	575.212 8	[M-H]^-	C₂₉H₃₆O₁₂	-1.09	209.75	Terpenoid	557.194 8, 497.185 7, 482.194 0, 453.192 7	Arisanlactone B or isomer	√	√
12	10.41	577.228 9	[M+H]⁺	C₂₉H₃₆O₁₂	1.60	213.53	Terpenoid	543.225 9, 485.213 1	Micradilactone A or isomer	√	√
13	10.42	561.232 9	[M+H]⁺	C₂₉H₃₆O₁₁	-0.18	211.64	Terpenoid	543.225 9, 507.203 3, 485.213 0	Schicagenin B or isomer	√
14	10.70	497.219 5	[M-H]^-	C₂₈H₃₄O₈	2.77	214.37	Lignan	387.136 9	Angeloylisogomisin O or isomer	√
15	10.89	559.218 7	[M-H]^-	C₂₉H₃₆O₁₁	0.30	209.42	Terpenoid	541.214 4, 465.152 1, 403.149 7, 383.145 1	Schindilactone C or isomer	√	√
16	11.14	561.233 2	[M+H]⁺	C₂₉H₃₆O₁₁	0.28	212.18	Terpenoid	543.219 3, 439.205 0, 425.176 4, 407.209 8	Schicagenin B or isomer	√	√
17	11.47	543.223 2	[M-H]^-	C₂₉H₃₆O₁₀	-0.70	222.66	Terpenoid	527.226 1, 473.247 7	Pre-schisanartanin N or isomer	√	√
18	11.51	527.226 2	[M+H]⁺	C₂₉H₃₄O₉	-2.49	206.62	Terpenoid	467.206 4, 419.185 0, 203.104 9, 185.094 6	Lancifodilactone D or isomer	√	√
19	11.63	549.232 7	[M+H]⁺	C₂₈H₃₆O₁₁	-0.62	216.71	Terpenoid	479.207 5, 387.179 5, 355.153 2	19(R)-Hydroxyl-wuweizidilactone H or isomer	√	√
20	11.75	559.218 5	[M-H]^-	C₂₉H₃₆O₁₁	-0.05	210.31	Terpenoid	469.222 6, 465.148 6, 413.197 5, 387.146 2, 347.157 5	Schicagenin B or isomer	√	√
21	11.82	543.223 5	[M-H]^-	C₂₉H₃₆O₁₀	-0.13	217.58	Terpenoid	463.211 7, 383.187 7, 365.196 6, 137.059 7	Pre-schisanartanin N or isomer	√	√
22	11.91	577.230 3	[M+H]⁺	C₂₉H₃₆O₁₂	4.10	215.81	Terpenoid	545.229 2, 525.181 0, 515.211 9, 495.204 6, 453.203 2	Arisanlactone B or isomer	√
23	12.09	559.218 3	[M-H]^-	C₂₉H₃₆O₁₁	-0.25	218.39	Terpenoid	497.217 5, 429.192 4	Schindilactone C	√	√
24	12.27	543.224 1	[M-H]^-	C₂₉H₃₆O₁₀	0.93	214.59	Terpenoid	483.135 8, 471.200 5, 463.208 3, 435.216 3	Pre-schisanartanin N or isomer	√	√
25	12.41	575.213 9	[M-H]^-	C₂₉H₃₆O₁₂	0.83	213.64	Terpenoid	515.191 9, 419.125 9, 413.161 4	Arisanlactone B or isomer	√	√
26	12.53	545.238 7	[M+H]⁺	C₂₉H₃₆O₁₀	1.05	211.05	Terpenoid	508.213 3, 451.215 6, 433.197 7, 391.175 5	Pre-schisanartanin N or isomer	√	√
27	12.84	527.227 5	[M+H]⁺	C₂₈H₃₆O₉	-1.50	209.72	Terpenoid	485.217 2, 453.222 8, 439.211 4, 423.221 8	Lancifodilactone D or isomer	√	√
28	13.17	561.233 2	[M+H]⁺	C₂₉H₃₆O₁₁	0.25	208.50	Terpenoid	527.222 3, 485.220 1, 467.207 1	Schindilactone C or isomer	√	√
29	13.42	515.228 6	[M-H]^-	C₂₈H₃₆O₉	-0.20	218.36	Terpenoid	437.203 4, 385.174 6	Wuweizidilactone N or isomer	√	√
30	13.70	417.192 1	[M+H]⁺	C₂₃H₂₈O₇	3.05	188.89	Lignan	385.169 1, 331.118 9, 315.080 0	Gomisin O or isomer	√	√
31	13.71	661.250 5	[M-H]^-	C₃₃H₄₂O₁₄	0.56	238.36	Terpenoid	369.137 8, 285.170 1	Schisandroside D or isomer	√
32	13.76	533.238 7	[M+H]⁺	C₂₈H₃₆O₁₀	1.03	213.75	Terpenoid	499.235 7, 479.204 3, 437.195 0	Wuweizidilactone H or isomer	√	√
33	13.88	369.168 8	[M+H]⁺	C₂₂H₂₄O₅	-2.31	181.98	Terpenoid	337.144 1, 323.130 5, 203.083 3	(8ξ, 14ξ)-17-Oxoestra-1, 3, 5(10), 9(11)-tetraene-3, 4-diyl diacetate or isomer	√	√
34	13.96	221.190 3	[M+H]⁺	C₁₅H₂₄O	1.26	150.76	Sesquiterpene	219.172 4, 189.125 6	α-Iso-cubebenol or isomer	√	√
35	14.13	545.239 2	[M+H]⁺	C₂₉H₃₆O₁₀	1.99	213.63	Terpenoid	485.217 6, 451.207 5, 433.203 2, 371.175 5	Pre-schisanartanin N or isomer	√	√
36	14.31	515.227 7	[M+H]⁺	C₂₈H₃₄O₉	0.19	210.80	Terpenoid	429.192 1, 401.196 0, 381.132 5	Wuweizidilactone O or isomer	√	√
37	14.41	545.238 1	[M+H]⁺	C₂₉H₃₆O₁₀	-0.08	207.63	Terpenoid	527.2327, 453.224 7, 437.230 9, 431.207 8	Pre-schisanartanin N or isomer	√	√
38^*	14.60	419.205 0	[M+H]⁺	C₂₃H₃₀O₇	-3.40	189.94	Lignan	401.196 1, 386.172 6, 333.127 9, 315.120 5	Gomisin H	√	√
39	14.76	529.243 3	[M+H]⁺	C₂₉H₃₆O₉	0.23	206.80	Terpenoid	509.215 7, 469.219 6, 449.196 5, 439.212 5, 421.201 3	Methyl acetoxyangolensate or isomer	√	√
40	14.84	517.244 1	[M+H]⁺	C₂₈H₃₆O₉	1.60	203.29	Terpenoid	499.233 5, 413.193 0, 343.117 4	Wuweizidilactone N or isomer	√	√
41	14.90	575.285 2	[M+H]⁺	C₃₁H₄₂O₁₀	0.21	221.29	Terpenoid	479.242 9, 437.232 3	Wuweizidilactone K or isomer	√	√
42	15.01	527.227 5	[M+H]⁺	C₂₉H₃₄O₉	-0.05	214.45	Terpenoid	509.222 2, 463.202 3, 449.193 9	Lancifodilactone D or isomer	√	√
43	15.06	417.191 1	[M+H]⁺	C₂₃H₂₈O₇	0.71	185.16	Lignan	386.173 4, 371.176 5	Gomisin O or isomer	√
44	15.09	557.202 5	[M-H]^-	C₃₁H₃₈O₁₀	-0.70	213.07	Terpenoid	513.214 2, 485.217 0, 481.150 8, 391.119 9, 365.139 1	Lancifodilactone N or isomer	√	√
45	15.28	387.179 9	[M+H]⁺	C₂₂H₂₆O₆	-0.86	188.43	Lignan	372.153 8, 356.161 8, 341.127 5, 300.096 5	(-)-Gomisin L or isomer	√	√
46	15.36	559.218 4	[M-H]^-	C₂₉H₃₆O₁₁	-0.08	209.30	Terpenoid	483.161 8, 457.191 1, 431.180 3, 413.195 2	Schindilactone C or isomer	√	√
47	15.61	545.237 9	[M+H]⁺	C₂₉H₃₆O₁₀	-0.43	216.79	Terpenoid	497.214 4, 463.212 4, 435.219 0, 391.181 7	Pre-schisanartanin N or isomer	√	√
48	15.77	527.228 2	[M-H]^-	C₂₉H₃₆O₉	-0.78	214.93	Terpenoid	497.218 2, 435.215 9, 407.183 7, 365.178 5	Wuweizidilactone L or isomer	√	√
49	15.98	515.229 6	[M-H]^-	C₂₈H₃₆O₉	1.75	211.39	Terpenoid	471.243 2, 411.182 1, 369.169 0	Wuweizidilactone N or isomer	√	√
50	16.03	415.211 7	[M+H]⁺	C₂₄H₃₀O₆	0.45	186.75	Terpenoid	385.194 5, 369.167 6, 353.170 6, 323.129 2, 165.064 3	Meprednisone acetate or isomer	√	√
51	16.09	527.229 0	[M+H]⁺	C₂₉H₃₄O₉	2.80	208.04	Terpenoid	483.236 5, 438.235 3, 423.211 6	Lancifodilactone D or isomer	√	√
52	16.26	529.242 9	[M+H]⁺	C₂₉H₃₆O₉	-0.50	210.27	Terpenoid	469.224 2, 451.213 5, 433.205 6	Methyl acetoxyangolensate or isomer	√	√
53	16.34	559.219 3	[M-H]^-	C₂₉H₃₆O₁₁	1.41	215.07	Terpenoid	499.195 6, 483.164 2, 457.187 5, 455.208 9, 399.179 4	Schicagenin B or isomer	√	√
54	16.52	527.228 6	[M+H]⁺	C₂₉H₃₄O₉	1.94	211.46	Terpenoid	483.205 1, 467.205 9, 455.240 1, 423.212 4	Lancifodilactone D or isomer	√	√
55	16.86	527.227 2	[M+H]⁺	C₂₉H₃₄O₉	-0.75	207.58	Terpenoid	473.209 3, 449.194 6	Lancifodilactone D or isomer	√	√
56	17.01	531.258 6	[M+H]⁺	C₂₉H₃₈O₉	-0.43	206.13	Terpenoid	513.242 4, 471.235 6, 435.219 0, 399.179 3	Pre-schisanartanin F or isomer	√	√
57	17.14	529.242 4	[M+H]⁺	C₂₉H₃₆O₉	-1.48	208.22	Terpenoid	453.218 2, 355.152 4, 299.090 2, 285.109 8	Pre-schisanartanin E or isomer	√
58^*	17.52	433.218 4	[M+H]⁺	C₂₄H₃₂O₇	-8.51	187.91	Lignan	415.211 0, 400.187 4, 374.165 8, 358.139 0, 361.161 2, 348.149 5	Schisandrol A	√	√
59	17.88	417.190 1	[M+H]⁺	C₂₃H₂₈O₇	-1.75	184.74	Lignan	373.165 0, 341.136 4, 329.100 7, 311.127 2	Gomisin O or isomer	√	√
60	18.10	615.280 7	[M+H]⁺	C₃₃H₄₂O₁₁	1.21	228.54	Terpenoid	597.274 6, 479.206 1, 437.197 5	Wuweizidilactone I or isomer	√
61	18.38	417.189 1	[M+H]⁺	C₂₃H₂₈O₇	-3.93	189.28	Lignan	370.180 1, 341.138 2, 331.106 9, 317.106 7	Gomisin O or isomer	√	√
62	18.45	657.290 4	[M+H]⁺	C₃₅H₄₄O₁₂	-0.25	236.73	Terpenoid	639.281 1, 479.205 5	Wuweizidilactone G or isomer	√	√
63	18.49	483.310 5	[M+H]⁺	C₃₀H₄₂O₅	0.00	210.35	Terpenoid	419.183 2, 377.119 9, 275.140 1, 151.053 0	Kadsuphilactone B or isomer
64^*	18.61	531.221 2	[M+H]⁺	C₂₈H₃₄O₁₀	-4.67	206.17	Lignan	401.159 1, 371.149 5, 357.132 9, 329.099 1	Gomisin D	√	√
65	18.69	481.293 8	[M+H]⁺	C₃₀H₄₀O₅	-2.18	206.91	Terpenoid	448.219 5, 417.284 9, 343.109 4	Schisanlactone C or isomer	√
66	18.90	341.137 2	[M+H]⁺	C₂₀H₂₀O₅	-3.27	172.62	Lignan	287.089 4, 219.100 2, 205.083 5, 122.036 1	D-Epigalbacin or isomer	√
67^*	18.93	389.194 8	[M+H]⁺	C₂₂H₂₈O₆	-2.83	180.02	Lignan	357.167 9, 325.141 9, 287.089 3, 227.068 9, 221.116 9	Gomisin J	√	√
68	19.16	587.250 3	[M-H]^-	C₂₉H₃₆O₉	0.90	229.45	Terpenoid	447.217 7, 403.225 6, 227.034 0	Pre-schisanartanin A or isomer	√	√
69	19.19	571.253 6	[M+H]⁺	C₃₁H₃₈O₁₀	-0.37	219.70	Terpenoid	511.233 5, 493.220 9, 469.222 3, 451.210 4	Wuweizidilactone M or isomer	√	√
70^*	19.42	399.179 5	[M-H₂O +H]⁺	C₂₃H₂₈O₇	-6.26	180.14	Lignan	369.167 8, 345.131 2, 329.100 7, 299.090 0, 285.074 0	Schisandrol B	√	√
71	19.57	589.264 9	[M-H]^-	C₃₁H₄₂O₁₁	-0.93	228.57	Terpenoid	467.241 6, 221.093 2	Pre-schisanartanin B or isomer	√	√
72	19.64	433.220 1	[M+H]⁺	C₂₄H₃₂O₇	-0.36	194.35	Lignan	415.211 1, 386.168 8, 339.121 8, 323.160 5	Schisandrin or isomer	√	√
73	19.83	401.158 3	[M+H]⁺	C₂₂H₂₄O₇	-2.95	182.28	Lignan	357.127 2, 341.101 3, 311.091 6, 299.089 2, 267.064 6	Methyl 2, 5-bis(3, 4-dimethoxyphenyl)-4, 5-dihydro-3-furancarboxylate or isomer	√	√
74	20.05	417.190 1	[M+H]⁺	C₂₃H₂₈O₇	-1.70	185.05	Lignan	401.196 4, 369.168 8, 339.121 8, 203.084 2	Gomisin O or isomer	√	√
75	20.23	387.180 5	[M-H]^-	C₂₂H₂₈O₆	-2.18	185.52	Lignan	341.139 1, 311.094 7, 275.066 7	Rubrisandrins A or isomer	√	√
76	20.59	531.222 6	[M-H]^-	C₂₈H₃₆O₁₀	-1.82	213.74	Terpenoid	401.159 1, 355.122 0, 341.098 3	Wuweizidilactone H or isomer	√	√
77	20.72	415.211 4	[M+H]⁺	C₂₄H₃₀O₆	-0.28	184.07	Terpenoid	385.195 3, 369.169 0, 353.174 9, 301.104 4	Meprednisone acetate or isomer	√	√
78	20.91	389.194 6	[M+H]⁺	C₂₂H₂₈O₆	-3.18	184.21	Lignan	374.164 0, 357.169 1, 341.135 9	Rubrisandrins A or isomer	√	√
79	21.17	515.227 2	[M+H]⁺	C₂₈H₃₄O₉	0.70	203.29	Terpenoid	469.223 6, 385.163 1, 355.153 2, 323.126 8	Wuweizidilactone O or isomer	√	√
80	21.34	389.194 0	[M+H]⁺	C₂₂H₂₈O₆	-4.72	183.08	Lignan	331.118 2, 235.074 2, 181.063 1	Rubrisandrins A or isomer	√	√
81	21.97	401.195 5	[M+H]⁺	C₂₃H₂₈O₆	-0.91	181.19	Lignan	370.177 4, 355.154 6, 323.127 2, 295.131 7, 165.066 0	Rubschisandrin or isomer	√	√
82^*	22.93	523.230 5	[M+Na]⁺	C₂₈H₃₆O₈	0.52	210.56	Lignan	431.205 9, 415.094 9, 356.160 5, 315.121 9, 267.099 7	Angeloylgomisin H	√
83^*	22.94	401.196 5	[M+H]⁺	C₂₃H₂₈O₆	-0.91	183.00	Lignan	386.170 0, 371.179 4, 356.160 5, 345.132 4, 221.093 4	Gomisin N	√	√
84	23.02	387.179 7	[M+H]⁺	C₂₂H₂₆O₆	-1.42	179.86	Lignan	372.157 5, 356.160 5, 327.121 1, 165.068 9	(-)-Gomisin L or isomer	√	√
85	23.49	415.174 1	[M+H]⁺	C₂₃H₂₆O₇	-2.49	180.88	Lignan	401.191 8, 355.145 0, 315.085 2, 181.063 8	Neoisostegane or isomer	√	√
86	24	433.212 4	[M+H]⁺	C₂₄H₃₂O₇	-1.23	189.16	Lignan	401.192 1, 387.180 9, 356.160 3, 341.137 6, 315.121 2	Schisandrin or isomer	√	√
87	24.03	341.136 8	[M+H]⁺	C₂₀H₂₀O₅	-4.60	168.22	Lignan	313.105 8, 285.110 3, 251.069 3, 165.068 2	Maceneolignan E or isomer	√	√
88	24.57	387.179 8	[M+H]⁺	C₂₄H₃₀O₇	-1.70	186.62	Lignan	372.155 6, 356.160 8, 341.136 9, 300.097 4, 165.068 7	(-)-Gomisin L or isomer	√	√
89^*	25.35	537.209 4	[M+H]⁺	C₃₀H₃₂O₉	-7.40	207.69	Lignan	416.176 6, 414.166 9, 371.149 2, 343.115 0, 285.073 8	Gomisin G	√
90	25.39	519.201 1	[M+H]⁺	C₃₀H₃₀O₈	-0.50	209.44	Lignan	415.173 9, 343.115 0, 219.079 6, 181.064 1	Schisanchinin A or isomer	√
91	25.70	483.309 8	[M+H]⁺	C₃₀H₄₂O₅	-1.49	207.08	Terpenoid	343.108 1, 253.129 1, 167.048 3	Henrischinin C or isomer	√
92	25.82	537.210 1	[M+H]⁺	C₃₀H₃₂O₉	-3.38	205.95	Lignan	416.176 4, 414.166 9, 371.148 5, 343.115 5, 312.098 5	Isomer of schisantherin A	√
93	26.42	403.210 7	[M+H]⁺	C₂₃H₃₀O₆	-2.03	185.97	Lignan	371.176 8, 341.137 3, 301.105 8, 287.090 5	Gomisin K2 or isomer	√	√
94	27.13	537.209 9	[M+H]⁺	C₃₀H₃₂O₉	-3.70	206.34	Lignan	416.177 0, 371.147 9, 343.115 1, 312.097 4	Isomer of schisantherin A	√	√
95	28.05	519.202 4	[M+H]⁺	C₃₀H₃₀O₈	1.94	207.95	Lignan	414.166 8, 398.170 6, 343.115 3, 285.073 8	Schisanchinin A or isomer	√
96^*	28.50	537.209 4	[M+H]⁺	C₃₀H₃₂O₉	-4.58	205.57	Lignan	416.179 5, 414.164 5, 371.148 3, 343.115 6, 312.098 2	Schisantherin A	√
97^*	28.51	553.184 3	[M+K]⁺	C₂₈H₃₄O₉	1.67	206.04	Lignan	416.179 4, 414.164 5, 371.148 3, 343.115 6	Schisantherin B	√
98^*	29.06	403.210 5	[M+H]⁺	C₂₃H₃₀O₆	-2.52	191.01	Lignan	357.167 8, 325.141 9, 301.106 7	Schisanhenol	√	√
99	31.15	415.210 4	[M+H]⁺	C₂₄H₃₀O₆	-2.69	188.75	Terpenoid	385.196 1, 369.168 5, 353.173 5, 323.126 9	Meprednisone acetate or isomer	√	√
100	32.12	415.210 5	[M+H]⁺	C₂₄H₃₀O₆	-2.45	187.92	Terpenoid	385.197 0, 369.168 6, 353.174 5, 323.126 6	Meprednisone acetate or isomer	√	√
101	35.48	399.178 4	[M+H]⁺	C₂₃H₂₆O₆	-4.56	184.94	Lignan	371.176 7, 301.105 7, 165.068 1	Allyl 2-O-benzoyl-3-O-benzyl-6-deoxy-α-L-mannopyranoside or isomer	√	√
102	37.35	417.226 3	[M+H]⁺	C₂₄H₃₂O₆	-2.08	190.55	Lignan	402.202 2, 387.179 2, 347.148 0, 301.105 9, 241.084 6	Schisandrin A or isomer	√	√
103	39.86	483.236 9	[M+H]⁺	C₂₈H₃₄O₇	-1.72	198.54	Terpenoid	453.216 1, 401.190 5, 323.124 4	Gedunin or isomer	√	√
104	40.26	401.194 5	[M+H]⁺	C₂₃H₂₈O₆	-3.41	186.38	Lignan	386.171 9, 331.114 8, 301.105 5, 285.075 3, 227.068 2	Schisandrin B or isomer	√	√
105	40.73	401.195 1	[M+H]⁺	C₂₃H₂₈O₆	-1.91	184.74	Lignan	386.171 0, 331.117 0, 301.103 7	Schisandrin B or isomer	√	√

No.

t_R /min

Observed m/z

Adduct

Formula

Mass error /×10^-6

Observed
CCS/Å²

Type

Fragment ion

Identification

HDMS^E

HDDDA

2.08

527.089 0

[M-H]^-

C₁₈H₂₄O₁₈

0.02

194.08

Glycoside

473.078 2, 421.103 7, 253.097 3, 165.079 1

4-Deoxy-β-L-threo-hex-4-enopyranuronosyl-(1- > 4)-α-D-galactopyranuronosyl-(1- > 4)-D-galactopyranuronic acid or isomer

√

2^*

3.41

153.018 2

[M-H]^-

C₇H₄O₄

-0.23

158.79

Organic acid

109.028 8

Protocatechuic acid

√

5.77

327.143 6

[M-H]^-

C₁₆H₂₄O₇

-4.12

188.05

Glycoside

272.088 9, 134.036 9

Thymoquinol 5-O-β-D-glucopyranoside or isomer

√

6.33

327.144 4

[M-H]^-

C₁₆H₂₄O₇

-1.49

185.24

Glycoside

161.024 1, 149.060 6

Thymoquinol 5-O-β-D-glucopyranoside or isomer

√

6.81

713.302 8

[M+H]⁺

C₃₄H₄₈O₁₆

1.85

173.65

Lignan

375.170 0, 165.066 0

1, 2, 13, 14-Tetramethoxydibenzo-cyclooctadiene 3, 12-O-β-D-diglucopyranoside or isomer

√

6^*

7.52

609.146 3

[M-H]^-

C₂₇H₃₀O₁₆

0.31

223.02

Flavonoid

301.033 9, 271.024 3, 255.028 7, 243.031 6, 227.031 9

Rutin

√

7.65

565.228 4

[M-H]^-

C₂₈H₃₈O₁₂

-1.20

237.91

Lignan

373.138 8

3, 7-Dihydroxy-1, 2, 13, 14-tetramethoxydibenzo-cyclooctadiene 12-O-β-D-glucopyranoside or isomer

√

7.85

463.087 9

[M-H]^-

C₂₁H₂₀O₁₂

-0.65

192.51

Glycoside

301.034 1, 271.022 8, 255.029 0, 243.027 4, 151.002 8

Hyperoside or isomer

√

8.48

473.202 4

[M-H]^-

C₂₂H₃₄O₁₁

-0.92

216.55

Glycoside

313.107 8, 271.024 5, 223.153 1

Schisandenoid A or isomer

√

8.93

565.229 6

[M-H]^-

C₂₈H₃₈O₁₂

0.94

229.49

Lignan

341.102 5, 326.078 0

3, 7-Dihydroxy-1, 2, 13, 14-tetramethoxydibenzo-cyclooctadiene 12-O-β-D-glucopyranoside or isomer

√

9.99

575.212 8

[M-H]^-

C₂₉H₃₆O₁₂

-1.09

209.75

Terpenoid

557.194 8, 497.185 7, 482.194 0, 453.192 7

Arisanlactone B or isomer

√

10.41

577.228 9

[M+H]⁺

C₂₉H₃₆O₁₂

1.60

213.53

Terpenoid

543.225 9, 485.213 1

Micradilactone A or isomer

√

10.42

561.232 9

[M+H]⁺

C₂₉H₃₆O₁₁

-0.18

211.64

Terpenoid

543.225 9, 507.203 3, 485.213 0

Schicagenin B or isomer

√

10.70

497.219 5

[M-H]^-

C₂₈H₃₄O₈

2.77

214.37

Lignan

387.136 9

Angeloylisogomisin O or isomer

√

10.89

559.218 7

[M-H]^-

C₂₉H₃₆O₁₁

0.30

209.42

Terpenoid

541.214 4, 465.152 1, 403.149 7, 383.145 1

Schindilactone C or isomer

√

11.14

561.233 2

[M+H]⁺

C₂₉H₃₆O₁₁

0.28

212.18

Terpenoid

543.219 3, 439.205 0, 425.176 4, 407.209 8

Schicagenin B or isomer

√

11.47

543.223 2

[M-H]^-

C₂₉H₃₆O₁₀

-0.70

222.66

Terpenoid

527.226 1, 473.247 7

Pre-schisanartanin N or isomer

√

11.51

527.226 2

[M+H]⁺

C₂₉H₃₄O₉

-2.49

206.62

Terpenoid

467.206 4, 419.185 0, 203.104 9, 185.094 6

Lancifodilactone D or isomer

√

11.63

549.232 7

[M+H]⁺

C₂₈H₃₆O₁₁

-0.62

216.71

Terpenoid

479.207 5, 387.179 5, 355.153 2

19(R)-Hydroxyl-wuweizidilactone H or isomer

√

11.75

559.218 5

[M-H]^-

C₂₉H₃₆O₁₁

-0.05

210.31

Terpenoid

469.222 6, 465.148 6, 413.197 5, 387.146 2, 347.157 5

Schicagenin B or isomer

√

11.82

543.223 5

[M-H]^-

C₂₉H₃₆O₁₀

-0.13

217.58

Terpenoid

463.211 7, 383.187 7, 365.196 6, 137.059 7

Pre-schisanartanin N or isomer

√

11.91

577.230 3

[M+H]⁺

C₂₉H₃₆O₁₂

4.10

215.81

Terpenoid

545.229 2, 525.181 0, 515.211 9, 495.204 6, 453.203 2

Arisanlactone B or isomer

√

12.09

559.218 3

[M-H]^-

C₂₉H₃₆O₁₁

-0.25

218.39

Terpenoid

497.217 5, 429.192 4

Schindilactone C

√

12.27

543.224 1

[M-H]^-

C₂₉H₃₆O₁₀

0.93

214.59

Terpenoid

483.135 8, 471.200 5, 463.208 3, 435.216 3

Pre-schisanartanin N or isomer

√

12.41

575.213 9

[M-H]^-

C₂₉H₃₆O₁₂

0.83

213.64

Terpenoid

515.191 9, 419.125 9, 413.161 4

Arisanlactone B or isomer

√

12.53

545.238 7

[M+H]⁺

C₂₉H₃₆O₁₀

1.05

211.05

Terpenoid

508.213 3, 451.215 6, 433.197 7, 391.175 5

Pre-schisanartanin N or isomer

√

12.84

527.227 5

[M+H]⁺

C₂₈H₃₆O₉

-1.50

209.72

Terpenoid

485.217 2, 453.222 8, 439.211 4, 423.221 8

Lancifodilactone D or isomer

√

13.17

561.233 2

[M+H]⁺

C₂₉H₃₆O₁₁

0.25

208.50

Terpenoid

527.222 3, 485.220 1, 467.207 1

Schindilactone C or isomer

√

13.42

515.228 6

[M-H]^-

C₂₈H₃₆O₉

-0.20

218.36

Terpenoid

437.203 4, 385.174 6

Wuweizidilactone N or isomer

√

13.70

417.192 1

[M+H]⁺

C₂₃H₂₈O₇

3.05

188.89

Lignan

385.169 1, 331.118 9, 315.080 0

Gomisin O or isomer

√

13.71

661.250 5

[M-H]^-

C₃₃H₄₂O₁₄

0.56

238.36

Terpenoid

369.137 8, 285.170 1

Schisandroside D or isomer

√

13.76

533.238 7

[M+H]⁺

C₂₈H₃₆O₁₀

1.03

213.75

Terpenoid

499.235 7, 479.204 3, 437.195 0

Wuweizidilactone H or isomer

√

13.88

369.168 8

[M+H]⁺

C₂₂H₂₄O₅

-2.31

181.98

Terpenoid

337.144 1, 323.130 5, 203.083 3

(8ξ, 14ξ)-17-Oxoestra-1, 3, 5(10), 9(11)-tetraene-3, 4-diyl diacetate or isomer

√

13.96

221.190 3

[M+H]⁺

C₁₅H₂₄O

1.26

150.76

Sesquiterpene

219.172 4, 189.125 6

α-Iso-cubebenol or isomer

√

14.13

545.239 2

[M+H]⁺

C₂₉H₃₆O₁₀

1.99

213.63

Terpenoid

485.217 6, 451.207 5, 433.203 2, 371.175 5

Pre-schisanartanin N or isomer

√

14.31

515.227 7

[M+H]⁺

C₂₈H₃₄O₉

0.19

210.80

Terpenoid

429.192 1, 401.196 0, 381.132 5

Wuweizidilactone O or isomer

√

14.41

545.238 1

[M+H]⁺

C₂₉H₃₆O₁₀

-0.08

207.63

Terpenoid

527.2327, 453.224 7, 437.230 9, 431.207 8

Pre-schisanartanin N or isomer

√

38^*

14.60

419.205 0

[M+H]⁺

C₂₃H₃₀O₇

-3.40

189.94

Lignan

401.196 1, 386.172 6, 333.127 9, 315.120 5

Gomisin H

√

14.76

529.243 3

[M+H]⁺

C₂₉H₃₆O₉

0.23

206.80

Terpenoid

509.215 7, 469.219 6, 449.196 5, 439.212 5, 421.201 3

Methyl acetoxyangolensate or isomer

√

14.84

517.244 1

[M+H]⁺

C₂₈H₃₆O₉

1.60

203.29

Terpenoid

499.233 5, 413.193 0, 343.117 4

Wuweizidilactone N or isomer

√

14.90

575.285 2

[M+H]⁺

C₃₁H₄₂O₁₀

0.21

221.29

Terpenoid

479.242 9, 437.232 3

Wuweizidilactone K or isomer

√

15.01

527.227 5

[M+H]⁺

C₂₉H₃₄O₉

-0.05

214.45

Terpenoid

509.222 2, 463.202 3, 449.193 9

Lancifodilactone D or isomer

√

15.06

417.191 1

[M+H]⁺

C₂₃H₂₈O₇

0.71

185.16

Lignan

386.173 4, 371.176 5

Gomisin O or isomer

√

15.09

557.202 5

[M-H]^-

C₃₁H₃₈O₁₀

-0.70

213.07

Terpenoid

513.214 2, 485.217 0, 481.150 8, 391.119 9, 365.139 1

Lancifodilactone N or isomer

√

15.28

387.179 9

[M+H]⁺

C₂₂H₂₆O₆

-0.86

188.43

Lignan

372.153 8, 356.161 8, 341.127 5, 300.096 5

(-)-Gomisin L or isomer

√

15.36

559.218 4

[M-H]^-

C₂₉H₃₆O₁₁

-0.08

209.30

Terpenoid

483.161 8, 457.191 1, 431.180 3, 413.195 2

Schindilactone C or isomer

√

15.61

545.237 9

[M+H]⁺

C₂₉H₃₆O₁₀

-0.43

216.79

Terpenoid

497.214 4, 463.212 4, 435.219 0, 391.181 7

Pre-schisanartanin N or isomer

√

15.77

527.228 2

[M-H]^-

C₂₉H₃₆O₉

-0.78

214.93

Terpenoid

497.218 2, 435.215 9, 407.183 7, 365.178 5

Wuweizidilactone L or isomer

√

15.98

515.229 6

[M-H]^-

C₂₈H₃₆O₉

1.75

211.39

Terpenoid

471.243 2, 411.182 1, 369.169 0

Wuweizidilactone N or isomer

√

16.03

415.211 7

[M+H]⁺

C₂₄H₃₀O₆

0.45

186.75

Terpenoid

385.194 5, 369.167 6, 353.170 6, 323.129 2, 165.064 3

Meprednisone acetate or isomer

√

16.09

527.229 0

[M+H]⁺

C₂₉H₃₄O₉

2.80

208.04

Terpenoid

483.236 5, 438.235 3, 423.211 6

Lancifodilactone D or isomer

√

16.26

529.242 9

[M+H]⁺

C₂₉H₃₆O₉

-0.50

210.27

Terpenoid

469.224 2, 451.213 5, 433.205 6

Methyl acetoxyangolensate or isomer

√

16.34

559.219 3

[M-H]^-

C₂₉H₃₆O₁₁

1.41

215.07

Terpenoid

499.195 6, 483.164 2, 457.187 5, 455.208 9, 399.179 4

Schicagenin B or isomer

√

16.52

527.228 6

[M+H]⁺

C₂₉H₃₄O₉

1.94

211.46

Terpenoid

483.205 1, 467.205 9, 455.240 1, 423.212 4

Lancifodilactone D or isomer

√

16.86

527.227 2

[M+H]⁺

C₂₉H₃₄O₉

-0.75

207.58

Terpenoid

473.209 3, 449.194 6

Lancifodilactone D or isomer

√

17.01

531.258 6

[M+H]⁺

C₂₉H₃₈O₉

-0.43

206.13

Terpenoid

513.242 4, 471.235 6, 435.219 0, 399.179 3

Pre-schisanartanin F or isomer

√

17.14

529.242 4

[M+H]⁺

C₂₉H₃₆O₉

-1.48

208.22

Terpenoid

453.218 2, 355.152 4, 299.090 2, 285.109 8

Pre-schisanartanin E or isomer

√

58^*

17.52

433.218 4

[M+H]⁺

C₂₄H₃₂O₇

-8.51

187.91

Lignan

415.211 0, 400.187 4, 374.165 8, 358.139 0, 361.161 2, 348.149 5

Schisandrol A

√

17.88

417.190 1

[M+H]⁺

C₂₃H₂₈O₇

-1.75

184.74

Lignan

373.165 0, 341.136 4, 329.100 7, 311.127 2

Gomisin O or isomer

√

18.10

615.280 7

[M+H]⁺

C₃₃H₄₂O₁₁

1.21

228.54

Terpenoid

597.274 6, 479.206 1, 437.197 5

Wuweizidilactone I or isomer

√

18.38

417.189 1

[M+H]⁺

C₂₃H₂₈O₇

-3.93

189.28

Lignan

370.180 1, 341.138 2, 331.106 9, 317.106 7

Gomisin O or isomer

√

18.45

657.290 4

[M+H]⁺

C₃₅H₄₄O₁₂

-0.25

236.73

Terpenoid

639.281 1, 479.205 5

Wuweizidilactone G or isomer

√

18.49

483.310 5

[M+H]⁺

C₃₀H₄₂O₅

0.00

210.35

Terpenoid

419.183 2, 377.119 9, 275.140 1, 151.053 0

Kadsuphilactone B or isomer

64^*

18.61

531.221 2

[M+H]⁺

C₂₈H₃₄O₁₀

-4.67

206.17

Lignan

401.159 1, 371.149 5, 357.132 9, 329.099 1

Gomisin D

√

18.69

481.293 8

[M+H]⁺

C₃₀H₄₀O₅

-2.18

206.91

Terpenoid

448.219 5, 417.284 9, 343.109 4

Schisanlactone C or isomer

√

18.90

341.137 2

[M+H]⁺

C₂₀H₂₀O₅

-3.27

172.62

Lignan

287.089 4, 219.100 2, 205.083 5, 122.036 1

D-Epigalbacin or isomer

√

67^*

18.93

389.194 8

[M+H]⁺

C₂₂H₂₈O₆

-2.83

180.02

Lignan

357.167 9, 325.141 9, 287.089 3, 227.068 9, 221.116 9

Gomisin J

√

19.16

587.250 3

[M-H]^-

C₂₉H₃₆O₉

0.90

229.45

Terpenoid

447.217 7, 403.225 6, 227.034 0

Pre-schisanartanin A or isomer

√

19.19

571.253 6

[M+H]⁺

C₃₁H₃₈O₁₀

-0.37

219.70

Terpenoid

511.233 5, 493.220 9, 469.222 3, 451.210 4

Wuweizidilactone M or isomer

√

70^*

19.42

399.179 5

[M-H₂O
+H]⁺

C₂₃H₂₈O₇

-6.26

180.14

Lignan

369.167 8, 345.131 2, 329.100 7, 299.090 0, 285.074 0

Schisandrol B

√

19.57

589.264 9

[M-H]^-

C₃₁H₄₂O₁₁

-0.93

228.57

Terpenoid

467.241 6, 221.093 2

Pre-schisanartanin B or isomer

√

19.64

433.220 1

[M+H]⁺

C₂₄H₃₂O₇

-0.36

194.35

Lignan

415.211 1, 386.168 8, 339.121 8, 323.160 5

Schisandrin or isomer

√

19.83

401.158 3

[M+H]⁺

C₂₂H₂₄O₇

-2.95

182.28

Lignan

357.127 2, 341.101 3, 311.091 6, 299.089 2, 267.064 6

Methyl 2, 5-bis(3, 4-dimethoxyphenyl)-4, 5-dihydro-3-furancarboxylate or isomer

√

20.05

417.190 1

[M+H]⁺

C₂₃H₂₈O₇

-1.70

185.05

Lignan

401.196 4, 369.168 8, 339.121 8, 203.084 2

Gomisin O or isomer

√

20.23

387.180 5

[M-H]^-

C₂₂H₂₈O₆

-2.18

185.52

Lignan

341.139 1, 311.094 7, 275.066 7

Rubrisandrins A or isomer

√

20.59

531.222 6

[M-H]^-

C₂₈H₃₆O₁₀

-1.82

213.74

Terpenoid

401.159 1, 355.122 0, 341.098 3

Wuweizidilactone H or isomer

√

20.72

415.211 4

[M+H]⁺

C₂₄H₃₀O₆

-0.28

184.07

Terpenoid

385.195 3, 369.169 0, 353.174 9, 301.104 4

Meprednisone acetate or isomer

√

20.91

389.194 6

[M+H]⁺

C₂₂H₂₈O₆

-3.18

184.21

Lignan

374.164 0, 357.169 1, 341.135 9

Rubrisandrins A or isomer

√

21.17

515.227 2

[M+H]⁺

C₂₈H₃₄O₉

0.70

203.29

Terpenoid

469.223 6, 385.163 1, 355.153 2, 323.126 8

Wuweizidilactone O or isomer

√

21.34

389.194 0

[M+H]⁺

C₂₂H₂₈O₆

-4.72

183.08

Lignan

331.118 2, 235.074 2, 181.063 1

Rubrisandrins A or isomer

√

21.97

401.195 5

[M+H]⁺

C₂₃H₂₈O₆

-0.91

181.19

Lignan

370.177 4, 355.154 6, 323.127 2, 295.131 7, 165.066 0

Rubschisandrin or isomer

√

82^*

22.93

523.230 5

[M+Na]⁺

C₂₈H₃₆O₈

0.52

210.56

Lignan

431.205 9, 415.094 9, 356.160 5, 315.121 9, 267.099 7

Angeloylgomisin H

√

83^*

22.94

401.196 5

[M+H]⁺

C₂₃H₂₈O₆

-0.91

183.00

Lignan

386.170 0, 371.179 4, 356.160 5, 345.132 4, 221.093 4

Gomisin N

√

23.02

387.179 7

[M+H]⁺

C₂₂H₂₆O₆

-1.42

179.86

Lignan

372.157 5, 356.160 5, 327.121 1, 165.068 9

(-)-Gomisin L or isomer

√

23.49

415.174 1

[M+H]⁺

C₂₃H₂₆O₇

-2.49

180.88

Lignan

401.191 8, 355.145 0, 315.085 2, 181.063 8

Neoisostegane or isomer

√

433.212 4

[M+H]⁺

C₂₄H₃₂O₇

-1.23

189.16

Lignan

401.192 1, 387.180 9, 356.160 3, 341.137 6, 315.121 2

Schisandrin or isomer

√

24.03

341.136 8

[M+H]⁺

C₂₀H₂₀O₅

-4.60

168.22

Lignan

313.105 8, 285.110 3, 251.069 3, 165.068 2

Maceneolignan E or isomer

√

24.57

387.179 8

[M+H]⁺

C₂₄H₃₀O₇

-1.70

186.62

Lignan

372.155 6, 356.160 8, 341.136 9, 300.097 4, 165.068 7

(-)-Gomisin L or isomer

√

89^*

25.35

537.209 4

[M+H]⁺

C₃₀H₃₂O₉

-7.40

207.69

Lignan

416.176 6, 414.166 9, 371.149 2, 343.115 0, 285.073 8

Gomisin G

√

25.39

519.201 1

[M+H]⁺

C₃₀H₃₀O₈

-0.50

209.44

Lignan

415.173 9, 343.115 0, 219.079 6, 181.064 1

Schisanchinin A or isomer

√

25.70

483.309 8

[M+H]⁺

C₃₀H₄₂O₅

-1.49

207.08

Terpenoid

343.108 1, 253.129 1, 167.048 3

Henrischinin C or isomer

√

25.82

537.210 1

[M+H]⁺

C₃₀H₃₂O₉

-3.38

205.95

Lignan

416.176 4, 414.166 9, 371.148 5, 343.115 5, 312.098 5

Isomer of schisantherin A

√

26.42

403.210 7

[M+H]⁺

C₂₃H₃₀O₆

-2.03

185.97

Lignan

371.176 8, 341.137 3, 301.105 8, 287.090 5

Gomisin K2 or isomer

√

27.13

537.209 9

[M+H]⁺

C₃₀H₃₂O₉

-3.70

206.34

Lignan

416.177 0, 371.147 9, 343.115 1, 312.097 4

Isomer of schisantherin A

√

28.05

519.202 4

[M+H]⁺

C₃₀H₃₀O₈

1.94

207.95

Lignan

414.166 8, 398.170 6, 343.115 3, 285.073 8

Schisanchinin A or isomer

√

96^*

28.50

537.209 4

[M+H]⁺

C₃₀H₃₂O₉

-4.58

205.57

Lignan

416.179 5, 414.164 5, 371.148 3, 343.115 6, 312.098 2

Schisantherin A

√

97^*

28.51

553.184 3

[M+K]⁺

C₂₈H₃₄O₉

1.67

206.04

Lignan

416.179 4, 414.164 5, 371.148 3, 343.115 6

Schisantherin B

√

98^*

29.06

403.210 5

[M+H]⁺

C₂₃H₃₀O₆

-2.52

191.01

Lignan

357.167 8, 325.141 9, 301.106 7

Schisanhenol

√

31.15

415.210 4

[M+H]⁺

C₂₄H₃₀O₆

-2.69

188.75

Terpenoid

385.196 1, 369.168 5, 353.173 5, 323.126 9

Meprednisone acetate or isomer

√

100

32.12

415.210 5

[M+H]⁺

C₂₄H₃₀O₆

-2.45

187.92

Terpenoid

385.197 0, 369.168 6, 353.174 5, 323.126 6

Meprednisone acetate or isomer

√

101

35.48

399.178 4

[M+H]⁺

C₂₃H₂₆O₆

-4.56

184.94

Lignan

371.176 7, 301.105 7, 165.068 1

Allyl 2-O-benzoyl-3-O-benzyl-6-deoxy-α-L-mannopyranoside or isomer

√

102

37.35

417.226 3

[M+H]⁺

C₂₄H₃₂O₆

-2.08

190.55

Lignan

402.202 2, 387.179 2, 347.148 0, 301.105 9, 241.084 6

Schisandrin A or isomer

√

103

39.86

483.236 9

[M+H]⁺

C₂₈H₃₄O₇

-1.72

198.54

Terpenoid

453.216 1, 401.190 5, 323.124 4

Gedunin or isomer

√

104

40.26

401.194 5

[M+H]⁺

C₂₃H₂₈O₆

-3.41

186.38

Lignan

386.171 9, 331.114 8, 301.105 5, 285.075 3, 227.068 2

Schisandrin B or isomer

√

105

40.73

401.195 1

[M+H]⁺

C₂₃H₂₈O₆

-1.91

184.74

Lignan

386.171 0, 331.117 0, 301.103 7

Schisandrin B or isomer

√

基于UHPLC/IM-QTOF-MS联用组合式扫描技术的中药五味子水煎液中化学成分系统表征与鉴定

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洪莉丽 , 王洪达 , 徐晓艳 , 胡万弟 , 刘靖源 , 王小莹 , 高秀梅 , 杨文志 ^*

药学学报 | 研究论文 2024,59(3): 678-692

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药学学报 | 研究论文 2024, 59(3): 678-692

基于UHPLC/IM-QTOF-MS联用组合式扫描技术的中药五味子水煎液中化学成分系统表征与鉴定

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洪莉丽, 王洪达, 徐晓艳, 胡万弟, 刘靖源, 王小莹, 高秀梅, 杨文志^*

作者信息

天津中医药大学, 组分中药国家重点实验室, 天津 301617

通讯作者:

^*杨文志, Tel: 17602666784, E-mail: wzyang0504@tjutcm.edu.cn

Systematic characterization and identification of the chemical constituents of the Schisandra chinensis decoction based on a hybrid scanning technique of UHPLC/IM-QTOF-MS

Li-li HONG, Hong-da WANG, Xiao-yan XU, Wan-di HU, Jing-yuan LIU, Xiao-ying WANG, Xiu-mei GAO, Wen-zhi YANG^*

Affiliations

State Key Laboratory of Component-based Chinese Medicine, Tianjin University of Traditional Chinese Medicine, Tianjin 301617, China

出版时间: 2024-03-12 doi: 10.16438/j.0513-4870.2023-0726

文章导航

摘要

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五味子是补虚强壮收涩类中药, 临床适用于久咳虚喘、心悸失眠等病症。本研究建立了一种离子淌度分离、数据非依赖采集与数据依赖采集交替进行的组合式质谱扫描方法(high-definition data-independent/data-dependent acquisition, HDDIDDA), 结合UNIFI软件自建数据库驱动的自动峰注解流程, 系统表征与鉴定五味子的多类别化学成分。使用HSS T3色谱柱(100 mm × 2.1 mm, 1.8 μm), 0.1%甲酸水-乙腈为流动相, 流速0.3 mL·min^-1, 柱温35 ℃, 在42 min内实现五味子成分较好的分离; 利用HDDIDDA扫描技术, 利用正、负离子模式分别进行数据采集。通过软件自动峰注解、标准品比对、二级质谱数据解析及文献分析等方法, 从五味子水煎液中共鉴定或推导出105种化合物, 包括56种萜类、42种木脂素类、5种苷类、1种有机酸类及1种黄酮类。HDDIDDA扫描能够改善数据采集的覆盖度, 提高鉴定的准确性, 同时CCS预测分析为离子淌度技术区分同分异构体提供了可能。研究结果为中药智能化的物质基础研究提供了参考。

关键词

五味子 / 离子淌度 / 高分辨质谱 / 组合式质谱扫描 / 化学成分表征

Abstract

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Schisandra chinensis is a traditional Chinese medicine with the functions of reinforcing deficiency, strengthening, and inducing astringency, appliable to treat the chronic cough and deficiency in breath, palpitation, and insomnia, etc. A hybrid mass spectrometry scanning strategy (high-definition data-independent/data-dependent acquisition, HDDIDDA), enabling the ion mobility separation and alternating data-independent acquisition/data-dependent acquisition, was established, which, in combination with in-house library-driven automatic peak annotation workflows facilitated by the UNIFI software, was utilized to systematically characterize the multi-classes of chemical components from S. chinensis. The use of an HSS T3 column (100 mm × 2.1 mm, 1.8 μm), 0.1% formic acid in H₂O-acetonitrile as the mobile phase running at the flow rate of 0.3 mL·min^-1, and column temperature at 35 ℃, could enable good separation of the S. chinensis components within 42 min. HDDIDDA scan in both the positive and negative ion modes was employed for data acquisition. Based on the automatic peak annotation, reference standards comparison, MS² data interpretation, and literature analysis, we were able to identify or tentatively characterize 105 compounds in the S. chinensis decoction, involving 56 terpenoids, 42 lignans, five glycosides, one organic acid, and one flavonoid. HDDIDDA scanning can improve the coverage of data acquisition and improve the accuracy of identification, while CCS prediction analysis provides the possibility to distinguish isomers by the ion mobility technology. The results provide reference for the intelligent material basis research of TCM.

Key words

Schisandra chinensis / ion mobility / high-definition mass spectrometry / hybrid mass spectrometric scan / chemical constituent characterization

引用本文

洪莉丽, 王洪达, 徐晓艳, 胡万弟, 刘靖源, 王小莹, 高秀梅, 杨文志. 基于UHPLC/IM-QTOF-MS联用组合式扫描技术的中药五味子水煎液中化学成分系统表征与鉴定. 药学学报, 2024 , 59 (3) : 678 -692 . DOI: 10.16438/j.0513-4870.2023-0726

Li-li HONG, Hong-da WANG, Xiao-yan XU, Wan-di HU, Jing-yuan LIU, Xiao-ying WANG, Xiu-mei GAO, Wen-zhi YANG. Systematic characterization and identification of the chemical constituents of the Schisandra chinensis decoction based on a hybrid scanning technique of UHPLC/IM-QTOF-MS[J]. Acta Pharmaceutica Sinica, 2024 , 59 (3) : 678 -692 . DOI: 10.16438/j.0513-4870.2023-0726

正文

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五味子为木兰科植物Schisandra chinensis (Turcz.) Baill. 的干燥成熟果实, 主产于中国东北部, 习称“北五味子”, 味酸、甘, 性温, 是收敛固涩、益气生津、补肾宁心的传统中药, 用于久咳虚喘、梦遗滑精、遗尿尿频、久泻不止等^[1]。现代药理研究表明^[2-4]五味子具有保护肝脏、抗衰老、抗肿瘤、抗氧化、保护中枢神经系统及心血管系统、抗哮喘等作用, 临床上广泛用于肝损伤、失眠焦虑、心脏病等的治疗, 因此五味子的进一步研究及开发具有非常广阔的前景和重要意义。物质基础研究是中药现代研究的基石, 为质量控制及药理研究奠定基础。五味子醇提物及水煎液口服一直是临床常见的两种用药形式。近期, Yu等^[5]基于超高效液相色谱/四极杆飞行时间质谱联用(ultra-high performance liquid chromatography/quadrupole time-of-flight mass spectrometry, UHPLC/QTOF-MS) 技术从五味子70%甲醇提取物中鉴定94种化合物, 包括57种联苯环辛烯型木脂素类、15种降三萜类及22种其他类型的化合物。然而, 关于传统应用, 五味子汤剂的化学成分尚缺乏系统的研究。

前期研究中, 主要采用紫外分光光度法、薄层色谱法、高效液相色谱、液相色谱-质谱联用等技术开展五味子的化学成分表征, 且大多都限于对木脂素类或有机酸类, 而对五味子其他类别化学成分的关注较少^[6-9]。随着分析技术的发展, 高分辨率的质谱仪器以及多样化的采集方法在提高中药成分检测的灵敏度, 增强鉴定结果的可靠性等方面优势显著。二级或多级质谱数据的采集可以分为数据依赖性采集(data-dependent acquisition, DDA) 与数据非依赖性采集(data-independent acquisition, DIA)。DDA扫描是基于一些规则(如强度排序top N) 仪器自动选择某些母离子碎裂, 所获得的二级或多级质谱图干扰少、质量高, 可直接解析; 但这种模式对低丰度化合物的检测存在不足, 易被忽略^[10]。在DIA扫描中, 仪器能够连续、无偏倚地获取所有质量范围内化合物的二级质谱(MS²) 信息, 具有最高的覆盖度, 同时支撑定性与定量分析; 但首先需要对原始数据进行处理, 通过商业化的软件或实验室自建的算法实现母离子与子离子的匹配, 容易引入干扰碎片或假阳性。而相较于单一采集模式, 在一个工作循环内包含DDA与DIA交替采集(组合式扫描), 理论上能够将DDA的高准确度与DIA高覆盖度优势相结合, 在复杂样品分析中表现显著的优势 ^[11]。此外, 离子淌度(ion mobility, IM) 分离能够根据大小、形状和电荷的不同, 实现气态离子的分离, 并提供与分析物结构相关的碰撞截面积(collision cross section, CCS) 信息。离子淌度分离与色谱分离、质量数分辨正交, 在区分同分异构体或分离共流出成分等方面具有潜力, 也为中药复杂体系的解析提供了新的策略^[12]。

本研究基于Vion IM-QTOF高分辨液质联用仪, 利用数据非依赖采集/数据依赖采集(high-definition data-independent/data-dependent acquisition, HDDIDDA) 维度增强组合扫描技术、UNIFI软件自建数据库驱动的自动峰注解流程, 构建了一种五味子水煎液多类别化学成分快速表征技术, 系统阐释其化学组成, 为五味子的深度开发与质量控制提供参考。

材料与方法

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仪器 Vion IM-QTOF高分辨液质联用仪(美国Waters公司); Vortex-2旋涡混匀仪(上海泸析实业有限公司); SB-4200DTS/P超声波提取仪(宁波新芝生物科技股份有限公司); 5804R低温高速离心机(德国Eppendorf公司); AX205十万分之一天平和BP121S万分之一天平(瑞士Mettler Toledo公司)。

药材与试剂 五味子样品(辽宁, 批号20210713) 购自北京同仁堂天津南开大药房有限公司, 经天津中医药大学李先宽副教授鉴定为木兰科植物Schisandra chinensis (Turcz.) Baill.的干燥成熟果实醋制后样品, 药材样品保存于天津中医药大学中医药研究院药学部中药标准化技术实验室。乙腈、甲醇、甲酸(美国Thermo Fisher Scientific公司, LC-MS级)。超纯水经Milli-Q Integral 5系统(美国Millipore公司) 纯化。13种对照品, 原儿茶酸(protocatechuic acid, 批号DSTDY008101)、芦丁(rutin, 批号DSTDL001702)、戈米辛H (gomisin H, 批号: DSTDG005201)、五味子醇甲(schisandrol A, 批号DSTW001001)、戈米辛D (gomisin D, 批号DST211104-040)、戈米辛J (gomisin J, 批号DSTDG003801)、五味子醇乙(schisandrol B, 批号DSTDW001301)、当归酰戈米辛H (angeloyl gomisin H, 批号DSTDD006101)、戈米辛N (gomisin N, 批号DST211103-037)、戈米辛G (gomisin G, 批号DST211011-039)、五味子酯甲(schisantherin A, 批号DST200330-012)、五味子酯乙(schisantherin B, 批号DST201218-011)、五味子酚(schisanhenol, 批号DST210606-015), 购自成都德思特生物技术有限公司。上述对照品纯度均大于98%, 结构信息见图 1。

样品制备 精密称取15 g五味子, 加入150 mL超纯水, 加热回流提取1 h, 冷却, 补足失重, 稀释成10 mg·mL^-1的溶液, 14 000 r·min^-1离心10 min, 取上清液即得供试品溶液。分别精密称取各对照品适量, 加入50%甲醇制成质量浓度为1 mg·mL^-1的对照品溶液储备液, 精密吸取各对照品储备液, 混合并稀释成含各化合物质量浓度约为10 μg·mL^-1混合对照品溶液。

五味子化学成分数据库构建及UNIFI^TM软件参数设置基于Web of Science (www.webofknowledge.com)、ChemSpider (www.chemspider.com)、PubChem (http://pubchem.ncbi.nlm.nih)、ChemicalBook (www.chemicalbook.com)、CNKI (http://www.cnki.net) 等数据库检索有关北五味子果实、种子、茎、叶中化学成分, 绘制化合物结构, 最终建立了201种包含化合物名称、分子式、质量数等信息的五味子化学成分数据库。使用UNIFI 1.9.3.0 (美国Waters公司) 软件对HDDIDDA采集的五味子HDDDA和HDMS^E数据进行自动峰校正、峰检出及峰注解, 软件关键参数如下: 查找4D峰(HDMS^E) 高能量阈值设置为20.0 counts, 低能量阈值设置为20.0 counts; 查找DDA质量(HDDDA) MS离子强度阈值设置为20.0 counts, MS/MS离子强度阈值设置为20.0 counts; 目标匹配偏差10.0 ppm; 碎片匹配偏差10.0 mDa。正离子模式加合形式: [M+H]⁺、[M+Na]⁺和[M+K]⁺; 负离子模式加合形式: [M-H]^-和[M+HCOO]^-。合并宽带: 扫描3次; 质量窗口: 0.5 m/z; 参比质量数: 556.276 6 (ESI+)/554.262 0 (ESI-); 参比电荷: +1/-1, 选定筛选所有同位素中的候选者, 从结构中生成预测碎片, 启动在源代码中寻找碎片功能。

色谱条件 ACQUITY UPLC^® HSS T3色谱柱(100 mm × 2.1 mm, 1.8 μm), 流动相0.1%甲酸水(A)-乙腈(B), 洗脱梯度如下: 0~4 min, 4%~14% B; 4~15 min, 14%~44% B; 15~21 min, 44%~47% B; 21~35 min, 47%~53% B; 35~38 min, 53%~56% B; 38~42 min, 56%~90% B。柱温为35 ℃, 流速为0.3 mL·min^-1, 进样量为3 μL。

质谱条件 使用HDDIDDA组合扫描方法, 分别在正离子与负离子模式下进行数据采集。毛细管电压(capillary voltage), ±1.0 kV; 锥孔电压(cone voltage), 60 V/-40 V; 源偏移(source offset), 80 V; 源温度(source temperature), 120 ℃; 脱溶剂气温度(desolvation gas temperature, N₂), 500 ℃; 去溶剂气体流速(desolvation gas flow, N₂), 800 L·h^-1; 锥形气体流速(cone gas flow, N₂), 50 L·h^-1。QTOF质谱分析仪在m/z 100~1 000的质量范围内以6 eV的低碰撞能量采集全扫描数据, HDMS^E中扫描时间为0.3 s, HDDDA中扫描时间0.15 s。在HDMS^E中设置了10~60 eV/-30~-70 eV斜坡碰撞能量(ramp collision energy, RCE)。在HDDDA中设置了质量依赖斜坡碰撞能量(mass-dependent ramp collision energy, MDRCE), 低质量斜坡15~40 eV/-30~-70 eV和高质量斜坡25~50 eV/-30~-70 eV。定义了行波离子淌度分离的默认参数, 并使用校准剂混合物进行CCS校准。通过以10 μL·min^-1的流速持续注入亮氨酸脑啡肽溶液(Sigma Aldrich, St. Louis, MO, USA; 200 ng·mL^-1) 进行MS数据的校准^[13]。

结果

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1 色谱及质谱参数的优化

为了尽可能多地鉴定五味子水煎液中的化学成分, 本实验对固定相及关键质谱参数等条件进行了优化(图 2)。首先对HSS T3等10种具有不同键合技术或键合基团的色谱柱进行筛选, 结果表明HSS T3色谱柱能够分离、提取到更多的色谱峰, 总体分离度好、峰型佳, 这与HSS T3色谱柱独特的固定相有关。作为一种极性修饰十八烷基硅烷键合硅胶色谱柱, 可兼容100%水相, 相较于其他类型固定相而言, 增强了萜类及木脂素类等极性分子的保留。进一步, 在正、负离子模式下分别选取了五味子中代表性化合物, 通过对6个水平毛细管电压及5个水平锥孔电压下各化合物的平均峰面积进行比较(n = 3), 另外对3个水平RCE以及4个水平MDRCE进行了优化, 综合考虑后最终设定毛细管电压为1.0 kV, 锥孔电压为60 V/-40 V, RCE为10~60 eV/-30~-70 eV, MDRCE为15~40/25~50 eV及-10~-40/-20~-60 eV。

2 五味子水煎液化学成分表征

基于五味子自建化学数据库, 利用UNIFI软件构建了自动峰注解流程, 并对采集的正离子与负离子模式HDDIDDA数据分别进行处理, 结合对照品信息、化合物裂解规律及文献分析等, 解析五味子水煎液的高分辨二级质谱数据。共鉴定或推导出105种化合物, 包括56种萜类(55种降三萜类和1种倍半萜类)、42种木脂素类、5种苷类、1种有机酸类和1种黄酮类。其中, 13种化合物通过标准品比对确证。正、负离子模式下五味子水煎液样品的基峰离子流图如图 3所示, 鉴定信息见表 1。

2.1 木脂素类化合物鉴定

木脂素类化合物是五味子中最主要成分, 具有保肝、抗氧化、抗肿瘤等作用^[14]。从五味子中共鉴定出42种木脂素类, 主要为联苯环辛烯型, 其中11种通过与标准品对比确证。根据结构和裂解方式, 联苯环辛烯类可以分为环辛二烯无含氧取代、C-6位酰氧基取代、C-7位羟基取代、6, 7-二羟基化合物及其酯类、十一元环内酯类, 其质谱裂解规律已被详细阐明^[15]。

2.1.1 环辛二烯无含氧取代类

无含氧取代的化合物会产生C-6与C-7键或C-8与C-9键及联苯键断裂后重排氢, 或分子离子失去C-7、C-8及其取代基, 并进一步失去氢的产物, 这类化合物包括戈米辛J、戈米辛N、五味子酚、五味子甲素等。化合物83 (t_R 22.94 min, CCS 183.00 Å²) 的准分子离子峰m/z 401.196 5 [M+H]⁺, 通过与标准品比对确定该化合物为戈米辛N。在其MS²图中, 准分子离子会发生中性分子CH₃的连续丢失, 得到碎片离子m/z 386.170 0 [M+H-CH₃]⁺、371.179 4 [M+H-2CH₃]⁺、356.160 5 [M+H-3CH₃]⁺, 碎片离子m/z 293.117 7 [M+H-3OCH₃-CH₃]⁺推测是由准分子离子丢失CH₃及OCH₃得到, 此外, C-7、C-8及其基团的丢失产生碎片离子m/z 345.132 4 [M+H-C₄H₈]⁺, 联苯键及C-6与C-7键的断裂形成碎片离子m/z 221.093 4 [M+H-C₁₀H₁₂O₃]⁺。其裂解途径见图 4。化合物88 (t_R 24.57 min, CCS 186.62 Å²) 的准分子离子峰m/z 387.179 8 [M+H]⁺, 故推断其分子式为C₂₂H₂₆O₆。碎片离子m/z 372.155 6[M+H-CH₃]⁺、m/z 356.160 8 [M+H-OCH₃]⁺、m/z 341.136 9 [M+H-CH₃-OCH₃]⁺分别被推测为准分子离子丢失CH₃、OCH₃得到, 此外, 准分子离子丢失C-7、C-8及其基团后再失去一分子OCH₃得到碎片m/z 300.097 4 [M+H-C₄H₈-OCH₃]⁺, 化合物联苯键及C-6与C-7间键的断裂从而产生特征碎片m/z 165.068 7 [M+H-C₁₃H₁₈O₃]⁺。根据裂解行为及数据库对比, 推断其为(-)-gomisin L或其同分异构体(图 4)。

2.1.2 C-7位有羟基取代

C-7位的羟基使化合物较难发生联苯键断裂, 分子离子可能会裂解失去C-7、C-8和C-6或C-9及其取代基, 如戈米辛H、当归酰戈米辛H、五味子醇甲、五味子醇乙等。化合物38 (t_R 14.60 min, CCS 189.94 Å²) 的准分子离子峰m/z 419.205 0 [M+H]⁺, 通过与标准品比对确定该化合物为戈米辛H。在其MS²图中, 准分子离子容易发生连续丢失中性分子H₂O、CH₃等得到碎片离子m/z 401.196 1 [M+H-H₂O]⁺、m/z 386.172 6 [M+H-H₂O-CH₃]⁺, 此外, 准分子离子裂解失去C-7、C-8以及C-6或C-9得到产物离子m/z 333.127 9 [M+H-C₅H₁₀O]⁺, 该碎片离子继续裂解丢失中性分子H₂O得到碎片离子m/z 315.120 5 [M+H-C₅H₁₀O-H₂O]⁺。化合物58 (t_R 17.52 min, CCS 187.91 Å²) 的准分子离子峰m/z 433.218 4 [M+H]⁺, 通过与标准品比对确定该化合物为五味子醇甲。在其MS²图中, 准分子离子同样为一系列中性分子如H₂O、CH₃的丢失, 得到碎片离子m/z 415.211 0 [M+H-H₂O]⁺, m/z 400.187 4 [M+H-H₂O-CH₃]⁺, 准分子离子重排后分别丢失CH₃CO+CH₃、CH₃COCHCH₃、CH₃CO+CH₃O得到碎片离子m/z 374.165 8、361.161 2、358.139 0, 此外八元环裂解产生五元环碎片m/z 348.149 5 [M+H-C₅H₁₀O]⁺ (图 4)。

2.1.3 6, 7-二羟基化合物及其酯类

本研究所鉴定的该类化合物均为C-6位酰氧基取代及C-7位羟基取代, 例如五味子酯甲、五味子酯乙、戈米辛G等, 裂解时, C-6位酰氧基及另一氢原子会消除得到m/z 414的离子, 进一步裂解失去CH₃CO得到m/z 371的离子, 或失去CH₃COCHCH₃ (或同时失氢) 得到m/z 343 (342) 的离子。化合物96 (t_R 28.50 min, CCS 205.57 Å²) 的准分子离子峰m/z 537.209 4 [M+H]⁺, 通过与标准品比对确定该化合物为五味子酯甲。在其MS²图中, 基峰离子容易丢失酰氧基团得到碎片m/z 416.179 5 [M+H-C₇H₅O₂]⁺, 碎片离子m/z 414.164 2、m/z 371.147 9、m/z 343.115 6、m/z 342.109 1分别通过上述途径得到, m/z 342.109 0继续丢失2分子CH₃得到离子m/z 312.098 2 (图 4)。依据该类化合物裂解规律, 化合物94 (t_R 27.13 min, CCS 206.34 Å²) 的准分子离子峰m/z 537.209 9 [M+H]⁺, 故推断其分子式为C₃₀H₃₂O₉。该化合物具有一系列类似的碎片离子m/z 416.177 6、m/z 371.147 9、m/z 342.109 5、m/z 312.097 4等, 根据裂解行为及数据库对比, 推断该化合物为五味子酯甲的同分异构体。

2.1.4 十一元环内酯类

以戈米辛D为例, 该化合物由于C-7位存在羟基, 因此会发生与2.1.2中类似的裂解途径。化合物64 (t_R 18.61 min, CCS 206.17 Å²) 的准分子离子峰m/z 531.221 2 [M+H]⁺, 通过与标准品比对确定该化合物为戈米辛D。该类化合物会失环得到碎片离子m/z 401.159 1 [M+H-C₆H₁₀O₃]⁺, 此外, 基峰离子重排后分别失去CH₃CO及CH₃COCHCH₃得到产物离子碎片m/z 357.132 9及m/z 329.099 1, 其裂解途径见图 5。

2.1.5 四氢呋喃类

四氢呋喃类化合物主要包括两种裂解途径, 即四氢呋喃环上的取代基断裂和脱氢裂解后得到芳香性的呋喃型离子以及四氢呋喃环单键断裂引起环开裂^[16]。化合物66 (t_R 18.90 min, CCS 172.62 Å²) 的准分子离子峰m/z 341.137 2 [M+H]⁺, 故推断其分子式为C₂₀H₂₀O₅。根据该类化合物裂解规律, 碎片离子m/z 219.100 2 [M+H-C₇H₅O₂]⁺被推断为准分子离子丢失呋喃环上基团得到, 碎片离子m/z 122.036 1则为呋喃环上丢失的基团, 随后呋喃环丢失一分子CH₃得到碎片离子m/z 205.083 5 [M+H-C₇H₅O₂-CH₃]⁺, 此外, 呋喃环会发生开环裂解得到碎片m/z 287.089 4 [M+H-C₄H₈]⁺。通过与文献中同类化合物及自建数据库对比, 推断该化合物为D-epigalbacin或其同分异构体^[16] (图 5)。

2.2 萜类化合物鉴定

降三萜类是从五味子水煎液中发现最多的一类化合物, 这是一类结构新奇、高度氧化且骨架重排脱去不同位置的C形成的三萜类化合物, 具有抗氧化、抗HIV、抗炎、抗肿瘤等作用^{[17, 18]}。在碰撞诱导解离时, 萜类化合物主要发生中性分子如H₂O等以及内酯环中的断裂损失CH₂COO等^{[5, 19]}。以化合物13 (t_R 10.42 min, CCS 211.64 Å²) 的准分子离子峰m/z 561.232 9 [M+H]⁺, 故推断其分子式为C₂₉H₃₆O₁₁。其碎片离子m/z 543.225 9及m/z 507.203 3被推测为准分子离子分别丢失一分子或3分子H₂O得到, 此外, 该类化合物会发生内酯环断裂丢失一分子CH₂COO, 特征碎片离子m/z 485.213 0 [M+H-CH₂COO-H₂O]⁺被推测为准分子内酯环裂解后丢失一分子H₂O所得。通过该类化合物裂解规律及与自建数据库对比, 推断该化合物为schicagenin B或其同分异构体^[20] (图 5)。

2.3 有机酸类化合物鉴定

有机酸类化合物的二级质谱裂解模式主要包括失去苯环取代基、脱羧、脱水及碳链碎裂等。本研究仅确定一种有机酸类化合物2 (t_R 3.41 min, CCS 158.79 Å²), 其准分子离子为m/z 153.018 2 [M-H]^-, 通过标准品对比确定该化合物为原儿茶酸, 在负离子模式下丢失苯环取代基得到特征碎片离子m/z 109.028 8 [M-H-COOH]^- (图 5)。

2.4 其他类型化合物

本实验共鉴定或推导出6种其他类型化合物, 包括5种苷类及1种黄酮类(芦丁)。

3 HDDIDDA采集优势分析

鉴于HDMS^E与HDDDA的各自优势, 在本工作中, 首先利用UNIFI软件对所采集到的HDDDA数据进行处理, 通过手动去重复剔除假阳性离子, 最终共鉴定出84种(47种萜类、33种木脂素类、2种苷类、1种倍半萜类、1种黄酮类) 具有较高质量MS²谱图的化合物, 其余21种由HDMS^E处理后补充得到。显然, 这种组合扫描技术不仅丰富了HDDDA数据, 并且提供了与化合物结构相关的CCS值等信息, 为五味子中大量共洗脱化合物及同分异构体化合物及的区分提供了有效参考。例如, 保留时间为11.9、15.0、18.9 min的共洗脱化合物以及m/z为387.17、431.20、545.23的同分异构体被IM显著分离(图 6A、B), 这在复杂中药多组分表征方面具备独特的优势。此外, 本研究基于机器学习算法结合一体化CCS信息数据库(https://CCSbase.net)^[21], 选择了4对同分异构体化合物进行CCS值预测与异构体匹配, 如图 6C所示, 选定的异构体∆CCS均小于4%, 这些例子表明, 在缺乏足够对照品的情况下, CCS值的应用能够用于进一步筛选和区分目标化合物, 但同时, 这一策略的准确性仍需要进一步验证。

讨论

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本研究基于UHPLC/IM-QTOF-MS联合HDDIDDA组合式扫描技术, 共鉴定或推导出五味子水煎液中105种化学成分, 包括56种萜类, 42种木脂素类, 5种苷类, 1种有机酸类以及1种黄酮类, 与常规策略相比, 所建立的HDDIDDA扫描方法能够提供高覆盖度及高质量的MS²谱, 计算机辅助及智能峰注解流程显著提高了分析效率, 此外, IM分离赋予的CCS值等信息为同分异构体及共流出成分的区分提供了有效参考。

与先前的五味子醇提物化学成分类别不同的是, 五味子水煎液中降三萜类化合物在数量上略多于联苯环辛烯型木脂素类化合物, 这可能与不同类别化合物的极性大小密切相关, 降三萜类化合物通常具有内酯环及羟基取代, 这使得该类化合物具有较大的极性, 因此, 更容易在水煎液中溶出, 当然, 这一结果也可能与化合物含量有关。此外, 五味子不同溶剂提取物药理活性也有所差异, 相关研究表明, 在五味子分级组分中, 五味子水提物重量占比高于醇提物, 醇提物抑制自由基活性高于水提物, 而水提物则具有镇静催眠的活性^[22]。临床常用的五味子颗粒(水煎液)、五味子糖浆(30%乙醇提取物) 被用于治疗心肾不足所致的失眠、多梦、头晕、神经衰弱症等, 而参芪五味子片、参芪五味子胶囊、参芪五味子颗粒(60%乙醇提取物) 则被用于气血不足、心脾两虚所致的失眠、多梦、健忘等^[1], 由于木脂素类化合物主要具有保肝、抗肿瘤、抗病毒、抗氧化和神经保护等作用, 降三萜类化合物则主要具有抗HIV、抗病毒、抗炎、抗肿瘤等作用, 因此, 这种化学组成的差异也从一方面阐释了五味子醇提物和水提物药理活性差异的潜在机制, 这提示着, 临床在使用五味子相关药物时应当根据疾病类型或症型合理选择, 以期达到更加理想的治疗效果。

目前, 五味子相关药理活性或新药开发研究仍大多基于木脂素类, 而对降三萜类关注较少, 这类新型骨架三萜类化合物为治疗艾滋病的药物提供了新的天然产物结构, 对于进一步结构修饰或先导药物的开发具有重要意义, 因此, 通过本实验结果, 有必要对降三萜类化合物做进一步研究, 以全面阐释五味子药效物质基础。

作者贡献: 本文由洪莉丽、王洪达负责实验实施、论文撰写与修改; 徐晓艳、胡万弟、刘靖源参与数据处理; 王小莹、高秀梅、杨文志负责实验思路设计、稿件修改等工作。

利益冲突: 本文的作者和所涉及的内容不存在潜在的利益冲突。

基金

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国家自然科学基金重大项目(82192914)
国家中医药管理局中医药创新团队及人才支持计划项目(ZYYCXTD-C-202009)

参考文献

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参考文献引证文献

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2024年第59卷第3期

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doi: 10.16438/j.0513-4870.2023-0726

接收时间：2023-06-08
首发时间：2025-11-28
出版时间：2024-03-12

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收稿日期：2023-06-08
修回日期：2023-07-29

基金

国家自然科学基金重大项目(82192914)

国家中医药管理局中医药创新团队及人才支持计划项目(ZYYCXTD-C-202009)

作者信息

天津中医药大学, 组分中药国家重点实验室, 天津 301617

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^*杨文志, Tel: 17602666784, E-mail: wzyang0504@tjutcm.edu.cn

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2种不同金属材料的力学参数

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

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No.	t_R /min	Observed m/z	Adduct	Formula	Mass error /×10^-6	Observed CCS/Å²	Type	Fragment ion	Identification	HDMS^E	HDDDA
1	2.08	527.089 0	[M-H]^-	C₁₈H₂₄O₁₈	0.02	194.08	Glycoside	473.078 2, 421.103 7, 253.097 3, 165.079 1	4-Deoxy-β-L-threo-hex-4-enopyranuronosyl-(1- > 4)-α-D-galactopyranuronosyl-(1- > 4)-D-galactopyranuronic acid or isomer	√	√
2^*	3.41	153.018 2	[M-H]^-	C₇H₄O₄	-0.23	158.79	Organic acid	109.028 8	Protocatechuic acid	√
3	5.77	327.143 6	[M-H]^-	C₁₆H₂₄O₇	-4.12	188.05	Glycoside	272.088 9, 134.036 9	Thymoquinol 5-O-β-D-glucopyranoside or isomer	√
4	6.33	327.144 4	[M-H]^-	C₁₆H₂₄O₇	-1.49	185.24	Glycoside	161.024 1, 149.060 6	Thymoquinol 5-O-β-D-glucopyranoside or isomer	√
5	6.81	713.302 8	[M+H]⁺	C₃₄H₄₈O₁₆	1.85	173.65	Lignan	375.170 0, 165.066 0	1, 2, 13, 14-Tetramethoxydibenzo-cyclooctadiene 3, 12-O-β-D-diglucopyranoside or isomer	√
6^*	7.52	609.146 3	[M-H]^-	C₂₇H₃₀O₁₆	0.31	223.02	Flavonoid	301.033 9, 271.024 3, 255.028 7, 243.031 6, 227.031 9	Rutin	√	√
7	7.65	565.228 4	[M-H]^-	C₂₈H₃₈O₁₂	-1.20	237.91	Lignan	373.138 8	3, 7-Dihydroxy-1, 2, 13, 14-tetramethoxydibenzo-cyclooctadiene 12-O-β-D-glucopyranoside or isomer	√
8	7.85	463.087 9	[M-H]^-	C₂₁H₂₀O₁₂	-0.65	192.51	Glycoside	301.034 1, 271.022 8, 255.029 0, 243.027 4, 151.002 8	Hyperoside or isomer	√	√
9	8.48	473.202 4	[M-H]^-	C₂₂H₃₄O₁₁	-0.92	216.55	Glycoside	313.107 8, 271.024 5, 223.153 1	Schisandenoid A or isomer	√
10	8.93	565.229 6	[M-H]^-	C₂₈H₃₈O₁₂	0.94	229.49	Lignan	341.102 5, 326.078 0	3, 7-Dihydroxy-1, 2, 13, 14-tetramethoxydibenzo-cyclooctadiene 12-O-β-D-glucopyranoside or isomer	√	√
11	9.99	575.212 8	[M-H]^-	C₂₉H₃₆O₁₂	-1.09	209.75	Terpenoid	557.194 8, 497.185 7, 482.194 0, 453.192 7	Arisanlactone B or isomer	√	√
12	10.41	577.228 9	[M+H]⁺	C₂₉H₃₆O₁₂	1.60	213.53	Terpenoid	543.225 9, 485.213 1	Micradilactone A or isomer	√	√
13	10.42	561.232 9	[M+H]⁺	C₂₉H₃₆O₁₁	-0.18	211.64	Terpenoid	543.225 9, 507.203 3, 485.213 0	Schicagenin B or isomer	√
14	10.70	497.219 5	[M-H]^-	C₂₈H₃₄O₈	2.77	214.37	Lignan	387.136 9	Angeloylisogomisin O or isomer	√
15	10.89	559.218 7	[M-H]^-	C₂₉H₃₆O₁₁	0.30	209.42	Terpenoid	541.214 4, 465.152 1, 403.149 7, 383.145 1	Schindilactone C or isomer	√	√
16	11.14	561.233 2	[M+H]⁺	C₂₉H₃₆O₁₁	0.28	212.18	Terpenoid	543.219 3, 439.205 0, 425.176 4, 407.209 8	Schicagenin B or isomer	√	√
17	11.47	543.223 2	[M-H]^-	C₂₉H₃₆O₁₀	-0.70	222.66	Terpenoid	527.226 1, 473.247 7	Pre-schisanartanin N or isomer	√	√
18	11.51	527.226 2	[M+H]⁺	C₂₉H₃₄O₉	-2.49	206.62	Terpenoid	467.206 4, 419.185 0, 203.104 9, 185.094 6	Lancifodilactone D or isomer	√	√
19	11.63	549.232 7	[M+H]⁺	C₂₈H₃₆O₁₁	-0.62	216.71	Terpenoid	479.207 5, 387.179 5, 355.153 2	19(R)-Hydroxyl-wuweizidilactone H or isomer	√	√
20	11.75	559.218 5	[M-H]^-	C₂₉H₃₆O₁₁	-0.05	210.31	Terpenoid	469.222 6, 465.148 6, 413.197 5, 387.146 2, 347.157 5	Schicagenin B or isomer	√	√
21	11.82	543.223 5	[M-H]^-	C₂₉H₃₆O₁₀	-0.13	217.58	Terpenoid	463.211 7, 383.187 7, 365.196 6, 137.059 7	Pre-schisanartanin N or isomer	√	√
22	11.91	577.230 3	[M+H]⁺	C₂₉H₃₆O₁₂	4.10	215.81	Terpenoid	545.229 2, 525.181 0, 515.211 9, 495.204 6, 453.203 2	Arisanlactone B or isomer	√
23	12.09	559.218 3	[M-H]^-	C₂₉H₃₆O₁₁	-0.25	218.39	Terpenoid	497.217 5, 429.192 4	Schindilactone C	√	√
24	12.27	543.224 1	[M-H]^-	C₂₉H₃₆O₁₀	0.93	214.59	Terpenoid	483.135 8, 471.200 5, 463.208 3, 435.216 3	Pre-schisanartanin N or isomer	√	√
25	12.41	575.213 9	[M-H]^-	C₂₉H₃₆O₁₂	0.83	213.64	Terpenoid	515.191 9, 419.125 9, 413.161 4	Arisanlactone B or isomer	√	√
26	12.53	545.238 7	[M+H]⁺	C₂₉H₃₆O₁₀	1.05	211.05	Terpenoid	508.213 3, 451.215 6, 433.197 7, 391.175 5	Pre-schisanartanin N or isomer	√	√
27	12.84	527.227 5	[M+H]⁺	C₂₈H₃₆O₉	-1.50	209.72	Terpenoid	485.217 2, 453.222 8, 439.211 4, 423.221 8	Lancifodilactone D or isomer	√	√
28	13.17	561.233 2	[M+H]⁺	C₂₉H₃₆O₁₁	0.25	208.50	Terpenoid	527.222 3, 485.220 1, 467.207 1	Schindilactone C or isomer	√	√
29	13.42	515.228 6	[M-H]^-	C₂₈H₃₆O₉	-0.20	218.36	Terpenoid	437.203 4, 385.174 6	Wuweizidilactone N or isomer	√	√
30	13.70	417.192 1	[M+H]⁺	C₂₃H₂₈O₇	3.05	188.89	Lignan	385.169 1, 331.118 9, 315.080 0	Gomisin O or isomer	√	√
31	13.71	661.250 5	[M-H]^-	C₃₃H₄₂O₁₄	0.56	238.36	Terpenoid	369.137 8, 285.170 1	Schisandroside D or isomer	√
32	13.76	533.238 7	[M+H]⁺	C₂₈H₃₆O₁₀	1.03	213.75	Terpenoid	499.235 7, 479.204 3, 437.195 0	Wuweizidilactone H or isomer	√	√
33	13.88	369.168 8	[M+H]⁺	C₂₂H₂₄O₅	-2.31	181.98	Terpenoid	337.144 1, 323.130 5, 203.083 3	(8ξ, 14ξ)-17-Oxoestra-1, 3, 5(10), 9(11)-tetraene-3, 4-diyl diacetate or isomer	√	√
34	13.96	221.190 3	[M+H]⁺	C₁₅H₂₄O	1.26	150.76	Sesquiterpene	219.172 4, 189.125 6	α-Iso-cubebenol or isomer	√	√
35	14.13	545.239 2	[M+H]⁺	C₂₉H₃₆O₁₀	1.99	213.63	Terpenoid	485.217 6, 451.207 5, 433.203 2, 371.175 5	Pre-schisanartanin N or isomer	√	√
36	14.31	515.227 7	[M+H]⁺	C₂₈H₃₄O₉	0.19	210.80	Terpenoid	429.192 1, 401.196 0, 381.132 5	Wuweizidilactone O or isomer	√	√
37	14.41	545.238 1	[M+H]⁺	C₂₉H₃₆O₁₀	-0.08	207.63	Terpenoid	527.2327, 453.224 7, 437.230 9, 431.207 8	Pre-schisanartanin N or isomer	√	√
38^*	14.60	419.205 0	[M+H]⁺	C₂₃H₃₀O₇	-3.40	189.94	Lignan	401.196 1, 386.172 6, 333.127 9, 315.120 5	Gomisin H	√	√
39	14.76	529.243 3	[M+H]⁺	C₂₉H₃₆O₉	0.23	206.80	Terpenoid	509.215 7, 469.219 6, 449.196 5, 439.212 5, 421.201 3	Methyl acetoxyangolensate or isomer	√	√
40	14.84	517.244 1	[M+H]⁺	C₂₈H₃₆O₉	1.60	203.29	Terpenoid	499.233 5, 413.193 0, 343.117 4	Wuweizidilactone N or isomer	√	√
41	14.90	575.285 2	[M+H]⁺	C₃₁H₄₂O₁₀	0.21	221.29	Terpenoid	479.242 9, 437.232 3	Wuweizidilactone K or isomer	√	√
42	15.01	527.227 5	[M+H]⁺	C₂₉H₃₄O₉	-0.05	214.45	Terpenoid	509.222 2, 463.202 3, 449.193 9	Lancifodilactone D or isomer	√	√
43	15.06	417.191 1	[M+H]⁺	C₂₃H₂₈O₇	0.71	185.16	Lignan	386.173 4, 371.176 5	Gomisin O or isomer	√
44	15.09	557.202 5	[M-H]^-	C₃₁H₃₈O₁₀	-0.70	213.07	Terpenoid	513.214 2, 485.217 0, 481.150 8, 391.119 9, 365.139 1	Lancifodilactone N or isomer	√	√
45	15.28	387.179 9	[M+H]⁺	C₂₂H₂₆O₆	-0.86	188.43	Lignan	372.153 8, 356.161 8, 341.127 5, 300.096 5	(-)-Gomisin L or isomer	√	√
46	15.36	559.218 4	[M-H]^-	C₂₉H₃₆O₁₁	-0.08	209.30	Terpenoid	483.161 8, 457.191 1, 431.180 3, 413.195 2	Schindilactone C or isomer	√	√
47	15.61	545.237 9	[M+H]⁺	C₂₉H₃₆O₁₀	-0.43	216.79	Terpenoid	497.214 4, 463.212 4, 435.219 0, 391.181 7	Pre-schisanartanin N or isomer	√	√
48	15.77	527.228 2	[M-H]^-	C₂₉H₃₆O₉	-0.78	214.93	Terpenoid	497.218 2, 435.215 9, 407.183 7, 365.178 5	Wuweizidilactone L or isomer	√	√
49	15.98	515.229 6	[M-H]^-	C₂₈H₃₆O₉	1.75	211.39	Terpenoid	471.243 2, 411.182 1, 369.169 0	Wuweizidilactone N or isomer	√	√
50	16.03	415.211 7	[M+H]⁺	C₂₄H₃₀O₆	0.45	186.75	Terpenoid	385.194 5, 369.167 6, 353.170 6, 323.129 2, 165.064 3	Meprednisone acetate or isomer	√	√
51	16.09	527.229 0	[M+H]⁺	C₂₉H₃₄O₉	2.80	208.04	Terpenoid	483.236 5, 438.235 3, 423.211 6	Lancifodilactone D or isomer	√	√
52	16.26	529.242 9	[M+H]⁺	C₂₉H₃₆O₉	-0.50	210.27	Terpenoid	469.224 2, 451.213 5, 433.205 6	Methyl acetoxyangolensate or isomer	√	√
53	16.34	559.219 3	[M-H]^-	C₂₉H₃₆O₁₁	1.41	215.07	Terpenoid	499.195 6, 483.164 2, 457.187 5, 455.208 9, 399.179 4	Schicagenin B or isomer	√	√
54	16.52	527.228 6	[M+H]⁺	C₂₉H₃₄O₉	1.94	211.46	Terpenoid	483.205 1, 467.205 9, 455.240 1, 423.212 4	Lancifodilactone D or isomer	√	√
55	16.86	527.227 2	[M+H]⁺	C₂₉H₃₄O₉	-0.75	207.58	Terpenoid	473.209 3, 449.194 6	Lancifodilactone D or isomer	√	√
56	17.01	531.258 6	[M+H]⁺	C₂₉H₃₈O₉	-0.43	206.13	Terpenoid	513.242 4, 471.235 6, 435.219 0, 399.179 3	Pre-schisanartanin F or isomer	√	√
57	17.14	529.242 4	[M+H]⁺	C₂₉H₃₆O₉	-1.48	208.22	Terpenoid	453.218 2, 355.152 4, 299.090 2, 285.109 8	Pre-schisanartanin E or isomer	√
58^*	17.52	433.218 4	[M+H]⁺	C₂₄H₃₂O₇	-8.51	187.91	Lignan	415.211 0, 400.187 4, 374.165 8, 358.139 0, 361.161 2, 348.149 5	Schisandrol A	√	√
59	17.88	417.190 1	[M+H]⁺	C₂₃H₂₈O₇	-1.75	184.74	Lignan	373.165 0, 341.136 4, 329.100 7, 311.127 2	Gomisin O or isomer	√	√
60	18.10	615.280 7	[M+H]⁺	C₃₃H₄₂O₁₁	1.21	228.54	Terpenoid	597.274 6, 479.206 1, 437.197 5	Wuweizidilactone I or isomer	√
61	18.38	417.189 1	[M+H]⁺	C₂₃H₂₈O₇	-3.93	189.28	Lignan	370.180 1, 341.138 2, 331.106 9, 317.106 7	Gomisin O or isomer	√	√
62	18.45	657.290 4	[M+H]⁺	C₃₅H₄₄O₁₂	-0.25	236.73	Terpenoid	639.281 1, 479.205 5	Wuweizidilactone G or isomer	√	√
63	18.49	483.310 5	[M+H]⁺	C₃₀H₄₂O₅	0.00	210.35	Terpenoid	419.183 2, 377.119 9, 275.140 1, 151.053 0	Kadsuphilactone B or isomer
64^*	18.61	531.221 2	[M+H]⁺	C₂₈H₃₄O₁₀	-4.67	206.17	Lignan	401.159 1, 371.149 5, 357.132 9, 329.099 1	Gomisin D	√	√
65	18.69	481.293 8	[M+H]⁺	C₃₀H₄₀O₅	-2.18	206.91	Terpenoid	448.219 5, 417.284 9, 343.109 4	Schisanlactone C or isomer	√
66	18.90	341.137 2	[M+H]⁺	C₂₀H₂₀O₅	-3.27	172.62	Lignan	287.089 4, 219.100 2, 205.083 5, 122.036 1	D-Epigalbacin or isomer	√
67^*	18.93	389.194 8	[M+H]⁺	C₂₂H₂₈O₆	-2.83	180.02	Lignan	357.167 9, 325.141 9, 287.089 3, 227.068 9, 221.116 9	Gomisin J	√	√
68	19.16	587.250 3	[M-H]^-	C₂₉H₃₆O₉	0.90	229.45	Terpenoid	447.217 7, 403.225 6, 227.034 0	Pre-schisanartanin A or isomer	√	√
69	19.19	571.253 6	[M+H]⁺	C₃₁H₃₈O₁₀	-0.37	219.70	Terpenoid	511.233 5, 493.220 9, 469.222 3, 451.210 4	Wuweizidilactone M or isomer	√	√
70^*	19.42	399.179 5	[M-H₂O +H]⁺	C₂₃H₂₈O₇	-6.26	180.14	Lignan	369.167 8, 345.131 2, 329.100 7, 299.090 0, 285.074 0	Schisandrol B	√	√
71	19.57	589.264 9	[M-H]^-	C₃₁H₄₂O₁₁	-0.93	228.57	Terpenoid	467.241 6, 221.093 2	Pre-schisanartanin B or isomer	√	√
72	19.64	433.220 1	[M+H]⁺	C₂₄H₃₂O₇	-0.36	194.35	Lignan	415.211 1, 386.168 8, 339.121 8, 323.160 5	Schisandrin or isomer	√	√
73	19.83	401.158 3	[M+H]⁺	C₂₂H₂₄O₇	-2.95	182.28	Lignan	357.127 2, 341.101 3, 311.091 6, 299.089 2, 267.064 6	Methyl 2, 5-bis(3, 4-dimethoxyphenyl)-4, 5-dihydro-3-furancarboxylate or isomer	√	√
74	20.05	417.190 1	[M+H]⁺	C₂₃H₂₈O₇	-1.70	185.05	Lignan	401.196 4, 369.168 8, 339.121 8, 203.084 2	Gomisin O or isomer	√	√
75	20.23	387.180 5	[M-H]^-	C₂₂H₂₈O₆	-2.18	185.52	Lignan	341.139 1, 311.094 7, 275.066 7	Rubrisandrins A or isomer	√	√
76	20.59	531.222 6	[M-H]^-	C₂₈H₃₆O₁₀	-1.82	213.74	Terpenoid	401.159 1, 355.122 0, 341.098 3	Wuweizidilactone H or isomer	√	√
77	20.72	415.211 4	[M+H]⁺	C₂₄H₃₀O₆	-0.28	184.07	Terpenoid	385.195 3, 369.169 0, 353.174 9, 301.104 4	Meprednisone acetate or isomer	√	√
78	20.91	389.194 6	[M+H]⁺	C₂₂H₂₈O₆	-3.18	184.21	Lignan	374.164 0, 357.169 1, 341.135 9	Rubrisandrins A or isomer	√	√
79	21.17	515.227 2	[M+H]⁺	C₂₈H₃₄O₉	0.70	203.29	Terpenoid	469.223 6, 385.163 1, 355.153 2, 323.126 8	Wuweizidilactone O or isomer	√	√
80	21.34	389.194 0	[M+H]⁺	C₂₂H₂₈O₆	-4.72	183.08	Lignan	331.118 2, 235.074 2, 181.063 1	Rubrisandrins A or isomer	√	√
81	21.97	401.195 5	[M+H]⁺	C₂₃H₂₈O₆	-0.91	181.19	Lignan	370.177 4, 355.154 6, 323.127 2, 295.131 7, 165.066 0	Rubschisandrin or isomer	√	√
82^*	22.93	523.230 5	[M+Na]⁺	C₂₈H₃₆O₈	0.52	210.56	Lignan	431.205 9, 415.094 9, 356.160 5, 315.121 9, 267.099 7	Angeloylgomisin H	√
83^*	22.94	401.196 5	[M+H]⁺	C₂₃H₂₈O₆	-0.91	183.00	Lignan	386.170 0, 371.179 4, 356.160 5, 345.132 4, 221.093 4	Gomisin N	√	√
84	23.02	387.179 7	[M+H]⁺	C₂₂H₂₆O₆	-1.42	179.86	Lignan	372.157 5, 356.160 5, 327.121 1, 165.068 9	(-)-Gomisin L or isomer	√	√
85	23.49	415.174 1	[M+H]⁺	C₂₃H₂₆O₇	-2.49	180.88	Lignan	401.191 8, 355.145 0, 315.085 2, 181.063 8	Neoisostegane or isomer	√	√
86	24	433.212 4	[M+H]⁺	C₂₄H₃₂O₇	-1.23	189.16	Lignan	401.192 1, 387.180 9, 356.160 3, 341.137 6, 315.121 2	Schisandrin or isomer	√	√
87	24.03	341.136 8	[M+H]⁺	C₂₀H₂₀O₅	-4.60	168.22	Lignan	313.105 8, 285.110 3, 251.069 3, 165.068 2	Maceneolignan E or isomer	√	√
88	24.57	387.179 8	[M+H]⁺	C₂₄H₃₀O₇	-1.70	186.62	Lignan	372.155 6, 356.160 8, 341.136 9, 300.097 4, 165.068 7	(-)-Gomisin L or isomer	√	√
89^*	25.35	537.209 4	[M+H]⁺	C₃₀H₃₂O₉	-7.40	207.69	Lignan	416.176 6, 414.166 9, 371.149 2, 343.115 0, 285.073 8	Gomisin G	√
90	25.39	519.201 1	[M+H]⁺	C₃₀H₃₀O₈	-0.50	209.44	Lignan	415.173 9, 343.115 0, 219.079 6, 181.064 1	Schisanchinin A or isomer	√
91	25.70	483.309 8	[M+H]⁺	C₃₀H₄₂O₅	-1.49	207.08	Terpenoid	343.108 1, 253.129 1, 167.048 3	Henrischinin C or isomer	√
92	25.82	537.210 1	[M+H]⁺	C₃₀H₃₂O₉	-3.38	205.95	Lignan	416.176 4, 414.166 9, 371.148 5, 343.115 5, 312.098 5	Isomer of schisantherin A	√
93	26.42	403.210 7	[M+H]⁺	C₂₃H₃₀O₆	-2.03	185.97	Lignan	371.176 8, 341.137 3, 301.105 8, 287.090 5	Gomisin K2 or isomer	√	√
94	27.13	537.209 9	[M+H]⁺	C₃₀H₃₂O₉	-3.70	206.34	Lignan	416.177 0, 371.147 9, 343.115 1, 312.097 4	Isomer of schisantherin A	√	√
95	28.05	519.202 4	[M+H]⁺	C₃₀H₃₀O₈	1.94	207.95	Lignan	414.166 8, 398.170 6, 343.115 3, 285.073 8	Schisanchinin A or isomer	√
96^*	28.50	537.209 4	[M+H]⁺	C₃₀H₃₂O₉	-4.58	205.57	Lignan	416.179 5, 414.164 5, 371.148 3, 343.115 6, 312.098 2	Schisantherin A	√
97^*	28.51	553.184 3	[M+K]⁺	C₂₈H₃₄O₉	1.67	206.04	Lignan	416.179 4, 414.164 5, 371.148 3, 343.115 6	Schisantherin B	√
98^*	29.06	403.210 5	[M+H]⁺	C₂₃H₃₀O₆	-2.52	191.01	Lignan	357.167 8, 325.141 9, 301.106 7	Schisanhenol	√	√
99	31.15	415.210 4	[M+H]⁺	C₂₄H₃₀O₆	-2.69	188.75	Terpenoid	385.196 1, 369.168 5, 353.173 5, 323.126 9	Meprednisone acetate or isomer	√	√
100	32.12	415.210 5	[M+H]⁺	C₂₄H₃₀O₆	-2.45	187.92	Terpenoid	385.197 0, 369.168 6, 353.174 5, 323.126 6	Meprednisone acetate or isomer	√	√
101	35.48	399.178 4	[M+H]⁺	C₂₃H₂₆O₆	-4.56	184.94	Lignan	371.176 7, 301.105 7, 165.068 1	Allyl 2-O-benzoyl-3-O-benzyl-6-deoxy-α-L-mannopyranoside or isomer	√	√
102	37.35	417.226 3	[M+H]⁺	C₂₄H₃₂O₆	-2.08	190.55	Lignan	402.202 2, 387.179 2, 347.148 0, 301.105 9, 241.084 6	Schisandrin A or isomer	√	√
103	39.86	483.236 9	[M+H]⁺	C₂₈H₃₄O₇	-1.72	198.54	Terpenoid	453.216 1, 401.190 5, 323.124 4	Gedunin or isomer	√	√
104	40.26	401.194 5	[M+H]⁺	C₂₃H₂₈O₆	-3.41	186.38	Lignan	386.171 9, 331.114 8, 301.105 5, 285.075 3, 227.068 2	Schisandrin B or isomer	√	√
105	40.73	401.195 1	[M+H]⁺	C₂₃H₂₈O₆	-1.91	184.74	Lignan	386.171 0, 331.117 0, 301.103 7	Schisandrin B or isomer	√	√

No.

t_R /min

Observed m/z

Adduct

Formula

Mass error /×10^-6

Observed
CCS/Å²

Type

Fragment ion

Identification

HDMS^E

HDDDA

2.08

527.089 0

[M-H]^-

C₁₈H₂₄O₁₈

0.02

194.08

Glycoside

473.078 2, 421.103 7, 253.097 3, 165.079 1

4-Deoxy-β-L-threo-hex-4-enopyranuronosyl-(1- > 4)-α-D-galactopyranuronosyl-(1- > 4)-D-galactopyranuronic acid or isomer

√

2^*

3.41

153.018 2

[M-H]^-

C₇H₄O₄

-0.23

158.79

Organic acid

109.028 8

Protocatechuic acid

√

5.77

327.143 6

[M-H]^-

C₁₆H₂₄O₇

-4.12

188.05

Glycoside

272.088 9, 134.036 9

Thymoquinol 5-O-β-D-glucopyranoside or isomer

√

6.33

327.144 4

[M-H]^-

C₁₆H₂₄O₇

-1.49

185.24

Glycoside

161.024 1, 149.060 6

Thymoquinol 5-O-β-D-glucopyranoside or isomer

√

6.81

713.302 8

[M+H]⁺

C₃₄H₄₈O₁₆

1.85

173.65

Lignan

375.170 0, 165.066 0

1, 2, 13, 14-Tetramethoxydibenzo-cyclooctadiene 3, 12-O-β-D-diglucopyranoside or isomer

√

6^*

7.52

609.146 3

[M-H]^-

C₂₇H₃₀O₁₆

0.31

223.02

Flavonoid

301.033 9, 271.024 3, 255.028 7, 243.031 6, 227.031 9

Rutin

√

7.65

565.228 4

[M-H]^-

C₂₈H₃₈O₁₂

-1.20

237.91

Lignan

373.138 8

3, 7-Dihydroxy-1, 2, 13, 14-tetramethoxydibenzo-cyclooctadiene 12-O-β-D-glucopyranoside or isomer

√

7.85

463.087 9

[M-H]^-

C₂₁H₂₀O₁₂

-0.65

192.51

Glycoside

301.034 1, 271.022 8, 255.029 0, 243.027 4, 151.002 8

Hyperoside or isomer

√

8.48

473.202 4

[M-H]^-

C₂₂H₃₄O₁₁

-0.92

216.55

Glycoside

313.107 8, 271.024 5, 223.153 1

Schisandenoid A or isomer

√

8.93

565.229 6

[M-H]^-

C₂₈H₃₈O₁₂

0.94

229.49

Lignan

341.102 5, 326.078 0

3, 7-Dihydroxy-1, 2, 13, 14-tetramethoxydibenzo-cyclooctadiene 12-O-β-D-glucopyranoside or isomer

√

9.99

575.212 8

[M-H]^-

C₂₉H₃₆O₁₂

-1.09

209.75

Terpenoid

557.194 8, 497.185 7, 482.194 0, 453.192 7

Arisanlactone B or isomer

√

10.41

577.228 9

[M+H]⁺

C₂₉H₃₆O₁₂

1.60

213.53

Terpenoid

543.225 9, 485.213 1

Micradilactone A or isomer

√

10.42

561.232 9

[M+H]⁺

C₂₉H₃₆O₁₁

-0.18

211.64

Terpenoid

543.225 9, 507.203 3, 485.213 0

Schicagenin B or isomer

√

10.70

497.219 5

[M-H]^-

C₂₈H₃₄O₈

2.77

214.37

Lignan

387.136 9

Angeloylisogomisin O or isomer

√

10.89

559.218 7

[M-H]^-

C₂₉H₃₆O₁₁

0.30

209.42

Terpenoid

541.214 4, 465.152 1, 403.149 7, 383.145 1

Schindilactone C or isomer

√

11.14

561.233 2

[M+H]⁺

C₂₉H₃₆O₁₁

0.28

212.18

Terpenoid

543.219 3, 439.205 0, 425.176 4, 407.209 8

Schicagenin B or isomer

√

11.47

543.223 2

[M-H]^-

C₂₉H₃₆O₁₀

-0.70

222.66

Terpenoid

527.226 1, 473.247 7

Pre-schisanartanin N or isomer

√

11.51

527.226 2

[M+H]⁺

C₂₉H₃₄O₉

-2.49

206.62

Terpenoid

467.206 4, 419.185 0, 203.104 9, 185.094 6

Lancifodilactone D or isomer

√

11.63

549.232 7

[M+H]⁺

C₂₈H₃₆O₁₁

-0.62

216.71

Terpenoid

479.207 5, 387.179 5, 355.153 2

19(R)-Hydroxyl-wuweizidilactone H or isomer

√

11.75

559.218 5

[M-H]^-

C₂₉H₃₆O₁₁

-0.05

210.31

Terpenoid

469.222 6, 465.148 6, 413.197 5, 387.146 2, 347.157 5

Schicagenin B or isomer

√

11.82

543.223 5

[M-H]^-

C₂₉H₃₆O₁₀

-0.13

217.58

Terpenoid

463.211 7, 383.187 7, 365.196 6, 137.059 7

Pre-schisanartanin N or isomer

√

11.91

577.230 3

[M+H]⁺

C₂₉H₃₆O₁₂

4.10

215.81

Terpenoid

545.229 2, 525.181 0, 515.211 9, 495.204 6, 453.203 2

Arisanlactone B or isomer

√

12.09

559.218 3

[M-H]^-

C₂₉H₃₆O₁₁

-0.25

218.39

Terpenoid

497.217 5, 429.192 4

Schindilactone C

√

12.27

543.224 1

[M-H]^-

C₂₉H₃₆O₁₀

0.93

214.59

Terpenoid

483.135 8, 471.200 5, 463.208 3, 435.216 3

Pre-schisanartanin N or isomer

√

12.41

575.213 9

[M-H]^-

C₂₉H₃₆O₁₂

0.83

213.64

Terpenoid

515.191 9, 419.125 9, 413.161 4

Arisanlactone B or isomer

√

12.53

545.238 7

[M+H]⁺

C₂₉H₃₆O₁₀

1.05

211.05

Terpenoid

508.213 3, 451.215 6, 433.197 7, 391.175 5

Pre-schisanartanin N or isomer

√

12.84

527.227 5

[M+H]⁺

C₂₈H₃₆O₉

-1.50

209.72

Terpenoid

485.217 2, 453.222 8, 439.211 4, 423.221 8

Lancifodilactone D or isomer

√

13.17

561.233 2

[M+H]⁺

C₂₉H₃₆O₁₁

0.25

208.50

Terpenoid

527.222 3, 485.220 1, 467.207 1

Schindilactone C or isomer

√

13.42

515.228 6

[M-H]^-

C₂₈H₃₆O₉

-0.20

218.36

Terpenoid

437.203 4, 385.174 6

Wuweizidilactone N or isomer

√

13.70

417.192 1

[M+H]⁺

C₂₃H₂₈O₇

3.05

188.89

Lignan

385.169 1, 331.118 9, 315.080 0

Gomisin O or isomer

√

13.71

661.250 5

[M-H]^-

C₃₃H₄₂O₁₄

0.56

238.36

Terpenoid

369.137 8, 285.170 1

Schisandroside D or isomer

√

13.76

533.238 7

[M+H]⁺

C₂₈H₃₆O₁₀

1.03

213.75

Terpenoid

499.235 7, 479.204 3, 437.195 0

Wuweizidilactone H or isomer

√

13.88

369.168 8

[M+H]⁺

C₂₂H₂₄O₅

-2.31

181.98

Terpenoid

337.144 1, 323.130 5, 203.083 3

(8ξ, 14ξ)-17-Oxoestra-1, 3, 5(10), 9(11)-tetraene-3, 4-diyl diacetate or isomer

√

13.96

221.190 3

[M+H]⁺

C₁₅H₂₄O

1.26

150.76

Sesquiterpene

219.172 4, 189.125 6

α-Iso-cubebenol or isomer

√

14.13

545.239 2

[M+H]⁺

C₂₉H₃₆O₁₀

1.99

213.63

Terpenoid

485.217 6, 451.207 5, 433.203 2, 371.175 5

Pre-schisanartanin N or isomer

√

14.31

515.227 7

[M+H]⁺

C₂₈H₃₄O₉

0.19

210.80

Terpenoid

429.192 1, 401.196 0, 381.132 5

Wuweizidilactone O or isomer

√

14.41

545.238 1

[M+H]⁺

C₂₉H₃₆O₁₀

-0.08

207.63

Terpenoid

527.2327, 453.224 7, 437.230 9, 431.207 8

Pre-schisanartanin N or isomer

√

38^*

14.60

419.205 0

[M+H]⁺

C₂₃H₃₀O₇

-3.40

189.94

Lignan

401.196 1, 386.172 6, 333.127 9, 315.120 5

Gomisin H

√

14.76

529.243 3

[M+H]⁺

C₂₉H₃₆O₉

0.23

206.80

Terpenoid

509.215 7, 469.219 6, 449.196 5, 439.212 5, 421.201 3

Methyl acetoxyangolensate or isomer

√

14.84

517.244 1

[M+H]⁺

C₂₈H₃₆O₉

1.60

203.29

Terpenoid

499.233 5, 413.193 0, 343.117 4

Wuweizidilactone N or isomer

√

14.90

575.285 2

[M+H]⁺

C₃₁H₄₂O₁₀

0.21

221.29

Terpenoid

479.242 9, 437.232 3

Wuweizidilactone K or isomer

√

15.01

527.227 5

[M+H]⁺

C₂₉H₃₄O₉

-0.05

214.45

Terpenoid

509.222 2, 463.202 3, 449.193 9

Lancifodilactone D or isomer

√

15.06

417.191 1

[M+H]⁺

C₂₃H₂₈O₇

0.71

185.16

Lignan

386.173 4, 371.176 5

Gomisin O or isomer

√

15.09

557.202 5

[M-H]^-

C₃₁H₃₈O₁₀

-0.70

213.07

Terpenoid

513.214 2, 485.217 0, 481.150 8, 391.119 9, 365.139 1

Lancifodilactone N or isomer

√

15.28

387.179 9

[M+H]⁺

C₂₂H₂₆O₆

-0.86

188.43

Lignan

372.153 8, 356.161 8, 341.127 5, 300.096 5

(-)-Gomisin L or isomer

√

15.36

559.218 4

[M-H]^-

C₂₉H₃₆O₁₁

-0.08

209.30

Terpenoid

483.161 8, 457.191 1, 431.180 3, 413.195 2

Schindilactone C or isomer

√

15.61

545.237 9

[M+H]⁺

C₂₉H₃₆O₁₀

-0.43

216.79

Terpenoid

497.214 4, 463.212 4, 435.219 0, 391.181 7

Pre-schisanartanin N or isomer

√

15.77

527.228 2

[M-H]^-

C₂₉H₃₆O₉

-0.78

214.93

Terpenoid

497.218 2, 435.215 9, 407.183 7, 365.178 5

Wuweizidilactone L or isomer

√

15.98

515.229 6

[M-H]^-

C₂₈H₃₆O₉

1.75

211.39

Terpenoid

471.243 2, 411.182 1, 369.169 0

Wuweizidilactone N or isomer

√

16.03

415.211 7

[M+H]⁺

C₂₄H₃₀O₆

0.45

186.75

Terpenoid

385.194 5, 369.167 6, 353.170 6, 323.129 2, 165.064 3

Meprednisone acetate or isomer

√

16.09

527.229 0

[M+H]⁺

C₂₉H₃₄O₉

2.80

208.04

Terpenoid

483.236 5, 438.235 3, 423.211 6

Lancifodilactone D or isomer

√

16.26

529.242 9

[M+H]⁺

C₂₉H₃₆O₉

-0.50

210.27

Terpenoid

469.224 2, 451.213 5, 433.205 6

Methyl acetoxyangolensate or isomer

√

16.34

559.219 3

[M-H]^-

C₂₉H₃₆O₁₁

1.41

215.07

Terpenoid

499.195 6, 483.164 2, 457.187 5, 455.208 9, 399.179 4

Schicagenin B or isomer

√

16.52

527.228 6

[M+H]⁺

C₂₉H₃₄O₉

1.94

211.46

Terpenoid

483.205 1, 467.205 9, 455.240 1, 423.212 4

Lancifodilactone D or isomer

√

16.86

527.227 2

[M+H]⁺

C₂₉H₃₄O₉

-0.75

207.58

Terpenoid

473.209 3, 449.194 6

Lancifodilactone D or isomer

√

17.01

531.258 6

[M+H]⁺

C₂₉H₃₈O₉

-0.43

206.13

Terpenoid

513.242 4, 471.235 6, 435.219 0, 399.179 3

Pre-schisanartanin F or isomer

√

17.14

529.242 4

[M+H]⁺

C₂₉H₃₆O₉

-1.48

208.22

Terpenoid

453.218 2, 355.152 4, 299.090 2, 285.109 8

Pre-schisanartanin E or isomer

√

58^*

17.52

433.218 4

[M+H]⁺

C₂₄H₃₂O₇

-8.51

187.91

Lignan

415.211 0, 400.187 4, 374.165 8, 358.139 0, 361.161 2, 348.149 5

Schisandrol A

√

17.88

417.190 1

[M+H]⁺

C₂₃H₂₈O₇

-1.75

184.74

Lignan

373.165 0, 341.136 4, 329.100 7, 311.127 2

Gomisin O or isomer

√

18.10

615.280 7

[M+H]⁺

C₃₃H₄₂O₁₁

1.21

228.54

Terpenoid

597.274 6, 479.206 1, 437.197 5

Wuweizidilactone I or isomer

√

18.38

417.189 1

[M+H]⁺

C₂₃H₂₈O₇

-3.93

189.28

Lignan

370.180 1, 341.138 2, 331.106 9, 317.106 7

Gomisin O or isomer

√

18.45

657.290 4

[M+H]⁺

C₃₅H₄₄O₁₂

-0.25

236.73

Terpenoid

639.281 1, 479.205 5

Wuweizidilactone G or isomer

√

18.49

483.310 5

[M+H]⁺

C₃₀H₄₂O₅

0.00

210.35

Terpenoid

419.183 2, 377.119 9, 275.140 1, 151.053 0

Kadsuphilactone B or isomer

64^*

18.61

531.221 2

[M+H]⁺

C₂₈H₃₄O₁₀

-4.67

206.17

Lignan

401.159 1, 371.149 5, 357.132 9, 329.099 1

Gomisin D

√

18.69

481.293 8

[M+H]⁺

C₃₀H₄₀O₅

-2.18

206.91

Terpenoid

448.219 5, 417.284 9, 343.109 4

Schisanlactone C or isomer

√

18.90

341.137 2

[M+H]⁺

C₂₀H₂₀O₅

-3.27

172.62

Lignan

287.089 4, 219.100 2, 205.083 5, 122.036 1

D-Epigalbacin or isomer

√

67^*

18.93

389.194 8

[M+H]⁺

C₂₂H₂₈O₆

-2.83

180.02

Lignan

357.167 9, 325.141 9, 287.089 3, 227.068 9, 221.116 9

Gomisin J

√

19.16

587.250 3

[M-H]^-

C₂₉H₃₆O₉

0.90

229.45

Terpenoid

447.217 7, 403.225 6, 227.034 0

Pre-schisanartanin A or isomer

√

19.19

571.253 6

[M+H]⁺

C₃₁H₃₈O₁₀

-0.37

219.70

Terpenoid

511.233 5, 493.220 9, 469.222 3, 451.210 4

Wuweizidilactone M or isomer

√

70^*

19.42

399.179 5

[M-H₂O
+H]⁺

C₂₃H₂₈O₇

-6.26

180.14

Lignan

369.167 8, 345.131 2, 329.100 7, 299.090 0, 285.074 0

Schisandrol B

√

19.57

589.264 9

[M-H]^-

C₃₁H₄₂O₁₁

-0.93

228.57

Terpenoid

467.241 6, 221.093 2

Pre-schisanartanin B or isomer

√

19.64

433.220 1

[M+H]⁺

C₂₄H₃₂O₇

-0.36

194.35

Lignan

415.211 1, 386.168 8, 339.121 8, 323.160 5

Schisandrin or isomer

√

19.83

401.158 3

[M+H]⁺

C₂₂H₂₄O₇

-2.95

182.28

Lignan

357.127 2, 341.101 3, 311.091 6, 299.089 2, 267.064 6

Methyl 2, 5-bis(3, 4-dimethoxyphenyl)-4, 5-dihydro-3-furancarboxylate or isomer

√

20.05

417.190 1

[M+H]⁺

C₂₃H₂₈O₇

-1.70

185.05

Lignan

401.196 4, 369.168 8, 339.121 8, 203.084 2

Gomisin O or isomer

√

20.23

387.180 5

[M-H]^-

C₂₂H₂₈O₆

-2.18

185.52

Lignan

341.139 1, 311.094 7, 275.066 7

Rubrisandrins A or isomer

√

20.59

531.222 6

[M-H]^-

C₂₈H₃₆O₁₀

-1.82

213.74

Terpenoid

401.159 1, 355.122 0, 341.098 3

Wuweizidilactone H or isomer

√

20.72

415.211 4

[M+H]⁺

C₂₄H₃₀O₆

-0.28

184.07

Terpenoid

385.195 3, 369.169 0, 353.174 9, 301.104 4

Meprednisone acetate or isomer

√

20.91

389.194 6

[M+H]⁺

C₂₂H₂₈O₆

-3.18

184.21

Lignan

374.164 0, 357.169 1, 341.135 9

Rubrisandrins A or isomer

√

21.17

515.227 2

[M+H]⁺

C₂₈H₃₄O₉

0.70

203.29

Terpenoid

469.223 6, 385.163 1, 355.153 2, 323.126 8

Wuweizidilactone O or isomer

√

21.34

389.194 0

[M+H]⁺

C₂₂H₂₈O₆

-4.72

183.08

Lignan

331.118 2, 235.074 2, 181.063 1

Rubrisandrins A or isomer

√

21.97

401.195 5

[M+H]⁺

C₂₃H₂₈O₆

-0.91

181.19

Lignan

370.177 4, 355.154 6, 323.127 2, 295.131 7, 165.066 0

Rubschisandrin or isomer

√

82^*

22.93

523.230 5

[M+Na]⁺

C₂₈H₃₆O₈

0.52

210.56

Lignan

431.205 9, 415.094 9, 356.160 5, 315.121 9, 267.099 7

Angeloylgomisin H

√

83^*

22.94

401.196 5

[M+H]⁺

C₂₃H₂₈O₆

-0.91

183.00

Lignan

386.170 0, 371.179 4, 356.160 5, 345.132 4, 221.093 4

Gomisin N

√

23.02

387.179 7

[M+H]⁺

C₂₂H₂₆O₆

-1.42

179.86

Lignan

372.157 5, 356.160 5, 327.121 1, 165.068 9

(-)-Gomisin L or isomer

√

23.49

415.174 1

[M+H]⁺

C₂₃H₂₆O₇

-2.49

180.88

Lignan

401.191 8, 355.145 0, 315.085 2, 181.063 8

Neoisostegane or isomer

√

433.212 4

[M+H]⁺

C₂₄H₃₂O₇

-1.23

189.16

Lignan

401.192 1, 387.180 9, 356.160 3, 341.137 6, 315.121 2

Schisandrin or isomer

√

24.03

341.136 8

[M+H]⁺

C₂₀H₂₀O₅

-4.60

168.22

Lignan

313.105 8, 285.110 3, 251.069 3, 165.068 2

Maceneolignan E or isomer

√

24.57

387.179 8

[M+H]⁺

C₂₄H₃₀O₇

-1.70

186.62

Lignan

372.155 6, 356.160 8, 341.136 9, 300.097 4, 165.068 7

(-)-Gomisin L or isomer

√

89^*

25.35

537.209 4

[M+H]⁺

C₃₀H₃₂O₉

-7.40

207.69

Lignan

416.176 6, 414.166 9, 371.149 2, 343.115 0, 285.073 8

Gomisin G

√

25.39

519.201 1

[M+H]⁺

C₃₀H₃₀O₈

-0.50

209.44

Lignan

415.173 9, 343.115 0, 219.079 6, 181.064 1

Schisanchinin A or isomer

√

25.70

483.309 8

[M+H]⁺

C₃₀H₄₂O₅

-1.49

207.08

Terpenoid

343.108 1, 253.129 1, 167.048 3

Henrischinin C or isomer

√

25.82

537.210 1

[M+H]⁺

C₃₀H₃₂O₉

-3.38

205.95

Lignan

416.176 4, 414.166 9, 371.148 5, 343.115 5, 312.098 5

Isomer of schisantherin A

√

26.42

403.210 7

[M+H]⁺

C₂₃H₃₀O₆

-2.03

185.97

Lignan

371.176 8, 341.137 3, 301.105 8, 287.090 5

Gomisin K2 or isomer

√

27.13

537.209 9

[M+H]⁺

C₃₀H₃₂O₉

-3.70

206.34

Lignan

416.177 0, 371.147 9, 343.115 1, 312.097 4

Isomer of schisantherin A

√

28.05

519.202 4

[M+H]⁺

C₃₀H₃₀O₈

1.94

207.95

Lignan

414.166 8, 398.170 6, 343.115 3, 285.073 8

Schisanchinin A or isomer

√

96^*

28.50

537.209 4

[M+H]⁺

C₃₀H₃₂O₉

-4.58

205.57

Lignan

416.179 5, 414.164 5, 371.148 3, 343.115 6, 312.098 2

Schisantherin A

√

97^*

28.51

553.184 3

[M+K]⁺

C₂₈H₃₄O₉

1.67

206.04

Lignan

416.179 4, 414.164 5, 371.148 3, 343.115 6

Schisantherin B

√

98^*

29.06

403.210 5

[M+H]⁺

C₂₃H₃₀O₆

-2.52

191.01

Lignan

357.167 8, 325.141 9, 301.106 7

Schisanhenol

√

31.15

415.210 4

[M+H]⁺

C₂₄H₃₀O₆

-2.69

188.75

Terpenoid

385.196 1, 369.168 5, 353.173 5, 323.126 9

Meprednisone acetate or isomer

√

100

32.12

415.210 5

[M+H]⁺

C₂₄H₃₀O₆

-2.45

187.92

Terpenoid

385.197 0, 369.168 6, 353.174 5, 323.126 6

Meprednisone acetate or isomer

√

101

35.48

399.178 4

[M+H]⁺

C₂₃H₂₆O₆

-4.56

184.94

Lignan

371.176 7, 301.105 7, 165.068 1

Allyl 2-O-benzoyl-3-O-benzyl-6-deoxy-α-L-mannopyranoside or isomer

√

102

37.35

417.226 3

[M+H]⁺

C₂₄H₃₂O₆

-2.08

190.55

Lignan

402.202 2, 387.179 2, 347.148 0, 301.105 9, 241.084 6

Schisandrin A or isomer

√

103

39.86

483.236 9

[M+H]⁺

C₂₈H₃₄O₇

-1.72

198.54

Terpenoid

453.216 1, 401.190 5, 323.124 4

Gedunin or isomer

√

104

40.26

401.194 5

[M+H]⁺

C₂₃H₂₈O₆

-3.41

186.38

Lignan

386.171 9, 331.114 8, 301.105 5, 285.075 3, 227.068 2

Schisandrin B or isomer

√

105

40.73

401.195 1

[M+H]⁺

C₂₃H₂₈O₆

-1.91

184.74

Lignan

386.171 0, 331.117 0, 301.103 7

Schisandrin B or isomer

√