药学学报

No.	t_R/min	Formula	MS (+)	Error (10^-6) (+)	MS/MS (+)	MS (-)	Error (10^-6) (-)	MS/MS (-)	Identification
1	5.52	C₂₇H₂₈O₁₈	641.132 63	3.45	479, 303	639.118 96	2.07	463, 301	Pentahydroxyflavone O-hex-O-gluA
2	5.58	C₂₁H₂₀O₁₀	433.111 39	3.55	415, 397, 379, 367, 337, 313, 283	431.098 02	0.81	-	Trihydroxy flavone C-glc^{[21, 22]}
3	5.95	C₂₇H₃₀O₁₆	611.158 26	3.94	593, 575, 565, 557, 545, 539, 527, 515, 497, 491, 473, 449, 355, 267, 221	609.144 47	2.69	591, 519, 489, 429, 399, 369	Luteolin-6, 8-di-C-glc^{[21, 22]}
4	5.95	C₂₇H₃₀O₁₅	595.163 51	3.76	577, 559, 541, 529, 523, 511, 499, 475, 457, 445, 415, 379, 337, 313	593.150 51	1.15	503, 473, 353, 311	Apigenin-6, 8-di-C-hex^{[21, 22]}
5	6.48	C₂₁H₂₀O₉	417.116 82	2.86	399, 381, 363, 351, 321, 297	415.102 78	1.62	295	Dihydroxy flavone C-glc^{[21, 22]}
6	6.71	C₂₇H₃₀O₁₅	595.163 51	3.76	577, 559, 541, 529, 523, 511, 499, 475, 457, 439, 421, 409, 379, 355	593.150 57	1.05	575, 503, 473, 383, 353	Apigenin-6, 8-di-C-hex^{[21, 22]}
7	6.87	C₂₂H₂₂O₁₀	447.126 83	3.91	429, 411, 393, 381, 351, 327	445.115 02	-2.24	-	Dihydroxy methoxyflavone C-glc^{[21, 22]}
8	7.15	C₂₇H₂₈O₁₈	641.133 24	2.50	479, 303	639.119 38	1.42	-	Pentahydroxyflavone O-hex-O-gluA
9	7.40	C₂₇H₃₀O₁₆	611.158 45	3.62	449, 431, 395, 383, 355, 329, 287, 267, 221	609.145 02	1.78	-	Tetrahydroxyflavone O-dihex
10	7.56	C₂₇H₂₆O₁₈	639.116 76	3.81	463, 445, 287	637.104 06	0.91	475, 351, 285	Luteolin-7-O-digluA^[4]
11	7.68	C₂₇H₃₀O₁₆	611.158 57	3.43	593, 491, 449, 431, 413, 383, 355, 329, 287, 267, 221	609.146 73	-1.02	489, 429, 357, 327	Kaempferol-6, 8-di-C-glc^{[21, 22]}
12	7.90	C₂₇H₃₀O₁₆	611.158 45	3.62	593, 565, 465, 449, 355, 303, 267, 221	609.144 96	1.88	463, 447, 301	Pentahydroxyflavone O-rha-O-hex
13	8.05	C₂₁H₂₀O₁₁	449.106 08	3.92	431, 413, 395, 383, 353, 329, 299	447.092 99	0.66	429, 411, 357, 327, 297	Isoorientin*
14	8.30	C₂₁H₁₈O₁₃	479.080 26	3.68	303	477.067 20	0.55	397, 373, 343, 301	Pentahydroxy flavone O-gluA
15	8.46	C₂₁H₂₀O₁₂	465.101 10	3.56	303	463.087 52	1.46	301	Pentahydroxyflavone O-hex
16	9.05	C₂₇H₃₀O₁₆	611.158 69	3.23	449, 355, 287	609.144 71	2.29	477, 447, 285	Tetrahydroxyflavone O-dihex
17	9.13	C₂₇H₂₆O₁₇	623.122 31	3.16	463, 447, 271	621.109 31	0.66	445, 351	Apigenin-7-O-digluA
18	9.59	C₂₉H₃₆O₁₆	641.205 26	3.67	623, 605, 487, 479, 461, 443, 325, 317	639.191 10	3.06	477, 315	Tetrahydroxymethoxyflavone O-dihex
19	9.70	C₂₇H₃₀O₁₅	595.163 76	3.34	449, 287	593.149 54	2.78	-	Luteolin-O-rutinoside or isomer^[4]
20	9.78	C₂₇H₃₀O₁₆	611.158 81	3.03	465, 449, 371, 335, 303, 267	609.145 08	1.69	343, 301, 300, 271, 255, 179	Rutin*
21	9.86	C₂₈H₂₈O₁₈	653.132 57	3.48	477, 459, 441, 397, 367, 343, 313, 301, 286, 258, 229	651.119 75	0.89	571, 457, 395, 371, 351, 299	Diosmetin-7-O-digluA or isomer^[4]
22	9.98	C₂₁H₂₀O₁₀	433.111 39	3.55	415, 397, 379, 367, 337, 313, 283	431.098 02	0.81	413, 341, 311	Trihydroxy flavone C-glc^{[21, 22]}
23	10.02	C₂₁H₂₀O₁₂	465.101 32	3.09	303	463.087 68	1.12	301, 300	Hyperoside*
24	10.25	C₂₁H₁₈O₁₃	479.080 75	2.65	461, 443, 325, 303	477.067 05	0.87	301	Pentahydroxyflavone O-gluA
25	10.38	C₂₁H₂₀O₁₂	465.100 98	3.82	303	463.087 59	1.31	301, 300	Isoquercitrin*
26	10.42	C₂₁H₂₀O₁₁	449.106 20	3.66	287	447.092 62	1.48	327, 285, 284	Kaempferol-3-O-galactoside^[20]
27	10.42	C₂₁H₁₈O₁₂	463.085 27	3.97	287	461.071 90	1.41	285, 175	Scutellarin*
28	10.42	C₂₈H₂₈O₁₈	653.132 45	3.67	477, 459, 397, 367, 343, 313, 301, 286, 258, 229	651.119 38	1.39	571, 457, 395, 371, 351, 341, 323, 299, 289	Diosmetin-7-O-digluA or isomer^[4]
29	10.54	C₂₈H₃₂O₁₆	625.174 26	3.29	479, 317, 302	623.162 29	-0.85	477, 315	Tetrahydroxymethoxyflavone O-rha-O-hex
30	10.57	C₂₁H₁₈O₁₂	463.085 17	4.18	287	461.071 59	2.08	381, 357, 327, 285	Luteolin-O-gluA^[4]
31	10.58	C₂₁H₁₈O₁₃	479.081 09	1.95	461, 435, 317, 303, 285, 275, 259	-	-	-	Pentahydroxyflavone O-gluA
32	10.61	C₂₁H₂₀O₁₁	449.106 45	3.10	287	447.092 62	1.48	327, 285	Luteolin-7-O-glc*
33	10.73	C₂₈H₃₀O₁₇	639.153 63	3.05	463, 301, 286, 258	637.140 75	0.43	619, 605, 447, 337, 299, 284, 256	Trihydroxymethoxyflavone O-gluA-O-hex
34	10.92	C₂₇H₃₀O₁₅	595.163 70	3.44	449, 287, 271	593.149 74	2.45	447, 285, 269	Luteolin-O-rutinoside or isomer^[4]
35	11.13	C₂₈H₃₀O₁₇	639.153 87	2.67	477, 459, 323, 301, 286, 258	637.139 47	2.43	-	Trihydroxymethoxyflavone O-hex-O-gluA
36	11.15	C₂₈H₃₂O₁₆	625.175 90	0.66	479, 317, 302	623.164 98	-5.16	-	Tetrahydroxymethoxyflavone O-rha-O-hex
37	11.21	C₂₂H₂₀O₁₃	493.095 92	3.55	317	491.082 34	1.57	357, 315	Tetrahydroxymethoxyflavone O-gluA
38	11.32	C₂₂H₂₂O₁₂	479.116 73	3.50	461, 317	477.103 49	0.75	462, 315, 314, 300, 299	Tetrahydroxymethoxyflavone 3-O-hex
39	11.44	C₂₈H₃₂O₁₆	625.174 26	3.29	479, 317, 302	623.161 13	1.01	477, 315	Tetrahydroxymethoxyflavone O-rha-O-hex
40	11.62	C₂₂H₂₀O₁₃	493.095 89	3.61	475, 317	491.082 64	0.96	357, 315	Tetrahydroxymethoxyflavone O-gluA
41	11.68	C₂₂H₂₂O₁₂	479.116 67	3.62	461, 317	477.103 49	0.75	462, 315, 300	Tetrahydroxymethoxyflavone O-hex
42	11.68	C₂₈H₃₀O₁₇	639.153 50	3.25	621, 477, 459, 301, 286, 258	637.140 26	1.20	-	Trihydroxymethoxyflavone O-hex-O-gluA
43	11.83	C₂₂H₂₀O₁₃	493.095 83	3.73	475, 317	491.082 18	1.90	-	Tetrahydroxymethoxyflavone O-gluA
44	11.84	C₂₂H₂₂O₁₂	479.116 82	3.31	461, 317	477.104 25	-0.84	-	Tetrahydroxymethoxyflavone O-hex
45	12.54	C₂₁H₂₀O₁₁	449.106 17	3.72	431, 287	447.092 90	0.86	327, 285, 284, 255	Astragaline*
46	12.70	C₂₇H₂₈O₁₅	593.147 77	3.93	447, 271	591.136 11	-0.96	-	Trihydroxyflavone O-rha-O-gluA
47	13.03	C₂₁H₂₀O₁₁	449.106 81	2.29	287	447.092 32	2.15	285	Luteolin-4′-O-hex
48	13.15	C₂₁H₂₀O₁₀	433.111 79	3.69	271	431.097 53	1.94	269	Apigenin-7-O-β-D-glc^[6]
49	13.23	C₂₇H₃₀O₁₄	579.169 07	3.05	433, 271	577.155 76	0.90	269	Trihydroxyflavone O-rha-O-hex
50	13.26	C₂₁H₁₈O₁₁	447.090 60	3.54	271	445.077 00	1.42	269, 175	Apigenin-7-O-β-D-gluA^[13]
51	13.49	C₂₈H₃₀O₁₆	623.158 81	2.98	447, 301, 286, 258	621.145 39	1.15	321, 299.284, 256	Trihydroxymethoxyflavone O-rha-O-gluA
52	13.73	C₂₈H₃₂O₁₅	609.179 32	3.41	463, 301, 286, 258	607.165 77	1.77	461, 443, 299, 285	Diosimin*
53	14.00	C₂₈H₃₀O₁₆	623.158 26	3.86	447, 301, 286, 258	621.145 20	1.46	477, 321, 299, 284	Trihydroxymethoxyflavone O-rha-O-gluA
54	14.07	C₂₂H₂₂O₁₁	463.121 28	4.78	301	461.108 49	0.96	446, 313, 299, 284	Diosmetin-7-O-β-D-glc or chrysoeriol-7-O-β-D-glc or isomer^{[6, 16]}
55	14.14	C₂₂H₂₀O₁₂	477.100 95	3.79	301, 286	475.087 62	1.22	371, 341, 299, 284, 175	5, 7, 4′-Dihydroxy-3′-methoxy flavone-7-O-β-D-galacturonide or isomer^[13]
56	14.14	C₂₈H₃₂O₁₅	609.179 44	3.22	463, 301, 286, 258	607.166 02	1.35	-	Trihydroxymethoxyflavone O-rha-O-hex
57	14.32	C₂₃H₂₂O₁₃	507.111 33	3.93	489, 331	505.098 39	0.74	-	Trihydroxydimethoxyflavone O-gluA
58	14.59	C₂₈H₃₂O₁₅	609.179 20	3.61	463, 301, 286, 258	607.166 75	0.15	-	Trihydroxymethoxyflavone O-rha-O-hex
59	14.63	C₂₈H₂₄O₁₄	585.122 01	3.20	567, 411, 345, 303, 283	583.108 34	1.69	463, 301	6″-O-(4-Hydroxybenzoyl) hyperoside^[13]
60	14.68	C₂₂H₂₂O₁₁	463.121 66	3.96	301, 287	461.108 76	0.38	-	Diosmetin-7-O-β-D-glc or chrysoeriol-7-O-β-D-glc or isomer^{[6, 16]}
61	14.71	C₂₂H₂₀O₁₂	477.100 74	4.23	301, 286	475.087 68	1.09	371, 341, 299, 284, 175	5, 7, 4′-Dihydroxy-3′-methoxy flavone-7-O-β-D-galacturonide or isomer^[13]
62	15.07	C₂₃H₂₄O₁₂	493.132 51	3.13	331	491.120 00	-1.02	-	Tricin-7-O-glc^{[18, 19]}
63	15.18	C₂₃H₂₂O₁₃	507.111 48	3.63	331	505.097 66	2.18	329	Trihydroxydimethoxyflavone O-gluA
64	15.30	C₂₈H₂₈O₁₇	637.138 00	3.03	619, 461, 443, 327, 285, 242	635.124 02	2.13	351	Acacetin-digluA^[17]
65	15.74	C₂₃H₂₂O₁₃	507.111 39	3.81	489, 331, 316	505.098 02	1.47	401, 371, 329, 175	Trihydroxydimethoxyflavone O-gluA
66	16.19	C₂₂H₂₀O₁₂	477.100 83	4.04	301, 287	475.087 95	0.52	299, 285	Luteolin-7-O-gluA-6″-methyl ester^[13]
67	17.87	C₂₂H₂₀O₁₂	477.100 80	4.10	301	475.087 74	0.97	-	5, 7, 4′-Dihydroxy-3′-methoxy flavone-7-O-β-D-galacturonide or isomer^[13]
68	17.87	C₂₂H₂₂O₁₁	463.121 73	3.80	301, 287	461.109 47	-1.16	-	Diosmetin-7-O-β-D-glc or chrysoeriol-7-O-β-D-glc or isomer^{[6, 16]}
69	18.63	C₂₃H₂₂O₁₂	491.116 46	3.96	315	489.103 18	1.37	313, 175	Dihydroxydimethoxyflavanone O-gluA
70	18.87	C₁₅H₁₀O₆	287.054 14	3.06	269, 259, 245, 241, 153	285.040 13	1.16	285, 243, 241, 217, 199, 175	Luteolin*
71	18.95	C₁₆H₁₂O₅	285.073 91	6.48	270, 253, 229, 225, 181, 137	283.059 72	5.2	268	Calycosin*
72	19.19	C₂₂H₂₀O₁₁	461.106 32	3.30	443, 271	459.093 72	-0.95	283, 269, 268	Trihydroxyflavone 3-O-gluA methyl ester
73	19.35	C₂₈H₃₀O₁₅	607.163 82	3.18	461, 285	605.150 63	0.93	321, 283, 268	Dihydroxymethoxyflavone O-rha-O-gluA
74	19.59	C₂₈H₃₂O₁₄	593.184 63	3.13	575, 447, 285	591.169 68	3.80	445, 283, 268	Dihydroxymethoxyflavone O-hex-O-rha
75	19.71	C₂₃H₂₂O₁₂	491.116 12	4.66	315, 301	489.103 52	0.67	-	Diosmetin-7-O-β-D-gluA methyl ester or isomer^[13]
76	19.82	C₃₀H₂₆O₁₃	595.142 27	3.95	329, 309, 287	593.129 15	1.54	327, 285	Tiliroside^[17]
77	19.90	C₂₃H₂₂O₁₂	491.116 58	3.72	315, 301	489.106 69	-5.80	-	Diosmetin-7-O-β-D-gluA methyl ester or isomer^[13]
78	20.14	C₂₂H₂₀O₁₁	461.106 23	3.49	285	459.092 86	0.92	283, 175	Wogonoside^[17]
79	20.29	C₂₃H₂₂O₁₂	491.116 39	4.11	315	489.103 15	1.43	-	Dihydroxydimethoxyflavanone O-gluA
80	20.33	C₁₇H₁₄O₇	331.080 99	0.72	316, 299, 271, 169, 123	-	-	-	Tricin or 5, 7, 4′-trihydroxy-3′, 5′-dimethoxyflavone^{[15, 18]}
81	21.03	C₁₅H₁₀O₅	271.059 57	1.96	271, 253, 243, 229, 225, 203, 163, 153, 145	269.045 23	1.17	269, 225, 201, 149	Apigenin*
82	21.51	C₁₆H₁₂O₆	301.069 95	2.38	286	299.055 79	1.07	284	Hispidulin*
83	24.02	C₁₆H₁₂O₅	285.075 65	0.35	285, 270, 257, 225, 211, 153	-	-	-	Apigenin-7-methyl ether^[14]
84	24.21	C₂₇H₃₀O₁₀	515.189 21	3.82	497, 479, 369, 313	513.176 39	0.45	367, 366, 351, 323	Baohuoside Ⅰ*

No.	t_R/min	Formula	MS (+)	Error (10^-6) (+)	MS/MS (+)	MS (-)	Error (10^-6) (-)	MS/MS (-)	Identification
1	5.52	C₂₇H₂₈O₁₈	641.132 63	3.45	479, 303	639.118 96	2.07	463, 301	Pentahydroxyflavone O-hex-O-gluA
2	5.58	C₂₁H₂₀O₁₀	433.111 39	3.55	415, 397, 379, 367, 337, 313, 283	431.098 02	0.81	-	Trihydroxy flavone C-glc^{[21, 22]}
3	5.95	C₂₇H₃₀O₁₆	611.158 26	3.94	593, 575, 565, 557, 545, 539, 527, 515, 497, 491, 473, 449, 355, 267, 221	609.144 47	2.69	591, 519, 489, 429, 399, 369	Luteolin-6, 8-di-C-glc^{[21, 22]}
4	5.95	C₂₇H₃₀O₁₅	595.163 51	3.76	577, 559, 541, 529, 523, 511, 499, 475, 457, 445, 415, 379, 337, 313	593.150 51	1.15	503, 473, 353, 311	Apigenin-6, 8-di-C-hex^{[21, 22]}
5	6.48	C₂₁H₂₀O₉	417.116 82	2.86	399, 381, 363, 351, 321, 297	415.102 78	1.62	295	Dihydroxy flavone C-glc^{[21, 22]}
6	6.71	C₂₇H₃₀O₁₅	595.163 51	3.76	577, 559, 541, 529, 523, 511, 499, 475, 457, 439, 421, 409, 379, 355	593.150 57	1.05	575, 503, 473, 383, 353	Apigenin-6, 8-di-C-hex^{[21, 22]}
7	6.87	C₂₂H₂₂O₁₀	447.126 83	3.91	429, 411, 393, 381, 351, 327	445.115 02	-2.24	-	Dihydroxy methoxyflavone C-glc^{[21, 22]}
8	7.15	C₂₇H₂₈O₁₈	641.133 24	2.50	479, 303	639.119 38	1.42	-	Pentahydroxyflavone O-hex-O-gluA
9	7.40	C₂₇H₃₀O₁₆	611.158 45	3.62	449, 431, 395, 383, 355, 329, 287, 267, 221	609.145 02	1.78	-	Tetrahydroxyflavone O-dihex
10	7.56	C₂₇H₂₆O₁₈	639.116 76	3.81	463, 445, 287	637.104 06	0.91	475, 351, 285	Luteolin-7-O-digluA^[4]
11	7.68	C₂₇H₃₀O₁₆	611.158 57	3.43	593, 491, 449, 431, 413, 383, 355, 329, 287, 267, 221	609.146 73	-1.02	489, 429, 357, 327	Kaempferol-6, 8-di-C-glc^{[21, 22]}
12	7.90	C₂₇H₃₀O₁₆	611.158 45	3.62	593, 565, 465, 449, 355, 303, 267, 221	609.144 96	1.88	463, 447, 301	Pentahydroxyflavone O-rha-O-hex
13	8.05	C₂₁H₂₀O₁₁	449.106 08	3.92	431, 413, 395, 383, 353, 329, 299	447.092 99	0.66	429, 411, 357, 327, 297	Isoorientin*
14	8.30	C₂₁H₁₈O₁₃	479.080 26	3.68	303	477.067 20	0.55	397, 373, 343, 301	Pentahydroxy flavone O-gluA
15	8.46	C₂₁H₂₀O₁₂	465.101 10	3.56	303	463.087 52	1.46	301	Pentahydroxyflavone O-hex
16	9.05	C₂₇H₃₀O₁₆	611.158 69	3.23	449, 355, 287	609.144 71	2.29	477, 447, 285	Tetrahydroxyflavone O-dihex
17	9.13	C₂₇H₂₆O₁₇	623.122 31	3.16	463, 447, 271	621.109 31	0.66	445, 351	Apigenin-7-O-digluA
18	9.59	C₂₉H₃₆O₁₆	641.205 26	3.67	623, 605, 487, 479, 461, 443, 325, 317	639.191 10	3.06	477, 315	Tetrahydroxymethoxyflavone O-dihex
19	9.70	C₂₇H₃₀O₁₅	595.163 76	3.34	449, 287	593.149 54	2.78	-	Luteolin-O-rutinoside or isomer^[4]
20	9.78	C₂₇H₃₀O₁₆	611.158 81	3.03	465, 449, 371, 335, 303, 267	609.145 08	1.69	343, 301, 300, 271, 255, 179	Rutin*
21	9.86	C₂₈H₂₈O₁₈	653.132 57	3.48	477, 459, 441, 397, 367, 343, 313, 301, 286, 258, 229	651.119 75	0.89	571, 457, 395, 371, 351, 299	Diosmetin-7-O-digluA or isomer^[4]
22	9.98	C₂₁H₂₀O₁₀	433.111 39	3.55	415, 397, 379, 367, 337, 313, 283	431.098 02	0.81	413, 341, 311	Trihydroxy flavone C-glc^{[21, 22]}
23	10.02	C₂₁H₂₀O₁₂	465.101 32	3.09	303	463.087 68	1.12	301, 300	Hyperoside*
24	10.25	C₂₁H₁₈O₁₃	479.080 75	2.65	461, 443, 325, 303	477.067 05	0.87	301	Pentahydroxyflavone O-gluA
25	10.38	C₂₁H₂₀O₁₂	465.100 98	3.82	303	463.087 59	1.31	301, 300	Isoquercitrin*
26	10.42	C₂₁H₂₀O₁₁	449.106 20	3.66	287	447.092 62	1.48	327, 285, 284	Kaempferol-3-O-galactoside^[20]
27	10.42	C₂₁H₁₈O₁₂	463.085 27	3.97	287	461.071 90	1.41	285, 175	Scutellarin*
28	10.42	C₂₈H₂₈O₁₈	653.132 45	3.67	477, 459, 397, 367, 343, 313, 301, 286, 258, 229	651.119 38	1.39	571, 457, 395, 371, 351, 341, 323, 299, 289	Diosmetin-7-O-digluA or isomer^[4]
29	10.54	C₂₈H₃₂O₁₆	625.174 26	3.29	479, 317, 302	623.162 29	-0.85	477, 315	Tetrahydroxymethoxyflavone O-rha-O-hex
30	10.57	C₂₁H₁₈O₁₂	463.085 17	4.18	287	461.071 59	2.08	381, 357, 327, 285	Luteolin-O-gluA^[4]
31	10.58	C₂₁H₁₈O₁₃	479.081 09	1.95	461, 435, 317, 303, 285, 275, 259	-	-	-	Pentahydroxyflavone O-gluA
32	10.61	C₂₁H₂₀O₁₁	449.106 45	3.10	287	447.092 62	1.48	327, 285	Luteolin-7-O-glc*
33	10.73	C₂₈H₃₀O₁₇	639.153 63	3.05	463, 301, 286, 258	637.140 75	0.43	619, 605, 447, 337, 299, 284, 256	Trihydroxymethoxyflavone O-gluA-O-hex
34	10.92	C₂₇H₃₀O₁₅	595.163 70	3.44	449, 287, 271	593.149 74	2.45	447, 285, 269	Luteolin-O-rutinoside or isomer^[4]
35	11.13	C₂₈H₃₀O₁₇	639.153 87	2.67	477, 459, 323, 301, 286, 258	637.139 47	2.43	-	Trihydroxymethoxyflavone O-hex-O-gluA
36	11.15	C₂₈H₃₂O₁₆	625.175 90	0.66	479, 317, 302	623.164 98	-5.16	-	Tetrahydroxymethoxyflavone O-rha-O-hex
37	11.21	C₂₂H₂₀O₁₃	493.095 92	3.55	317	491.082 34	1.57	357, 315	Tetrahydroxymethoxyflavone O-gluA
38	11.32	C₂₂H₂₂O₁₂	479.116 73	3.50	461, 317	477.103 49	0.75	462, 315, 314, 300, 299	Tetrahydroxymethoxyflavone 3-O-hex
39	11.44	C₂₈H₃₂O₁₆	625.174 26	3.29	479, 317, 302	623.161 13	1.01	477, 315	Tetrahydroxymethoxyflavone O-rha-O-hex
40	11.62	C₂₂H₂₀O₁₃	493.095 89	3.61	475, 317	491.082 64	0.96	357, 315	Tetrahydroxymethoxyflavone O-gluA
41	11.68	C₂₂H₂₂O₁₂	479.116 67	3.62	461, 317	477.103 49	0.75	462, 315, 300	Tetrahydroxymethoxyflavone O-hex
42	11.68	C₂₈H₃₀O₁₇	639.153 50	3.25	621, 477, 459, 301, 286, 258	637.140 26	1.20	-	Trihydroxymethoxyflavone O-hex-O-gluA
43	11.83	C₂₂H₂₀O₁₃	493.095 83	3.73	475, 317	491.082 18	1.90	-	Tetrahydroxymethoxyflavone O-gluA
44	11.84	C₂₂H₂₂O₁₂	479.116 82	3.31	461, 317	477.104 25	-0.84	-	Tetrahydroxymethoxyflavone O-hex
45	12.54	C₂₁H₂₀O₁₁	449.106 17	3.72	431, 287	447.092 90	0.86	327, 285, 284, 255	Astragaline*
46	12.70	C₂₇H₂₈O₁₅	593.147 77	3.93	447, 271	591.136 11	-0.96	-	Trihydroxyflavone O-rha-O-gluA
47	13.03	C₂₁H₂₀O₁₁	449.106 81	2.29	287	447.092 32	2.15	285	Luteolin-4′-O-hex
48	13.15	C₂₁H₂₀O₁₀	433.111 79	3.69	271	431.097 53	1.94	269	Apigenin-7-O-β-D-glc^[6]
49	13.23	C₂₇H₃₀O₁₄	579.169 07	3.05	433, 271	577.155 76	0.90	269	Trihydroxyflavone O-rha-O-hex
50	13.26	C₂₁H₁₈O₁₁	447.090 60	3.54	271	445.077 00	1.42	269, 175	Apigenin-7-O-β-D-gluA^[13]
51	13.49	C₂₈H₃₀O₁₆	623.158 81	2.98	447, 301, 286, 258	621.145 39	1.15	321, 299.284, 256	Trihydroxymethoxyflavone O-rha-O-gluA
52	13.73	C₂₈H₃₂O₁₅	609.179 32	3.41	463, 301, 286, 258	607.165 77	1.77	461, 443, 299, 285	Diosimin*
53	14.00	C₂₈H₃₀O₁₆	623.158 26	3.86	447, 301, 286, 258	621.145 20	1.46	477, 321, 299, 284	Trihydroxymethoxyflavone O-rha-O-gluA
54	14.07	C₂₂H₂₂O₁₁	463.121 28	4.78	301	461.108 49	0.96	446, 313, 299, 284	Diosmetin-7-O-β-D-glc or chrysoeriol-7-O-β-D-glc or isomer^{[6, 16]}
55	14.14	C₂₂H₂₀O₁₂	477.100 95	3.79	301, 286	475.087 62	1.22	371, 341, 299, 284, 175	5, 7, 4′-Dihydroxy-3′-methoxy flavone-7-O-β-D-galacturonide or isomer^[13]
56	14.14	C₂₈H₃₂O₁₅	609.179 44	3.22	463, 301, 286, 258	607.166 02	1.35	-	Trihydroxymethoxyflavone O-rha-O-hex
57	14.32	C₂₃H₂₂O₁₃	507.111 33	3.93	489, 331	505.098 39	0.74	-	Trihydroxydimethoxyflavone O-gluA
58	14.59	C₂₈H₃₂O₁₅	609.179 20	3.61	463, 301, 286, 258	607.166 75	0.15	-	Trihydroxymethoxyflavone O-rha-O-hex
59	14.63	C₂₈H₂₄O₁₄	585.122 01	3.20	567, 411, 345, 303, 283	583.108 34	1.69	463, 301	6″-O-(4-Hydroxybenzoyl) hyperoside^[13]
60	14.68	C₂₂H₂₂O₁₁	463.121 66	3.96	301, 287	461.108 76	0.38	-	Diosmetin-7-O-β-D-glc or chrysoeriol-7-O-β-D-glc or isomer^{[6, 16]}
61	14.71	C₂₂H₂₀O₁₂	477.100 74	4.23	301, 286	475.087 68	1.09	371, 341, 299, 284, 175	5, 7, 4′-Dihydroxy-3′-methoxy flavone-7-O-β-D-galacturonide or isomer^[13]
62	15.07	C₂₃H₂₄O₁₂	493.132 51	3.13	331	491.120 00	-1.02	-	Tricin-7-O-glc^{[18, 19]}
63	15.18	C₂₃H₂₂O₁₃	507.111 48	3.63	331	505.097 66	2.18	329	Trihydroxydimethoxyflavone O-gluA
64	15.30	C₂₈H₂₈O₁₇	637.138 00	3.03	619, 461, 443, 327, 285, 242	635.124 02	2.13	351	Acacetin-digluA^[17]
65	15.74	C₂₃H₂₂O₁₃	507.111 39	3.81	489, 331, 316	505.098 02	1.47	401, 371, 329, 175	Trihydroxydimethoxyflavone O-gluA
66	16.19	C₂₂H₂₀O₁₂	477.100 83	4.04	301, 287	475.087 95	0.52	299, 285	Luteolin-7-O-gluA-6″-methyl ester^[13]
67	17.87	C₂₂H₂₀O₁₂	477.100 80	4.10	301	475.087 74	0.97	-	5, 7, 4′-Dihydroxy-3′-methoxy flavone-7-O-β-D-galacturonide or isomer^[13]
68	17.87	C₂₂H₂₂O₁₁	463.121 73	3.80	301, 287	461.109 47	-1.16	-	Diosmetin-7-O-β-D-glc or chrysoeriol-7-O-β-D-glc or isomer^{[6, 16]}
69	18.63	C₂₃H₂₂O₁₂	491.116 46	3.96	315	489.103 18	1.37	313, 175	Dihydroxydimethoxyflavanone O-gluA
70	18.87	C₁₅H₁₀O₆	287.054 14	3.06	269, 259, 245, 241, 153	285.040 13	1.16	285, 243, 241, 217, 199, 175	Luteolin*
71	18.95	C₁₆H₁₂O₅	285.073 91	6.48	270, 253, 229, 225, 181, 137	283.059 72	5.2	268	Calycosin*
72	19.19	C₂₂H₂₀O₁₁	461.106 32	3.30	443, 271	459.093 72	-0.95	283, 269, 268	Trihydroxyflavone 3-O-gluA methyl ester
73	19.35	C₂₈H₃₀O₁₅	607.163 82	3.18	461, 285	605.150 63	0.93	321, 283, 268	Dihydroxymethoxyflavone O-rha-O-gluA
74	19.59	C₂₈H₃₂O₁₄	593.184 63	3.13	575, 447, 285	591.169 68	3.80	445, 283, 268	Dihydroxymethoxyflavone O-hex-O-rha
75	19.71	C₂₃H₂₂O₁₂	491.116 12	4.66	315, 301	489.103 52	0.67	-	Diosmetin-7-O-β-D-gluA methyl ester or isomer^[13]
76	19.82	C₃₀H₂₆O₁₃	595.142 27	3.95	329, 309, 287	593.129 15	1.54	327, 285	Tiliroside^[17]
77	19.90	C₂₃H₂₂O₁₂	491.116 58	3.72	315, 301	489.106 69	-5.80	-	Diosmetin-7-O-β-D-gluA methyl ester or isomer^[13]
78	20.14	C₂₂H₂₀O₁₁	461.106 23	3.49	285	459.092 86	0.92	283, 175	Wogonoside^[17]
79	20.29	C₂₃H₂₂O₁₂	491.116 39	4.11	315	489.103 15	1.43	-	Dihydroxydimethoxyflavanone O-gluA
80	20.33	C₁₇H₁₄O₇	331.080 99	0.72	316, 299, 271, 169, 123	-	-	-	Tricin or 5, 7, 4′-trihydroxy-3′, 5′-dimethoxyflavone^{[15, 18]}
81	21.03	C₁₅H₁₀O₅	271.059 57	1.96	271, 253, 243, 229, 225, 203, 163, 153, 145	269.045 23	1.17	269, 225, 201, 149	Apigenin*
82	21.51	C₁₆H₁₂O₆	301.069 95	2.38	286	299.055 79	1.07	284	Hispidulin*
83	24.02	C₁₆H₁₂O₅	285.075 65	0.35	285, 270, 257, 225, 211, 153	-	-	-	Apigenin-7-methyl ether^[14]
84	24.21	C₂₇H₃₀O₁₀	515.189 21	3.82	497, 479, 369, 313	513.176 39	0.45	367, 366, 351, 323	Baohuoside Ⅰ*

No.	t_R/min	Formula	MS (+)	Error (10^-6) (+)	Other adduct ion (+)	MS/MS (+)	MS (-)	Error (10^-6) (-)	MS/MS (-)	Other adduct ion (-)	Identification
1	5.68	C₄₁H₅₆O₂₅	966.344 36	0.56	971.298 89(+Na)	–	947.302 86	0.98	785, 623	983.277 89(+Cl)	β-D-Glp, (dihydroxypheny) ethyl O-hex-O-hex-O-rha, caff
2	6.03	C₄₀H₅₄O₂₅	952.326 97	2.43	935.301 45(+H), 957.282 23(+Na)	773, 611, 479, 457, 325, 295	933.287 05	1.17	801, 771, 753, 639, 609, 591, 477, 459, 447	969.263 85(+Cl)	β-D-Glp, (dihydroxypheny) ethyl O-hex-O-hex-O-pen, caff
3	6.11	C₃₅H₄₆O₂₁	820.284 73	2.81	825.239 87(+Na)	785, 623, 587, 477, 459, 325	801.244 75	1.41	783, 691, 639, 621, 529	837.221 37(+Cl)	Suspensaside-O-hex^{[26, 30]}
4	6.11	C₄₁H₅₆O₂₅	966.342 96	2.04	971.298 40(+Na)	–	947.302 37	1.50	785, 767, 639, 623, 605, 461	–	β-D-Glp, (dihydroxypheny) ethyl O-hex-O-hex-O-rha, caff
5	6.36	C₄₁H₅₆O₂₅	966.344 06	0.88	–	–	947.303 10	0.73	785, 623	–	β-D-Glp, (dihydroxypheny) ethyl O-hex-O-hex-O-rha, caff
6	6.36	C₁₆H₂₀O₉	374.143 59	2.72	–	339, 195, 177	355.103 06	1.11	193	–	Glucose ester of (E)-ferulic acid^[16]
7	6.52	C₄₁H₅₆O₂₅	966.343 75	1.21	971.298 40(+Na)	787, 625, 479, 325	947.303 16	0.67	785, 767, 639, 623, 605, 461	–	β-D-Glp, (dihydroxypheny) ethyl O-hex-O-hex-O-rha, caff
8	6.55	C₄₁H₅₆O₂₆	982.338 13	1.74	987.293 27(+Na)	803, 649, 641, 487, 479, 325	963.298 10	0.63	801, 783, 639, 621, 477, 459	999.274 35 (+Cl)	β-D-Glp, (dihydroxypheny) ethyl O-hex-O-hex-O-hex, caff
9	6.75	C₃₅H₄₆O₂₁	820.285 46	1.90	803.258 24(+H), 825.240 42(+Na)	803, 641, 487, 479, 461, 443, 325, 317, 307, 263	801.243 77	2.63	783, 639, 621, 485, 477, 459, 305	837.220 28(+Cl)	Maxoside or Lagotiside C or isomer^{[26, 27]}
10	6.75	C₂₉H₃₆O₁₇	674.227 11	2.99	679.182 62(+Na)	639, 621, 487, 477, 459, 325	655.186 71	1.93	637, 545, 503, 493, 475, 383, 323, 251	691.163 27(+Cl)	β-Hydroxyl-plantamajoside or isomer^{[26, 30]}
11	6.83	C₄₀H₅₄O₂₄	936.332 34	2.17	941.287 48(+Na)	757, 625, 611, 603, 479, 471, 457, 325	917.291 69	1.67	785, 771, 755, 737, 623, 609, 477, 461	953.267 82(+Cl), 963.297 06(+COOH)	β-D-Glp, (dihydroxypheny) ethyl O-hex-O-rha-O-pen, caff
12	6.87	C₄₁H₅₆O₂₅	966.343 14	1.85	971.298 03(+Na)	787, 625, 471, 325	947.302 92	0.92	785, 771, 623, 605, 461	983.278 32(+Cl)	β-D-Glp, (dihydroxypheny) ethyl O-hex-O-hex-O-rha, caff
13	6.91	C₂₉H₃₆O₁₇	674.227 05	3.09	679.182 31(+Na)	639, 621, 487, 477, 459, 325	655.187 19	1.19	637, 545, 503, 493, 475, 383, 323, 251	691.163 64(+Cl)	β-Hydroxyl-plantamajoside or isomer^{[26, 30]}
14	7.11	C₄₁H₅₆O₂₅	966.343 14	1.85	971.298 71(+Na)	787, 625, 493, 471, 339	947.302 86	0.98	815, 785, 771, 753, 639, 621	983.276 31(+Cl)	β-D-Glp, (dihydroxypheny) ethyl O-hex-O-hex-O-pen, feru
15	7.32	C₄₁H₅₆O₂₅	966.344 42	0.50	971.298 89(+Na)	-	947.302 61	1.25	785, 771, 753, 623, 605, 461	-	β-D-Glp, (dihydroxypheny) ethyl O-hex-O-hex-O-rha, caff
16	7.36	C₂₉H₃₆O₁₆	658.231 87	3.58	641.205 44(+H), 663.187 38(+Na)	641, 479, 461, 325	639.192 02	3.58	477, 459, 315	675.169 25(+Cl)	β-D-Glp, (dihydroxyphenyl) ethyl O-hex, caff (isomer of Plantamajoside)
17	7.40	C₄₂H₅₆O₂₆	994.337 34	2.53	999.292 91(+Na)	815, 661, 529, 457, 367, 325	975.297 97	0.75	933, 843, 813, 795, 771, 753, 681, 639, 621, 609	1 011.274 17(+Cl)	β-D-Glp, (dihydroxypheny) ethyl O-hex-O-hex-O-pen-acetyl, caff
18	7.60	C₂₉H₃₆O₁₆	658.231 81	3.67	663.187 07(+Na)	641, 623, 477, 471, 325	639.192 44	0.97	621, 529, 487, 477, 469, 459, 441, 179	675.166 20(+Cl)	Suspensaside^{[26, 30]}
19	7.76	C₃₅H₄₆O₂₀	804.289 98	2.66	787.263 79(+H), 809.245 36(+Na)	641, 633, 625, 607, 487, 479, 471, 461, 443, 435, 417, 325, 309	785.248 96	2.55	767, 639, 623, 605, 477, 461, 443, 315	821.225 10(+Cl)	Echinacoside*
20	7.90	C₄₂H₅₈O₂₆	996.353 27	2.24	1 001.307 62(+Na)	663, 493, 339	977.312 93	1.46	815, 801, 783, 653, 639, 621	1 013.290 71(+Cl)	β-D-Glp, (dihydroxypheny) ethyl O-hex-O-hex-O-hex, feru
21	7.90	C₄₃H₅₈O₂₇	1 024.347 90	2.46	1 029.303 47(+Na)	-	1 005.307 62	1.64	843, 801, 783, 681, 639, 585	1 041.284 91(+Cl)	β-D-Glp, (dihydroxypheny) ethyl O-hex-O-hex-O-hex-acetyl, caff
22	8.21	C₃₇H₄₈O₂₂	862.295 53	2.39	867.250 79(+Na)	691, 683, 529, 511, 479, 367, 325	843.255 31	1.35	801, 681, 639, 621, 519, 477, 459	879.231 51(+Cl)	β-D-Glp, (dihydroxyphenyl) ethyl O-hex-O-hex-acetyl, caff
23	8.21	C₃₁H₃₈O₁₈	716.237 49	3.08	721.192 87(+Na)	681, 529, 477, 459, 367, 325	697.197 81	1.04	679, 655, 637, 587, 535, 517, 475, 457	733.176 09(+Cl)	β-Hydroxyl-acetyl-plantamajoside or isomer^{[26, 30]}
24	8.46	C₃₁H₃₈O₁₈	716.237 79	2.65	721.192 87(+Na)	681, 529, 477, 367, 325	697.197 57	1.39	679, 655, 637, 587, 535, 517, 475	733.174 50(+Cl)	β-Hydroxyl-acetyl-plantamajoside or isomer^{[26, 30]}
25	8.57	C₃₄H₄₄O₂₀	790.274 72	2.20	795.230 16(+Na)	479, 461, 457, 325, 295, 277	771.234 50	1.06	639, 609, 591, 477, 447, 315	807.209 66(+Cl)	β-D-Glp, (dihydroxyphenyl) ethyl O-hex-O-pen, caff
26	8.66	C₄₀H₅₄O₂₄	936.332 21	2.31	941.287 23(+Na)	–	917.291 69	1.67	755, 623, 593, 461	953.266 97(+Cl), 963.295 10(+COOH)	β-D-Glp, (dihydroxypheny) ethyl O-hex-O-rha-O-pen, caff
27	9.05	C₃₄H₄₄O₂₀	790.274 48	2.51	773.247 99(+H), 795.229 68(+Na)	611, 593, 487, 479, 457, 325, 307, 295, 277	771.233 95	1.77	639, 609, 591, 477, 447, 429, 323, 315, 297, 275	807.209 90(+Cl)	β-D-Glp, (dihydroxyphenyl) ethyl O-hex-O-pen, caff
28	9.17	C₃₅H₄₆O₂₁	820.285 22	2.20	803.258 85(+H), 825.240 23(+Na)	803, 649, 641, 487, 479, 461, 443, 325, 317, 307	801.243 47	3.01	639, 621, 477, 459, 323, 315, 297, 263	837.219 79(+Cl)	Maxoside or lagotiside C or isomer^{[26, 27]}
29	9.28	C₃₅H₄₆O₂₀	804.290 10	2.50	809.246 09(+Na)	787, 641, 633, 625, 487, 479, 471, 435, 325, 309	785.250 73	0.30	639, 623, 605, 477, 461, 315	821.227 23(+Cl)	β-D-Glp, (dihydroxyphenyl) ethyl O-rha-O-hex, caff (isomer of echinacoside)
30	9.41	C₄₁H₅₆O₂₅	966.343 20	1.79	971.298 58(+Na)	–	947.302 86	0.98	801, 785, 767, 639, 623, 605, 461	983.278 81(+Cl)	β-D-Glp, (dihydroxypheny) ethyl O-hex-O-hex-O-rha, caff
31	9.49	C₃₅H₄₆O₂₀	804.290 34	2.20	787.262 70(+H), 809.245 73(+Na)	787, 625, 607, 571, 479, 471, 461, 435, 417, 325, 317, 309, 291, 273	785.250 55	0.53	639, 623, 605, 477, 461	821.226 87(+Cl)	β-D-Glp, (dihydroxyphenyl) ethyl O-rha-O-hex, caff (isomer of echinacoside)
32	9.53	C₃₆H₄₈O₂₀	818.305 42	2.87	801.279 05(+H), 823.260 74(+Na)	801, 647, 639, 493, 485, 475, 339	799.264 53	2.61	637, 623, 605, 477, 461, 315, 305	835.241 03(+Cl)	Jionoside A1 or isomer^[26]
33	9.59	C₂₉H₃₆O₁₆	658.232 42	2.72	641.205 26(+H), 663.187 68(+Na)	641, 487, 479, 461, 443, 325, 317, 307	639.191 10	3.06	477, 459, 315, 297, 179	675.167 72(+Cl)	Plantamajoside*
34	9.74	C₃₅H₄₆O₂₀	804.289 79	2.90	787.261 41(+H), 809.245 12(+Na)	787, 633, 625, 487, 479, 471, 461, 453, 435, 325, 309	785.250 00	1.23	639, 623, 605, 477, 461, 443, 307	821.226 07(+Cl)	β-D-Glp, (dihydroxyphenyl) ethyl O-rha-O-hex, caff (isomer of echinacoside)
35	9.98	C₃₄H₄₄O₁₉	774.279 24	2.99	779.234 56(+Na)	757, 625, 479, 471, 325	755.239 87	0.70	609, 593, 575, 461, 447, 443	791.216 37(+Cl), 801.245 42(+COOH)	Ehrenoside or isomer^[31]
36	10.22	C₃₀H₃₈O₁₆	672.247 44	3.62	655.220 95(+H), 677.202 58(+Na)	655, 471, 325	653.209 35	-0.98	635, 621, 543, 487, 459	689.186 65(+Cl), 699.214 72(+COOH)	Suspensaside methyl ether^{[26, 30]}
37	10.34	C₂₃H₂₆O₁₁	501.134 92(+Na)	3.63	496.179 60	347, 321	477.139 77	0.97	315, 301, 297, 179, 161	–	β-D-Glp, (dihydroxypheny) ethyl, caff
38	10.46	C₃₄H₄₄O₁₉	774.279 60	2.52	779.234 99(+Na)	757, 625, 479, 471, 457, 325	755.239 56	1.11	623, 609, 593, 575, 461, 447, 443, 315	791.216 13(+Cl)	Ehrenoside or isomer^[31]
39	10.81	C₃₅H₄₆O₂₀	804.290 22	2.35	809.245 30(+Na)	625, 479, 471, 325, 317	785.250 67	0.38	623, 477, 461	821.227 11(+Cl)	β-D-Glp, (dihydroxyphenyl) ethyl O-rha-O-hex, caff (isomer of echinacoside)
40	10.81	C₃₇H₅₀O₂₁	848.316 83	1.75	853.271 97(+Na)	507, 339	829.277 16	0.03	667, 653, 635, 491, 473	865.252 01(+Cl)	β-D-Glp, (hydroxymethoxyphenyl) ethyl O-hex-O-hex, feru
41	11.00	C₂₉H₃₆O₁₅	642.237 49	2.81	625.210 88(+H), 647.192 75(+Na)	625, 607, 589, 571, 479, 471, 435, 325, 309, 301	623.196 47	2.68	477, 461, 443, 323, 315, 297, 251, 179	659.173 03(+Cl)	Verbascoside/Acteoside*
42	11.00	C₂₉H₃₄O₁₅	640.221 92	2.69	623.190 61(+H)	623, 605, 587, 477, 459, 325, 281, 263	621.181 40	1.76	487, 469, 459, 179	–	Suspensaside A^{[26, 30]}
43	11.17	C₃₅H₄₆O₂₁	820.285 28	2.12	803.256 29(+H), 825.240 78(+Na)	649, 479, 325,	801.244 51	1.71	639, 621, 477, 459, 323, 315	837.220 95(+Cl)	Maxoside or lagotiside C or isomer^{[26, 27]}
44	11.25	C₃₇H₄₈O₂₂	862.296 33	1.44	845.269 17(+H), 867.251 46(+Na)	691, 683, 529, 511, 479, 367, 325	843.254 76	2.00	801, 783, 681, 639, 621, 519, 477, 459	879.230 71(+Cl)	β-D-Glp, (dihydroxyphenyl) ethyl O-hex-O-hex-acetyl, caff
45	11.40	C₂₉H₃₆O₁₆	658.232 06	3.28	641.205 44(+H), 663.187 13(+Na)	641, 487, 479, 461, 443, 325, 307	639.192 32	1.15	477, 459, 323, 315, 305, 297, 251, 179	675.168 95(+Cl)	Plantainoside D^[27]
46	11.44	C₃₆H₄₆O₂₁	832.285 16	2.24	837.240 36(+Na)	683, 661, 529, 499, 479, 457, 367, 325, 295	813.244 87	1.24	771, 753, 681, 651, 633, 609, 591, 519, 477, 447	849.221 19(+Cl)	β-D-Glp, (dihydroxyphenyl) ethyl O-hex-O-pen-acetyl, caff
47	11.52	C₂₉H₃₆O₁₅	642.237 55	2.72	625.174 68(+H), 647.192 81(+Na)	625, 479, 471, 463, 325, 309	623.197 20	1.51	477, 461, 315	–	β-D-Glp, (dihydroxyphenyl) ethyl O-rha, caff (isomer of isoacteoside)
48	11.64	C₃₅H₄₆O₂₀	804.290 04	2.58	787.263 43(+H), 809.245 48(+Na)	625, 501, 493, 471, 339, 309, 291	785.250 37	0.76	653, 623, 609, 591, 491, 477, 459, 447, 315, 297	821.226 75(+Cl)	β-D-Glp, (dihydroxyphenyl) ethyl O-pen-O-hex, feru
49	11.80	C₃₆H₄₈O₂₁	834.300 84	2.20	839.255 86(+Na)	655, 501, 493, 339	815.260 80	0.90	653, 639, 621, 491, 477, 473, 459	851.237 49(+Cl)	β-D-Glp, (dihydroxyphenyl) ethyl O-hex-O-hex, feru
50	11.86	C₃₁H₃₈O₁₇	700.242 31	3.10	683.215 76(+H), 705.197 81(+Na)	683, 665, 647, 529, 511, 479, 367, 325, 307	681.201 90	2.53	639, 621, 519, 477, 459, 315	717.172 36(+Cl)	Hemiphroside B*
51	11.86	C₃₃H₄₂O₁₇	728.273 38	3.72	733.216 13(+Na)	529, 367, 325, 307	–	–	–	–	β-D-Glp, (dimethoxyphenyl) ethyl O-hex-acetyl, caff
52	12.02	C₃₆H₄₈O₂₀	818.305 91	2.26	801.279 85(+H), 823.261 17(+Na)	655, 647, 639, 501, 493, 485, 339, 283	799.265 50	1.40	781, 653, 637, 623, 605, 491, 477, 461	835.241 88(+Cl)	Jionoside A1 or isomer^[26]
53	12.06	C₃₄H₄₄O₂₀	790.274 72	2.20	773.247 92(+H), 795.229 86(+Na)	611, 479, 457, 325, 295	771.234 38	1.21	735, 639, 609, 591, 477, 447, 429, 323, 315, 251	807.210 75(+Cl)	β-D-Glp, (dihydroxyphenyl) ethyl O-hex-O-pen, caff
54	12.10	C₃₁H₃₈O₁₇	700.242 80	2.82	683.215 39(+H), 705.198 12(+Na)	683, 529, 479, 367, 325	681.202 94	1.00	639, 621, 519, 477, 459	–	2′-O-Acetyl-plantamajoside^[27]
55	12.34	C₃₀H₃₈O₁₆	672.247 86	2.98	655.221 19(+H), 677.203 06(+Na)	655, 501, 493, 339	653.207 76	1.45	491, 477, 459, 315, 297	689.184 27(+Cl), 699.213 20(+COOH)	β-D-Glp, (dihydroxyphenyl) ethyl O-hex, feru
56	12.38	C₂₉H₃₆O₁₅	642.237 49	2.81	625.210 82(+H), 647.192 75(+Na)	625, 607, 479, 471, 461, 435, 325, 309	623.197 33	1.30	477, 461, 443, 323, 315, 297, 251, 179	659.174 01(+Cl)	Isoacteoside*
57	12.42	C₃₁H₃₈O₁₇	700.242 37	3.45	705.197 75(+Na)	521, 367, 325	681.202 76	1.27	639, 519, 477, 459	–	β-D-Glp, (dihydroxyphenyl) ethyl O-hex-acetyl, caff (isomer of hemiphroside B)
58	12.62	C₃₇H₅₀O₂₀	832.321 41	2.41	815.294 25(+H), 837.276 55(+Na)	653, 507, 485, 339, 323, 305	813.281 56	0.87	667, 651, 637, 619, 491, 475, 473, 457, 427, 329, 287	849.257 75(+Cl)	Cistanoside B or glucopyranosyl (1-6) martynoside or isomer^{[26, 29]}
59	12.80	C₂₉H₃₆O₁₅	642.237 24	3.21	625.210 14(+H), 647.192 44(+Na)	625, 607, 589, 571, 553, 479, 471, 461, 453, 443, 435, 417, 325, 317, 309, 301, 291, 273, 255	623.197 27	1.40	477, 461, 443, 315, 297, 179	659.171 20(+Cl)	β-D-Glp, (dihydroxyphenyl) ethyl O-rha, caff (isomer of verbascoside)
60	12.87	C₃₀H₃₈O₁₆	672.247 62	3.36	655.220 76(+H), 677.203 00(+Na)	655, 501, 493, 339	653.208 07	0.98	491, 477, 459	689.185 06(+Cl), 699.213 01(+COOH)	β-D-Glp, (dihydroxyphenyl) ethyl O-hex, feru
61	13.15	C₂₉H₃₆O₁₄	626.242 55	2.93	631.198 12(+Na)	463, 325	607.202 33	1.48	461, 445	643.178 77(+Cl)	β-D-Glp, (hydroxyphenyl) ethyl O-rha, caff
62	13.30	C₃₀H₃₈O₁₆	672.247 80	3.07	677.203 06(+Na)	493, 475, 457, 325	653.207 52	1.82	491, 477, 315	689.184 20(+Cl), 699.216 43(+COOH)	β-D-Glp, (hydroxymethoxyphenyl) ethyl O-hex, caff
63	13.34	C₃₇H₅₀O₂₀	832.321 41	2.41	837.276 86(+Na)	653, 339, 323	813.281 13	1.40	651, 637, 619, 491, 475	849.256 90(+Cl)	Cistanoside B or isomer^[26]
64	13.37	C₃₁H₃₈O₁₇	700.243 10	2.38	705.198 43(+Na)	665, 529, 511, 479, 461, 367, 349, 325	681.202 70	1.35	639, 621, 519, 477, 459	–	β-D-Glp, (dihydroxyphenyl) ethyl O-hex-acetyl, caff (isomer of hemiphroside B)
65	13.41	C₂₉H₃₆O₁₄	626.241 88	4.03	609.214 78(+H), 631.197 27(+Na)	609, 463, 455, 309	607.202 76	0.77	461, 443, 315	643.179 32(+Cl)	Lipedoside A or isomer^[26]
66	13.89	C₃₅H₄₆O₁₈	772.300 29	2.59	777.255 62(+Na)	755, 593, 471, 447, 325, 309	753.260 25	1.18	591	789.237 85(+Cl)	Kankanoside I^[28]
67	14.17	C₃₀H₃₈O₁₅	656.252 93	3.08	639.226 38(+H), 661.208 37(+Na)	639, 493, 485, 339, 323, 277	637.212 59	1.89	491, 475, 461, 443, 315, 305, 297, 193	673.189 21(+Cl), 683.217 90(+COOH)	Leucosceptoside A^[26]
68	14.56	C₂₉H₃₆O₁₄	626.241 94	3.93	631.197 75(+Na)	609, 591, 463, 455, 437, 309, 293, 275	607.202 64	0.97	461, 443, 315	643.178 22(+Cl)	Lipedoside A or isomer^[26]
69	15.07	C₃₀H₃₈O₁₅	656.253 36	2.41	639.226 68(+H), 661.208 62(+Na)	639, 493, 471, 325	637.212 52	2.00	475, 329	673.188 48(+Cl)	β-D-Glp, (hydroxymethoxyphenyl) ethyl O-rha, caff
70	15.10	C₃₆H₄₈O₂₀	818.306 40	1.65	801.281 19(+H), 823.261 47(+Na)	639, 507, 471, 339, 309	799.265 81	1.01	667, 637, 623, 605, 491, 473, 461	835.241 94(+Cl), 845.271 24(+COOH)	β-D-Glp, (hydroxymethoxyphenyl) ethyl O-hex-O-pen, feru
71	15.39	C₃₇H₅₀O₂₀	832.321 90	1.80	815.295 10(+H), 837.277 22(+Na)	815, 785, 669, 653, 647, 507, 501, 485, 339	813.281 43	1.03	667, 651, 637, 619, 491, 475, 473, 457, 329, 305	849.257 63(+Cl)	Cistanoside B or isomer^[26]
72	15.43	C₃₃H₄₀O₁₈	742.253 30	2.75	747.208 74(+Na)	725, 707, 571, 503, 367, 247	723.213 62	0.78	681, 663, 639, 621, 561, 519, 501, 477, 459	759.191 89(+Cl)	β-D-Glp, (dihydroxyphenyl) ethyl O-hex-acetyl-acetyl, caff
73	15.47	C₃₀H₃₈O₁₅	656.252 99	2.99	661.208 68(+Na)	639, 621, 493, 485, 475, 467, 457, 449, 431, 339, 323, 305	637.213 50	0.46	491, 475, 461	673.189 88(+Cl), 683.219 60(+COOH)	Leucosceptoside A^[26]
74	15.54	C₃₇H₅₀O₂₁	848.316 96	1.59	853.272 16(+Na)	669, 507, 339	829.276 49	0.83	667, 653, 635, 505, 491, 473, 425, 329, 311, 265	865.252 75(+Cl)	β-D-Glp, (hydroxymethoxyphenyl) ethyl O-hex-O-hex, feru
75	15.90	C₃₇H₅₀O₂₀	832.321 53	2.26	–	653, 339, 323	813.281 37	1.10	667, 651, 637, 619, 491, 475, 473, 457, 305	849.258 06(+Cl)	Cistanoside B or isomer^[26]
76	15.99	C₃₂H₄₀O₁₇	714.258 73	2.36	719.213 87(+Na)	697, 529, 367, 325	695.218 44	1.20	653, 635, 519, 501, 491	731.195 56(+Cl)	β-D-Glp, (hydroxymethoxyphenyl) ethyl O-hex-acetyl, caff
77	16.36	C₃₁H₃₈O₁₇	700.242 61	3.10	683.216 13(+H), 705.197 88(+Na)	683, 529, 367, 325	681.202 70	1.35	639, 621, 519, 477, 459	–	β-D-Glp, (dihydroxyphenyl) ethyl O-hex-acetyl, caff (isomer of hemiphroside B)
78	16.44	C₃₁H₄₀O₁₆	686.263 24	3.32	669.235 90(+H), 691.218 57(+Na)	507, 501, 471, 339, 277	667.223 82	0.81	505, 491, 473, 329, 311, 193	703.200 32(+Cl), 713.229 19(+COOH)	β-D-Glp, (hydroxymethoxyphenyl) ethyl O-hex, feru
79	17.03	C₃₆H₄₈O₁₉	802.310 73	2.65	785.285 40(+H), 807.266 36(+Na)	339	783.270 51	1.52	651, 637, 607, 589, 475, 461, 457, 443	819.247 86(+Cl), 829.276 25(+COOH)	Lagotoside^[29]
80	17.29	C₃₉H₅₂O₂₁	874.332 34	1.86	879.287 54(+Na)	839, 671, 527, 339	855.291 56	1.49	813, 795, 709, 679, 667, 651, 637, 619, 601, 491	891.267 21(+Cl)	Uranoside A or isomer^[26]
81	17.45	C₃₉H₅₂O₂₁	874.331 85	2.43	879.287 17(+Na)	839, 671, 339	855.291 44	1.63	813, 795, 693, 679, 667, 651, 637, 619, 601, 491, 475, 473	891.267 76(+Cl)	Uranoside A or isomer^[26]
82	18.47	C₃₁H₄₀O₁₅	670.268 74	2.77	653.242 19(+H), 675.224 00(+Na)	653, 507, 485, 339, 323	651.228 70	1.14	505, 487, 475, 457, 329, 289, 265, 193	687.205 32(+Cl), 697.234 01(+COOH)	Martynoside or cistanoside D or isomer^{[13, 14]}
83	19.16	C₃₃H₄₂O₁₇	728.273 62	3.39	733.229 06(+Na)	543, 381, 339	709.234 25	0.95	667, 649, 533	–	β-D-Glp, (hydroxymethoxyphenyl) ethyl O-hex-acetyl, feru

No.	t_R/min	Formula	MS (+)	Error (10^-6) (+)	Other adduct ion (+)	MS/MS (+)	MS (-)	Error (10^-6) (-)	MS/MS (-)	Other adduct ion (-)	Identification
1	5.68	C₄₁H₅₆O₂₅	966.344 36	0.56	971.298 89(+Na)	–	947.302 86	0.98	785, 623	983.277 89(+Cl)	β-D-Glp, (dihydroxypheny) ethyl O-hex-O-hex-O-rha, caff
2	6.03	C₄₀H₅₄O₂₅	952.326 97	2.43	935.301 45(+H), 957.282 23(+Na)	773, 611, 479, 457, 325, 295	933.287 05	1.17	801, 771, 753, 639, 609, 591, 477, 459, 447	969.263 85(+Cl)	β-D-Glp, (dihydroxypheny) ethyl O-hex-O-hex-O-pen, caff
3	6.11	C₃₅H₄₆O₂₁	820.284 73	2.81	825.239 87(+Na)	785, 623, 587, 477, 459, 325	801.244 75	1.41	783, 691, 639, 621, 529	837.221 37(+Cl)	Suspensaside-O-hex^{[26, 30]}
4	6.11	C₄₁H₅₆O₂₅	966.342 96	2.04	971.298 40(+Na)	–	947.302 37	1.50	785, 767, 639, 623, 605, 461	–	β-D-Glp, (dihydroxypheny) ethyl O-hex-O-hex-O-rha, caff
5	6.36	C₄₁H₅₆O₂₅	966.344 06	0.88	–	–	947.303 10	0.73	785, 623	–	β-D-Glp, (dihydroxypheny) ethyl O-hex-O-hex-O-rha, caff
6	6.36	C₁₆H₂₀O₉	374.143 59	2.72	–	339, 195, 177	355.103 06	1.11	193	–	Glucose ester of (E)-ferulic acid^[16]
7	6.52	C₄₁H₅₆O₂₅	966.343 75	1.21	971.298 40(+Na)	787, 625, 479, 325	947.303 16	0.67	785, 767, 639, 623, 605, 461	–	β-D-Glp, (dihydroxypheny) ethyl O-hex-O-hex-O-rha, caff
8	6.55	C₄₁H₅₆O₂₆	982.338 13	1.74	987.293 27(+Na)	803, 649, 641, 487, 479, 325	963.298 10	0.63	801, 783, 639, 621, 477, 459	999.274 35 (+Cl)	β-D-Glp, (dihydroxypheny) ethyl O-hex-O-hex-O-hex, caff
9	6.75	C₃₅H₄₆O₂₁	820.285 46	1.90	803.258 24(+H), 825.240 42(+Na)	803, 641, 487, 479, 461, 443, 325, 317, 307, 263	801.243 77	2.63	783, 639, 621, 485, 477, 459, 305	837.220 28(+Cl)	Maxoside or Lagotiside C or isomer^{[26, 27]}
10	6.75	C₂₉H₃₆O₁₇	674.227 11	2.99	679.182 62(+Na)	639, 621, 487, 477, 459, 325	655.186 71	1.93	637, 545, 503, 493, 475, 383, 323, 251	691.163 27(+Cl)	β-Hydroxyl-plantamajoside or isomer^{[26, 30]}
11	6.83	C₄₀H₅₄O₂₄	936.332 34	2.17	941.287 48(+Na)	757, 625, 611, 603, 479, 471, 457, 325	917.291 69	1.67	785, 771, 755, 737, 623, 609, 477, 461	953.267 82(+Cl), 963.297 06(+COOH)	β-D-Glp, (dihydroxypheny) ethyl O-hex-O-rha-O-pen, caff
12	6.87	C₄₁H₅₆O₂₅	966.343 14	1.85	971.298 03(+Na)	787, 625, 471, 325	947.302 92	0.92	785, 771, 623, 605, 461	983.278 32(+Cl)	β-D-Glp, (dihydroxypheny) ethyl O-hex-O-hex-O-rha, caff
13	6.91	C₂₉H₃₆O₁₇	674.227 05	3.09	679.182 31(+Na)	639, 621, 487, 477, 459, 325	655.187 19	1.19	637, 545, 503, 493, 475, 383, 323, 251	691.163 64(+Cl)	β-Hydroxyl-plantamajoside or isomer^{[26, 30]}
14	7.11	C₄₁H₅₆O₂₅	966.343 14	1.85	971.298 71(+Na)	787, 625, 493, 471, 339	947.302 86	0.98	815, 785, 771, 753, 639, 621	983.276 31(+Cl)	β-D-Glp, (dihydroxypheny) ethyl O-hex-O-hex-O-pen, feru
15	7.32	C₄₁H₅₆O₂₅	966.344 42	0.50	971.298 89(+Na)	-	947.302 61	1.25	785, 771, 753, 623, 605, 461	-	β-D-Glp, (dihydroxypheny) ethyl O-hex-O-hex-O-rha, caff
16	7.36	C₂₉H₃₆O₁₆	658.231 87	3.58	641.205 44(+H), 663.187 38(+Na)	641, 479, 461, 325	639.192 02	3.58	477, 459, 315	675.169 25(+Cl)	β-D-Glp, (dihydroxyphenyl) ethyl O-hex, caff (isomer of Plantamajoside)
17	7.40	C₄₂H₅₆O₂₆	994.337 34	2.53	999.292 91(+Na)	815, 661, 529, 457, 367, 325	975.297 97	0.75	933, 843, 813, 795, 771, 753, 681, 639, 621, 609	1 011.274 17(+Cl)	β-D-Glp, (dihydroxypheny) ethyl O-hex-O-hex-O-pen-acetyl, caff
18	7.60	C₂₉H₃₆O₁₆	658.231 81	3.67	663.187 07(+Na)	641, 623, 477, 471, 325	639.192 44	0.97	621, 529, 487, 477, 469, 459, 441, 179	675.166 20(+Cl)	Suspensaside^{[26, 30]}
19	7.76	C₃₅H₄₆O₂₀	804.289 98	2.66	787.263 79(+H), 809.245 36(+Na)	641, 633, 625, 607, 487, 479, 471, 461, 443, 435, 417, 325, 309	785.248 96	2.55	767, 639, 623, 605, 477, 461, 443, 315	821.225 10(+Cl)	Echinacoside*
20	7.90	C₄₂H₅₈O₂₆	996.353 27	2.24	1 001.307 62(+Na)	663, 493, 339	977.312 93	1.46	815, 801, 783, 653, 639, 621	1 013.290 71(+Cl)	β-D-Glp, (dihydroxypheny) ethyl O-hex-O-hex-O-hex, feru
21	7.90	C₄₃H₅₈O₂₇	1 024.347 90	2.46	1 029.303 47(+Na)	-	1 005.307 62	1.64	843, 801, 783, 681, 639, 585	1 041.284 91(+Cl)	β-D-Glp, (dihydroxypheny) ethyl O-hex-O-hex-O-hex-acetyl, caff
22	8.21	C₃₇H₄₈O₂₂	862.295 53	2.39	867.250 79(+Na)	691, 683, 529, 511, 479, 367, 325	843.255 31	1.35	801, 681, 639, 621, 519, 477, 459	879.231 51(+Cl)	β-D-Glp, (dihydroxyphenyl) ethyl O-hex-O-hex-acetyl, caff
23	8.21	C₃₁H₃₈O₁₈	716.237 49	3.08	721.192 87(+Na)	681, 529, 477, 459, 367, 325	697.197 81	1.04	679, 655, 637, 587, 535, 517, 475, 457	733.176 09(+Cl)	β-Hydroxyl-acetyl-plantamajoside or isomer^{[26, 30]}
24	8.46	C₃₁H₃₈O₁₈	716.237 79	2.65	721.192 87(+Na)	681, 529, 477, 367, 325	697.197 57	1.39	679, 655, 637, 587, 535, 517, 475	733.174 50(+Cl)	β-Hydroxyl-acetyl-plantamajoside or isomer^{[26, 30]}
25	8.57	C₃₄H₄₄O₂₀	790.274 72	2.20	795.230 16(+Na)	479, 461, 457, 325, 295, 277	771.234 50	1.06	639, 609, 591, 477, 447, 315	807.209 66(+Cl)	β-D-Glp, (dihydroxyphenyl) ethyl O-hex-O-pen, caff
26	8.66	C₄₀H₅₄O₂₄	936.332 21	2.31	941.287 23(+Na)	–	917.291 69	1.67	755, 623, 593, 461	953.266 97(+Cl), 963.295 10(+COOH)	β-D-Glp, (dihydroxypheny) ethyl O-hex-O-rha-O-pen, caff
27	9.05	C₃₄H₄₄O₂₀	790.274 48	2.51	773.247 99(+H), 795.229 68(+Na)	611, 593, 487, 479, 457, 325, 307, 295, 277	771.233 95	1.77	639, 609, 591, 477, 447, 429, 323, 315, 297, 275	807.209 90(+Cl)	β-D-Glp, (dihydroxyphenyl) ethyl O-hex-O-pen, caff
28	9.17	C₃₅H₄₆O₂₁	820.285 22	2.20	803.258 85(+H), 825.240 23(+Na)	803, 649, 641, 487, 479, 461, 443, 325, 317, 307	801.243 47	3.01	639, 621, 477, 459, 323, 315, 297, 263	837.219 79(+Cl)	Maxoside or lagotiside C or isomer^{[26, 27]}
29	9.28	C₃₅H₄₆O₂₀	804.290 10	2.50	809.246 09(+Na)	787, 641, 633, 625, 487, 479, 471, 435, 325, 309	785.250 73	0.30	639, 623, 605, 477, 461, 315	821.227 23(+Cl)	β-D-Glp, (dihydroxyphenyl) ethyl O-rha-O-hex, caff (isomer of echinacoside)
30	9.41	C₄₁H₅₆O₂₅	966.343 20	1.79	971.298 58(+Na)	–	947.302 86	0.98	801, 785, 767, 639, 623, 605, 461	983.278 81(+Cl)	β-D-Glp, (dihydroxypheny) ethyl O-hex-O-hex-O-rha, caff
31	9.49	C₃₅H₄₆O₂₀	804.290 34	2.20	787.262 70(+H), 809.245 73(+Na)	787, 625, 607, 571, 479, 471, 461, 435, 417, 325, 317, 309, 291, 273	785.250 55	0.53	639, 623, 605, 477, 461	821.226 87(+Cl)	β-D-Glp, (dihydroxyphenyl) ethyl O-rha-O-hex, caff (isomer of echinacoside)
32	9.53	C₃₆H₄₈O₂₀	818.305 42	2.87	801.279 05(+H), 823.260 74(+Na)	801, 647, 639, 493, 485, 475, 339	799.264 53	2.61	637, 623, 605, 477, 461, 315, 305	835.241 03(+Cl)	Jionoside A1 or isomer^[26]
33	9.59	C₂₉H₃₆O₁₆	658.232 42	2.72	641.205 26(+H), 663.187 68(+Na)	641, 487, 479, 461, 443, 325, 317, 307	639.191 10	3.06	477, 459, 315, 297, 179	675.167 72(+Cl)	Plantamajoside*
34	9.74	C₃₅H₄₆O₂₀	804.289 79	2.90	787.261 41(+H), 809.245 12(+Na)	787, 633, 625, 487, 479, 471, 461, 453, 435, 325, 309	785.250 00	1.23	639, 623, 605, 477, 461, 443, 307	821.226 07(+Cl)	β-D-Glp, (dihydroxyphenyl) ethyl O-rha-O-hex, caff (isomer of echinacoside)
35	9.98	C₃₄H₄₄O₁₉	774.279 24	2.99	779.234 56(+Na)	757, 625, 479, 471, 325	755.239 87	0.70	609, 593, 575, 461, 447, 443	791.216 37(+Cl), 801.245 42(+COOH)	Ehrenoside or isomer^[31]
36	10.22	C₃₀H₃₈O₁₆	672.247 44	3.62	655.220 95(+H), 677.202 58(+Na)	655, 471, 325	653.209 35	-0.98	635, 621, 543, 487, 459	689.186 65(+Cl), 699.214 72(+COOH)	Suspensaside methyl ether^{[26, 30]}
37	10.34	C₂₃H₂₆O₁₁	501.134 92(+Na)	3.63	496.179 60	347, 321	477.139 77	0.97	315, 301, 297, 179, 161	–	β-D-Glp, (dihydroxypheny) ethyl, caff
38	10.46	C₃₄H₄₄O₁₉	774.279 60	2.52	779.234 99(+Na)	757, 625, 479, 471, 457, 325	755.239 56	1.11	623, 609, 593, 575, 461, 447, 443, 315	791.216 13(+Cl)	Ehrenoside or isomer^[31]
39	10.81	C₃₅H₄₆O₂₀	804.290 22	2.35	809.245 30(+Na)	625, 479, 471, 325, 317	785.250 67	0.38	623, 477, 461	821.227 11(+Cl)	β-D-Glp, (dihydroxyphenyl) ethyl O-rha-O-hex, caff (isomer of echinacoside)
40	10.81	C₃₇H₅₀O₂₁	848.316 83	1.75	853.271 97(+Na)	507, 339	829.277 16	0.03	667, 653, 635, 491, 473	865.252 01(+Cl)	β-D-Glp, (hydroxymethoxyphenyl) ethyl O-hex-O-hex, feru
41	11.00	C₂₉H₃₆O₁₅	642.237 49	2.81	625.210 88(+H), 647.192 75(+Na)	625, 607, 589, 571, 479, 471, 435, 325, 309, 301	623.196 47	2.68	477, 461, 443, 323, 315, 297, 251, 179	659.173 03(+Cl)	Verbascoside/Acteoside*
42	11.00	C₂₉H₃₄O₁₅	640.221 92	2.69	623.190 61(+H)	623, 605, 587, 477, 459, 325, 281, 263	621.181 40	1.76	487, 469, 459, 179	–	Suspensaside A^{[26, 30]}
43	11.17	C₃₅H₄₆O₂₁	820.285 28	2.12	803.256 29(+H), 825.240 78(+Na)	649, 479, 325,	801.244 51	1.71	639, 621, 477, 459, 323, 315	837.220 95(+Cl)	Maxoside or lagotiside C or isomer^{[26, 27]}
44	11.25	C₃₇H₄₈O₂₂	862.296 33	1.44	845.269 17(+H), 867.251 46(+Na)	691, 683, 529, 511, 479, 367, 325	843.254 76	2.00	801, 783, 681, 639, 621, 519, 477, 459	879.230 71(+Cl)	β-D-Glp, (dihydroxyphenyl) ethyl O-hex-O-hex-acetyl, caff
45	11.40	C₂₉H₃₆O₁₆	658.232 06	3.28	641.205 44(+H), 663.187 13(+Na)	641, 487, 479, 461, 443, 325, 307	639.192 32	1.15	477, 459, 323, 315, 305, 297, 251, 179	675.168 95(+Cl)	Plantainoside D^[27]
46	11.44	C₃₆H₄₆O₂₁	832.285 16	2.24	837.240 36(+Na)	683, 661, 529, 499, 479, 457, 367, 325, 295	813.244 87	1.24	771, 753, 681, 651, 633, 609, 591, 519, 477, 447	849.221 19(+Cl)	β-D-Glp, (dihydroxyphenyl) ethyl O-hex-O-pen-acetyl, caff
47	11.52	C₂₉H₃₆O₁₅	642.237 55	2.72	625.174 68(+H), 647.192 81(+Na)	625, 479, 471, 463, 325, 309	623.197 20	1.51	477, 461, 315	–	β-D-Glp, (dihydroxyphenyl) ethyl O-rha, caff (isomer of isoacteoside)
48	11.64	C₃₅H₄₆O₂₀	804.290 04	2.58	787.263 43(+H), 809.245 48(+Na)	625, 501, 493, 471, 339, 309, 291	785.250 37	0.76	653, 623, 609, 591, 491, 477, 459, 447, 315, 297	821.226 75(+Cl)	β-D-Glp, (dihydroxyphenyl) ethyl O-pen-O-hex, feru
49	11.80	C₃₆H₄₈O₂₁	834.300 84	2.20	839.255 86(+Na)	655, 501, 493, 339	815.260 80	0.90	653, 639, 621, 491, 477, 473, 459	851.237 49(+Cl)	β-D-Glp, (dihydroxyphenyl) ethyl O-hex-O-hex, feru
50	11.86	C₃₁H₃₈O₁₇	700.242 31	3.10	683.215 76(+H), 705.197 81(+Na)	683, 665, 647, 529, 511, 479, 367, 325, 307	681.201 90	2.53	639, 621, 519, 477, 459, 315	717.172 36(+Cl)	Hemiphroside B*
51	11.86	C₃₃H₄₂O₁₇	728.273 38	3.72	733.216 13(+Na)	529, 367, 325, 307	–	–	–	–	β-D-Glp, (dimethoxyphenyl) ethyl O-hex-acetyl, caff
52	12.02	C₃₆H₄₈O₂₀	818.305 91	2.26	801.279 85(+H), 823.261 17(+Na)	655, 647, 639, 501, 493, 485, 339, 283	799.265 50	1.40	781, 653, 637, 623, 605, 491, 477, 461	835.241 88(+Cl)	Jionoside A1 or isomer^[26]
53	12.06	C₃₄H₄₄O₂₀	790.274 72	2.20	773.247 92(+H), 795.229 86(+Na)	611, 479, 457, 325, 295	771.234 38	1.21	735, 639, 609, 591, 477, 447, 429, 323, 315, 251	807.210 75(+Cl)	β-D-Glp, (dihydroxyphenyl) ethyl O-hex-O-pen, caff
54	12.10	C₃₁H₃₈O₁₇	700.242 80	2.82	683.215 39(+H), 705.198 12(+Na)	683, 529, 479, 367, 325	681.202 94	1.00	639, 621, 519, 477, 459	–	2′-O-Acetyl-plantamajoside^[27]
55	12.34	C₃₀H₃₈O₁₆	672.247 86	2.98	655.221 19(+H), 677.203 06(+Na)	655, 501, 493, 339	653.207 76	1.45	491, 477, 459, 315, 297	689.184 27(+Cl), 699.213 20(+COOH)	β-D-Glp, (dihydroxyphenyl) ethyl O-hex, feru
56	12.38	C₂₉H₃₆O₁₅	642.237 49	2.81	625.210 82(+H), 647.192 75(+Na)	625, 607, 479, 471, 461, 435, 325, 309	623.197 33	1.30	477, 461, 443, 323, 315, 297, 251, 179	659.174 01(+Cl)	Isoacteoside*
57	12.42	C₃₁H₃₈O₁₇	700.242 37	3.45	705.197 75(+Na)	521, 367, 325	681.202 76	1.27	639, 519, 477, 459	–	β-D-Glp, (dihydroxyphenyl) ethyl O-hex-acetyl, caff (isomer of hemiphroside B)
58	12.62	C₃₇H₅₀O₂₀	832.321 41	2.41	815.294 25(+H), 837.276 55(+Na)	653, 507, 485, 339, 323, 305	813.281 56	0.87	667, 651, 637, 619, 491, 475, 473, 457, 427, 329, 287	849.257 75(+Cl)	Cistanoside B or glucopyranosyl (1-6) martynoside or isomer^{[26, 29]}
59	12.80	C₂₉H₃₆O₁₅	642.237 24	3.21	625.210 14(+H), 647.192 44(+Na)	625, 607, 589, 571, 553, 479, 471, 461, 453, 443, 435, 417, 325, 317, 309, 301, 291, 273, 255	623.197 27	1.40	477, 461, 443, 315, 297, 179	659.171 20(+Cl)	β-D-Glp, (dihydroxyphenyl) ethyl O-rha, caff (isomer of verbascoside)
60	12.87	C₃₀H₃₈O₁₆	672.247 62	3.36	655.220 76(+H), 677.203 00(+Na)	655, 501, 493, 339	653.208 07	0.98	491, 477, 459	689.185 06(+Cl), 699.213 01(+COOH)	β-D-Glp, (dihydroxyphenyl) ethyl O-hex, feru
61	13.15	C₂₉H₃₆O₁₄	626.242 55	2.93	631.198 12(+Na)	463, 325	607.202 33	1.48	461, 445	643.178 77(+Cl)	β-D-Glp, (hydroxyphenyl) ethyl O-rha, caff
62	13.30	C₃₀H₃₈O₁₆	672.247 80	3.07	677.203 06(+Na)	493, 475, 457, 325	653.207 52	1.82	491, 477, 315	689.184 20(+Cl), 699.216 43(+COOH)	β-D-Glp, (hydroxymethoxyphenyl) ethyl O-hex, caff
63	13.34	C₃₇H₅₀O₂₀	832.321 41	2.41	837.276 86(+Na)	653, 339, 323	813.281 13	1.40	651, 637, 619, 491, 475	849.256 90(+Cl)	Cistanoside B or isomer^[26]
64	13.37	C₃₁H₃₈O₁₇	700.243 10	2.38	705.198 43(+Na)	665, 529, 511, 479, 461, 367, 349, 325	681.202 70	1.35	639, 621, 519, 477, 459	–	β-D-Glp, (dihydroxyphenyl) ethyl O-hex-acetyl, caff (isomer of hemiphroside B)
65	13.41	C₂₉H₃₆O₁₄	626.241 88	4.03	609.214 78(+H), 631.197 27(+Na)	609, 463, 455, 309	607.202 76	0.77	461, 443, 315	643.179 32(+Cl)	Lipedoside A or isomer^[26]
66	13.89	C₃₅H₄₆O₁₈	772.300 29	2.59	777.255 62(+Na)	755, 593, 471, 447, 325, 309	753.260 25	1.18	591	789.237 85(+Cl)	Kankanoside I^[28]
67	14.17	C₃₀H₃₈O₁₅	656.252 93	3.08	639.226 38(+H), 661.208 37(+Na)	639, 493, 485, 339, 323, 277	637.212 59	1.89	491, 475, 461, 443, 315, 305, 297, 193	673.189 21(+Cl), 683.217 90(+COOH)	Leucosceptoside A^[26]
68	14.56	C₂₉H₃₆O₁₄	626.241 94	3.93	631.197 75(+Na)	609, 591, 463, 455, 437, 309, 293, 275	607.202 64	0.97	461, 443, 315	643.178 22(+Cl)	Lipedoside A or isomer^[26]
69	15.07	C₃₀H₃₈O₁₅	656.253 36	2.41	639.226 68(+H), 661.208 62(+Na)	639, 493, 471, 325	637.212 52	2.00	475, 329	673.188 48(+Cl)	β-D-Glp, (hydroxymethoxyphenyl) ethyl O-rha, caff
70	15.10	C₃₆H₄₈O₂₀	818.306 40	1.65	801.281 19(+H), 823.261 47(+Na)	639, 507, 471, 339, 309	799.265 81	1.01	667, 637, 623, 605, 491, 473, 461	835.241 94(+Cl), 845.271 24(+COOH)	β-D-Glp, (hydroxymethoxyphenyl) ethyl O-hex-O-pen, feru
71	15.39	C₃₇H₅₀O₂₀	832.321 90	1.80	815.295 10(+H), 837.277 22(+Na)	815, 785, 669, 653, 647, 507, 501, 485, 339	813.281 43	1.03	667, 651, 637, 619, 491, 475, 473, 457, 329, 305	849.257 63(+Cl)	Cistanoside B or isomer^[26]
72	15.43	C₃₃H₄₀O₁₈	742.253 30	2.75	747.208 74(+Na)	725, 707, 571, 503, 367, 247	723.213 62	0.78	681, 663, 639, 621, 561, 519, 501, 477, 459	759.191 89(+Cl)	β-D-Glp, (dihydroxyphenyl) ethyl O-hex-acetyl-acetyl, caff
73	15.47	C₃₀H₃₈O₁₅	656.252 99	2.99	661.208 68(+Na)	639, 621, 493, 485, 475, 467, 457, 449, 431, 339, 323, 305	637.213 50	0.46	491, 475, 461	673.189 88(+Cl), 683.219 60(+COOH)	Leucosceptoside A^[26]
74	15.54	C₃₇H₅₀O₂₁	848.316 96	1.59	853.272 16(+Na)	669, 507, 339	829.276 49	0.83	667, 653, 635, 505, 491, 473, 425, 329, 311, 265	865.252 75(+Cl)	β-D-Glp, (hydroxymethoxyphenyl) ethyl O-hex-O-hex, feru
75	15.90	C₃₇H₅₀O₂₀	832.321 53	2.26	–	653, 339, 323	813.281 37	1.10	667, 651, 637, 619, 491, 475, 473, 457, 305	849.258 06(+Cl)	Cistanoside B or isomer^[26]
76	15.99	C₃₂H₄₀O₁₇	714.258 73	2.36	719.213 87(+Na)	697, 529, 367, 325	695.218 44	1.20	653, 635, 519, 501, 491	731.195 56(+Cl)	β-D-Glp, (hydroxymethoxyphenyl) ethyl O-hex-acetyl, caff
77	16.36	C₃₁H₃₈O₁₇	700.242 61	3.10	683.216 13(+H), 705.197 88(+Na)	683, 529, 367, 325	681.202 70	1.35	639, 621, 519, 477, 459	–	β-D-Glp, (dihydroxyphenyl) ethyl O-hex-acetyl, caff (isomer of hemiphroside B)
78	16.44	C₃₁H₄₀O₁₆	686.263 24	3.32	669.235 90(+H), 691.218 57(+Na)	507, 501, 471, 339, 277	667.223 82	0.81	505, 491, 473, 329, 311, 193	703.200 32(+Cl), 713.229 19(+COOH)	β-D-Glp, (hydroxymethoxyphenyl) ethyl O-hex, feru
79	17.03	C₃₆H₄₈O₁₉	802.310 73	2.65	785.285 40(+H), 807.266 36(+Na)	339	783.270 51	1.52	651, 637, 607, 589, 475, 461, 457, 443	819.247 86(+Cl), 829.276 25(+COOH)	Lagotoside^[29]
80	17.29	C₃₉H₅₂O₂₁	874.332 34	1.86	879.287 54(+Na)	839, 671, 527, 339	855.291 56	1.49	813, 795, 709, 679, 667, 651, 637, 619, 601, 491	891.267 21(+Cl)	Uranoside A or isomer^[26]
81	17.45	C₃₉H₅₂O₂₁	874.331 85	2.43	879.287 17(+Na)	839, 671, 339	855.291 44	1.63	813, 795, 693, 679, 667, 651, 637, 619, 601, 491, 475, 473	891.267 76(+Cl)	Uranoside A or isomer^[26]
82	18.47	C₃₁H₄₀O₁₅	670.268 74	2.77	653.242 19(+H), 675.224 00(+Na)	653, 507, 485, 339, 323	651.228 70	1.14	505, 487, 475, 457, 329, 289, 265, 193	687.205 32(+Cl), 697.234 01(+COOH)	Martynoside or cistanoside D or isomer^{[13, 14]}
83	19.16	C₃₃H₄₂O₁₇	728.273 62	3.39	733.229 06(+Na)	543, 381, 339	709.234 25	0.95	667, 649, 533	–	β-D-Glp, (hydroxymethoxyphenyl) ethyl O-hex-acetyl, feru

基于UHPLC-LTQ-orbitrap-MS方法分析藏药洪连(短管兔耳草) 中黄酮与苯乙醇苷类成分

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耿昭 ¹^,³ , 高必兴 ¹^,² , 钟恋 ¹^,² , 齐景梁 ² , 苟琰 ¹^,^* , 蒋运斌 ⁴^,^* , 杨蕾 ¹ , 袁军 ¹ , 郭力 ² , 王一涛 ³

药学学报 | 研究论文 2022,57(9): 2821-2838

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药学学报 | 研究论文 2022, 57(9): 2821-2838

基于UHPLC-LTQ-orbitrap-MS方法分析藏药洪连(短管兔耳草) 中黄酮与苯乙醇苷类成分

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耿昭¹^,³, 高必兴¹^,², 钟恋¹^,², 齐景梁², 苟琰¹^,^*, 蒋运斌⁴^,^*, 杨蕾¹, 袁军¹, 郭力², 王一涛³

作者信息

1.四川省药品检验研究院/国家药品监督管理局中成药质量评价重点实验室, 四川成都 611731

2.成都中医药大学药学院, 四川成都 611137

3.澳门大学中华医药研究院中药质量研究国家重点实验室, 澳门 999078

4.西南大学药学院·中医药学院, 重庆 400715

通讯作者:

*苟琰, Tel: 86-28-87877195, E-mail: gouyan0101@hotmail.com;

蒋运斌, Tel: 13368082556, E-mail: yunbinjiang@swu.edu.cn

Analysis of flavonoids and phenylethanoid glycosides in the Tibetan herb Lagotis brevituba Maxim based on UHPLC-LTQ-orbitrap-MS

Zhao GENG¹^,³, Bi-xing GAO¹^,², Lian ZHONG¹^,², Jing-liang QI², Yan GOU¹^,^*, Yun-bin JIANG⁴^,^*, Lei YANG¹, Jun YUAN¹, Li GUO², Yi-tao WANG³

Affiliations

1. NMPA Key Laboratory for Quality Evaluation of Traditional Chinese Medicine (Traditional Chinese Patent Medicine), Sichuan Institute for Drug Control (Sichuan Testing Center of Medical Devices), Chengdu 611731, China

2. College of Pharmacy, Chengdu University of Traditional Chinese Medicine, Chengdu 611137, China

3. State Key Laboratory of Quality Research in Chinese Medicine, Institute of Chinese Medical Sciences, University of Macau, Macau 999078, China

4. College of Pharmaceutical Sciences, Southwest University, Chongqing 400715, China

出版时间: 2022-09-12 doi: 10.16438/j.0513-4870.2022-0504

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摘要

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采用超高效液相色谱-串联线性离子阱-轨道阱组合高分辨质谱(UHPLC-LTQ-orbitrap-MS) 技术对藏药洪连(中国药典收载基原短管兔耳草) 中黄酮类和苯乙醇苷类成分进行定性分析。采用与动态排除相结合的数据依赖性扫描, 在电喷雾离子源正、负离子模式下分别分析黄酮类和苯乙醇苷类成分的精确分子量、碎片离子及保留时间等信息, 并结合相关文献系统全面地鉴别藏药洪连中这两类成分。最终共鉴定了167个化合物, 其中黄酮类成分84个, 苯乙醇苷类成分83个, 极大地丰富了洪连及兔耳草属植物中黄酮和苯乙醇苷类成分的数量和种类, 特别是首次从兔耳草属植物中发现了黄酮化合物宝藿苷I、脱氧己糖与葡萄糖醛酸组合的二糖氧苷黄酮4个、碳苷黄酮9个、四糖苯乙醇苷15个以及β位有取代基的苯乙醇苷5个, 为阐明洪连物质基础并整体提升其质量控制水平以及进一步规范相关基原品种的临床应用提供数据基础和科学依据。

关键词

洪连 / UHPLC-LTQ-orbitrap-MS / 黄酮 / 苯乙醇苷 / 兔耳草属

Abstract

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Ultra high performance liquid chromatography tandem linear ion trap orbitrap mass spectrometry (UHPLC-LTQ-orbitrap-MS) was applied to analyze and identify flavonoids and phenylethanoid glycosides in the Tibetan herb Lagotis brevituba Maxim. A method of data-dependent scan coupling with dynamic exclusion was developed for analyzing flavonoids and phenylethanoid glycosides under positive and negative ion mode of electrospray ionization (ESI). The compounds of Lagotis brevituba Maxim. were systematically identified through exact molecular mass, fragmentation patterns, retention time and reported references. A total of 167 compounds were detected, of which 84 were flavonoids and 83 were phenylethanoid glycosides, which greatly enriched the number and types of flavonoids and phenylethanol glycosides in Lagotis genus medicinal plants. Baohuoside Ⅰ, 4 disaccharide O-glycoside flavonoids (composed of deoxyhexose and glucuronic acid), 9 C-glycoside flavonoids, 15 tetrasaccharide phenylethanoid glycosides and 5 phenylethanoid glycosides with substituents on the β-position of the phenylethyl group were identified in Lagotis genus medicinal plants for the first time. This study provides scientific support for elucidating the material basis and improving the quality control of Lagotis brevituba Maxim.

Key words

Lagotis brevituba Maxim. / UHPLC-LTQ-orbitrap-MS / flavonoid / phenylethanoid glycoside / Lagotis genus

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耿昭, 高必兴, 钟恋, 齐景梁, 苟琰, 蒋运斌, 杨蕾, 袁军, 郭力, 王一涛. 基于UHPLC-LTQ-orbitrap-MS方法分析藏药洪连(短管兔耳草) 中黄酮与苯乙醇苷类成分. 药学学报, 2022 , 57 (9) : 2821 -2838 . DOI: 10.16438/j.0513-4870.2022-0504

Zhao GENG, Bi-xing GAO, Lian ZHONG, Jing-liang QI, Yan GOU, Yun-bin JIANG, Lei YANG, Jun YUAN, Li GUO, Yi-tao WANG. Analysis of flavonoids and phenylethanoid glycosides in the Tibetan herb Lagotis brevituba Maxim based on UHPLC-LTQ-orbitrap-MS[J]. Acta Pharmaceutica Sinica, 2022 , 57 (9) : 2821 -2838 . DOI: 10.16438/j.0513-4870.2022-0504

正文

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洪连为玄参科植物短管兔耳草Lagotis brevituba Maxim., 又称兔耳草, 主要分布于甘肃、青海、四川及西藏等地, 为常用藏药, 在《月王药诊》《四部医典》《晶珠本草》等藏医古籍中均有记载^[1-4], 目前收载于《中国药典》2020年版一部, 具有清热、解毒、利湿、平肝、行血、调经等功效^[5]。洪连全草入药, 味苦性凉, 藏医主要用于治疗全身发热、肾炎、肺病、高血压、动脉粥样硬化、月经不调、综合性毒物中毒等疾病^{[4, 6]}, 具有较高的药用价值, 近年来越来越受到关注, 具有良好的开发与应用前景。

阐明物质基础的是现代中药研发的基础, 是临床合理用药的依据, 目前对洪连化学成分的研究还处于起步阶段, 从其中分离鉴定的化学成分主要为黄酮、苯乙醇苷、环烯醚萜、有机酸等^{[6, 7]}。并且兔耳草属植物基原复杂, 我国即有17种之多^[7], 本课题组前期研究也发现^{[8, 9]}, 目前市售及临床使用的洪连为兔耳草属多种植物, 不同基原兔耳草的功效主治和用法用量也存在一定差异, 因此有必要对洪连及其同属植物的药效物质基础进行系统深入的研究。

液质联用技术以其快速分离、高分辨率、高灵敏度的特点已逐步取代传统中药化学提取分离纯化的研究方法, 在中药化学成分研究中的应用日益广泛, 成为分离鉴定化合物最为有效的手段之一^[10-12]。本研究以藏药洪连药典收载基原短管兔耳草为研究对象, 应用超高效液相色谱-串联线性离子阱-轨道阱组合高分辨质谱(UHPLC-LTQ-orbitrap-MS) 技术, 对其甲醇提取物中的黄酮类和苯乙醇苷类成分, 根据一级质谱、二级质谱数据及参考文献信息等进行研究, 为进一步阐明洪连物质基础并提高其质量控制水平提供借鉴和参考。

材料与方法

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仪器 LTQ Orbitrap XL线性离子阱-轨道阱组合高分辨质谱(美国Thermo Fishergs公司), 配有Dionex UltiMate 3000超高效液相色谱仪、电喷雾离子源(ESI) 及Xcalibur 2.1数据处理系统; BP211D十万分之一电子天平(德国Sartorious公司); 超声波清洗器(美国Branson公司); Milli-Q纯水系统(美国Millipore公司)。

药材与试剂 实验用洪连采于青海, 经西北高原植物所卢学峰研究员及四川省药品检验研究院黎跃成主任中药师鉴定为玄参科植物短管兔耳草Lagotis brevituba Maxim.的干燥全草。

对照品: 毛蕊异黄酮(批号MUST-19120901, 99.84%)、木犀草素(批号MUST-19102418, 98.92%)、紫云英苷(批号MUST-19070311, 98.62%)、金丝桃苷(批号MUST-19061210, 98.49%)、异槲皮苷(批号MUST-19051005, 99.74%)、地奥司明(批号MUST-19060801, 98.17%)、异类叶升麻苷(批号MUST-19103104, 99.16%) 购自成都曼斯特生物科技有限公司。芹菜素(批号111901-202004, 99.4%)、木犀草苷(批号111720-201810, 93.5%)、芦丁(批号100080-201811, 92.4%)、野黄芩苷(批号110842-202010, 91.5%)、宝藿苷I (批号111852-201603, 99.9%)、异荭草苷(批号111974-201401, 94.0%)、大车前苷(批号111914-201604, 90.2%)、毛蕊花糖苷(批号111530-201914, 95.2%)、松果菊苷(批号111670-201907, 91.8%)、山柰酚(批号110861-202013, 93.2%)、汉黄芩素(批号111514-201706)、异鼠李素(批号110860-202012, 99.1%)、黄芩苷(批号110715-202122, 94.2%)、槐角苷(批号111695-201703, 99.6%)、牡荆苷(批号111687-202105, 99.1%)、染料木苷(批号111709-201702, 99.9%)、荭草苷(批号111777-202003, 98.0%) 购自中国食品药品检定研究院。高车前素(批号PS2161-0010, 98.0%)、鞭打绣球苷B (批号PS1881-0010, 98.0%) 购自成都普思生物科技股份有限公司。色谱级甲醇、乙腈、甲酸、甲酸铵(德国Merck公司), 水为超纯水, 其他试剂均为分析纯。

色谱条件 色谱柱为Waters ACQUITY UPLC HSS T3色谱柱(100 mm × 2.1 mm, 1.8 μm); 柱温40 ℃; 进样量1 μL; 流速0.3 mL·min^-1; 流动相为乙腈(含0.1%甲酸) (A)-0.1%甲酸水溶液(B), 梯度洗脱: 0~3 min, 0%~14% A; 3~16 min, 14%~24% A; 16~20 min, 24%~40% A; 20~23 min, 40%~60% A; 23~26 min, 60%~90% A; 26~31 min, 90%~95% A。

质谱条件 采用ESI源, 正、负离子模式分别扫描; 鞘气流速: 60 arb; 辅助气流速: 20 arb; 喷雾电压: 4.5 kV (+)/4.0 kV (-); 吹扫气流速: 0 arb; 毛细管温度: 380 ℃; 毛细管电压: 35 V/-35 V; 管透镜电压: 100 V/ -100 V。扫描模式为一级质谱采用FTMS模式进行全扫描, 分辨率为30 000, 扫描范围m/z 100~1 500; 二级质谱采用与动态排除相结合的数据依赖性扫描, 动态排除功能设置参数: 重复次数2, 重复时间6 s, 排除列表范围500, 排除时间6 s。碰撞诱导解离设定归一化碰撞能量为35.0%。

对照品溶液的制备 取各对照品适量, 精密称定, 分别加甲醇溶解并定容至10 mL, 制成单一对照品储备液, 于4 ℃冰箱中避光保存, 备用。临用前取各对照品储备液适量并混合, 用甲醇稀释至各对照品浓度约为10 μg·mL^-1的混合对照品溶液。

供试品溶液的制备 称取洪连粉末(过三号筛) 约1 g, 精密称定, 置具塞锥形瓶中, 精密加入甲醇20 mL, 称定质量, 超声处理(功率230 W, 频率35 kHz) 30 min, 再称定质量, 用甲醇补足减失的质量, 摇匀, 滤过, 取续滤液, 即得。

数据处理 为了便于对洪连中黄酮及苯乙醇苷类成分进行系统定性的分析, 本研究首先对已有对照品进行质谱分析, 总结出其色谱保留行为、裂解规律以及特征碎片离子等。再通过PubChem、SciFinder、Chemspider及CNKI等数据库和相关文献的检索对有关兔耳草属的黄酮及苯乙醇苷类成分信息进行收集汇总, 包括名称、分子式、结构式等。然后, 采用Xcalibur分析软件对一级质谱提供的精确准分子离子进行分析, 计算未知化合物的元素组成和可能的分子式, 再选择目标化合物的二级质谱碎片离子信息, 与对照品、数据库及文献报道提供的保留时间、裂解规律等信息进行比对, 进一步确认化学成分及结构, 并分析推导化合物的质谱裂解规律。

结果

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取洪连供试品溶液及混合对照品溶液适量, 按上述色谱条件和质谱条件分别进样分析, 得正、负离子模式下的总离子流图(total ion chromatograms, TIC), 见图 1。对洪连中黄酮类和苯乙醇苷类成分色谱峰进行提取和匹配, 结果共鉴定了167个化合物, 其中黄酮类成分84个, 苯乙醇苷类成分83个。

1 黄酮类成分鉴定

黄酮类成分在植物中大部分以游离或与糖结合成氧苷类或碳苷形式存在, 且一般链接1或2个糖基。氧苷类黄酮的糖苷常通过C-O键以苷元C-3或C-7的羟基作为糖基化位点, 而碳苷类黄酮的糖苷通常通过C-C键直接连接到苷元的C-6和C-8位置。在本研究中, 除了采用毛蕊异黄酮等13个黄酮类对照品进行分析和确认, 还同时使用了山柰酚、汉黄芩素、异鼠李素、黄芩苷、槐角苷、牡荆苷、染木料苷、荭草苷等黄酮类对照品, 虽然由于保留时间不匹配而被排除, 但是其在本研究所用液质联用上表现的裂解规律, 对于定性确认仍有一定参考意义。最终通过对照品裂解规律的研究, 结合兔耳草属已分离出化合物及相关质谱文献报道, 鉴定了84个黄酮类成分, 具体信息见表 1^{[4, 6, 13-22]}, 其中以黄酮苷类为主。

目前对黄酮类成分进行分析时采用正离子或负离子模式采集数据均有报道, 本研究分别采集了正离子及负离子模式, 发现某些黄酮类成分在负离子模式下裂解规律更具有特征性, 而某些黄酮类则在正离子模式情况下响应更好, 两种模式下裂解的碎片离子信息可以为结构鉴定提供更多依据并相互佐证。首先采用文献^[23]中提取关键离子的方式, 确定可能的黄酮类成分, 其中的游离黄酮基本均由现成对照品确认其保留时间及一级质谱和二级质谱。而由于氧苷的结构特性, 发现本研究洪连中检出的氧苷黄酮与游离黄酮苷元在ESI源质谱上相同的碰撞能量下, 不论正离子或负离子模式, 氧苷黄酮中的基峰基本均为典型的脱掉整个糖基后的苷元碎片, 即明显的丢失146、162、176及190 Da的碎片离子, 对应的糖为脱氧己糖如鼠李糖(C₆H₁₀O₄)、己糖(C₆H₁₀O₅) 如葡萄糖和半乳糖、葡萄糖醛酸(C₆H₈O₆) 及葡萄糖醛酸甲酯(C₇H₁₀O₆) 等。

由于糖取代位置的差异, 产生的二级碎片离子会有一定的差异。特别是在负离子模式下, 当糖在C-3位取代时会与其他位置产生较为明显差别, 以木犀草苷和紫云英苷为例(图 2), 两者互为同分异构体, 区别在于两者糖取代分别位于C-3和C-7位, 在正离子模式下二级质谱中的碎片离子基本一致; 在负离子模式下, 紫云英苷的二级质谱中的碎片离子m/z 285明显小于m/z 284, 苷元碎片离子m/z 285先失去2个H又失去一分子CO后再生成m/z 255, 而木犀草苷的二级质谱中的碎片离子中基本仅可见m/z 285, 一般认为m/z 284和m/z 285是由脱去葡萄糖基的裂解方式差异造成的, 分别为均裂和异裂方式形成^[24]。这一特征碎片离子可以作为判断是否为C-3取代的依据, 如化合物23、25、26、38、45和72等, 其他情况下各取代位置则不易判断。

就洪连中的氧苷黄酮来讲, 本研究发现的相关二糖苷29个, 此前仅有少数文献^{[4, 17, 25]}报道了10个, 而无论是一糖苷或二糖苷, 己糖和葡萄糖醛酸都是其中最常见的糖种类, 含有葡萄糖醛酸甲酯的化合物仅有4个, 即化合物66、72、75和77, 且保留时间均较晚。含有脱氧己糖的情况通常存在于二糖苷中, 仅有宝藿苷I (化合物84) 是例外, 而该成分是首次从兔耳草属植物中发现。脱氧己糖通常需要己糖和葡萄糖醛酸组合搭配, 其与葡萄糖醛酸组合的二糖苷黄酮(化合物46、51、53和73), 为首次从兔耳草属植物中发现。己糖和葡萄糖醛酸可以各自组合搭配, 值得注意的是, 葡萄糖醛酸由于含有-COOH, 在负离子模式下响应较好, 在一糖苷二级质谱中经常出现[C₆H₈O₆-H]^- m/z 175的碎片离子, 而当两个葡萄糖醛酸相连时其二级质谱中则会出现[C₁₂H₁₆O₁₂-H]^- m/z 351的碎片离子, 且常为基峰, 可以作为该类型的特征碎片离子, 如化合物10、17、21、28和64。

本研究中发现的碳苷黄酮为兔耳草属植物中首次报道, 即化合物2~7、11、13和22共9个。其主要裂解规律与氧苷黄酮有显著差异, 主要为糖环内部的裂解, 以化合物6为例, 在正离子模式下, 准分子离子[M+H]⁺ m/z 595.163 51, 得到分子式为C₂₇H₃₀O₁₅, 二级质谱中出现碎片离子[M+H-18]⁺ m/z 577、[M+H-36]⁺ m/z 559、[M+H-54]⁺ m/z 541、[M+H-72]⁺ m/z 523等, 推测有准分子离子连续丢失H₂O (18) 产生。[M+H]⁺ m/z 595离子产生脱去120 Da (C₄H₈O₄) 的碎片离子m/z 475, 推测为m/z 595发生己糖六元环的O-C1键和C2-C3键开环断裂形成, 碎片离子m/z 457由m/z 475脱水产生。碎片离子m/z 379, 推测为准分子离子m/z 595脱去糖上3H₂O产生的碎片离子m/z 541又经苷元C环发生逆狄尔斯-阿德尔反应(RDA) 方式裂解反应断裂O-C_8a键和C₄-C_4a键形成。在负离子模式下, 准分子离子[M-H]^- m/z 593.150 57, 与正离子模式得到分子式相互验证, 双糖环裂解产生脱去90 Da (C₃H₆O₃)、120 Da (C₄H₈O₄), 以及连续脱去90和120 Da的碎片离子。由此可确认该化合物为二糖碳苷黄酮类, 经与参考文献^{[21, 22]}比对, 推断其为apigenin-6, 8-di-C-hexoside, 其正、负离子模式二级质谱及裂解途径见图 3和图 4。

2 苯乙醇苷类成分鉴定

苯乙醇苷是一类含有C6-C3芳香核片段的天然糖苷类化合物, 通常以β-葡萄糖为母核, 与α-羟基苯乙基苷化或同时再与苯丙烯酸酯化, 广泛存在于药用植物中, 由于大部分化合物糖上都连有咖啡酰基或阿魏酰基, 所以又被称为苯丙素苷化合物。这类化合物的结构具有以下共同特征: 作为苷元的取代苯乙基连在核心β-D-吡喃葡萄糖的1-位, 取代苯丙烯酰基通常是反式结构, 连接于核心葡萄糖的2, 4, 6-位, 而糖核的2, 3, 4, 6-位还常连接葡萄糖、半乳糖、木糖、呋喃阿拉伯糖、呋喃芹菜糖和鼠李糖等单糖或二糖, 由糖核上连接的糖种类、位置和支链顺序的差异, 以及苯丙烯酰基和苯乙基上取代基团的差异, 造成了苯乙醇苷化合物结构的多样性。

本研究同样通过正离子及负离子模式的数据信息对苯乙醇苷类成分进行结构鉴定, 最终通过对照品裂解规律的研究, 结合兔耳草属已分离出成分及相关质谱文献报道, 鉴定了83个苯乙醇苷类成分, 具体信息见表 2^{[13, 14, 16, 26-31]}。根据以往文献^{[26, 30]}报道, 苯乙醇苷类主要分为两类, 主要区别为苯乙醇基β位有无取代基, 当苯乙醇基β位上有取代基时裂解规律会有一定差异, 本研究发现洪连中的苯乙醇苷类绝大多数是苯乙醇基β位上无取代的。由于质谱的局限性, 糖苷键、乙酰基的准确位置及糖、双键的构型暂时难以确定, 但基本可以确定苯乙醇苷的基团类型和结构。

在负离子模式下, β位上无取代的苯乙醇苷的准分子离子基本均为[M-H]^-, 同时通常伴随着响应明显更低的[M+Cl]^-, 化合物整体响应较高时[M+COOH]^-也经常能检出。二级质谱的裂解规律非常相似, 多表现为连续的中性丢失18 Da (H₂O) 的碎片离子; 苯丙素部分的基团也极易丢失, 对应176 Da的阿魏酰基(C₁₀H₈O₃)、162 Da的咖啡酰基(caff, C₉H₆O₃) 和146 Da的香豆酰基(C₉H₆O₂) 等; 糖基部分丢失掉132、146和162 Da的中性碎片离子, 对应的糖为戊糖(C₅H₈O₄) 如阿拉伯糖、芹菜糖和木糖等、脱氧己糖如鼠李糖(C₆H₁₀O₄) 和己糖如葡萄糖(C₆H₁₀O₅) 等; 另外如有乙酰基(C₂H₂O, 42 Da) 也极易丢失。

以松果菊苷、大车前苷和鞭打绣球苷B为例, 松果菊苷的准分子离子[M-H]^- m/z 785.248 96, 得到分子式为C₃₅H₄₆O₂₀, 二级质谱中主要碎片离子为[M-H-H₂O]^- m/z 767、[M-H-rha]^- m/z 639、[M-H-caff]^- m/z 623、[M-H-caff-H₂O]^- m/z 605、[M-H-caff-rha]^- m/z 477、[M-H-caff-glc]^- m/z 461、[M-H-caff-glc-H₂O]^- m/z 443、[M-H-caff-glc-rha]^- m/z 315, 见图 5。

类似地, 大车前苷的准分子离子[M-H]^- m/z 639.191 10, 得到分子式为C₂₉H₃₆O₁₆, 二级质谱中主要碎片离子为[M-H-caff]^- m/z 477、[M-H-Caff-H₂O]^- m/z 459、[M-H-caff-glc]^- m/z 315、[M-H-caff-glc-H₂O]^- m/z 297、[caff]^- m/z 179。

鞭打绣球苷B的准分子离子[M-H]^- m/z 681.201 90, 与大车前苷的主要差异为多了一个乙酰基, 因此二级质谱中产生的主要碎片离子为[M-H-acetyl]^- m/z 639、[M-H-acetyl-H₂O]^- m/z 621、[M-H-caff]^- m/z 519、[M-H-acetyl-caff]^- m/z 477、[M-H-acetyl-caff-H₂O]^- m/z 459、[M-H-acetyl-caff-glc]^- m/z 315等的差异也体现在乙酰基的丢失上。通过对上述对照品的解析发现, [M-H-caff]^-多为负离子模式下的基峰, 由此推断, 当取代基由咖啡酰基变换为阿魏酰基或香豆酰基时, 相应的丢失176或146 Da后的碎片离子也应为其基峰, 可以作为苯乙醇苷类成分在负离子模式下重要的特征碎片离子, 如化合物14、20、32、48、49、和78~83中, 即为阿魏酰基取代, 而香豆酰基取代相对其他两种取代方式在洪连中也属少见, 仅有2个为化合物65和68, 而本研究中所检出的83个苯乙醇苷类成分中, 含有咖啡酰基取代的近48个, 占半数以上。另外还有不同糖基的取代, 如化合物2、11、14、17、25~27、35、38、46、48、53、70和79等中, 存在阿拉伯糖、芹菜糖和木糖取代。

在正离子模式下, 本研究中苯乙醇苷类化合物的准分子离子多为[M+NH₄]⁺, 同时可以见到明显的[M+Na]⁺, 而[M+H]⁺一般响应较低, 需将图谱放大数倍才可看到, 且经常无法获取其二级质谱。正离子与负离子模式的情况相似的是, 苯乙醇苷在脱去NH₄⁺后的二级碎片离子裂解规律表现仍然为连续的中性丢失18 Da (H₂O) 的碎片离子, 糖基部分丢失掉132 (C₅H₈O₄)、146 (C₆H₁₀O₄) 和162 (C₆H₁₀O₅) Da的中性碎片离子等, 但与负离子模式相比最重要的差异为不会轻易丢失咖啡酰基、阿魏酰基或香豆酰基取代部分, 而会产生丢失苯乙醇基(phenyl ethanol, phe) 取代部分的碎片离子, 这一部分的碎片离子丢失通常也可以反映其苯环上取代基的变化: 在大多数情况下其苯环上通常为2个-OH取代, 对应丢失154 Da (C₈H₁₀O₃) 的碎片离子, 如松果菊苷、大车前苷和鞭打绣球苷B等; 有一小部分化合物的苯乙醇基苯环上为1个-OH和1个-OCH₃取代, 对应丢失168 Da (C₉H₁₂O₃) 的碎片离子, 如化合物40、62、63、69~71、74~76、78~83等; 还有少见的个别情况为苯乙醇基苯环上无取代基(化合物83) 或只有1个-OH (化合物79) 或2个-OCH₃ (化合物51), 对应丢失的碎片离子分别为122 (C₈H₁₀O)、138 (C₈H₁₀O₂) 和182 (C₁₀H₁₄O₃) Da。

同样以松果菊苷、大车前苷和鞭打绣球苷B为例, 松果菊苷的准分子离子[M+NH₄]⁺ m/z 804.289 98, 得到分子式与负离子模式一致, 二级质谱中主要碎片离子为[M+H-Rha]⁺ m/z 641、[M+H-Phe]⁺ m/z 633、[M+H-glc]⁺ m/z 625、[M+H-glc-H₂O]⁺ m/z 607、[M+H-phe-rha]⁺ m/z 487、[M+H-glc-rha]⁺ m/z 479、[M+H-phe-glc]⁺ m/z 471, [M+H-phe-glc-rha]⁺ m/z 325, 见图 6。

类似地, 大车前苷的准分子离子[+NH₄]⁺ m/z 658.232 42, 得到分子式与负离子模式一致, 二级质谱中主要碎片离子为[M+H-phe]⁺ m/z 487、[M+H-glc]⁺ m/z 479、[M+H-glc-H₂O]⁺ m/z 461、[M+H-glc-2H₂O]⁺ m/z 443和[M+H-phe-glc]⁺ m/z 325。

鞭打绣球苷B的准分子离子[M+NH₄]⁺给出m/z 700.242 31, 得到分子式与负离子模式一致, 与大车前苷的差异同样体现在乙酰基的丢失上, 二级质谱中主要碎片离子为[M+H-H₂O]⁺ m/z 665、[M+H-2H₂O]⁺ m/z 647、[M+H-phe]⁺ m/z 529、[M+H-phe-H₂O]⁺ m/z 511、[M+H-glc-acetyl]⁺ m/z 479、[M+H-phe-glc]⁺ m/z 367、[M+H-phe-glc-acetyl]⁺ m/z 325、[M+H-phe-glc-acetyl-H₂O]⁺ m/z 307。较为特别的是, 在鞭打绣球苷B结构中, 乙酰基本身连接在支链葡萄糖而非核心β-D-吡喃葡萄糖上, 但在正离子模式下有时会出现乙酰基并未随支链葡萄糖一起丢失的碎片离子, 即碎片离子367, 有可能是该类化合物在裂解过程中发生了重排。

在正离子模式下的碎片离子m/z 325、339和309的存在可以分别佐证结构中存在咖啡酰基、阿魏酰基和香豆酰基, 且常为基峰, 对于碎片离子m/z 367和381则分别为咖啡酰基取代和阿魏酰基取代时化合物结构中存在乙酰基的碎片离子, 同时也可以作为苯乙醇苷中存在乙酰基的特征碎片。

根据前述裂解规律, 本研究首次在兔耳草属中发现四糖苯乙醇苷, 即化合物1、2、4、5、7、8、11、12、14、15、17、20、21、28和30共15个, 目前已有报道的四糖苯乙醇苷仅有十余个^{[32, 33]}, 因此这些四糖苯乙醇苷为新化合物的可能性极大。

对于另一类苯乙醇基β位有取代基的苯乙醇苷化合物, 经与参考文献^{[26, 30]}比对, 本研究在洪连中共检出8个, 其取代基大多为-OH, 如化合物3、10、13、18、23、24和42等, 仅有化合物36为-OCH₃取代, 其中化合物3、10、13、23和24为首次在兔耳草属中发现。在负离子模式下, 其基峰大多为丢失β位的-OH或-OCH₃后的碎片离子, 同时会产生丢失苯乙醇基部分的碎片, 对应丢失的碎片质量数为134 (C₈H₆O₂) 和152 (C₈H₈O₃) Da, 这是与β位无取代基类苯乙醇苷化合物的主要差异; 同样地, 也会产生丢失咖啡酰基和H₂O后的碎片离子。而在正离子模式下, 与β位无取代基类苯乙醇苷化合物裂解规律类似, 首先准分子离子仍为[M+NH₄]⁺, 脱去NH₄⁺后的丢失H₂O、糖基部分和苯乙醇基取代部分的碎片离子, 也会产生特征碎片离子325等。

讨论

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我国是世界上民族医药文化及相关药用资源最为丰富的国家, 藏医药即是民族医药中最重要的代表之一, 具有独特完整的医药理论体系, 在藏区的医疗体系中发挥着重要且不可代替的作用, 发展藏药的科技和产业对于藏区的社会、经济、文化和生态的全面发展具有重要意义。然而, 由于藏药的地理环境及市场流通的特殊性, 不同藏区使用的药材品种和基源常具有地域性和局限性的特点, 容易造成“一药多名”“一药多物”“地方习用品或代用品多”等情况, 加之相关资源学、药理学、化学等基础研究相对滞后, 严重影响了藏药的合理开发和现代化发展。因此, 对藏药进行深入系统的研究是非常有必要的。

本课题组以藏药洪连为例, 前期深入青海、四川、西藏藏区医院进行走访考察, 调查洪连在藏医中的实际使用情况, 又以实地调研和走访调查相结合的方法, 确定其药用资源分布情况, 并收集到多批次且有代表性的样品。由于发现目前市售及临床使用的洪连为兔耳草属的多种植物, 不同基原植物的化学成分或多或少会存在一定差异, 因此首先选择了药典收载基原品种, 采用UHPLC-LTQ-orbitrap-MS技术, 以正、负离子模式分别采集分析相互验证补充的方式, 针对其中黄酮和苯乙醇苷类成分进行了鉴定分析, 为确定兔耳草属不同植物的药效物质及作用机制研究提供数据基础。目前兔耳草属植物中已有报道的黄酮类成分30余个, 苯乙醇苷类成分20余个, 本研究极大地丰富了洪连及兔耳草属植物中黄酮和苯乙醇苷类成分的数量和种类, 特别是首次从兔耳草属植物中发现碳苷黄酮和四糖苯乙醇苷等新类型的化合物, 为进一步整体提升藏药洪连的质量控制水平和规范相关基原品种的临床应用提供科学依据。另外, 针对洪连中其他重要的化学成分如环烯醚萜类等, 本课题组同步开展了相关研究, 具体情况将另文报道。

作者贡献: 耿昭、高必兴、钟恋、齐景梁进行了本文方法建立、数据处理、文章撰写及对返修意见进行修改等; 苟琰、蒋运斌、杨蕾对实验思路、方法建立、数据处理及文章修改进行专业的指导; 袁军、郭力、王一涛主要进行本文的选题与设计、实验思路、方法建立的指导及文章修改。

利益冲突: 所有作者均声明不存在利益冲突。

基金

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国家药品监督管理局注册司专项“特色民族药材检验方法研究”三期
四川省药品监督管理局科研计划项目
重庆市自然科学基金面上项目(cstc2020jcyj-msxmX0146)

参考文献

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2022年第57卷第9期

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doi: 10.16438/j.0513-4870.2022-0504

接收时间：2022-04-27
首发时间：2025-12-24
出版时间：2022-09-12

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收稿日期：2022-04-27
修回日期：2022-06-22

基金

国家药品监督管理局注册司专项“特色民族药材检验方法研究”三期

四川省药品监督管理局科研计划项目

重庆市自然科学基金面上项目(cstc2020jcyj-msxmX0146)

作者信息

1.四川省药品检验研究院/国家药品监督管理局中成药质量评价重点实验室, 四川成都 611731

2.成都中医药大学药学院, 四川成都 611137

3.澳门大学中华医药研究院中药质量研究国家重点实验室, 澳门 999078

4.西南大学药学院·中医药学院, 重庆 400715

通讯作者:

*苟琰, Tel: 86-28-87877195, E-mail: gouyan0101@hotmail.com;

蒋运斌, Tel: 13368082556, E-mail: yunbinjiang@swu.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	Formula	MS (+)	Error (10^-6) (+)	MS/MS (+)	MS (-)	Error (10^-6) (-)	MS/MS (-)	Identification
1	5.52	C₂₇H₂₈O₁₈	641.132 63	3.45	479, 303	639.118 96	2.07	463, 301	Pentahydroxyflavone O-hex-O-gluA
2	5.58	C₂₁H₂₀O₁₀	433.111 39	3.55	415, 397, 379, 367, 337, 313, 283	431.098 02	0.81	-	Trihydroxy flavone C-glc^{[21, 22]}
3	5.95	C₂₇H₃₀O₁₆	611.158 26	3.94	593, 575, 565, 557, 545, 539, 527, 515, 497, 491, 473, 449, 355, 267, 221	609.144 47	2.69	591, 519, 489, 429, 399, 369	Luteolin-6, 8-di-C-glc^{[21, 22]}
4	5.95	C₂₇H₃₀O₁₅	595.163 51	3.76	577, 559, 541, 529, 523, 511, 499, 475, 457, 445, 415, 379, 337, 313	593.150 51	1.15	503, 473, 353, 311	Apigenin-6, 8-di-C-hex^{[21, 22]}
5	6.48	C₂₁H₂₀O₉	417.116 82	2.86	399, 381, 363, 351, 321, 297	415.102 78	1.62	295	Dihydroxy flavone C-glc^{[21, 22]}
6	6.71	C₂₇H₃₀O₁₅	595.163 51	3.76	577, 559, 541, 529, 523, 511, 499, 475, 457, 439, 421, 409, 379, 355	593.150 57	1.05	575, 503, 473, 383, 353	Apigenin-6, 8-di-C-hex^{[21, 22]}
7	6.87	C₂₂H₂₂O₁₀	447.126 83	3.91	429, 411, 393, 381, 351, 327	445.115 02	-2.24	-	Dihydroxy methoxyflavone C-glc^{[21, 22]}
8	7.15	C₂₇H₂₈O₁₈	641.133 24	2.50	479, 303	639.119 38	1.42	-	Pentahydroxyflavone O-hex-O-gluA
9	7.40	C₂₇H₃₀O₁₆	611.158 45	3.62	449, 431, 395, 383, 355, 329, 287, 267, 221	609.145 02	1.78	-	Tetrahydroxyflavone O-dihex
10	7.56	C₂₇H₂₆O₁₈	639.116 76	3.81	463, 445, 287	637.104 06	0.91	475, 351, 285	Luteolin-7-O-digluA^[4]
11	7.68	C₂₇H₃₀O₁₆	611.158 57	3.43	593, 491, 449, 431, 413, 383, 355, 329, 287, 267, 221	609.146 73	-1.02	489, 429, 357, 327	Kaempferol-6, 8-di-C-glc^{[21, 22]}
12	7.90	C₂₇H₃₀O₁₆	611.158 45	3.62	593, 565, 465, 449, 355, 303, 267, 221	609.144 96	1.88	463, 447, 301	Pentahydroxyflavone O-rha-O-hex
13	8.05	C₂₁H₂₀O₁₁	449.106 08	3.92	431, 413, 395, 383, 353, 329, 299	447.092 99	0.66	429, 411, 357, 327, 297	Isoorientin*
14	8.30	C₂₁H₁₈O₁₃	479.080 26	3.68	303	477.067 20	0.55	397, 373, 343, 301	Pentahydroxy flavone O-gluA
15	8.46	C₂₁H₂₀O₁₂	465.101 10	3.56	303	463.087 52	1.46	301	Pentahydroxyflavone O-hex
16	9.05	C₂₇H₃₀O₁₆	611.158 69	3.23	449, 355, 287	609.144 71	2.29	477, 447, 285	Tetrahydroxyflavone O-dihex
17	9.13	C₂₇H₂₆O₁₇	623.122 31	3.16	463, 447, 271	621.109 31	0.66	445, 351	Apigenin-7-O-digluA
18	9.59	C₂₉H₃₆O₁₆	641.205 26	3.67	623, 605, 487, 479, 461, 443, 325, 317	639.191 10	3.06	477, 315	Tetrahydroxymethoxyflavone O-dihex
19	9.70	C₂₇H₃₀O₁₅	595.163 76	3.34	449, 287	593.149 54	2.78	-	Luteolin-O-rutinoside or isomer^[4]
20	9.78	C₂₇H₃₀O₁₆	611.158 81	3.03	465, 449, 371, 335, 303, 267	609.145 08	1.69	343, 301, 300, 271, 255, 179	Rutin*
21	9.86	C₂₈H₂₈O₁₈	653.132 57	3.48	477, 459, 441, 397, 367, 343, 313, 301, 286, 258, 229	651.119 75	0.89	571, 457, 395, 371, 351, 299	Diosmetin-7-O-digluA or isomer^[4]
22	9.98	C₂₁H₂₀O₁₀	433.111 39	3.55	415, 397, 379, 367, 337, 313, 283	431.098 02	0.81	413, 341, 311	Trihydroxy flavone C-glc^{[21, 22]}
23	10.02	C₂₁H₂₀O₁₂	465.101 32	3.09	303	463.087 68	1.12	301, 300	Hyperoside*
24	10.25	C₂₁H₁₈O₁₃	479.080 75	2.65	461, 443, 325, 303	477.067 05	0.87	301	Pentahydroxyflavone O-gluA
25	10.38	C₂₁H₂₀O₁₂	465.100 98	3.82	303	463.087 59	1.31	301, 300	Isoquercitrin*
26	10.42	C₂₁H₂₀O₁₁	449.106 20	3.66	287	447.092 62	1.48	327, 285, 284	Kaempferol-3-O-galactoside^[20]
27	10.42	C₂₁H₁₈O₁₂	463.085 27	3.97	287	461.071 90	1.41	285, 175	Scutellarin*
28	10.42	C₂₈H₂₈O₁₈	653.132 45	3.67	477, 459, 397, 367, 343, 313, 301, 286, 258, 229	651.119 38	1.39	571, 457, 395, 371, 351, 341, 323, 299, 289	Diosmetin-7-O-digluA or isomer^[4]
29	10.54	C₂₈H₃₂O₁₆	625.174 26	3.29	479, 317, 302	623.162 29	-0.85	477, 315	Tetrahydroxymethoxyflavone O-rha-O-hex
30	10.57	C₂₁H₁₈O₁₂	463.085 17	4.18	287	461.071 59	2.08	381, 357, 327, 285	Luteolin-O-gluA^[4]
31	10.58	C₂₁H₁₈O₁₃	479.081 09	1.95	461, 435, 317, 303, 285, 275, 259	-	-	-	Pentahydroxyflavone O-gluA
32	10.61	C₂₁H₂₀O₁₁	449.106 45	3.10	287	447.092 62	1.48	327, 285	Luteolin-7-O-glc*
33	10.73	C₂₈H₃₀O₁₇	639.153 63	3.05	463, 301, 286, 258	637.140 75	0.43	619, 605, 447, 337, 299, 284, 256	Trihydroxymethoxyflavone O-gluA-O-hex
34	10.92	C₂₇H₃₀O₁₅	595.163 70	3.44	449, 287, 271	593.149 74	2.45	447, 285, 269	Luteolin-O-rutinoside or isomer^[4]
35	11.13	C₂₈H₃₀O₁₇	639.153 87	2.67	477, 459, 323, 301, 286, 258	637.139 47	2.43	-	Trihydroxymethoxyflavone O-hex-O-gluA
36	11.15	C₂₈H₃₂O₁₆	625.175 90	0.66	479, 317, 302	623.164 98	-5.16	-	Tetrahydroxymethoxyflavone O-rha-O-hex
37	11.21	C₂₂H₂₀O₁₃	493.095 92	3.55	317	491.082 34	1.57	357, 315	Tetrahydroxymethoxyflavone O-gluA
38	11.32	C₂₂H₂₂O₁₂	479.116 73	3.50	461, 317	477.103 49	0.75	462, 315, 314, 300, 299	Tetrahydroxymethoxyflavone 3-O-hex
39	11.44	C₂₈H₃₂O₁₆	625.174 26	3.29	479, 317, 302	623.161 13	1.01	477, 315	Tetrahydroxymethoxyflavone O-rha-O-hex
40	11.62	C₂₂H₂₀O₁₃	493.095 89	3.61	475, 317	491.082 64	0.96	357, 315	Tetrahydroxymethoxyflavone O-gluA
41	11.68	C₂₂H₂₂O₁₂	479.116 67	3.62	461, 317	477.103 49	0.75	462, 315, 300	Tetrahydroxymethoxyflavone O-hex
42	11.68	C₂₈H₃₀O₁₇	639.153 50	3.25	621, 477, 459, 301, 286, 258	637.140 26	1.20	-	Trihydroxymethoxyflavone O-hex-O-gluA
43	11.83	C₂₂H₂₀O₁₃	493.095 83	3.73	475, 317	491.082 18	1.90	-	Tetrahydroxymethoxyflavone O-gluA
44	11.84	C₂₂H₂₂O₁₂	479.116 82	3.31	461, 317	477.104 25	-0.84	-	Tetrahydroxymethoxyflavone O-hex
45	12.54	C₂₁H₂₀O₁₁	449.106 17	3.72	431, 287	447.092 90	0.86	327, 285, 284, 255	Astragaline*
46	12.70	C₂₇H₂₈O₁₅	593.147 77	3.93	447, 271	591.136 11	-0.96	-	Trihydroxyflavone O-rha-O-gluA
47	13.03	C₂₁H₂₀O₁₁	449.106 81	2.29	287	447.092 32	2.15	285	Luteolin-4′-O-hex
48	13.15	C₂₁H₂₀O₁₀	433.111 79	3.69	271	431.097 53	1.94	269	Apigenin-7-O-β-D-glc^[6]
49	13.23	C₂₇H₃₀O₁₄	579.169 07	3.05	433, 271	577.155 76	0.90	269	Trihydroxyflavone O-rha-O-hex
50	13.26	C₂₁H₁₈O₁₁	447.090 60	3.54	271	445.077 00	1.42	269, 175	Apigenin-7-O-β-D-gluA^[13]
51	13.49	C₂₈H₃₀O₁₆	623.158 81	2.98	447, 301, 286, 258	621.145 39	1.15	321, 299.284, 256	Trihydroxymethoxyflavone O-rha-O-gluA
52	13.73	C₂₈H₃₂O₁₅	609.179 32	3.41	463, 301, 286, 258	607.165 77	1.77	461, 443, 299, 285	Diosimin*
53	14.00	C₂₈H₃₀O₁₆	623.158 26	3.86	447, 301, 286, 258	621.145 20	1.46	477, 321, 299, 284	Trihydroxymethoxyflavone O-rha-O-gluA
54	14.07	C₂₂H₂₂O₁₁	463.121 28	4.78	301	461.108 49	0.96	446, 313, 299, 284	Diosmetin-7-O-β-D-glc or chrysoeriol-7-O-β-D-glc or isomer^{[6, 16]}
55	14.14	C₂₂H₂₀O₁₂	477.100 95	3.79	301, 286	475.087 62	1.22	371, 341, 299, 284, 175	5, 7, 4′-Dihydroxy-3′-methoxy flavone-7-O-β-D-galacturonide or isomer^[13]
56	14.14	C₂₈H₃₂O₁₅	609.179 44	3.22	463, 301, 286, 258	607.166 02	1.35	-	Trihydroxymethoxyflavone O-rha-O-hex
57	14.32	C₂₃H₂₂O₁₃	507.111 33	3.93	489, 331	505.098 39	0.74	-	Trihydroxydimethoxyflavone O-gluA
58	14.59	C₂₈H₃₂O₁₅	609.179 20	3.61	463, 301, 286, 258	607.166 75	0.15	-	Trihydroxymethoxyflavone O-rha-O-hex
59	14.63	C₂₈H₂₄O₁₄	585.122 01	3.20	567, 411, 345, 303, 283	583.108 34	1.69	463, 301	6″-O-(4-Hydroxybenzoyl) hyperoside^[13]
60	14.68	C₂₂H₂₂O₁₁	463.121 66	3.96	301, 287	461.108 76	0.38	-	Diosmetin-7-O-β-D-glc or chrysoeriol-7-O-β-D-glc or isomer^{[6, 16]}
61	14.71	C₂₂H₂₀O₁₂	477.100 74	4.23	301, 286	475.087 68	1.09	371, 341, 299, 284, 175	5, 7, 4′-Dihydroxy-3′-methoxy flavone-7-O-β-D-galacturonide or isomer^[13]
62	15.07	C₂₃H₂₄O₁₂	493.132 51	3.13	331	491.120 00	-1.02	-	Tricin-7-O-glc^{[18, 19]}
63	15.18	C₂₃H₂₂O₁₃	507.111 48	3.63	331	505.097 66	2.18	329	Trihydroxydimethoxyflavone O-gluA
64	15.30	C₂₈H₂₈O₁₇	637.138 00	3.03	619, 461, 443, 327, 285, 242	635.124 02	2.13	351	Acacetin-digluA^[17]
65	15.74	C₂₃H₂₂O₁₃	507.111 39	3.81	489, 331, 316	505.098 02	1.47	401, 371, 329, 175	Trihydroxydimethoxyflavone O-gluA
66	16.19	C₂₂H₂₀O₁₂	477.100 83	4.04	301, 287	475.087 95	0.52	299, 285	Luteolin-7-O-gluA-6″-methyl ester^[13]
67	17.87	C₂₂H₂₀O₁₂	477.100 80	4.10	301	475.087 74	0.97	-	5, 7, 4′-Dihydroxy-3′-methoxy flavone-7-O-β-D-galacturonide or isomer^[13]
68	17.87	C₂₂H₂₂O₁₁	463.121 73	3.80	301, 287	461.109 47	-1.16	-	Diosmetin-7-O-β-D-glc or chrysoeriol-7-O-β-D-glc or isomer^{[6, 16]}
69	18.63	C₂₃H₂₂O₁₂	491.116 46	3.96	315	489.103 18	1.37	313, 175	Dihydroxydimethoxyflavanone O-gluA
70	18.87	C₁₅H₁₀O₆	287.054 14	3.06	269, 259, 245, 241, 153	285.040 13	1.16	285, 243, 241, 217, 199, 175	Luteolin*
71	18.95	C₁₆H₁₂O₅	285.073 91	6.48	270, 253, 229, 225, 181, 137	283.059 72	5.2	268	Calycosin*
72	19.19	C₂₂H₂₀O₁₁	461.106 32	3.30	443, 271	459.093 72	-0.95	283, 269, 268	Trihydroxyflavone 3-O-gluA methyl ester
73	19.35	C₂₈H₃₀O₁₅	607.163 82	3.18	461, 285	605.150 63	0.93	321, 283, 268	Dihydroxymethoxyflavone O-rha-O-gluA
74	19.59	C₂₈H₃₂O₁₄	593.184 63	3.13	575, 447, 285	591.169 68	3.80	445, 283, 268	Dihydroxymethoxyflavone O-hex-O-rha
75	19.71	C₂₃H₂₂O₁₂	491.116 12	4.66	315, 301	489.103 52	0.67	-	Diosmetin-7-O-β-D-gluA methyl ester or isomer^[13]
76	19.82	C₃₀H₂₆O₁₃	595.142 27	3.95	329, 309, 287	593.129 15	1.54	327, 285	Tiliroside^[17]
77	19.90	C₂₃H₂₂O₁₂	491.116 58	3.72	315, 301	489.106 69	-5.80	-	Diosmetin-7-O-β-D-gluA methyl ester or isomer^[13]
78	20.14	C₂₂H₂₀O₁₁	461.106 23	3.49	285	459.092 86	0.92	283, 175	Wogonoside^[17]
79	20.29	C₂₃H₂₂O₁₂	491.116 39	4.11	315	489.103 15	1.43	-	Dihydroxydimethoxyflavanone O-gluA
80	20.33	C₁₇H₁₄O₇	331.080 99	0.72	316, 299, 271, 169, 123	-	-	-	Tricin or 5, 7, 4′-trihydroxy-3′, 5′-dimethoxyflavone^{[15, 18]}
81	21.03	C₁₅H₁₀O₅	271.059 57	1.96	271, 253, 243, 229, 225, 203, 163, 153, 145	269.045 23	1.17	269, 225, 201, 149	Apigenin*
82	21.51	C₁₆H₁₂O₆	301.069 95	2.38	286	299.055 79	1.07	284	Hispidulin*
83	24.02	C₁₆H₁₂O₅	285.075 65	0.35	285, 270, 257, 225, 211, 153	-	-	-	Apigenin-7-methyl ether^[14]
84	24.21	C₂₇H₃₀O₁₀	515.189 21	3.82	497, 479, 369, 313	513.176 39	0.45	367, 366, 351, 323	Baohuoside Ⅰ*

No.

t_R/min

Formula

MS (+)

Error (10^-6) (+)

MS/MS (+)

MS (-)

Error (10^-6) (-)

MS/MS (-)

Identification

5.52

C₂₇H₂₈O₁₈

641.132 63

3.45

479, 303

639.118 96

2.07

463, 301

Pentahydroxyflavone O-hex-O-gluA

5.58

C₂₁H₂₀O₁₀

433.111 39

3.55

415, 397, 379, 367, 337, 313, 283

431.098 02

0.81

Trihydroxy flavone C-glc^{[21, 22]}

5.95

C₂₇H₃₀O₁₆

611.158 26

3.94

593, 575, 565, 557, 545, 539, 527, 515, 497, 491, 473, 449, 355, 267, 221

609.144 47

2.69

591, 519, 489, 429, 399, 369

Luteolin-6, 8-di-C-glc^{[21, 22]}

5.95

C₂₇H₃₀O₁₅

595.163 51

3.76

577, 559, 541, 529, 523, 511, 499, 475, 457, 445, 415, 379, 337, 313

593.150 51

1.15

503, 473, 353, 311

Apigenin-6, 8-di-C-hex^{[21, 22]}

6.48

C₂₁H₂₀O₉

417.116 82

2.86

399, 381, 363, 351, 321, 297

415.102 78

1.62

295

Dihydroxy flavone C-glc^{[21, 22]}

6.71

C₂₇H₃₀O₁₅

595.163 51

3.76

577, 559, 541, 529, 523, 511, 499, 475, 457, 439, 421, 409, 379, 355

593.150 57

1.05

575, 503, 473, 383, 353

Apigenin-6, 8-di-C-hex^{[21, 22]}

6.87

C₂₂H₂₂O₁₀

447.126 83

3.91

429, 411, 393, 381, 351, 327

445.115 02

-2.24

Dihydroxy methoxyflavone C-glc^{[21, 22]}

7.15

C₂₇H₂₈O₁₈

641.133 24

2.50

479, 303

639.119 38

1.42

Pentahydroxyflavone O-hex-O-gluA

7.40

C₂₇H₃₀O₁₆

611.158 45

3.62

449, 431, 395, 383, 355, 329, 287, 267, 221

609.145 02

1.78

Tetrahydroxyflavone O-dihex

7.56

C₂₇H₂₆O₁₈

639.116 76

3.81

463, 445, 287

637.104 06

0.91

475, 351, 285

Luteolin-7-O-digluA^[4]

7.68

C₂₇H₃₀O₁₆

611.158 57

3.43

593, 491, 449, 431, 413, 383, 355, 329, 287, 267, 221

609.146 73

-1.02

489, 429, 357, 327

Kaempferol-6, 8-di-C-glc^{[21, 22]}

7.90

C₂₇H₃₀O₁₆

611.158 45

3.62

593, 565, 465, 449, 355, 303, 267, 221

609.144 96

1.88

463, 447, 301

Pentahydroxyflavone O-rha-O-hex

8.05

C₂₁H₂₀O₁₁

449.106 08

3.92

431, 413, 395, 383, 353, 329, 299

447.092 99

0.66

429, 411, 357, 327, 297

Isoorientin*

8.30

C₂₁H₁₈O₁₃

479.080 26

3.68

303

477.067 20

0.55

397, 373, 343, 301

Pentahydroxy flavone O-gluA

8.46

C₂₁H₂₀O₁₂

465.101 10

3.56

303

463.087 52

1.46

301

Pentahydroxyflavone O-hex

9.05

C₂₇H₃₀O₁₆

611.158 69

3.23

449, 355, 287

609.144 71

2.29

477, 447, 285

Tetrahydroxyflavone O-dihex

9.13

C₂₇H₂₆O₁₇

623.122 31

3.16

463, 447, 271

621.109 31

0.66

445, 351

Apigenin-7-O-digluA

9.59

C₂₉H₃₆O₁₆

641.205 26

3.67

623, 605, 487, 479, 461, 443, 325, 317

639.191 10

3.06

477, 315

Tetrahydroxymethoxyflavone O-dihex

9.70

C₂₇H₃₀O₁₅

595.163 76

3.34

449, 287

593.149 54

2.78

Luteolin-O-rutinoside or isomer^[4]

9.78

C₂₇H₃₀O₁₆

611.158 81

3.03

465, 449, 371, 335, 303, 267

609.145 08

1.69

343, 301, 300, 271, 255, 179

Rutin*

9.86

C₂₈H₂₈O₁₈

653.132 57

3.48

477, 459, 441, 397, 367, 343, 313, 301, 286, 258, 229

651.119 75

0.89

571, 457, 395, 371, 351, 299

Diosmetin-7-O-digluA or isomer^[4]

9.98

C₂₁H₂₀O₁₀

433.111 39

3.55

415, 397, 379, 367, 337, 313, 283

431.098 02

0.81

413, 341, 311

Trihydroxy flavone C-glc^{[21, 22]}

10.02

C₂₁H₂₀O₁₂

465.101 32

3.09

303

463.087 68

1.12

301, 300

Hyperoside*

10.25

C₂₁H₁₈O₁₃

479.080 75

2.65

461, 443, 325, 303

477.067 05

0.87

301

Pentahydroxyflavone O-gluA

10.38

C₂₁H₂₀O₁₂

465.100 98

3.82

303

463.087 59

1.31

301, 300

Isoquercitrin*

10.42

C₂₁H₂₀O₁₁

449.106 20

3.66

287

447.092 62

1.48

327, 285, 284

Kaempferol-3-O-galactoside^[20]

10.42

C₂₁H₁₈O₁₂

463.085 27

3.97

287

461.071 90

1.41

285, 175

Scutellarin*

10.42

C₂₈H₂₈O₁₈

653.132 45

3.67

477, 459, 397, 367, 343, 313, 301, 286, 258, 229

651.119 38

1.39

571, 457, 395, 371, 351, 341, 323, 299, 289

Diosmetin-7-O-digluA or isomer^[4]

10.54

C₂₈H₃₂O₁₆

625.174 26

3.29

479, 317, 302

623.162 29

-0.85

477, 315

Tetrahydroxymethoxyflavone O-rha-O-hex

10.57

C₂₁H₁₈O₁₂

463.085 17

4.18

287

461.071 59

2.08

381, 357, 327, 285

Luteolin-O-gluA^[4]

10.58

C₂₁H₁₈O₁₃

479.081 09

1.95

461, 435, 317, 303, 285, 275, 259

Pentahydroxyflavone O-gluA

10.61

C₂₁H₂₀O₁₁

449.106 45

3.10

287

447.092 62

1.48

327, 285

Luteolin-7-O-glc*

10.73

C₂₈H₃₀O₁₇

639.153 63

3.05

463, 301, 286, 258

637.140 75

0.43

619, 605, 447, 337, 299, 284, 256

Trihydroxymethoxyflavone O-gluA-O-hex

10.92

C₂₇H₃₀O₁₅

595.163 70

3.44

449, 287, 271

593.149 74

2.45

447, 285, 269

Luteolin-O-rutinoside or isomer^[4]

11.13

C₂₈H₃₀O₁₇

639.153 87

2.67

477, 459, 323, 301, 286, 258

637.139 47

2.43

Trihydroxymethoxyflavone O-hex-O-gluA

11.15

C₂₈H₃₂O₁₆

625.175 90

0.66

479, 317, 302

623.164 98

-5.16

Tetrahydroxymethoxyflavone O-rha-O-hex

11.21

C₂₂H₂₀O₁₃

493.095 92

3.55

317

491.082 34

1.57

357, 315

Tetrahydroxymethoxyflavone O-gluA

11.32

C₂₂H₂₂O₁₂

479.116 73

3.50

461, 317

477.103 49

0.75

462, 315, 314, 300, 299

Tetrahydroxymethoxyflavone 3-O-hex

11.44

C₂₈H₃₂O₁₆

625.174 26

3.29

479, 317, 302

623.161 13

1.01

477, 315

Tetrahydroxymethoxyflavone O-rha-O-hex

11.62

C₂₂H₂₀O₁₃

493.095 89

3.61

475, 317

491.082 64

0.96

357, 315

Tetrahydroxymethoxyflavone O-gluA

11.68

C₂₂H₂₂O₁₂

479.116 67

3.62

461, 317

477.103 49

0.75

462, 315, 300

Tetrahydroxymethoxyflavone O-hex

11.68

C₂₈H₃₀O₁₇

639.153 50

3.25

621, 477, 459, 301, 286, 258

637.140 26

1.20

Trihydroxymethoxyflavone O-hex-O-gluA

11.83

C₂₂H₂₀O₁₃

493.095 83

3.73

475, 317

491.082 18

1.90

Tetrahydroxymethoxyflavone O-gluA

11.84

C₂₂H₂₂O₁₂

479.116 82

3.31

461, 317

477.104 25

-0.84

Tetrahydroxymethoxyflavone O-hex

12.54

C₂₁H₂₀O₁₁

449.106 17

3.72

431, 287

447.092 90

0.86

327, 285, 284, 255

Astragaline*

12.70

C₂₇H₂₈O₁₅

593.147 77

3.93

447, 271

591.136 11

-0.96

Trihydroxyflavone O-rha-O-gluA

13.03

C₂₁H₂₀O₁₁

449.106 81

2.29

287

447.092 32

2.15

285

Luteolin-4′-O-hex

13.15

C₂₁H₂₀O₁₀

433.111 79

3.69

271

431.097 53

1.94

269

Apigenin-7-O-β-D-glc^[6]

13.23

C₂₇H₃₀O₁₄

579.169 07

3.05

433, 271

577.155 76

0.90

269

Trihydroxyflavone O-rha-O-hex

13.26

C₂₁H₁₈O₁₁

447.090 60

3.54

271

445.077 00

1.42

269, 175

Apigenin-7-O-β-D-gluA^[13]

13.49

C₂₈H₃₀O₁₆

623.158 81

2.98

447, 301, 286, 258

621.145 39

1.15

321, 299.284, 256

Trihydroxymethoxyflavone O-rha-O-gluA

13.73

C₂₈H₃₂O₁₅

609.179 32

3.41

463, 301, 286, 258

607.165 77

1.77

461, 443, 299, 285

Diosimin*

14.00

C₂₈H₃₀O₁₆

623.158 26

3.86

447, 301, 286, 258

621.145 20

1.46

477, 321, 299, 284

Trihydroxymethoxyflavone O-rha-O-gluA

14.07

C₂₂H₂₂O₁₁

463.121 28

4.78

301

461.108 49

0.96

446, 313, 299, 284

Diosmetin-7-O-β-D-glc or chrysoeriol-7-O-β-D-glc or isomer^{[6, 16]}

14.14

C₂₂H₂₀O₁₂

477.100 95

3.79

301, 286

475.087 62

1.22

371, 341, 299, 284, 175

5, 7, 4′-Dihydroxy-3′-methoxy flavone-7-O-β-D-galacturonide or isomer^[13]

14.14

C₂₈H₃₂O₁₅

609.179 44

3.22

463, 301, 286, 258

607.166 02

1.35

Trihydroxymethoxyflavone O-rha-O-hex

14.32

C₂₃H₂₂O₁₃

507.111 33

3.93

489, 331

505.098 39

0.74

Trihydroxydimethoxyflavone O-gluA

14.59

C₂₈H₃₂O₁₅

609.179 20

3.61

463, 301, 286, 258

607.166 75

0.15

Trihydroxymethoxyflavone O-rha-O-hex

14.63

C₂₈H₂₄O₁₄

585.122 01

3.20

567, 411, 345, 303, 283

583.108 34

1.69

463, 301

6″-O-(4-Hydroxybenzoyl) hyperoside^[13]

14.68

C₂₂H₂₂O₁₁

463.121 66

3.96

301, 287

461.108 76

0.38

Diosmetin-7-O-β-D-glc or chrysoeriol-7-O-β-D-glc or isomer^{[6, 16]}

14.71

C₂₂H₂₀O₁₂

477.100 74

4.23

301, 286

475.087 68

1.09

371, 341, 299, 284, 175

5, 7, 4′-Dihydroxy-3′-methoxy flavone-7-O-β-D-galacturonide or isomer^[13]

15.07

C₂₃H₂₄O₁₂

493.132 51

3.13

331

491.120 00

-1.02

Tricin-7-O-glc^{[18, 19]}

15.18

C₂₃H₂₂O₁₃

507.111 48

3.63

331

505.097 66

2.18

329

Trihydroxydimethoxyflavone O-gluA

15.30

C₂₈H₂₈O₁₇

637.138 00

3.03

619, 461, 443, 327, 285, 242

635.124 02

2.13

351

Acacetin-digluA^[17]

15.74

C₂₃H₂₂O₁₃

507.111 39

3.81

489, 331, 316

505.098 02

1.47

401, 371, 329, 175

Trihydroxydimethoxyflavone O-gluA

16.19

C₂₂H₂₀O₁₂

477.100 83

4.04

301, 287

475.087 95

0.52

299, 285

Luteolin-7-O-gluA-6″-methyl ester^[13]

17.87

C₂₂H₂₀O₁₂

477.100 80

4.10

301

475.087 74

0.97

5, 7, 4′-Dihydroxy-3′-methoxy flavone-7-O-β-D-galacturonide or isomer^[13]

17.87

C₂₂H₂₂O₁₁

463.121 73

3.80

301, 287

461.109 47

-1.16

Diosmetin-7-O-β-D-glc or chrysoeriol-7-O-β-D-glc or isomer^{[6, 16]}

18.63

C₂₃H₂₂O₁₂

491.116 46

3.96

315

489.103 18

1.37

313, 175

Dihydroxydimethoxyflavanone O-gluA

18.87

C₁₅H₁₀O₆

287.054 14

3.06

269, 259, 245, 241, 153

285.040 13

1.16

285, 243, 241, 217, 199, 175

Luteolin*

18.95

C₁₆H₁₂O₅

285.073 91

6.48

270, 253, 229, 225, 181, 137

283.059 72

5.2

268

Calycosin*

19.19

C₂₂H₂₀O₁₁

461.106 32

3.30

443, 271

459.093 72

-0.95

283, 269, 268

Trihydroxyflavone 3-O-gluA methyl ester

19.35

C₂₈H₃₀O₁₅

607.163 82

3.18

461, 285

605.150 63

0.93

321, 283, 268

Dihydroxymethoxyflavone O-rha-O-gluA

19.59

C₂₈H₃₂O₁₄

593.184 63

3.13

575, 447, 285

591.169 68

3.80

445, 283, 268

Dihydroxymethoxyflavone O-hex-O-rha

19.71

C₂₃H₂₂O₁₂

491.116 12

4.66

315, 301

489.103 52

0.67

Diosmetin-7-O-β-D-gluA methyl ester or isomer^[13]

19.82

C₃₀H₂₆O₁₃

595.142 27

3.95

329, 309, 287

593.129 15

1.54

327, 285

Tiliroside^[17]

19.90

C₂₃H₂₂O₁₂

491.116 58

3.72

315, 301

489.106 69

-5.80

Diosmetin-7-O-β-D-gluA methyl ester or isomer^[13]

20.14

C₂₂H₂₀O₁₁

461.106 23

3.49

285

459.092 86

0.92

283, 175

Wogonoside^[17]

20.29

C₂₃H₂₂O₁₂

491.116 39

4.11

315

489.103 15

1.43

Dihydroxydimethoxyflavanone O-gluA

20.33

C₁₇H₁₄O₇

331.080 99

0.72

316, 299, 271, 169, 123

Tricin or 5, 7, 4′-trihydroxy-3′, 5′-dimethoxyflavone^{[15, 18]}

21.03

C₁₅H₁₀O₅

271.059 57

1.96

271, 253, 243, 229, 225, 203, 163, 153, 145

269.045 23

1.17

269, 225, 201, 149

Apigenin*

21.51

C₁₆H₁₂O₆

301.069 95

2.38

286

299.055 79

1.07

284

Hispidulin*

24.02

C₁₆H₁₂O₅

285.075 65

0.35

285, 270, 257, 225, 211, 153

Apigenin-7-methyl ether^[14]

24.21

C₂₇H₃₀O₁₀

515.189 21

3.82

497, 479, 369, 313

513.176 39

0.45

367, 366, 351, 323

Baohuoside Ⅰ*

No.	t_R/min	Formula	MS (+)	Error (10^-6) (+)	Other adduct ion (+)	MS/MS (+)	MS (-)	Error (10^-6) (-)	MS/MS (-)	Other adduct ion (-)	Identification
1	5.68	C₄₁H₅₆O₂₅	966.344 36	0.56	971.298 89(+Na)	–	947.302 86	0.98	785, 623	983.277 89(+Cl)	β-D-Glp, (dihydroxypheny) ethyl O-hex-O-hex-O-rha, caff
2	6.03	C₄₀H₅₄O₂₅	952.326 97	2.43	935.301 45(+H), 957.282 23(+Na)	773, 611, 479, 457, 325, 295	933.287 05	1.17	801, 771, 753, 639, 609, 591, 477, 459, 447	969.263 85(+Cl)	β-D-Glp, (dihydroxypheny) ethyl O-hex-O-hex-O-pen, caff
3	6.11	C₃₅H₄₆O₂₁	820.284 73	2.81	825.239 87(+Na)	785, 623, 587, 477, 459, 325	801.244 75	1.41	783, 691, 639, 621, 529	837.221 37(+Cl)	Suspensaside-O-hex^{[26, 30]}
4	6.11	C₄₁H₅₆O₂₅	966.342 96	2.04	971.298 40(+Na)	–	947.302 37	1.50	785, 767, 639, 623, 605, 461	–	β-D-Glp, (dihydroxypheny) ethyl O-hex-O-hex-O-rha, caff
5	6.36	C₄₁H₅₆O₂₅	966.344 06	0.88	–	–	947.303 10	0.73	785, 623	–	β-D-Glp, (dihydroxypheny) ethyl O-hex-O-hex-O-rha, caff
6	6.36	C₁₆H₂₀O₉	374.143 59	2.72	–	339, 195, 177	355.103 06	1.11	193	–	Glucose ester of (E)-ferulic acid^[16]
7	6.52	C₄₁H₅₆O₂₅	966.343 75	1.21	971.298 40(+Na)	787, 625, 479, 325	947.303 16	0.67	785, 767, 639, 623, 605, 461	–	β-D-Glp, (dihydroxypheny) ethyl O-hex-O-hex-O-rha, caff
8	6.55	C₄₁H₅₆O₂₆	982.338 13	1.74	987.293 27(+Na)	803, 649, 641, 487, 479, 325	963.298 10	0.63	801, 783, 639, 621, 477, 459	999.274 35 (+Cl)	β-D-Glp, (dihydroxypheny) ethyl O-hex-O-hex-O-hex, caff
9	6.75	C₃₅H₄₆O₂₁	820.285 46	1.90	803.258 24(+H), 825.240 42(+Na)	803, 641, 487, 479, 461, 443, 325, 317, 307, 263	801.243 77	2.63	783, 639, 621, 485, 477, 459, 305	837.220 28(+Cl)	Maxoside or Lagotiside C or isomer^{[26, 27]}
10	6.75	C₂₉H₃₆O₁₇	674.227 11	2.99	679.182 62(+Na)	639, 621, 487, 477, 459, 325	655.186 71	1.93	637, 545, 503, 493, 475, 383, 323, 251	691.163 27(+Cl)	β-Hydroxyl-plantamajoside or isomer^{[26, 30]}
11	6.83	C₄₀H₅₄O₂₄	936.332 34	2.17	941.287 48(+Na)	757, 625, 611, 603, 479, 471, 457, 325	917.291 69	1.67	785, 771, 755, 737, 623, 609, 477, 461	953.267 82(+Cl), 963.297 06(+COOH)	β-D-Glp, (dihydroxypheny) ethyl O-hex-O-rha-O-pen, caff
12	6.87	C₄₁H₅₆O₂₅	966.343 14	1.85	971.298 03(+Na)	787, 625, 471, 325	947.302 92	0.92	785, 771, 623, 605, 461	983.278 32(+Cl)	β-D-Glp, (dihydroxypheny) ethyl O-hex-O-hex-O-rha, caff
13	6.91	C₂₉H₃₆O₁₇	674.227 05	3.09	679.182 31(+Na)	639, 621, 487, 477, 459, 325	655.187 19	1.19	637, 545, 503, 493, 475, 383, 323, 251	691.163 64(+Cl)	β-Hydroxyl-plantamajoside or isomer^{[26, 30]}
14	7.11	C₄₁H₅₆O₂₅	966.343 14	1.85	971.298 71(+Na)	787, 625, 493, 471, 339	947.302 86	0.98	815, 785, 771, 753, 639, 621	983.276 31(+Cl)	β-D-Glp, (dihydroxypheny) ethyl O-hex-O-hex-O-pen, feru
15	7.32	C₄₁H₅₆O₂₅	966.344 42	0.50	971.298 89(+Na)	-	947.302 61	1.25	785, 771, 753, 623, 605, 461	-	β-D-Glp, (dihydroxypheny) ethyl O-hex-O-hex-O-rha, caff
16	7.36	C₂₉H₃₆O₁₆	658.231 87	3.58	641.205 44(+H), 663.187 38(+Na)	641, 479, 461, 325	639.192 02	3.58	477, 459, 315	675.169 25(+Cl)	β-D-Glp, (dihydroxyphenyl) ethyl O-hex, caff (isomer of Plantamajoside)
17	7.40	C₄₂H₅₆O₂₆	994.337 34	2.53	999.292 91(+Na)	815, 661, 529, 457, 367, 325	975.297 97	0.75	933, 843, 813, 795, 771, 753, 681, 639, 621, 609	1 011.274 17(+Cl)	β-D-Glp, (dihydroxypheny) ethyl O-hex-O-hex-O-pen-acetyl, caff
18	7.60	C₂₉H₃₆O₁₆	658.231 81	3.67	663.187 07(+Na)	641, 623, 477, 471, 325	639.192 44	0.97	621, 529, 487, 477, 469, 459, 441, 179	675.166 20(+Cl)	Suspensaside^{[26, 30]}
19	7.76	C₃₅H₄₆O₂₀	804.289 98	2.66	787.263 79(+H), 809.245 36(+Na)	641, 633, 625, 607, 487, 479, 471, 461, 443, 435, 417, 325, 309	785.248 96	2.55	767, 639, 623, 605, 477, 461, 443, 315	821.225 10(+Cl)	Echinacoside*
20	7.90	C₄₂H₅₈O₂₆	996.353 27	2.24	1 001.307 62(+Na)	663, 493, 339	977.312 93	1.46	815, 801, 783, 653, 639, 621	1 013.290 71(+Cl)	β-D-Glp, (dihydroxypheny) ethyl O-hex-O-hex-O-hex, feru
21	7.90	C₄₃H₅₈O₂₇	1 024.347 90	2.46	1 029.303 47(+Na)	-	1 005.307 62	1.64	843, 801, 783, 681, 639, 585	1 041.284 91(+Cl)	β-D-Glp, (dihydroxypheny) ethyl O-hex-O-hex-O-hex-acetyl, caff
22	8.21	C₃₇H₄₈O₂₂	862.295 53	2.39	867.250 79(+Na)	691, 683, 529, 511, 479, 367, 325	843.255 31	1.35	801, 681, 639, 621, 519, 477, 459	879.231 51(+Cl)	β-D-Glp, (dihydroxyphenyl) ethyl O-hex-O-hex-acetyl, caff
23	8.21	C₃₁H₃₈O₁₈	716.237 49	3.08	721.192 87(+Na)	681, 529, 477, 459, 367, 325	697.197 81	1.04	679, 655, 637, 587, 535, 517, 475, 457	733.176 09(+Cl)	β-Hydroxyl-acetyl-plantamajoside or isomer^{[26, 30]}
24	8.46	C₃₁H₃₈O₁₈	716.237 79	2.65	721.192 87(+Na)	681, 529, 477, 367, 325	697.197 57	1.39	679, 655, 637, 587, 535, 517, 475	733.174 50(+Cl)	β-Hydroxyl-acetyl-plantamajoside or isomer^{[26, 30]}
25	8.57	C₃₄H₄₄O₂₀	790.274 72	2.20	795.230 16(+Na)	479, 461, 457, 325, 295, 277	771.234 50	1.06	639, 609, 591, 477, 447, 315	807.209 66(+Cl)	β-D-Glp, (dihydroxyphenyl) ethyl O-hex-O-pen, caff
26	8.66	C₄₀H₅₄O₂₄	936.332 21	2.31	941.287 23(+Na)	–	917.291 69	1.67	755, 623, 593, 461	953.266 97(+Cl), 963.295 10(+COOH)	β-D-Glp, (dihydroxypheny) ethyl O-hex-O-rha-O-pen, caff
27	9.05	C₃₄H₄₄O₂₀	790.274 48	2.51	773.247 99(+H), 795.229 68(+Na)	611, 593, 487, 479, 457, 325, 307, 295, 277	771.233 95	1.77	639, 609, 591, 477, 447, 429, 323, 315, 297, 275	807.209 90(+Cl)	β-D-Glp, (dihydroxyphenyl) ethyl O-hex-O-pen, caff
28	9.17	C₃₅H₄₆O₂₁	820.285 22	2.20	803.258 85(+H), 825.240 23(+Na)	803, 649, 641, 487, 479, 461, 443, 325, 317, 307	801.243 47	3.01	639, 621, 477, 459, 323, 315, 297, 263	837.219 79(+Cl)	Maxoside or lagotiside C or isomer^{[26, 27]}
29	9.28	C₃₅H₄₆O₂₀	804.290 10	2.50	809.246 09(+Na)	787, 641, 633, 625, 487, 479, 471, 435, 325, 309	785.250 73	0.30	639, 623, 605, 477, 461, 315	821.227 23(+Cl)	β-D-Glp, (dihydroxyphenyl) ethyl O-rha-O-hex, caff (isomer of echinacoside)
30	9.41	C₄₁H₅₆O₂₅	966.343 20	1.79	971.298 58(+Na)	–	947.302 86	0.98	801, 785, 767, 639, 623, 605, 461	983.278 81(+Cl)	β-D-Glp, (dihydroxypheny) ethyl O-hex-O-hex-O-rha, caff
31	9.49	C₃₅H₄₆O₂₀	804.290 34	2.20	787.262 70(+H), 809.245 73(+Na)	787, 625, 607, 571, 479, 471, 461, 435, 417, 325, 317, 309, 291, 273	785.250 55	0.53	639, 623, 605, 477, 461	821.226 87(+Cl)	β-D-Glp, (dihydroxyphenyl) ethyl O-rha-O-hex, caff (isomer of echinacoside)
32	9.53	C₃₆H₄₈O₂₀	818.305 42	2.87	801.279 05(+H), 823.260 74(+Na)	801, 647, 639, 493, 485, 475, 339	799.264 53	2.61	637, 623, 605, 477, 461, 315, 305	835.241 03(+Cl)	Jionoside A1 or isomer^[26]
33	9.59	C₂₉H₃₆O₁₆	658.232 42	2.72	641.205 26(+H), 663.187 68(+Na)	641, 487, 479, 461, 443, 325, 317, 307	639.191 10	3.06	477, 459, 315, 297, 179	675.167 72(+Cl)	Plantamajoside*
34	9.74	C₃₅H₄₆O₂₀	804.289 79	2.90	787.261 41(+H), 809.245 12(+Na)	787, 633, 625, 487, 479, 471, 461, 453, 435, 325, 309	785.250 00	1.23	639, 623, 605, 477, 461, 443, 307	821.226 07(+Cl)	β-D-Glp, (dihydroxyphenyl) ethyl O-rha-O-hex, caff (isomer of echinacoside)
35	9.98	C₃₄H₄₄O₁₉	774.279 24	2.99	779.234 56(+Na)	757, 625, 479, 471, 325	755.239 87	0.70	609, 593, 575, 461, 447, 443	791.216 37(+Cl), 801.245 42(+COOH)	Ehrenoside or isomer^[31]
36	10.22	C₃₀H₃₈O₁₆	672.247 44	3.62	655.220 95(+H), 677.202 58(+Na)	655, 471, 325	653.209 35	-0.98	635, 621, 543, 487, 459	689.186 65(+Cl), 699.214 72(+COOH)	Suspensaside methyl ether^{[26, 30]}
37	10.34	C₂₃H₂₆O₁₁	501.134 92(+Na)	3.63	496.179 60	347, 321	477.139 77	0.97	315, 301, 297, 179, 161	–	β-D-Glp, (dihydroxypheny) ethyl, caff
38	10.46	C₃₄H₄₄O₁₉	774.279 60	2.52	779.234 99(+Na)	757, 625, 479, 471, 457, 325	755.239 56	1.11	623, 609, 593, 575, 461, 447, 443, 315	791.216 13(+Cl)	Ehrenoside or isomer^[31]
39	10.81	C₃₅H₄₆O₂₀	804.290 22	2.35	809.245 30(+Na)	625, 479, 471, 325, 317	785.250 67	0.38	623, 477, 461	821.227 11(+Cl)	β-D-Glp, (dihydroxyphenyl) ethyl O-rha-O-hex, caff (isomer of echinacoside)
40	10.81	C₃₇H₅₀O₂₁	848.316 83	1.75	853.271 97(+Na)	507, 339	829.277 16	0.03	667, 653, 635, 491, 473	865.252 01(+Cl)	β-D-Glp, (hydroxymethoxyphenyl) ethyl O-hex-O-hex, feru
41	11.00	C₂₉H₃₆O₁₅	642.237 49	2.81	625.210 88(+H), 647.192 75(+Na)	625, 607, 589, 571, 479, 471, 435, 325, 309, 301	623.196 47	2.68	477, 461, 443, 323, 315, 297, 251, 179	659.173 03(+Cl)	Verbascoside/Acteoside*
42	11.00	C₂₉H₃₄O₁₅	640.221 92	2.69	623.190 61(+H)	623, 605, 587, 477, 459, 325, 281, 263	621.181 40	1.76	487, 469, 459, 179	–	Suspensaside A^{[26, 30]}
43	11.17	C₃₅H₄₆O₂₁	820.285 28	2.12	803.256 29(+H), 825.240 78(+Na)	649, 479, 325,	801.244 51	1.71	639, 621, 477, 459, 323, 315	837.220 95(+Cl)	Maxoside or lagotiside C or isomer^{[26, 27]}
44	11.25	C₃₇H₄₈O₂₂	862.296 33	1.44	845.269 17(+H), 867.251 46(+Na)	691, 683, 529, 511, 479, 367, 325	843.254 76	2.00	801, 783, 681, 639, 621, 519, 477, 459	879.230 71(+Cl)	β-D-Glp, (dihydroxyphenyl) ethyl O-hex-O-hex-acetyl, caff
45	11.40	C₂₉H₃₆O₁₆	658.232 06	3.28	641.205 44(+H), 663.187 13(+Na)	641, 487, 479, 461, 443, 325, 307	639.192 32	1.15	477, 459, 323, 315, 305, 297, 251, 179	675.168 95(+Cl)	Plantainoside D^[27]
46	11.44	C₃₆H₄₆O₂₁	832.285 16	2.24	837.240 36(+Na)	683, 661, 529, 499, 479, 457, 367, 325, 295	813.244 87	1.24	771, 753, 681, 651, 633, 609, 591, 519, 477, 447	849.221 19(+Cl)	β-D-Glp, (dihydroxyphenyl) ethyl O-hex-O-pen-acetyl, caff
47	11.52	C₂₉H₃₆O₁₅	642.237 55	2.72	625.174 68(+H), 647.192 81(+Na)	625, 479, 471, 463, 325, 309	623.197 20	1.51	477, 461, 315	–	β-D-Glp, (dihydroxyphenyl) ethyl O-rha, caff (isomer of isoacteoside)
48	11.64	C₃₅H₄₆O₂₀	804.290 04	2.58	787.263 43(+H), 809.245 48(+Na)	625, 501, 493, 471, 339, 309, 291	785.250 37	0.76	653, 623, 609, 591, 491, 477, 459, 447, 315, 297	821.226 75(+Cl)	β-D-Glp, (dihydroxyphenyl) ethyl O-pen-O-hex, feru
49	11.80	C₃₆H₄₈O₂₁	834.300 84	2.20	839.255 86(+Na)	655, 501, 493, 339	815.260 80	0.90	653, 639, 621, 491, 477, 473, 459	851.237 49(+Cl)	β-D-Glp, (dihydroxyphenyl) ethyl O-hex-O-hex, feru
50	11.86	C₃₁H₃₈O₁₇	700.242 31	3.10	683.215 76(+H), 705.197 81(+Na)	683, 665, 647, 529, 511, 479, 367, 325, 307	681.201 90	2.53	639, 621, 519, 477, 459, 315	717.172 36(+Cl)	Hemiphroside B*
51	11.86	C₃₃H₄₂O₁₇	728.273 38	3.72	733.216 13(+Na)	529, 367, 325, 307	–	–	–	–	β-D-Glp, (dimethoxyphenyl) ethyl O-hex-acetyl, caff
52	12.02	C₃₆H₄₈O₂₀	818.305 91	2.26	801.279 85(+H), 823.261 17(+Na)	655, 647, 639, 501, 493, 485, 339, 283	799.265 50	1.40	781, 653, 637, 623, 605, 491, 477, 461	835.241 88(+Cl)	Jionoside A1 or isomer^[26]
53	12.06	C₃₄H₄₄O₂₀	790.274 72	2.20	773.247 92(+H), 795.229 86(+Na)	611, 479, 457, 325, 295	771.234 38	1.21	735, 639, 609, 591, 477, 447, 429, 323, 315, 251	807.210 75(+Cl)	β-D-Glp, (dihydroxyphenyl) ethyl O-hex-O-pen, caff
54	12.10	C₃₁H₃₈O₁₇	700.242 80	2.82	683.215 39(+H), 705.198 12(+Na)	683, 529, 479, 367, 325	681.202 94	1.00	639, 621, 519, 477, 459	–	2′-O-Acetyl-plantamajoside^[27]
55	12.34	C₃₀H₃₈O₁₆	672.247 86	2.98	655.221 19(+H), 677.203 06(+Na)	655, 501, 493, 339	653.207 76	1.45	491, 477, 459, 315, 297	689.184 27(+Cl), 699.213 20(+COOH)	β-D-Glp, (dihydroxyphenyl) ethyl O-hex, feru
56	12.38	C₂₉H₃₆O₁₅	642.237 49	2.81	625.210 82(+H), 647.192 75(+Na)	625, 607, 479, 471, 461, 435, 325, 309	623.197 33	1.30	477, 461, 443, 323, 315, 297, 251, 179	659.174 01(+Cl)	Isoacteoside*
57	12.42	C₃₁H₃₈O₁₇	700.242 37	3.45	705.197 75(+Na)	521, 367, 325	681.202 76	1.27	639, 519, 477, 459	–	β-D-Glp, (dihydroxyphenyl) ethyl O-hex-acetyl, caff (isomer of hemiphroside B)
58	12.62	C₃₇H₅₀O₂₀	832.321 41	2.41	815.294 25(+H), 837.276 55(+Na)	653, 507, 485, 339, 323, 305	813.281 56	0.87	667, 651, 637, 619, 491, 475, 473, 457, 427, 329, 287	849.257 75(+Cl)	Cistanoside B or glucopyranosyl (1-6) martynoside or isomer^{[26, 29]}
59	12.80	C₂₉H₃₆O₁₅	642.237 24	3.21	625.210 14(+H), 647.192 44(+Na)	625, 607, 589, 571, 553, 479, 471, 461, 453, 443, 435, 417, 325, 317, 309, 301, 291, 273, 255	623.197 27	1.40	477, 461, 443, 315, 297, 179	659.171 20(+Cl)	β-D-Glp, (dihydroxyphenyl) ethyl O-rha, caff (isomer of verbascoside)
60	12.87	C₃₀H₃₈O₁₆	672.247 62	3.36	655.220 76(+H), 677.203 00(+Na)	655, 501, 493, 339	653.208 07	0.98	491, 477, 459	689.185 06(+Cl), 699.213 01(+COOH)	β-D-Glp, (dihydroxyphenyl) ethyl O-hex, feru
61	13.15	C₂₉H₃₆O₁₄	626.242 55	2.93	631.198 12(+Na)	463, 325	607.202 33	1.48	461, 445	643.178 77(+Cl)	β-D-Glp, (hydroxyphenyl) ethyl O-rha, caff
62	13.30	C₃₀H₃₈O₁₆	672.247 80	3.07	677.203 06(+Na)	493, 475, 457, 325	653.207 52	1.82	491, 477, 315	689.184 20(+Cl), 699.216 43(+COOH)	β-D-Glp, (hydroxymethoxyphenyl) ethyl O-hex, caff
63	13.34	C₃₇H₅₀O₂₀	832.321 41	2.41	837.276 86(+Na)	653, 339, 323	813.281 13	1.40	651, 637, 619, 491, 475	849.256 90(+Cl)	Cistanoside B or isomer^[26]
64	13.37	C₃₁H₃₈O₁₇	700.243 10	2.38	705.198 43(+Na)	665, 529, 511, 479, 461, 367, 349, 325	681.202 70	1.35	639, 621, 519, 477, 459	–	β-D-Glp, (dihydroxyphenyl) ethyl O-hex-acetyl, caff (isomer of hemiphroside B)
65	13.41	C₂₉H₃₆O₁₄	626.241 88	4.03	609.214 78(+H), 631.197 27(+Na)	609, 463, 455, 309	607.202 76	0.77	461, 443, 315	643.179 32(+Cl)	Lipedoside A or isomer^[26]
66	13.89	C₃₅H₄₆O₁₈	772.300 29	2.59	777.255 62(+Na)	755, 593, 471, 447, 325, 309	753.260 25	1.18	591	789.237 85(+Cl)	Kankanoside I^[28]
67	14.17	C₃₀H₃₈O₁₅	656.252 93	3.08	639.226 38(+H), 661.208 37(+Na)	639, 493, 485, 339, 323, 277	637.212 59	1.89	491, 475, 461, 443, 315, 305, 297, 193	673.189 21(+Cl), 683.217 90(+COOH)	Leucosceptoside A^[26]
68	14.56	C₂₉H₃₆O₁₄	626.241 94	3.93	631.197 75(+Na)	609, 591, 463, 455, 437, 309, 293, 275	607.202 64	0.97	461, 443, 315	643.178 22(+Cl)	Lipedoside A or isomer^[26]
69	15.07	C₃₀H₃₈O₁₅	656.253 36	2.41	639.226 68(+H), 661.208 62(+Na)	639, 493, 471, 325	637.212 52	2.00	475, 329	673.188 48(+Cl)	β-D-Glp, (hydroxymethoxyphenyl) ethyl O-rha, caff
70	15.10	C₃₆H₄₈O₂₀	818.306 40	1.65	801.281 19(+H), 823.261 47(+Na)	639, 507, 471, 339, 309	799.265 81	1.01	667, 637, 623, 605, 491, 473, 461	835.241 94(+Cl), 845.271 24(+COOH)	β-D-Glp, (hydroxymethoxyphenyl) ethyl O-hex-O-pen, feru
71	15.39	C₃₇H₅₀O₂₀	832.321 90	1.80	815.295 10(+H), 837.277 22(+Na)	815, 785, 669, 653, 647, 507, 501, 485, 339	813.281 43	1.03	667, 651, 637, 619, 491, 475, 473, 457, 329, 305	849.257 63(+Cl)	Cistanoside B or isomer^[26]
72	15.43	C₃₃H₄₀O₁₈	742.253 30	2.75	747.208 74(+Na)	725, 707, 571, 503, 367, 247	723.213 62	0.78	681, 663, 639, 621, 561, 519, 501, 477, 459	759.191 89(+Cl)	β-D-Glp, (dihydroxyphenyl) ethyl O-hex-acetyl-acetyl, caff
73	15.47	C₃₀H₃₈O₁₅	656.252 99	2.99	661.208 68(+Na)	639, 621, 493, 485, 475, 467, 457, 449, 431, 339, 323, 305	637.213 50	0.46	491, 475, 461	673.189 88(+Cl), 683.219 60(+COOH)	Leucosceptoside A^[26]
74	15.54	C₃₇H₅₀O₂₁	848.316 96	1.59	853.272 16(+Na)	669, 507, 339	829.276 49	0.83	667, 653, 635, 505, 491, 473, 425, 329, 311, 265	865.252 75(+Cl)	β-D-Glp, (hydroxymethoxyphenyl) ethyl O-hex-O-hex, feru
75	15.90	C₃₇H₅₀O₂₀	832.321 53	2.26	–	653, 339, 323	813.281 37	1.10	667, 651, 637, 619, 491, 475, 473, 457, 305	849.258 06(+Cl)	Cistanoside B or isomer^[26]
76	15.99	C₃₂H₄₀O₁₇	714.258 73	2.36	719.213 87(+Na)	697, 529, 367, 325	695.218 44	1.20	653, 635, 519, 501, 491	731.195 56(+Cl)	β-D-Glp, (hydroxymethoxyphenyl) ethyl O-hex-acetyl, caff
77	16.36	C₃₁H₃₈O₁₇	700.242 61	3.10	683.216 13(+H), 705.197 88(+Na)	683, 529, 367, 325	681.202 70	1.35	639, 621, 519, 477, 459	–	β-D-Glp, (dihydroxyphenyl) ethyl O-hex-acetyl, caff (isomer of hemiphroside B)
78	16.44	C₃₁H₄₀O₁₆	686.263 24	3.32	669.235 90(+H), 691.218 57(+Na)	507, 501, 471, 339, 277	667.223 82	0.81	505, 491, 473, 329, 311, 193	703.200 32(+Cl), 713.229 19(+COOH)	β-D-Glp, (hydroxymethoxyphenyl) ethyl O-hex, feru
79	17.03	C₃₆H₄₈O₁₉	802.310 73	2.65	785.285 40(+H), 807.266 36(+Na)	339	783.270 51	1.52	651, 637, 607, 589, 475, 461, 457, 443	819.247 86(+Cl), 829.276 25(+COOH)	Lagotoside^[29]
80	17.29	C₃₉H₅₂O₂₁	874.332 34	1.86	879.287 54(+Na)	839, 671, 527, 339	855.291 56	1.49	813, 795, 709, 679, 667, 651, 637, 619, 601, 491	891.267 21(+Cl)	Uranoside A or isomer^[26]
81	17.45	C₃₉H₅₂O₂₁	874.331 85	2.43	879.287 17(+Na)	839, 671, 339	855.291 44	1.63	813, 795, 693, 679, 667, 651, 637, 619, 601, 491, 475, 473	891.267 76(+Cl)	Uranoside A or isomer^[26]
82	18.47	C₃₁H₄₀O₁₅	670.268 74	2.77	653.242 19(+H), 675.224 00(+Na)	653, 507, 485, 339, 323	651.228 70	1.14	505, 487, 475, 457, 329, 289, 265, 193	687.205 32(+Cl), 697.234 01(+COOH)	Martynoside or cistanoside D or isomer^{[13, 14]}
83	19.16	C₃₃H₄₂O₁₇	728.273 62	3.39	733.229 06(+Na)	543, 381, 339	709.234 25	0.95	667, 649, 533	–	β-D-Glp, (hydroxymethoxyphenyl) ethyl O-hex-acetyl, feru

No.

t_R/min

Formula

MS (+)

Error (10^-6) (+)

Other adduct ion (+)

MS/MS (+)

MS (-)

Error (10^-6) (-)

MS/MS (-)

Other adduct ion (-)

Identification

5.68

C₄₁H₅₆O₂₅

966.344 36

0.56

971.298 89(+Na)

–

947.302 86

0.98

785, 623

983.277 89(+Cl)

β-D-Glp, (dihydroxypheny) ethyl O-hex-O-hex-O-rha, caff

6.03

C₄₀H₅₄O₂₅

952.326 97

2.43

935.301 45(+H), 957.282 23(+Na)

773, 611, 479, 457, 325, 295

933.287 05

1.17

801, 771, 753, 639, 609, 591, 477, 459, 447

969.263 85(+Cl)

β-D-Glp, (dihydroxypheny) ethyl O-hex-O-hex-O-pen, caff

6.11

C₃₅H₄₆O₂₁

820.284 73

2.81

825.239 87(+Na)

785, 623, 587, 477, 459, 325

801.244 75

1.41

783, 691, 639, 621, 529

837.221 37(+Cl)

Suspensaside-O-hex^{[26, 30]}

6.11

C₄₁H₅₆O₂₅

966.342 96

2.04

971.298 40(+Na)

–

947.302 37

1.50

785, 767, 639, 623, 605, 461

–

β-D-Glp, (dihydroxypheny) ethyl O-hex-O-hex-O-rha, caff

6.36

C₄₁H₅₆O₂₅

966.344 06

0.88

–

947.303 10

0.73

785, 623

–

β-D-Glp, (dihydroxypheny) ethyl O-hex-O-hex-O-rha, caff

6.36

C₁₆H₂₀O₉

374.143 59

2.72

–

339, 195, 177

355.103 06

1.11

193

–

Glucose ester of (E)-ferulic acid^[16]

6.52

C₄₁H₅₆O₂₅

966.343 75

1.21

971.298 40(+Na)

787, 625, 479, 325

947.303 16

0.67

785, 767, 639, 623, 605, 461

–

β-D-Glp, (dihydroxypheny) ethyl O-hex-O-hex-O-rha, caff

6.55

C₄₁H₅₆O₂₆

982.338 13

1.74

987.293 27(+Na)

803, 649, 641, 487, 479, 325

963.298 10

0.63

801, 783, 639, 621, 477, 459

999.274 35 (+Cl)

β-D-Glp, (dihydroxypheny) ethyl O-hex-O-hex-O-hex, caff

6.75

C₃₅H₄₆O₂₁

820.285 46

1.90

803.258 24(+H), 825.240 42(+Na)

803, 641, 487, 479, 461, 443, 325, 317, 307, 263

801.243 77

2.63

783, 639, 621, 485, 477, 459, 305

837.220 28(+Cl)

Maxoside or Lagotiside C or isomer^{[26, 27]}

6.75

C₂₉H₃₆O₁₇

674.227 11

2.99

679.182 62(+Na)

639, 621, 487, 477, 459, 325

655.186 71

1.93

637, 545, 503, 493, 475, 383, 323, 251

691.163 27(+Cl)

β-Hydroxyl-plantamajoside or isomer^{[26, 30]}

6.83

C₄₀H₅₄O₂₄

936.332 34

2.17

941.287 48(+Na)

757, 625, 611, 603, 479, 471, 457, 325

917.291 69

1.67

785, 771, 755, 737, 623, 609, 477, 461

953.267 82(+Cl), 963.297 06(+COOH)

β-D-Glp, (dihydroxypheny) ethyl O-hex-O-rha-O-pen, caff

6.87

C₄₁H₅₆O₂₅

966.343 14

1.85

971.298 03(+Na)

787, 625, 471, 325

947.302 92

0.92

785, 771, 623, 605, 461

983.278 32(+Cl)

β-D-Glp, (dihydroxypheny) ethyl O-hex-O-hex-O-rha, caff

6.91

C₂₉H₃₆O₁₇

674.227 05

3.09

679.182 31(+Na)

639, 621, 487, 477, 459, 325

655.187 19

1.19

637, 545, 503, 493, 475, 383, 323, 251

691.163 64(+Cl)

β-Hydroxyl-plantamajoside or isomer^{[26, 30]}

7.11

C₄₁H₅₆O₂₅

966.343 14

1.85

971.298 71(+Na)

787, 625, 493, 471, 339

947.302 86

0.98

815, 785, 771, 753, 639, 621

983.276 31(+Cl)

β-D-Glp, (dihydroxypheny) ethyl O-hex-O-hex-O-pen, feru

7.32

C₄₁H₅₆O₂₅

966.344 42

0.50

971.298 89(+Na)

947.302 61

1.25

785, 771, 753, 623, 605, 461

β-D-Glp, (dihydroxypheny) ethyl O-hex-O-hex-O-rha, caff

7.36

C₂₉H₃₆O₁₆

658.231 87

3.58

641.205 44(+H), 663.187 38(+Na)

641, 479, 461, 325

639.192 02

3.58

477, 459, 315

675.169 25(+Cl)

β-D-Glp, (dihydroxyphenyl) ethyl O-hex, caff (isomer of Plantamajoside)

7.40

C₄₂H₅₆O₂₆

994.337 34

2.53

999.292 91(+Na)

815, 661, 529, 457, 367, 325

975.297 97

0.75

933, 843, 813, 795, 771, 753, 681, 639, 621, 609

1 011.274 17(+Cl)

β-D-Glp, (dihydroxypheny) ethyl O-hex-O-hex-O-pen-acetyl, caff

7.60

C₂₉H₃₆O₁₆

658.231 81

3.67

663.187 07(+Na)

641, 623, 477, 471, 325

639.192 44

0.97

621, 529, 487, 477, 469, 459, 441, 179

675.166 20(+Cl)

Suspensaside^{[26, 30]}

7.76

C₃₅H₄₆O₂₀

804.289 98

2.66

787.263 79(+H), 809.245 36(+Na)

641, 633, 625, 607, 487, 479, 471, 461, 443, 435, 417, 325, 309

785.248 96

2.55

767, 639, 623, 605, 477, 461, 443, 315

821.225 10(+Cl)

Echinacoside*

7.90

C₄₂H₅₈O₂₆

996.353 27

2.24

1 001.307 62(+Na)

663, 493, 339

977.312 93

1.46

815, 801, 783, 653, 639, 621

1 013.290 71(+Cl)

β-D-Glp, (dihydroxypheny) ethyl O-hex-O-hex-O-hex, feru

7.90

C₄₃H₅₈O₂₇

1 024.347 90

2.46

1 029.303 47(+Na)

1 005.307 62

1.64

843, 801, 783, 681, 639, 585

1 041.284 91(+Cl)

β-D-Glp, (dihydroxypheny) ethyl O-hex-O-hex-O-hex-acetyl, caff

8.21

C₃₇H₄₈O₂₂

862.295 53

2.39

867.250 79(+Na)

691, 683, 529, 511, 479, 367, 325

843.255 31

1.35

801, 681, 639, 621, 519, 477, 459

879.231 51(+Cl)

β-D-Glp, (dihydroxyphenyl) ethyl O-hex-O-hex-acetyl, caff

8.21

C₃₁H₃₈O₁₈

716.237 49

3.08

721.192 87(+Na)

681, 529, 477, 459, 367, 325

697.197 81

1.04

679, 655, 637, 587, 535, 517, 475, 457

733.176 09(+Cl)

β-Hydroxyl-acetyl-plantamajoside or isomer^{[26, 30]}

8.46

C₃₁H₃₈O₁₈

716.237 79

2.65

721.192 87(+Na)

681, 529, 477, 367, 325

697.197 57

1.39

679, 655, 637, 587, 535, 517, 475

733.174 50(+Cl)

β-Hydroxyl-acetyl-plantamajoside or isomer^{[26, 30]}

8.57

C₃₄H₄₄O₂₀

790.274 72

2.20

795.230 16(+Na)

479, 461, 457, 325, 295, 277

771.234 50

1.06

639, 609, 591, 477, 447, 315

807.209 66(+Cl)

β-D-Glp, (dihydroxyphenyl) ethyl O-hex-O-pen, caff

8.66

C₄₀H₅₄O₂₄

936.332 21

2.31

941.287 23(+Na)

–

917.291 69

1.67

755, 623, 593, 461

953.266 97(+Cl), 963.295 10(+COOH)

β-D-Glp, (dihydroxypheny) ethyl O-hex-O-rha-O-pen, caff

9.05

C₃₄H₄₄O₂₀

790.274 48

2.51

773.247 99(+H), 795.229 68(+Na)

611, 593, 487, 479, 457, 325, 307, 295, 277

771.233 95

1.77

639, 609, 591, 477, 447, 429, 323, 315, 297, 275

807.209 90(+Cl)

β-D-Glp, (dihydroxyphenyl) ethyl O-hex-O-pen, caff

9.17

C₃₅H₄₆O₂₁

820.285 22

2.20

803.258 85(+H), 825.240 23(+Na)

803, 649, 641, 487, 479, 461, 443, 325, 317, 307

801.243 47

3.01

639, 621, 477, 459, 323, 315, 297, 263

837.219 79(+Cl)

Maxoside or lagotiside C or isomer^{[26, 27]}

9.28

C₃₅H₄₆O₂₀

804.290 10

2.50

809.246 09(+Na)

787, 641, 633, 625, 487, 479, 471, 435, 325, 309

785.250 73

0.30

639, 623, 605, 477, 461, 315

821.227 23(+Cl)

β-D-Glp, (dihydroxyphenyl) ethyl O-rha-O-hex, caff (isomer of echinacoside)

9.41

C₄₁H₅₆O₂₅

966.343 20

1.79

971.298 58(+Na)

–

947.302 86

0.98

801, 785, 767, 639, 623, 605, 461

983.278 81(+Cl)

β-D-Glp, (dihydroxypheny) ethyl O-hex-O-hex-O-rha, caff

9.49

C₃₅H₄₆O₂₀

804.290 34

2.20

787.262 70(+H), 809.245 73(+Na)

787, 625, 607, 571, 479, 471, 461, 435, 417, 325, 317, 309, 291, 273

785.250 55

0.53

639, 623, 605, 477, 461

821.226 87(+Cl)

β-D-Glp, (dihydroxyphenyl) ethyl O-rha-O-hex, caff (isomer of echinacoside)

9.53

C₃₆H₄₈O₂₀

818.305 42

2.87

801.279 05(+H), 823.260 74(+Na)

801, 647, 639, 493, 485, 475, 339

799.264 53

2.61

637, 623, 605, 477, 461, 315, 305

835.241 03(+Cl)

Jionoside A1 or isomer^[26]

9.59

C₂₉H₃₆O₁₆

658.232 42

2.72

641.205 26(+H), 663.187 68(+Na)

641, 487, 479, 461, 443, 325, 317, 307

639.191 10

3.06

477, 459, 315, 297, 179

675.167 72(+Cl)

Plantamajoside*

9.74

C₃₅H₄₆O₂₀

804.289 79

2.90

787.261 41(+H), 809.245 12(+Na)

787, 633, 625, 487, 479, 471, 461, 453, 435, 325, 309

785.250 00

1.23

639, 623, 605, 477, 461, 443, 307

821.226 07(+Cl)

β-D-Glp, (dihydroxyphenyl) ethyl O-rha-O-hex, caff (isomer of echinacoside)

9.98

C₃₄H₄₄O₁₉

774.279 24

2.99

779.234 56(+Na)

757, 625, 479, 471, 325

755.239 87

0.70

609, 593, 575, 461, 447, 443

791.216 37(+Cl), 801.245 42(+COOH)

Ehrenoside or isomer^[31]

10.22

C₃₀H₃₈O₁₆

672.247 44

3.62

655.220 95(+H),
677.202 58(+Na)

655, 471, 325

653.209 35

-0.98

635, 621, 543, 487, 459

689.186 65(+Cl), 699.214 72(+COOH)

Suspensaside methyl ether^{[26, 30]}

10.34

C₂₃H₂₆O₁₁

501.134 92(+Na)

3.63

496.179 60

347, 321

477.139 77

0.97

315, 301, 297, 179, 161

–

β-D-Glp, (dihydroxypheny) ethyl, caff

10.46

C₃₄H₄₄O₁₉

774.279 60

2.52

779.234 99(+Na)

757, 625, 479, 471, 457, 325

755.239 56

1.11

623, 609, 593, 575, 461, 447, 443, 315

791.216 13(+Cl)

Ehrenoside or isomer^[31]

10.81

C₃₅H₄₆O₂₀

804.290 22

2.35

809.245 30(+Na)

625, 479, 471, 325, 317

785.250 67

0.38

623, 477, 461

821.227 11(+Cl)

β-D-Glp, (dihydroxyphenyl) ethyl O-rha-O-hex, caff (isomer of echinacoside)

10.81

C₃₇H₅₀O₂₁

848.316 83

1.75

853.271 97(+Na)

507, 339

829.277 16

0.03

667, 653, 635, 491, 473

865.252 01(+Cl)

β-D-Glp, (hydroxymethoxyphenyl) ethyl O-hex-O-hex, feru

11.00

C₂₉H₃₆O₁₅

642.237 49

2.81

625.210 88(+H), 647.192 75(+Na)

625, 607, 589, 571, 479, 471, 435, 325, 309, 301

623.196 47

2.68

477, 461, 443, 323, 315, 297, 251, 179

659.173 03(+Cl)

Verbascoside/Acteoside*

11.00

C₂₉H₃₄O₁₅

640.221 92

2.69

623.190 61(+H)

623, 605, 587, 477, 459, 325, 281, 263

621.181 40

1.76

487, 469, 459, 179

–

Suspensaside A^{[26, 30]}

11.17

C₃₅H₄₆O₂₁

820.285 28

2.12

803.256 29(+H), 825.240 78(+Na)

649, 479, 325,

801.244 51

1.71

639, 621, 477, 459, 323, 315

837.220 95(+Cl)

Maxoside or lagotiside C or isomer^{[26, 27]}

11.25

C₃₇H₄₈O₂₂

862.296 33

1.44

845.269 17(+H), 867.251 46(+Na)

691, 683, 529, 511, 479, 367, 325

843.254 76

2.00

801, 783, 681, 639, 621, 519, 477, 459

879.230 71(+Cl)

β-D-Glp, (dihydroxyphenyl) ethyl O-hex-O-hex-acetyl, caff

11.40

C₂₉H₃₆O₁₆

658.232 06

3.28

641.205 44(+H), 663.187 13(+Na)

641, 487, 479, 461, 443, 325, 307

639.192 32

1.15

477, 459, 323, 315, 305, 297, 251, 179

675.168 95(+Cl)

Plantainoside D^[27]

11.44

C₃₆H₄₆O₂₁

832.285 16

2.24

837.240 36(+Na)

683, 661, 529, 499, 479, 457, 367, 325, 295

813.244 87

1.24

771, 753, 681, 651, 633, 609, 591, 519, 477, 447

849.221 19(+Cl)

β-D-Glp, (dihydroxyphenyl) ethyl O-hex-O-pen-acetyl, caff

11.52

C₂₉H₃₆O₁₅

642.237 55

2.72

625.174 68(+H), 647.192 81(+Na)

625, 479, 471, 463, 325, 309

623.197 20

1.51

477, 461, 315

–

β-D-Glp, (dihydroxyphenyl) ethyl O-rha, caff (isomer of isoacteoside)

11.64

C₃₅H₄₆O₂₀

804.290 04

2.58

787.263 43(+H), 809.245 48(+Na)

625, 501, 493, 471, 339, 309, 291

785.250 37

0.76

653, 623, 609, 591, 491, 477, 459, 447, 315, 297

821.226 75(+Cl)

β-D-Glp, (dihydroxyphenyl) ethyl O-pen-O-hex, feru

11.80

C₃₆H₄₈O₂₁

834.300 84

2.20

839.255 86(+Na)

655, 501, 493, 339

815.260 80

0.90

653, 639, 621, 491, 477, 473, 459

851.237 49(+Cl)

β-D-Glp, (dihydroxyphenyl) ethyl O-hex-O-hex, feru

11.86

C₃₁H₃₈O₁₇

700.242 31

3.10

683.215 76(+H), 705.197 81(+Na)

683, 665, 647, 529, 511, 479, 367, 325, 307

681.201 90

2.53

639, 621, 519, 477, 459, 315

717.172 36(+Cl)

Hemiphroside B*

11.86

C₃₃H₄₂O₁₇

728.273 38

3.72

733.216 13(+Na)

529, 367, 325, 307

–

β-D-Glp, (dimethoxyphenyl) ethyl O-hex-acetyl, caff

12.02

C₃₆H₄₈O₂₀

818.305 91

2.26

801.279 85(+H), 823.261 17(+Na)

655, 647, 639, 501, 493, 485, 339, 283

799.265 50

1.40

781, 653, 637, 623, 605, 491, 477, 461

835.241 88(+Cl)

Jionoside A1 or isomer^[26]

12.06

C₃₄H₄₄O₂₀

790.274 72

2.20

773.247 92(+H), 795.229 86(+Na)

611, 479, 457, 325, 295

771.234 38

1.21

735, 639, 609, 591, 477, 447, 429, 323, 315, 251

807.210 75(+Cl)

β-D-Glp, (dihydroxyphenyl) ethyl O-hex-O-pen, caff

12.10

C₃₁H₃₈O₁₇

700.242 80

2.82

683.215 39(+H), 705.198 12(+Na)

683, 529, 479, 367, 325

681.202 94

1.00

639, 621, 519, 477, 459

–

2′-O-Acetyl-plantamajoside^[27]

12.34

C₃₀H₃₈O₁₆

672.247 86

2.98

655.221 19(+H), 677.203 06(+Na)

655, 501, 493, 339

653.207 76

1.45

491, 477, 459, 315, 297

689.184 27(+Cl), 699.213 20(+COOH)

β-D-Glp, (dihydroxyphenyl) ethyl O-hex, feru

12.38

C₂₉H₃₆O₁₅

642.237 49

2.81

625.210 82(+H), 647.192 75(+Na)

625, 607, 479, 471, 461, 435, 325, 309

623.197 33

1.30

477, 461, 443, 323, 315, 297, 251, 179

659.174 01(+Cl)

Isoacteoside*

12.42

C₃₁H₃₈O₁₇

700.242 37

3.45

705.197 75(+Na)

521, 367, 325

681.202 76

1.27

639, 519, 477, 459

–

β-D-Glp, (dihydroxyphenyl) ethyl O-hex-acetyl, caff (isomer of hemiphroside B)

12.62

C₃₇H₅₀O₂₀

832.321 41

2.41

815.294 25(+H), 837.276 55(+Na)

653, 507, 485, 339, 323, 305

813.281 56

0.87

667, 651, 637, 619, 491, 475, 473, 457, 427, 329, 287

849.257 75(+Cl)

Cistanoside B or glucopyranosyl (1-6) martynoside or isomer^{[26, 29]}

12.80

C₂₉H₃₆O₁₅

642.237 24

3.21

625.210 14(+H), 647.192 44(+Na)

625, 607, 589, 571, 553, 479, 471, 461, 453, 443, 435, 417, 325, 317, 309, 301, 291, 273, 255

623.197 27

1.40

477, 461, 443, 315, 297, 179

659.171 20(+Cl)

β-D-Glp, (dihydroxyphenyl) ethyl O-rha, caff (isomer of verbascoside)

12.87

C₃₀H₃₈O₁₆

672.247 62

3.36

655.220 76(+H), 677.203 00(+Na)

655, 501, 493, 339

653.208 07

0.98

491, 477, 459

689.185 06(+Cl), 699.213 01(+COOH)

β-D-Glp, (dihydroxyphenyl) ethyl O-hex, feru

13.15

C₂₉H₃₆O₁₄

626.242 55

2.93

631.198 12(+Na)

463, 325

607.202 33

1.48

461, 445

643.178 77(+Cl)

β-D-Glp, (hydroxyphenyl) ethyl O-rha, caff

13.30

C₃₀H₃₈O₁₆

672.247 80

3.07

677.203 06(+Na)

493, 475, 457, 325

653.207 52

1.82

491, 477, 315

689.184 20(+Cl), 699.216 43(+COOH)

β-D-Glp, (hydroxymethoxyphenyl) ethyl O-hex, caff

13.34

C₃₇H₅₀O₂₀

832.321 41

2.41

837.276 86(+Na)

653, 339, 323

813.281 13

1.40

651, 637, 619, 491, 475

849.256 90(+Cl)

Cistanoside B or isomer^[26]

13.37

C₃₁H₃₈O₁₇

700.243 10

2.38

705.198 43(+Na)

665, 529, 511, 479, 461, 367, 349, 325

681.202 70

1.35

639, 621, 519, 477, 459

–

β-D-Glp, (dihydroxyphenyl) ethyl O-hex-acetyl, caff (isomer of hemiphroside B)

13.41

C₂₉H₃₆O₁₄

626.241 88

4.03

609.214 78(+H), 631.197 27(+Na)

609, 463, 455, 309

607.202 76

0.77

461, 443, 315

643.179 32(+Cl)

Lipedoside A or isomer^[26]

13.89

C₃₅H₄₆O₁₈

772.300 29

2.59

777.255 62(+Na)

755, 593, 471, 447, 325, 309

753.260 25

1.18

591

789.237 85(+Cl)

Kankanoside I^[28]

14.17

C₃₀H₃₈O₁₅

656.252 93

3.08

639.226 38(+H), 661.208 37(+Na)

639, 493, 485, 339, 323, 277

637.212 59

1.89

491, 475, 461, 443, 315, 305, 297, 193

673.189 21(+Cl), 683.217 90(+COOH)

Leucosceptoside A^[26]

14.56

C₂₉H₃₆O₁₄

626.241 94

3.93

631.197 75(+Na)

609, 591, 463, 455, 437, 309, 293, 275

607.202 64

0.97

461, 443, 315

643.178 22(+Cl)

Lipedoside A or isomer^[26]

15.07

C₃₀H₃₈O₁₅

656.253 36

2.41

639.226 68(+H), 661.208 62(+Na)

639, 493, 471, 325

637.212 52

2.00

475, 329

673.188 48(+Cl)

β-D-Glp, (hydroxymethoxyphenyl) ethyl O-rha, caff

15.10

C₃₆H₄₈O₂₀

818.306 40

1.65

801.281 19(+H), 823.261 47(+Na)

639, 507, 471, 339, 309

799.265 81

1.01

667, 637, 623, 605, 491, 473, 461

835.241 94(+Cl), 845.271 24(+COOH)

β-D-Glp, (hydroxymethoxyphenyl) ethyl O-hex-O-pen, feru

15.39

C₃₇H₅₀O₂₀

832.321 90

1.80

815.295 10(+H), 837.277 22(+Na)

815, 785, 669, 653, 647, 507, 501, 485, 339

813.281 43

1.03

667, 651, 637, 619, 491, 475, 473, 457, 329, 305

849.257 63(+Cl)

Cistanoside B or isomer^[26]

15.43

C₃₃H₄₀O₁₈

742.253 30

2.75

747.208 74(+Na)

725, 707, 571, 503, 367, 247

723.213 62

0.78

681, 663, 639, 621, 561, 519, 501, 477, 459

759.191 89(+Cl)

β-D-Glp, (dihydroxyphenyl) ethyl O-hex-acetyl-acetyl, caff

15.47

C₃₀H₃₈O₁₅

656.252 99

2.99

661.208 68(+Na)

639, 621, 493, 485, 475, 467, 457, 449, 431, 339, 323, 305

637.213 50

0.46

491, 475, 461

673.189 88(+Cl), 683.219 60(+COOH)

Leucosceptoside A^[26]

15.54

C₃₇H₅₀O₂₁

848.316 96

1.59

853.272 16(+Na)

669, 507, 339

829.276 49

0.83

667, 653, 635, 505, 491, 473, 425, 329, 311, 265

865.252 75(+Cl)

β-D-Glp, (hydroxymethoxyphenyl) ethyl O-hex-O-hex, feru

15.90

C₃₇H₅₀O₂₀

832.321 53

2.26

–

653, 339, 323

813.281 37

1.10

667, 651, 637, 619, 491, 475, 473, 457, 305

849.258 06(+Cl)

Cistanoside B or isomer^[26]

15.99

C₃₂H₄₀O₁₇

714.258 73

2.36

719.213 87(+Na)

697, 529, 367, 325

695.218 44

1.20

653, 635, 519, 501, 491

731.195 56(+Cl)

β-D-Glp, (hydroxymethoxyphenyl) ethyl O-hex-acetyl, caff

16.36

C₃₁H₃₈O₁₇

700.242 61

3.10

683.216 13(+H), 705.197 88(+Na)

683, 529, 367, 325

681.202 70

1.35

639, 621, 519, 477, 459

–

β-D-Glp, (dihydroxyphenyl) ethyl O-hex-acetyl, caff (isomer of hemiphroside B)

16.44

C₃₁H₄₀O₁₆

686.263 24

3.32

669.235 90(+H), 691.218 57(+Na)

507, 501, 471, 339, 277

667.223 82

0.81

505, 491, 473, 329, 311, 193

703.200 32(+Cl), 713.229 19(+COOH)

β-D-Glp, (hydroxymethoxyphenyl) ethyl O-hex, feru

17.03

C₃₆H₄₈O₁₉

802.310 73

2.65

785.285 40(+H), 807.266 36(+Na)

339

783.270 51

1.52

651, 637, 607, 589, 475, 461, 457, 443

819.247 86(+Cl), 829.276 25(+COOH)

Lagotoside^[29]

17.29

C₃₉H₅₂O₂₁

874.332 34

1.86

879.287 54(+Na)

839, 671, 527, 339

855.291 56

1.49

813, 795, 709, 679, 667, 651, 637, 619, 601, 491

891.267 21(+Cl)

Uranoside A or isomer^[26]

17.45

C₃₉H₅₂O₂₁

874.331 85

2.43

879.287 17(+Na)

839, 671, 339

855.291 44

1.63

813, 795, 693, 679, 667, 651, 637, 619, 601, 491, 475, 473

891.267 76(+Cl)

Uranoside A or isomer^[26]

18.47

C₃₁H₄₀O₁₅

670.268 74

2.77

653.242 19(+H), 675.224 00(+Na)

653, 507, 485, 339, 323

651.228 70

1.14

505, 487, 475, 457, 329, 289, 265, 193

687.205 32(+Cl), 697.234 01(+COOH)

Martynoside or cistanoside D or isomer^{[13, 14]}

19.16

C₃₃H₄₂O₁₇

728.273 62

3.39

733.229 06(+Na)

543, 381, 339

709.234 25

0.95

667, 649, 533

–

β-D-Glp, (hydroxymethoxyphenyl) ethyl O-hex-acetyl, feru