药学学报

Serial number	Retention time/min	Compound	Molecular formula	ES^-	ES⁺	Error/×10^-6	Classification	Ref.
1*	1.10	Sucrose*	C₁₂H₂₂O₁₁	341.108 3[M-H]^-	179	365.107 5[M+Na]⁺	325, 175, 145	-0.29	Oligosaccharide	[9]
2	1.31	Maltotriose	C₁₈H₃₂O₁₆	503.162 0[M-H]^-	341, 311, 179	527.158 3[M+Na]⁺	343, 325, 175, 163, 145	1.59	Oligosaccharide	[9]
3	1.41	Maltopentaose	C₃₀H₅₂O₂₆	827.267 4[M-H]^-	665, 503, 341, 311	-	-	0.60	Oligosaccharide	[9]
4	1.47	Maltohexaose	C₃₆H₆₂O₃₁	989.329 0[M-H]^-	827, 665	-	-	2.02	Oligosaccharide	[9]
5	1.54	Cyclomaltoheptaose	C₄₂H₇₀O₃₅	-	-	1 135.385 0[M+H]⁺	649, 487, 325, 163, 145	6.52	Oligosaccharide	[9]
6	1.55	Maltoheptaose	C₄₂H₇₂O₃₆	1 151.374 1 [M-H]^-	989, 827, 665, 503, 341	1 153.388 2[M+H]⁺	811, 649, 487, 325, 163, 145	1.39	Oligosaccharide	[9]
7*	1.74	Citric acid*	C₆H₈O₇	191.018 8[M-H]^-	111	-	-	-2.09	Other types	[10]
8	2.38	Desbenzoylpaeoniflorin	C₁₆H₂₄O₁₀	375.129 6[M-H]^-	345, 195, 165	399.123 0[M+Na]⁺	396, 331, 179, 151	1.30	Monoterpenoids	[10]
9	2.61	Oxiglutatione	C₂₀H₃₂N₆O₁₂S₂	611.142 7[M-H]^-	481, 331	613.160 0[M+H]⁺	487, 484	0.33	Other types	[11]
10	3.15	Galloylglucose	C₁₃H₁₆O₁₀	331.064 8[M-H]^-	169, 125	355.062 4[M+Na]⁺	325, 290, 208, 153, 145	-5.10	Polyphenols	[12]
11*	3.30	Adenosine*	C₁₀H₁₃N₅O₄	-	-	268.103 8[M+H]⁺	136, 153, 268	-2.98	Other types	[11]
12	3.35	Galloylglucose isomer	C₁₃H₁₆O₁₀	331.067 2[M-H]^-	169	-	-	2.11	Polyphenols	[12]
13	3.44	Galloylsucrose isomer	C₁₉H₂₆O₁₅	493.115 8[M-H]^-	331, 313, 283, 169	517.118 8[M+Na]⁺	325, 268, 153, 136	-7.09	Polyphenols	[13]
14	3.79	Desbenzoylpaeoniflorin isomer	C₁₆H₂₄O₁₀	-	-	399.123 0[M+Na]⁺	325, 215, 197, 151	5.60	Monoterpenoids	[10]
15	4.08	Glucopyranosyl paeonisuffrone	C₁₆H₂₄O₉	359.132 3[M-H]^-	311, 179	383.129 4[M+Na]⁺	325, 287, 163	-5.29	Monoterpenoids	[14]
16	4.48	Glucopyranosyl paeonisuffrone isomer	C₁₆H₂₄O₉	359.132 3[M-H]^-	311, 179	383.129 4[M+Na]⁺	325, 287, 163	-5.29	Monoterpenoids	[14]
17	5.36	Galloylsucrose isomer	C₁₉H₂₆O₁₅	493.115 8[M-H]^-	331, 313, 283	517.118 8[M+Na]⁺	433, 315, 153	-7.09	Polyphenols	[13]
18	5.72	Galloylsucrose isomer	C₁₉H₂₆O₁₅	493.115 8[M-H]^-	331, 313, 283	-	-	-7.09	Polyphenols	[13]
19	5.84	Galloylsucrose isomer	C₁₉H₂₆O₁₅	493.115 4[M-H]^-	331, 313, 283	517.118 8[M+Na]⁺	433, 315, 153	-7.91	Polyphenols	[13]
20	6.40	Digalloylglucose	C₂₀H₂₀O₁₄	483.073 8[M-H]^-	331, 313, 169	-	-	-7.66	Polyphenols	[15]
21	6.57	Galloyl desbenzoylpaeoniflorin	C₂₃H₂₈O₁₄	527.140 9[M-H]^-	169, 125	551.137 1[M+Na]⁺	496, 445, 345, 297, 164	1.52	Monoterpenoids	[16]
22	6.72	Glucopyranosyl lactinolide	C₁₆H₂₆O₉	361.151 6[M-H]^-	179	385.145 0[M+Na]⁺	205, 188, 144	4.71	Monoterpenoids	[17]
23	6.79	Digalloylglucose isomer	C₂₀H₂₀O₁₄	483.073 8[M-H]^-	331, 313, 169	-	-	-7.66	Polyphenols	[15]
24	6.92	Strictinin	C₂₇H₂₂O₁₈	633.073 5[M-H]^-	481, 301, 169	657.073 1[M+Na]⁺	367, 261	1.11	Polyphenols	[18]
25	7.00	Mudanpioside F	C₁₆H₂₄O₈	343.138 3[M-H]^-	181, 150	-	-	-2.91	Monoterpenoids	[19]
26	7.04	Galloyl desbenzoylpaeoniflorin isomer	C₂₃H₂₈O₁₄	527.142 1[M-H]^-	497, 169	551.137 1[M+Na]⁺	481, 365, 221, 281, 179	3.79	Monoterpenoids	[16]
27	7.18	Catechin glucoside	C₂₁H₂₄O₁₁	451.127 5[M-H]^-	289, 245, 169	475.117 7[M+Na]⁺	441, 291, 139	7.76	Polyphenols	[16]
28	7.23	Trigalloylglucose isomer	C₂₇H₂₄O₁₈	635.089 1[M-H]^-	465, 169, 313, 125	-	-	1.10	Polyphenols	[20]
29*	7.33	Procyanidin B1*	C₃₀H₂₆O₁₂	577.132 1[M-H]^-	289, 245, 203	579.150 9[M+H]⁺	409, 127	-4.30	Polyphenols	[21]
30	7.53	Oxypaeoniflorin isomer	C₂₃H₂₈O₁₂	495.149 8[M-H]^-	465, 345, 333, 281	519.150 9[M+Na]⁺	121	-1.01	Monoterpenoids	[22]
31	7.61	Procyanidin B2	C₃₀H₂₆O₁₂	577.132 1[M-H]^-	289, 245, 203	-	-	-4.30	Polyphenols	[21]
32	7.70	Trigalloylglucose isomer	C₂₇H₂₄O₁₈	635.089 1[M-H]^-	465, 169, 313, 125	-	-	1.10	Polyphenols	[20]
33*	7.76	Methyl gallate*	C₈H₈O₅	183.030 2[M-H]^-	168	-	-	4.92	Polyphenols	[23]
34*	7.82	Oxypaeoniflorin*	C₂₃H₂₈O₁₂	495.149 8[M-H]^-	465, 345, 333, 281	519.150 9[M+Na]⁺	291, 139	-1.01	Monoterpenoids	[22]
35	7.85	Trigalloylglucose isomer	C₂₇H₂₄O₁₈	635.089 1[M-H]^-	465, 169, 313, 125	-	-	1.10	Polyphenols	[20]
36*	7.89	Catechin*	C₁₅H₁₄O₆	289.072 2[M-H]^-	245, 203, 169	291.088 4[M+H]⁺	179, 147	3.50	Polyphenols	[24]
37	8.00	Procyanidin C	C₄₅H₃₈O₁₈	865.201 2[M-H]^-	577, 289, 245, 203	867.212 6[M+H]⁺	579, 245, 123	3.70	Polyphenols	[21]
38	8.35	Mudanpioside E	C₂₄H₃₀O₁₃	525.163 5[M-H]^-	495, 479	549.156 1[M+Na]⁺	349, 179	5.14	Monoterpenoids	[25]
39	8.45	Trigalloylglucose isomer	C₂₇H₂₄O₁₈	635.089 1[M-H]^-	465, 169, 313, 125	-	-	1.10	Polyphenols	[20]
40	8.52	Trigalloylglucose isomer	C₂₇H₂₄O₁₈	635.089 1[M-H]^-	465, 169, 313, 125	-	-	1.10	Polyphenols	[20]
41	8.65	Glucosylpaeoniflorin	C₂₉H₃₈O₁₆	641.209 0[M-H]^-	611, 489, 165 121	665.201 0[M+Na]⁺	483, 105	1.25	Monoterpenoids	[26]
42	8.94	Diglucosylpaeoniflorin	C₃₅H₄₈O₂₁	803.268 1[M-H]^-	773, 755, 641, 611, 489, 165	827.265 0[M+Na]⁺	409, 393, 371	-2.86	Monoterpenoids	[26]
43	9.06	Trigalloylglucose isomer	C₂₇H₂₄O₁₈	635.089 1[M-H]^-	465, 169, 313, 125	-	-	1.10	Polyphenols	[20]
44	9.30	Glucosylpaeoniflorin isomer	C₂₉H₃₈O₁₆	687.213 9 [M+COOH]^-	611, 489, 165, 121	665.201 0[M+Na]⁺	393, 153	1.31	Monoterpenoids	[26]
45*	9.50	1, 3, 6-Trigalloylglucose*	C₂₇H₂₄O₁₈	635.089 1[M-H]^-	465, 169, 313, 125	659.080 0[M+Na]⁺	619, 526, 467, 297, 153	1.10	Polyphenols	[27]
46*	9.60	Albiflorin*	C₂₃H₂₈O₁₁	525.162 5 [M+COOH]^-	525, 435, 449, 357, 327	481.174 9[M+H]⁺	319, 197, 105	3.24	Monoterpenoids	[28]
47	9.79	Glucosylpaeoniflorin isomer	C₂₉H₃₈O₁₆	641.209 0[M-H]^-	611, 489, 165, 121	655.156 1[M+Na]⁺	519	1.25	Monoterpenoids	[26]
48	10.06	Galloylpaeoniflorin	C₃₀H₃₂O₁₅	631.167 2[M-H]^-	481, 365, 221, 281, 179	655.160 2[M+Na]⁺	519, 503, 437, 153, 121	1.43	Monoterpenoids	[30]
49	10.20	Tetragalloylglucose isomer	C₃₄H₂₈O₂₂	787.103 5[M-H]^-	465, 169, 313, 125	-	-	5.21	Polyphenols	[27]
50*	10.20	Paeoniflorin*	C₂₃H₂₈O₁₁	479.155 0[M-H]^-	525, 449, 357, 327, 165 121, 77	503.153 1[M+Na]⁺	463, 179, 151	3.24	Monoterpenoids	[29]
51*	10.49	Ethyl gallate*	C₉H₁₀O₅	197.045 9[M-H]^-	169, 124	-	-	4.57	Polyphenols	[25]
52	11.34	Tetragalloylglucose isomer	C₃₄H₂₈O₂₂	787.097 9[M-H]^-	635, 617, 169	811.094 7[M+Na]⁺	641, 619, 525, 153	-1.91	Polyphenols	[31]
53*	11.78	1, 2, 3, 6-Tetragalloylglucose*	C₃₄H₂₈O₂₂	787.097 9[M-H]^-	787, 635, 617, 169	811.094 7[M+Na]⁺	641, 619, 525, 153	-1.91	Polyphenols	[27]
54*	12.30	Ellagic acid*	C₁₄H₆O₈	300.998 8[M-H]^-	245, 185, 175	-	-	1.33	Polyphenols	[23]
55*	12.98	6'-O-Galloylpaeoniflorin*	C₃₀H₃₂O₁₅	631.168 9[M-H]^-	481, 365, 221, 281, 179	655.160 2[M+Na]⁺	179, 153	1.43	Monoterpenoids	[30]
56	13.46	Galloylpaeoniflorin isomer	C₃₀H₃₂O₁₅	631.168 9[M-H]^-	481, 365, 221, 281, 179	655.167 4[M+Na]⁺	629, 613, 487, 153	1.43	Monoterpenoids	[30]
57*	13.58	1, 2, 3, 4, 6-Pentagalloylglucose*	C₄₁H₃₂O₂₆	939.113 6[M-H]^-	631, 469, 169	963.104 4[M+Na]⁺	771, 153	3.40	Polyphenols	[32]
58	13.84	Pentagalloylglucose isomer	C₄₁H₃₂O₂₆	939.116 9[M-H]^-	631, 469, 169	-	-	6.92	Polyphenols	[32]
59	14.00	Pentagalloylglucose isomer	C₄₁H₃₂O₂₆	-	-	963.104 4[M+Na]⁺	481, 365, 221, 281, 179	6.65	Polyphenols	[32]
60	14.22	Pentagalloylglucose isomer	C₄₁H₃₂O₂₆	-	-	963.104 4[M+Na]⁺	481, 365, 221, 281, 179	6.65	Polyphenols	[32]
61	14.28	Galloylpaeoniflorin isomer	C₃₀H₃₂O₁₅	631.168 9[M-H]^-	481, 365, 221, 281, 179	-	-	1.43	Monoterpenoids	[30]
62	14.80	Galloylpaeoniflorin isomer	C₃₀H₃₂O₁₅	631.168 9[M-H]^-	481, 365, 221, 281, 179	633.180 7[M+H]⁺	633, 267, 153, 105	-1.90	Monoterpenoids	[30]
63	15.11	Hexagalloylglucose	C₄₈H₃₆O₃₀	1 091.114 1[M-H]^-	939, 769, 169	1 115.110 8[M+Na]⁺	923, 771	-6.14	Polyphenols	[20]
64	15.60	Mudanpioside I	C₂₃H₂₈O₁₁	525.162 5[M+COOH]^-	357, 327, 283	481.174 9[M+H]⁺	503, 481, 319, 197, 133	3.24	Monoterpenoids	[33]
65	15.70	Hexagalloylglucose isomer	C₄₈H₃₆O₃₀	-	-	1 115.110 8[M+Na]⁺	923, 771	-7.26	Polyphenols	[20]
66	15.82	Hexagalloylglucose isomer	C₄₈H₃₆O₃₀	1 091.114 1[M-H]^-	939, 769, 169	1 115.110 8[M+Na]⁺	923, 771	-6.14	Polyphenols	[20]
67	17.13	Galloylpaeoniflorin isomer	C₃₀H₃₂O₁₅	631.167 2[M-H]^-	481, 365, 221, 281, 179	655.160 2[M+Na]⁺	613, 511, 153	1.43	Monoterpenoids	[30]
68	17.26	Digalloylpaeoniflorin	C₃₇H₃₆O₁₉	783.176 [M-H]^-	783, 643, 313, 169	-	-	-1.53	Monoterpenoids	[32]
69	17.55	Mudanpioside H	C₃₀H₃₂O₁₄	615.167 0[M-H]^-	493, 313	-	-	-7.15	Monoterpenoids	[34]
70	17.80	Pinane-10-yl vicianoside	C₂₁H₃₆O₁₀	447.222 3[M-H]^-	447, 315, 169	471.224 4[M+H]⁺	471, 349, 177	-1.57	Monoterpenoids	[35]
71*	17.61	Benzoyloxypaeoniflorin*	C₃₀H₃₂O₁₃	599.179 4[M-H]^-	165, 137, 121	-	-	4.84	Monoterpenoids	[28]
72	17.99	Galloylpaeoniflorin isomer	C₃₀H₃₂O₁₅	631.167 2[M-H]^-	481, 365, 221, 281, 179	-	-	1.11	Monoterpenoids	[30]
73	18.06	Pinen-10-yl vicianoside	C₂₁H₃₄O₁₀	445.205 7[M-H]^-	293, 149	-	-	-3.82	Monoterpenoids	[35]
74	18.31	Cineole rhamnosyl glucoside	C₂₂H₃₈O₁₀	461.239 0[M-H]^-	447, 163	485.234 3[M+H]⁺	355, 153	0.65	Monoterpenoids	[9]
75*	18.55	Benzoylpaeoniflorin*	C₃₀H₃₂O₁₂	583.182 9[M-H]^-	583, 553, 431, 165	607.179 4[M+Na]⁺	427, 267, 249, 179, 151	2.23	Monoterpenoids	[28]
76	18.63	Benzoylpaeoniflorin isomer	C₃₀H₃₂O₁₂	583.182 9[M-H]^-	629, 583	607.179 4[M+Na]⁺	427, 267, 249, 179, 151	5.09	Monoterpenoids	[28]
77	18.77	Paeonin D	C₃₇H₃₆O₁₆	735.192 5[M-H]^-	613, 583, 169	-	-	0.10	Monoterpenoids	[23]
78	18.98	Paeonin D isomer	C₃₇H₃₆O₁₆	735.192 5[M-H]^-	613, 583, 169	-	-	0.10	Monoterpenoids	[23]
79	19.07	Benzoylpaeoniflorin isomer	C₃₀H₃₂O₁₂	583.182 9[M-H]^-	463, 319, 267, 197	607.179 4[M+Na]⁺	427, 267, 249, 179, 151	2.23	Monoterpenoids	[28]

Serial number	Retention time/min	Compound	Molecular formula	ES^-	ES⁺	Error/×10^-6	Classification	Ref.
1*	1.10	Sucrose*	C₁₂H₂₂O₁₁	341.108 3[M-H]^-	179	365.107 5[M+Na]⁺	325, 175, 145	-0.29	Oligosaccharide	[9]
2	1.31	Maltotriose	C₁₈H₃₂O₁₆	503.162 0[M-H]^-	341, 311, 179	527.158 3[M+Na]⁺	343, 325, 175, 163, 145	1.59	Oligosaccharide	[9]
3	1.41	Maltopentaose	C₃₀H₅₂O₂₆	827.267 4[M-H]^-	665, 503, 341, 311	-	-	0.60	Oligosaccharide	[9]
4	1.47	Maltohexaose	C₃₆H₆₂O₃₁	989.329 0[M-H]^-	827, 665	-	-	2.02	Oligosaccharide	[9]
5	1.54	Cyclomaltoheptaose	C₄₂H₇₀O₃₅	-	-	1 135.385 0[M+H]⁺	649, 487, 325, 163, 145	6.52	Oligosaccharide	[9]
6	1.55	Maltoheptaose	C₄₂H₇₂O₃₆	1 151.374 1 [M-H]^-	989, 827, 665, 503, 341	1 153.388 2[M+H]⁺	811, 649, 487, 325, 163, 145	1.39	Oligosaccharide	[9]
7*	1.74	Citric acid*	C₆H₈O₇	191.018 8[M-H]^-	111	-	-	-2.09	Other types	[10]
8	2.38	Desbenzoylpaeoniflorin	C₁₆H₂₄O₁₀	375.129 6[M-H]^-	345, 195, 165	399.123 0[M+Na]⁺	396, 331, 179, 151	1.30	Monoterpenoids	[10]
9	2.61	Oxiglutatione	C₂₀H₃₂N₆O₁₂S₂	611.142 7[M-H]^-	481, 331	613.160 0[M+H]⁺	487, 484	0.33	Other types	[11]
10	3.15	Galloylglucose	C₁₃H₁₆O₁₀	331.064 8[M-H]^-	169, 125	355.062 4[M+Na]⁺	325, 290, 208, 153, 145	-5.10	Polyphenols	[12]
11*	3.30	Adenosine*	C₁₀H₁₃N₅O₄	-	-	268.103 8[M+H]⁺	136, 153, 268	-2.98	Other types	[11]
12	3.35	Galloylglucose isomer	C₁₃H₁₆O₁₀	331.067 2[M-H]^-	169	-	-	2.11	Polyphenols	[12]
13	3.44	Galloylsucrose isomer	C₁₉H₂₆O₁₅	493.115 8[M-H]^-	331, 313, 283, 169	517.118 8[M+Na]⁺	325, 268, 153, 136	-7.09	Polyphenols	[13]
14	3.79	Desbenzoylpaeoniflorin isomer	C₁₆H₂₄O₁₀	-	-	399.123 0[M+Na]⁺	325, 215, 197, 151	5.60	Monoterpenoids	[10]
15	4.08	Glucopyranosyl paeonisuffrone	C₁₆H₂₄O₉	359.132 3[M-H]^-	311, 179	383.129 4[M+Na]⁺	325, 287, 163	-5.29	Monoterpenoids	[14]
16	4.48	Glucopyranosyl paeonisuffrone isomer	C₁₆H₂₄O₉	359.132 3[M-H]^-	311, 179	383.129 4[M+Na]⁺	325, 287, 163	-5.29	Monoterpenoids	[14]
17	5.36	Galloylsucrose isomer	C₁₉H₂₆O₁₅	493.115 8[M-H]^-	331, 313, 283	517.118 8[M+Na]⁺	433, 315, 153	-7.09	Polyphenols	[13]
18	5.72	Galloylsucrose isomer	C₁₉H₂₆O₁₅	493.115 8[M-H]^-	331, 313, 283	-	-	-7.09	Polyphenols	[13]
19	5.84	Galloylsucrose isomer	C₁₉H₂₆O₁₅	493.115 4[M-H]^-	331, 313, 283	517.118 8[M+Na]⁺	433, 315, 153	-7.91	Polyphenols	[13]
20	6.40	Digalloylglucose	C₂₀H₂₀O₁₄	483.073 8[M-H]^-	331, 313, 169	-	-	-7.66	Polyphenols	[15]
21	6.57	Galloyl desbenzoylpaeoniflorin	C₂₃H₂₈O₁₄	527.140 9[M-H]^-	169, 125	551.137 1[M+Na]⁺	496, 445, 345, 297, 164	1.52	Monoterpenoids	[16]
22	6.72	Glucopyranosyl lactinolide	C₁₆H₂₆O₉	361.151 6[M-H]^-	179	385.145 0[M+Na]⁺	205, 188, 144	4.71	Monoterpenoids	[17]
23	6.79	Digalloylglucose isomer	C₂₀H₂₀O₁₄	483.073 8[M-H]^-	331, 313, 169	-	-	-7.66	Polyphenols	[15]
24	6.92	Strictinin	C₂₇H₂₂O₁₈	633.073 5[M-H]^-	481, 301, 169	657.073 1[M+Na]⁺	367, 261	1.11	Polyphenols	[18]
25	7.00	Mudanpioside F	C₁₆H₂₄O₈	343.138 3[M-H]^-	181, 150	-	-	-2.91	Monoterpenoids	[19]
26	7.04	Galloyl desbenzoylpaeoniflorin isomer	C₂₃H₂₈O₁₄	527.142 1[M-H]^-	497, 169	551.137 1[M+Na]⁺	481, 365, 221, 281, 179	3.79	Monoterpenoids	[16]
27	7.18	Catechin glucoside	C₂₁H₂₄O₁₁	451.127 5[M-H]^-	289, 245, 169	475.117 7[M+Na]⁺	441, 291, 139	7.76	Polyphenols	[16]
28	7.23	Trigalloylglucose isomer	C₂₇H₂₄O₁₈	635.089 1[M-H]^-	465, 169, 313, 125	-	-	1.10	Polyphenols	[20]
29*	7.33	Procyanidin B1*	C₃₀H₂₆O₁₂	577.132 1[M-H]^-	289, 245, 203	579.150 9[M+H]⁺	409, 127	-4.30	Polyphenols	[21]
30	7.53	Oxypaeoniflorin isomer	C₂₃H₂₈O₁₂	495.149 8[M-H]^-	465, 345, 333, 281	519.150 9[M+Na]⁺	121	-1.01	Monoterpenoids	[22]
31	7.61	Procyanidin B2	C₃₀H₂₆O₁₂	577.132 1[M-H]^-	289, 245, 203	-	-	-4.30	Polyphenols	[21]
32	7.70	Trigalloylglucose isomer	C₂₇H₂₄O₁₈	635.089 1[M-H]^-	465, 169, 313, 125	-	-	1.10	Polyphenols	[20]
33*	7.76	Methyl gallate*	C₈H₈O₅	183.030 2[M-H]^-	168	-	-	4.92	Polyphenols	[23]
34*	7.82	Oxypaeoniflorin*	C₂₃H₂₈O₁₂	495.149 8[M-H]^-	465, 345, 333, 281	519.150 9[M+Na]⁺	291, 139	-1.01	Monoterpenoids	[22]
35	7.85	Trigalloylglucose isomer	C₂₇H₂₄O₁₈	635.089 1[M-H]^-	465, 169, 313, 125	-	-	1.10	Polyphenols	[20]
36*	7.89	Catechin*	C₁₅H₁₄O₆	289.072 2[M-H]^-	245, 203, 169	291.088 4[M+H]⁺	179, 147	3.50	Polyphenols	[24]
37	8.00	Procyanidin C	C₄₅H₃₈O₁₈	865.201 2[M-H]^-	577, 289, 245, 203	867.212 6[M+H]⁺	579, 245, 123	3.70	Polyphenols	[21]
38	8.35	Mudanpioside E	C₂₄H₃₀O₁₃	525.163 5[M-H]^-	495, 479	549.156 1[M+Na]⁺	349, 179	5.14	Monoterpenoids	[25]
39	8.45	Trigalloylglucose isomer	C₂₇H₂₄O₁₈	635.089 1[M-H]^-	465, 169, 313, 125	-	-	1.10	Polyphenols	[20]
40	8.52	Trigalloylglucose isomer	C₂₇H₂₄O₁₈	635.089 1[M-H]^-	465, 169, 313, 125	-	-	1.10	Polyphenols	[20]
41	8.65	Glucosylpaeoniflorin	C₂₉H₃₈O₁₆	641.209 0[M-H]^-	611, 489, 165 121	665.201 0[M+Na]⁺	483, 105	1.25	Monoterpenoids	[26]
42	8.94	Diglucosylpaeoniflorin	C₃₅H₄₈O₂₁	803.268 1[M-H]^-	773, 755, 641, 611, 489, 165	827.265 0[M+Na]⁺	409, 393, 371	-2.86	Monoterpenoids	[26]
43	9.06	Trigalloylglucose isomer	C₂₇H₂₄O₁₈	635.089 1[M-H]^-	465, 169, 313, 125	-	-	1.10	Polyphenols	[20]
44	9.30	Glucosylpaeoniflorin isomer	C₂₉H₃₈O₁₆	687.213 9 [M+COOH]^-	611, 489, 165, 121	665.201 0[M+Na]⁺	393, 153	1.31	Monoterpenoids	[26]
45*	9.50	1, 3, 6-Trigalloylglucose*	C₂₇H₂₄O₁₈	635.089 1[M-H]^-	465, 169, 313, 125	659.080 0[M+Na]⁺	619, 526, 467, 297, 153	1.10	Polyphenols	[27]
46*	9.60	Albiflorin*	C₂₃H₂₈O₁₁	525.162 5 [M+COOH]^-	525, 435, 449, 357, 327	481.174 9[M+H]⁺	319, 197, 105	3.24	Monoterpenoids	[28]
47	9.79	Glucosylpaeoniflorin isomer	C₂₉H₃₈O₁₆	641.209 0[M-H]^-	611, 489, 165, 121	655.156 1[M+Na]⁺	519	1.25	Monoterpenoids	[26]
48	10.06	Galloylpaeoniflorin	C₃₀H₃₂O₁₅	631.167 2[M-H]^-	481, 365, 221, 281, 179	655.160 2[M+Na]⁺	519, 503, 437, 153, 121	1.43	Monoterpenoids	[30]
49	10.20	Tetragalloylglucose isomer	C₃₄H₂₈O₂₂	787.103 5[M-H]^-	465, 169, 313, 125	-	-	5.21	Polyphenols	[27]
50*	10.20	Paeoniflorin*	C₂₃H₂₈O₁₁	479.155 0[M-H]^-	525, 449, 357, 327, 165 121, 77	503.153 1[M+Na]⁺	463, 179, 151	3.24	Monoterpenoids	[29]
51*	10.49	Ethyl gallate*	C₉H₁₀O₅	197.045 9[M-H]^-	169, 124	-	-	4.57	Polyphenols	[25]
52	11.34	Tetragalloylglucose isomer	C₃₄H₂₈O₂₂	787.097 9[M-H]^-	635, 617, 169	811.094 7[M+Na]⁺	641, 619, 525, 153	-1.91	Polyphenols	[31]
53*	11.78	1, 2, 3, 6-Tetragalloylglucose*	C₃₄H₂₈O₂₂	787.097 9[M-H]^-	787, 635, 617, 169	811.094 7[M+Na]⁺	641, 619, 525, 153	-1.91	Polyphenols	[27]
54*	12.30	Ellagic acid*	C₁₄H₆O₈	300.998 8[M-H]^-	245, 185, 175	-	-	1.33	Polyphenols	[23]
55*	12.98	6'-O-Galloylpaeoniflorin*	C₃₀H₃₂O₁₅	631.168 9[M-H]^-	481, 365, 221, 281, 179	655.160 2[M+Na]⁺	179, 153	1.43	Monoterpenoids	[30]
56	13.46	Galloylpaeoniflorin isomer	C₃₀H₃₂O₁₅	631.168 9[M-H]^-	481, 365, 221, 281, 179	655.167 4[M+Na]⁺	629, 613, 487, 153	1.43	Monoterpenoids	[30]
57*	13.58	1, 2, 3, 4, 6-Pentagalloylglucose*	C₄₁H₃₂O₂₆	939.113 6[M-H]^-	631, 469, 169	963.104 4[M+Na]⁺	771, 153	3.40	Polyphenols	[32]
58	13.84	Pentagalloylglucose isomer	C₄₁H₃₂O₂₆	939.116 9[M-H]^-	631, 469, 169	-	-	6.92	Polyphenols	[32]
59	14.00	Pentagalloylglucose isomer	C₄₁H₃₂O₂₆	-	-	963.104 4[M+Na]⁺	481, 365, 221, 281, 179	6.65	Polyphenols	[32]
60	14.22	Pentagalloylglucose isomer	C₄₁H₃₂O₂₆	-	-	963.104 4[M+Na]⁺	481, 365, 221, 281, 179	6.65	Polyphenols	[32]
61	14.28	Galloylpaeoniflorin isomer	C₃₀H₃₂O₁₅	631.168 9[M-H]^-	481, 365, 221, 281, 179	-	-	1.43	Monoterpenoids	[30]
62	14.80	Galloylpaeoniflorin isomer	C₃₀H₃₂O₁₅	631.168 9[M-H]^-	481, 365, 221, 281, 179	633.180 7[M+H]⁺	633, 267, 153, 105	-1.90	Monoterpenoids	[30]
63	15.11	Hexagalloylglucose	C₄₈H₃₆O₃₀	1 091.114 1[M-H]^-	939, 769, 169	1 115.110 8[M+Na]⁺	923, 771	-6.14	Polyphenols	[20]
64	15.60	Mudanpioside I	C₂₃H₂₈O₁₁	525.162 5[M+COOH]^-	357, 327, 283	481.174 9[M+H]⁺	503, 481, 319, 197, 133	3.24	Monoterpenoids	[33]
65	15.70	Hexagalloylglucose isomer	C₄₈H₃₆O₃₀	-	-	1 115.110 8[M+Na]⁺	923, 771	-7.26	Polyphenols	[20]
66	15.82	Hexagalloylglucose isomer	C₄₈H₃₆O₃₀	1 091.114 1[M-H]^-	939, 769, 169	1 115.110 8[M+Na]⁺	923, 771	-6.14	Polyphenols	[20]
67	17.13	Galloylpaeoniflorin isomer	C₃₀H₃₂O₁₅	631.167 2[M-H]^-	481, 365, 221, 281, 179	655.160 2[M+Na]⁺	613, 511, 153	1.43	Monoterpenoids	[30]
68	17.26	Digalloylpaeoniflorin	C₃₇H₃₆O₁₉	783.176 [M-H]^-	783, 643, 313, 169	-	-	-1.53	Monoterpenoids	[32]
69	17.55	Mudanpioside H	C₃₀H₃₂O₁₄	615.167 0[M-H]^-	493, 313	-	-	-7.15	Monoterpenoids	[34]
70	17.80	Pinane-10-yl vicianoside	C₂₁H₃₆O₁₀	447.222 3[M-H]^-	447, 315, 169	471.224 4[M+H]⁺	471, 349, 177	-1.57	Monoterpenoids	[35]
71*	17.61	Benzoyloxypaeoniflorin*	C₃₀H₃₂O₁₃	599.179 4[M-H]^-	165, 137, 121	-	-	4.84	Monoterpenoids	[28]
72	17.99	Galloylpaeoniflorin isomer	C₃₀H₃₂O₁₅	631.167 2[M-H]^-	481, 365, 221, 281, 179	-	-	1.11	Monoterpenoids	[30]
73	18.06	Pinen-10-yl vicianoside	C₂₁H₃₄O₁₀	445.205 7[M-H]^-	293, 149	-	-	-3.82	Monoterpenoids	[35]
74	18.31	Cineole rhamnosyl glucoside	C₂₂H₃₈O₁₀	461.239 0[M-H]^-	447, 163	485.234 3[M+H]⁺	355, 153	0.65	Monoterpenoids	[9]
75*	18.55	Benzoylpaeoniflorin*	C₃₀H₃₂O₁₂	583.182 9[M-H]^-	583, 553, 431, 165	607.179 4[M+Na]⁺	427, 267, 249, 179, 151	2.23	Monoterpenoids	[28]
76	18.63	Benzoylpaeoniflorin isomer	C₃₀H₃₂O₁₂	583.182 9[M-H]^-	629, 583	607.179 4[M+Na]⁺	427, 267, 249, 179, 151	5.09	Monoterpenoids	[28]
77	18.77	Paeonin D	C₃₇H₃₆O₁₆	735.192 5[M-H]^-	613, 583, 169	-	-	0.10	Monoterpenoids	[23]
78	18.98	Paeonin D isomer	C₃₇H₃₆O₁₆	735.192 5[M-H]^-	613, 583, 169	-	-	0.10	Monoterpenoids	[23]
79	19.07	Benzoylpaeoniflorin isomer	C₃₀H₃₂O₁₂	583.182 9[M-H]^-	463, 319, 267, 197	607.179 4[M+Na]⁺	427, 267, 249, 179, 151	2.23	Monoterpenoids	[28]

白芍抗抑郁组分及其化学成分的鉴定

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郑大华 ¹ , 于猛 ² , 金朝 ³ , 吴明 ² , 王平 ¹^,^* , 邹忠梅 ²^,^*

药学学报 | 研究论文 2023,58(5): 1307-1316

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药学学报 | 研究论文 2023, 58(5): 1307-1316

白芍抗抑郁组分及其化学成分的鉴定

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郑大华¹, 于猛², 金朝³, 吴明², 王平¹^,^*, 邹忠梅²^,^*

作者信息

1.浙江工业大学药学院, 浙江杭州 310014

2.中国医学科学院、北京协和医学院药用植物研究所, 北京 100193

3.遵义医科大学药学院, 贵州遵义 563000

通讯作者:

*王平,Tel: 13634108877, E-mail: wangping45@zjut.edu.cn;

邹忠梅,Tel: 86-10-57833290, E-mail: zmzou@implad.ac.cn

Identification of the antidepressant fraction and its major chemical constituents of Radix Paeoniae Alba

Da-hua ZHENG¹, Meng YU², Zhao JIN³, Ming WU², Ping WANG¹^,^*, Zhong-mei ZOU²^,^*

Affiliations

1. College of Pharmaceutical Sciences, Zhejiang University of Technology, Hangzhou 310014, China

2. Institute of Medicinal Plant Development, Chinese Academy of Medical Sciences and Peking Union Medical College, Beijing 100193, China

3. College of Pharmacy, Zunyi Medical University, Zunyi 563000, China

出版时间: 2023-05-12 doi: 10.16438/j.0513-4870.2022-1165

文章导航

摘要

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筛选白芍抗抑郁组分, 并对其主要化学成分进行鉴定。本文采用皮质酮诱导的PC12神经细胞损伤模型和小鼠行为绝望模型对白芍醇提物(Bai-Shao ethanol extract, BS-E) 及其大孔树脂不同洗脱组分(BS-10E, BS-60E, BS-95E) 的抗抑郁作用进行评价, 筛选获得白芍抗抑郁组分。动物实验经过中国医学科学院药用植物研究所动物伦理委员会批准(批准号: SLXD-20210618051)。结果发现, BS-E、BS-10E和BS-60E对皮质酮诱导的PC12细胞损伤具有保护作用, 其中组分BS-60E的保护作用最强; 行为绝望小鼠行为学结果表明, BS-60E可显著缩短小鼠强迫游泳和悬尾不动时间, 为白芍抗抑郁活性组分。采用超高效液相色谱四级杆飞行时间质谱(UPLC-Q-TOF/MS) 联用系统对BS-60E的化学成分进行鉴定, 并对其可能的质谱裂解规律进行推导。从BS-60E中共鉴定出79个化学成分, 主要包括单萜类成分36个, 多酚类成分34个, 寡糖类成分6个, 其他类成分3个, 表明单萜类及多酚类成分可能是其主要的药效成分。

关键词

白芍 / 抗抑郁组分 / UPLC-Q-TOF/MS / 单萜 / 多酚

Abstract

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The goal of this work was to investigate the antidepressant fraction from Radix Paeoniae Alba and identify its major chemical constituents. Corticosterone injured rat phaeochromocytoma (PC12) cells and behavioral despair depression models of mice were used to evaluate the antidepressant effects of Radix Paeoniae Alba (Bai-Shao) ethanol extract (BS-E) and its three fractions (BS-10E, BS-60E, BS-95E) isolated by macroporous resin column chromatography. Animal experimental procedures were approved by the Animal Ethics Committee of the Institute of Medicinal Plant Development, Chinese Academy of Medical Sciences and Peking Union Medical College (approval No.: SLXD-20210618051). The results showed that BS-E, BS-10E and BS-60E had protective effects against PC12 cells injury induced by corticosterone, among which BS-60E had the strongest protective effect. BS-60E could significantly shorten the time of forced swimming and tail suspension in despair depression models of mice, and was identified as the antidepressant fraction of Radix Paeoniae Alba. The major chemical constituents in the antidepressant fraction were identified by ultra-performance liquid chromatography coupled with quadrupole time-of-flight mass spectrometry (UPLC-Q-TOF/MS), and their proposed fragmentation pathways in MS spectra were deduced. A total of 79 chemical constituents were identified from BS-60E, including 36 monoterpenes, 34 polyphenols, 6 oligosaccharides, and 3 other constituents, and monoterpenes and polyphenols may be major effective constituents of BS-60E.

Key words

Radix Paeoniae Alba / antidepressant fraction / UPLC-Q-TOF/MS / monoterpene / polyphenol

引用本文

郑大华, 于猛, 金朝, 吴明, 王平, 邹忠梅. 白芍抗抑郁组分及其化学成分的鉴定. 药学学报, 2023 , 58 (5) : 1307 -1316 . DOI: 10.16438/j.0513-4870.2022-1165

Da-hua ZHENG, Meng YU, Zhao JIN, Ming WU, Ping WANG, Zhong-mei ZOU. Identification of the antidepressant fraction and its major chemical constituents of Radix Paeoniae Alba[J]. Acta Pharmaceutica Sinica, 2023 , 58 (5) : 1307 -1316 . DOI: 10.16438/j.0513-4870.2022-1165

正文

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常用中药白芍为毛茛科多年生草本植物芍药Paeonia lactiflora Pall. 的干燥根, 味苦、酸, 性微寒, 归肝、脾经, 具有养血调经、敛阴止汗、柔肝止痛和平抑肝阳等功效^[1]。现代药理研究表明, 白芍具有神经保护、抗炎、抗氧化、免疫调节等多种活性, 近年来其抗抑郁作用引起关注^[2]。白芍作为多个疏肝解郁方剂如柴胡疏肝散^[3]、逍遥散^[4]、四逆散^[5]等的重要组成药物, 在组方频次和用药剂量上, 都占有重要的位置。虽然已有文献报道白芍中的单萜及其苷类成分, 如芍药苷可能是其主要的抗抑郁成分^[6], 但白芍抗抑郁的药效物质至今尚无明确的定论。

因此, 本论文应用皮质酮诱导PC12细胞神经损伤模型结合小鼠行为绝望模型, 对白芍醇提物(Bai-Shao ethanol extract, BS-E) 及其大孔树脂不同洗脱组分(BS-10E, BS-60E, BS-95E)的抗抑郁作用进行评价, 筛选获得白芍抗抑郁活性组分; 然后采用超高效液相色谱四级杆飞行时间质谱(UPLC-Q-TOF/MS) 法对抗抑郁活性组分的化学成分进行全面表征, 以期为白芍的抗抑郁药效物质基础研究提供参考。

材料与方法

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试剂与药材 盐酸氯丙咪嗪片(规格为25 mg × 50片, 批号: 20130402) (江苏恩华药业股份有限公司产品); 大鼠嗜铬细胞瘤PC12细胞(中国医学科学院基础医学研究所); 特级胎牛血清(美国赛默飞世尔科技公司)、DMEM培养液和胰蛋白酶(美国HyClone公司); 甲醇、乙腈、甲酸(LC-MS级) (美国赛默飞世尔科技公司); 超纯水(广州屈臣氏食品饮料有限公司); 皮质酮、二苯基四氮唑溴盐[3-(4, 5-dimethylthiazol-2-yl)-2, 5-diphenyltetrazolium bromide, MTT] 和二甲基亚砜(dimethyl sulfoxide, DMSO, 美国Sigma公司); 大孔吸附树脂D101 (上海玻尔化学试剂有限公司); 芍药苷(paeoniflorin, 批号: 20190123, 质量分数≥ 98%)、氧化芍药苷(oxypaeoniflorin, 批号: 201912, 质量分数≥ 98%)、苯甲酰芍药苷(benzoylypaeoniflorin, 批号: 20190628, 质量分数≥ 95%) 购于上海惠诚生物科技有限公司; 芍药内酯苷(albiflorin, 批号: 14090602, 质量分数≥ 98%) 购于上海纯优生物科技有限公司; 没食子酰芍药苷(galloylpaeoniflorin, 批号: PS01094, 质量分数≥ 98%)、苯甲酰氧化芍药苷(benzoyloxypaeoniflorin, 批号: PS012411, 质量分数≥ 95%)、1, 3, 6-三没食子酰葡萄糖(1, 3, 6-trigalloylglucose, 批号: PS211103-01, 质量分数≥ 97%)、1, 2, 3, 6-四没食子酰葡萄糖(1, 2, 3, 6-tetragalloylglucose, 批号: PS012574, 质量分数≥ 98%)、1, 2, 3, 4, 6-五没食子酰葡萄糖(1, 2, 3, 4, 6-pentagalloylglucose, 批号: PS011427, 质量分数≥ 98%) 购于成都普思生物科技公司; 原花青素B1 (procyanidin B1, 批号: BSCI-NCL007006-NX-1, 质量分数≥ 98%)、柠檬酸(citric acid, 批号: SCI-NCL006879, 质量分数≥ 98%)、蔗糖(sucrose, 批号: SCI-NCL001868, 质量分数≥ 98%)、儿茶素(catechin, 批号: SCI-NCL005127, 质量分数≥ 98%)、鞣花酸(ellagic acid, 批号: SCI-NCL000196, 质量分数≥ 98%)、没食子酸甲酯(methyl gallate, 批号: SCI-NCL003154-NX-1, 质量分数≥ 98%)、没食子酸乙酯(ethyl gallate, 批号: SCI-NCL000608-NX-4, 质量分数≥ 98%)、腺苷(adenosine, 批号: SCI-NCL005881, 质量分数≥ 98%) 来源于中国医学科学院药用植物研究所国家中药化合物库。

白芍药材购于北京同仁堂股份有限公司, 经中国医学科学院药用植物研究所张丽萍研究员鉴定为白芍(Paeonia lactiflora Pall.) 的根。

仪器 ACQUITY^TM UPLC^®超高效液相色谱串联SYNAPT G2 HDMS高分辨质谱联用系统和MassLynx^TM工作站(Version 4.1) (美国沃特世公司); KQ-500E型超声波清洗器(昆山市超声仪器有限公司); ET3301全自动氮吹浓缩仪(上海欧陆科仪有限公司); T75培养瓶(美国康宁公司); MCO-15AC型CO₂恒温细胞培养箱(日本三洋公司); ZHJH-C 1115B型超净工作台(上海智成分析仪器制造有限公司); CKX41型倒置相差显微镜(日本奥林巴斯公司); MQX 200型酶标光度计(美国伯腾仪器有限公司); MSA125P-100-DU型电子分析天平(德国Sartorius称重技术有限公司); Legend Micro17R低温高速旋转离心机(美国赛默飞世尔科技公司); S0200-230V-EU微型涡旋混合仪(美国莱伯特公司); 自制小鼠悬尾实验观察箱(20 cm × 20 cm × 40 cm)。

实验动物 雄性ICR小鼠, 体重为20 ± 2 g, 购自北京维通利华实验动物技术有限公司, 许可证编号: SCXK (京) 2014-0004。小鼠每笼10只群养, 自由摄食饮水, 室温23~25 ℃, 湿度50% ± 10%, 7:00~19:00光照; 动物在新环境中适应7天后开始实验。所有动物实验均经过中国医学科学院药用植物研究所动物伦理委员会批准(批准号: SLXD-20210618051)。

BS-E、BS-10E、BS-60E和BS-95E的制备 取白芍药材1 200 g, 加70%乙醇浸泡过夜(1∶8, W/V), 回流提取2次, 每次3 h, 趁热过滤, 将所得滤液合并, 减压浓缩, 冷冻干燥, 得到BS-E, 提取率为17.65%。BS-E经浓缩至无醇, 加水稀释至相当于生药量0.5 g·mL^-1, 离心, 过滤, 去除不溶物, 上清液经大孔树脂柱层析吸附, 依次用水、10%、60%、95%乙醇溶液洗脱, 洗脱液经浓缩, 冷冻干燥, 分别得到大孔树脂水洗脱组分(18.4 g, 得率为8.70%)、BS-10E (12.6 g, 得率为5.95%)、BS-60E (37.8 g, 得率为17.84%) 和BS-95E (0.396 g, 得率为0.19%)。

细胞培养与分组 保持37 ℃, 95%空气和5% CO₂的湿润条件下, 将PC12细胞置于青霉素(100 µg·mL^-1)、链霉素(100 µg·mL^-1)、5%胎牛血清和10%马血清的DMEM培养基中。细胞实验分组: 空白对照组为正常细胞(control); 模型组(model) 为200 μmol·L^-1皮质酮; 给药组为BS-E (100 µg·mL^-1)、BS-10E (100 µg·mL^-1)、BS-60E (100 µg·mL^-1)、BS-95E (100 µg·mL^-1)。

细胞活力测定通过MTT实验评估细胞存活情况, 取对数生长期细胞, 调整细胞密度为100 000·mL^-1, 接种于96孔板, 每孔100 μL, 放置5% CO₂, 37 ℃条件下孵育24 h。吸出培养液, 每孔分别加入200 μmol·L^-1的皮质酮作用48 h, 然后再分别加入BS-E、BS-10E、BS-60E和BS-95E作用24 h。每孔加入0.5 mg·mL^-1 MTT的20 μL (注意避光)。继续培养4 h后, 吸去培养基, 每孔加入150 μL DMSO, 置振荡器上混匀10 min, 以使蓝紫色颗粒充分溶解。然后置于自动酶联免疫分析仪以波长570 nm测各孔吸光度。

动物分组 实验动物分为4组, 每组10只小鼠, 分别为模型组(CMC-Na, vehicle)、阳性药盐酸氯丙咪嗪组(40 mg·kg^-1, clomipramine hydrochloride)、BS-E组(相当于生药量7.28 g·kg^-1)、BS-60E组(相当于生药量7.28 g·kg^-1), 各实验组均连续灌胃14天, 最后一次给药1 h后开始行为学实验。

小鼠悬尾应激实验 实验采用Steru等^[7]建立的方法: 箱子顶部中心设置一个夹子, 将胶布粘在小鼠尾端约2 cm处, 然后夹子夹住胶布, 使小鼠呈倒悬状态, 四周以板隔离视线, 观察6 min, 记录后4 min内小鼠累积不动时间, 即悬尾不动时间(tail suspension immobility time, TST)。实验采用盲法, 实验人员不知道动物的给药情况, 且实验前统一训练实验人员和统一实验评判标准, 操作方式和实验命令口号等, 并且保证实验环境的隔离和安静。

小鼠强迫游泳实验 实验依据Porsolt等^[8]建立的方法, 将小鼠放玻璃缸中, 缸中水深约15 cm, 水温(25 ± 1) ℃, 开始观察, 持续6 min, 累计后4 min内小鼠在水中停止挣扎、呈漂浮状态、仅有细小的肢体运动并保持头部浮在水面的持续时间, 即强迫游泳不动时间(forced swimming immobility time, FST)。实验采用盲法, 实验人员不知道动物的给药情况, 且实验前统一训练实验人员和统一实验评判标准, 操作方式和实验命令口号等, 并且保证实验环境的隔离和安静。

UPLC-Q-TOF/MS分析条件 采用的色谱柱: ACQUITY UPLC HSS T3 (2.1 mm × 100 mm, 1.8 μm); 流动相: 0.1%甲酸水溶液(A)-0.1%甲酸乙腈(B); 采用梯度洗脱: 0~4 min, 1%~4% B; 4~6 min, 4%~12% B; 6~16 min, 12%~23% B; 16~18 min, 23%~50% B; 18~20 min, 50%~99% B; 流速: 0.3 mL·min^-1; 柱温40 ℃; 检测波长为190~400 nm; 进样量5 µL。采用Waters SYNAPT G2 HDMS系统, 氮气作为质谱ESI离子源的雾化、锥孔气; 电喷雾电离: 正负离子模式; 毛细管电压: 正离子3.0 kV, 负离子2.1 kV; 锥孔电压: 40 V; 萃取锥孔电压: 3 V; 离子源温度: 100 ℃; 脱溶剂气温度: 400 ℃; 反向锥孔气流: 50 L·h^-1; 脱溶剂气流速: 600 L·h^-1; 碰撞气流速: 0.5 mL·min^-1; 扫描时间: 0.5 s; 扫描时间间隔: 0.02 s; 质荷比范围: m/z 50~1 200; 数据采集形式: Continuum; 灵敏性: Normal; 动态范围: Extended; 采用亮氨酸－脑啡肽进行精确质量校正(锁定质量数: 正离子模式下m/z 556.277 1; 负离子模式下m/z 554.261 5)。

供试品溶液的制备 精密称取BS-60E冻干粉约10 mg, 置于2 mL Ep管中, 加入50%甲醇水溶液1 mL, 超声辅助溶解, 并于13 000 r·min^-1离心15 min后, 取上清液, 过0.2 µm微孔滤膜, 待测。

对照品溶液的制备 精密称取芍药苷、芍药内酯苷、氧化芍药苷、苯甲酰芍药苷、没食子酰芍药苷、苯甲酰氧化芍药苷、1, 3, 6-三没食子酰葡萄糖、1, 2, 3, 6-四没食子酰葡萄糖、1, 2, 3, 4, 6-五没食子酰葡萄糖、原花青素B1、柠檬酸、蔗糖、儿茶素、没食子酸甲酯、没食子酸乙酯对照品适量, 甲醇溶解; 鞣花酸、腺苷对照品适量, 纯水溶解, 得到相应对照品储备液, 稀释后用于定性分析。

数据分析 实验数据采用SPSS 17.0数据处理软件进行统计分析, 以平均值±标准偏差(x ± s) 表示, 单因素ANOVA方差分析方法进行显著性检验, 以P < 0.05表示差异具有显著性意义, P < 0.01表示差异具有非常显著性意义。

结果

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1 BS-E、BS-10E、BS-60E和BS-95E对皮质酮诱导PC12细胞的保护作用

MTT实验结果如图 1A所示, 与空白对照组相比, 模型组中皮质酮诱导PC12细胞活力显著下降, 加入BS-E保护24 h后, 细胞活力显著回升; 加入三个组分后, BS-10E和BS-60E均能显著增加PC12细胞的活力, 其中BS-60E的效果更为显著, 且与BS-E的药效相当, 但BS-95E无调控作用。

2 BS-E和BS-60E对行为绝望模型小鼠TST和FST的影响

小鼠行为学结果如图 1B、C所示, BS-60E能显著缩短小鼠TST和FST, 与阳性药盐酸氯丙咪嗪的作用相当, 但其药效明显好于BS-E。上述研究进一步证实, BS-60E具有显著的抗抑郁作用。

3 BS-60E化学成分的定性分析

为了明确BS-60E中的化学成分, 按照UPLC-Q/TOF MS分析条件, 采集BS-60E的质谱数据, 分别得到正、负离子模式下色谱(未提供)、质谱图(图 2)。从BS-60E中共鉴定79个化学成分(负离子模式鉴定74个、正离子模式鉴定51个, 其中46个成分同时在正、负离子模式下检测到), 包括单萜类成分36个, 多酚类成分34个, 寡糖类成分6个, 其他类成分3个。其中芍药苷、氧化芍药苷、苯甲酰芍药苷、芍药内酯苷、没食子酰芍药苷、苯甲酰氧化芍药苷、1, 3, 6-三没食子酰葡萄糖、1, 2, 3, 6-四没食子酰葡萄糖、1, 2, 3, 4, 6-五没食子酰葡萄糖、原花青素B1、柠檬酸、蔗糖、儿茶素、没食子酸甲酯、没食子酸乙酯、鞣花酸、腺苷等17个成分与对照品进行了比对, 鉴定的结果见表 1^[9-35]。

4 主要化学成分鉴定及质谱裂解规律的推导

4.1 单萜类成分的鉴定

单萜类成分结构大多以蒎烷作为基本骨架, 该类化合物在质谱中一般会出现m/z 165.055 1的特征碎片离子。以化合物46和50为例, 在ESI-MS负离子扫描模式下, 两者保留时间分别为9.60和10.20 min, 二者的准分子离子峰相同, 均为m/z 479.155 0 [M-H]^- (C₂₃H₂₈O₁₁, ∆m/z -3.24 ppm), 且具有m/z 165.055 1的特征碎片离子, 推测化合物50可能为单萜类成分, 且二者可能为同分异构体; 在二级质谱图中, 二者碎片离子的种类具有差异, 其中m/z 375.126 0是化合物46的特征碎片离子, m/z 449.139 3是化合物50的特征碎片离子。同时两者的色谱峰在230和254 nm处均有紫外特征吸收, 通过与文献^{[28, 29]}及对照品进行比对, 确定化合物46为芍药内酯苷, 化合物50为芍药苷, 二者可能的质谱裂解规律如图 3所示。

4.2 多酚类成分的鉴定

以化合物63为例, 在ESI-MS负离子扫描模式下, 保留时间为15.11 min的准分子离子峰为m/z 1 091.114 1 [M-H]^- (C₄₈H₃₆O₃₀, ∆ m/z -6.14 ppm), 在二级质谱中, 存在m/z 169.011 0的特征质谱碎片离子, 推测化合物63可能是没食子酸类成分。其丰度较大的碎片离子还包括m/z 939和m/z769, 其中m/z 939为化合物63脱去一分子没食子酰亚组分(C₇H₄O₄) 形成[M-H-152]^-碎片离子, m/z 769是由m/z 939碎片离子继续脱去一分子没食子酸(C₇H₆O₅)形成的[M-H-152-170]^-碎片离子, 再继续脱去一分子没食子酰亚组分(C₇H₄O₄) 产生m/z 617的碎片离子。该化合物的色谱峰在217和279 nm处有紫外特征吸收, 通过与文献^[20]比对, 初步判断为六没食子酰葡萄糖, 其可能的质谱裂解规律如图 4所示。

以化合物29为例, 在ESI-MS负离子扫描模式下, 保留时间为7.33 min的峰, 其准分子离子峰为m/z 577.132 1 [M-H]^- (C₃₀H₂₆O₁₂, ∆ m/z -4.30 ppm), 该化合物的色谱峰在216和278 nm处有紫外特征吸收, 初步推断可能为黄酮类成分; 在二级质谱中, 其丰度较大的碎片离子为m/z 425和m/z289, 其中m/z 425是由化合物29失去一分子C₇H₄O₄所产生的[M-H-152]^-碎片离子, m/z 289是化合物29失去一分子C₁₅H₁₃O₆所产生的[M-H-288]^-碎片离子。通过查阅文献^[21]及与对照品进行比对, 推断为原花青素B1, 其可能的质谱裂解规律见图 5。

4.3 寡糖类成分的鉴定

以化合物6为例, 在ESI-MS负离子扫描模式下, 保留时间为1.55 min的准分子离子峰为m/z 1 151.374 1 [M-H]^- (C₄₂H₇₂O₃₆, ∆ m/z 1.39 ppm), 在二级质谱中, 主要的碎片离子有m/z 989、827、665、503、341, 其中m/z 989.315 1是由准分子离子峰[M-H]^-丢失一分子葡萄糖残基(C₆H₁₀O₅)所产生的[M-H-162]^-碎片离子, 然后再继续失去一分子葡萄糖残基逐步生成m/z 827、665、503、341。通过与文献^[9]相比较, 初步推断为麦芽七糖, 可能的质谱裂解规律如图 6所示。

讨论

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本论文采用皮质酮诱导的PC12细胞损伤模型结合行为绝望小鼠模型, 对BS-E, BS-10E, BS-60E和BS-95E的神经保护作用进行了研究, 结果发现BS-60E对皮质酮诱导的PC12细胞损伤具有明确的保护作用, 同时能够显著改善行为绝望小鼠的抑郁样行为, 是白芍发挥抗抑郁作用的药效组分。

文献^[36]报道, BS-E能够显著改善慢性不可预知应激抑郁大鼠的抑郁样行为, 具有明确的抗抑郁作用, 因此本文选择BS-E作为研究对象, 并应用大孔树脂柱层析的方法制备不同极性组分。采用10%乙醇洗脱富集极性大的小分子醇及糖类成分, 60%乙醇洗脱富集单萜类成分, 95%乙醇洗脱富集低极性成分。此外, 针对不同极性组分的药效评价, 首先采用体外皮质酮诱导的PC12细胞损伤模型进行初步筛选, 然后再利用小鼠行为绝望模型进行体内药效确证, 研究结果证实, BS-60E是白芍发挥抗抑郁作用的组分。

为了明确BS-60E中的化学成分组成, 本文建立了UPLC-Q-TOF/MS的定性分析方法, 首先对UPLC色谱条件进行了优化, 考察了不同极性的色谱柱如Agilent Extend C18、Waters HSS T3、Phenomenex Kinetex C18、HALO 90 PFP等。结果发现, Waters HSS T3色谱柱对BS-60E中色谱峰的分离效果较好, 因此本实验选择Waters HSS T3色谱柱进行后续分析。本实验还考察了不同流动相组成, 如乙腈-水、乙腈-水(0.1%甲酸)、乙腈(0.1%甲酸)-水(0.1%甲酸)等, 结果发现, 流动相中加入甲酸可以增强白芍中主要化学成分的分离效果, 但流动相为乙腈-水(0.1%甲酸) 和乙腈(0.1%甲酸)-水(0.1%甲酸)对色谱峰的分离无明显差异, 为了提高样品在质谱中的响应, 本实验最终选择乙腈(0.1%甲酸)-水(0.1%甲酸)作为流动相。此外, 实验过程中也对柱温、洗脱梯度等色谱条件, 以及离子源温度、毛细管电压等质谱条件进行了考察, 最终确定了BS-60E的定向分析方法。

通过对BS-60E中化学成分的鉴定发现, 以芍药苷为代表的单萜类和以1, 2, 3, 4, 6-五没食子酰葡萄糖为代表的多酚类成分是BS-60E的主要成分。研究证实, 芍药苷具有明确的抗抑郁作用, 可对氯化钴诱导的PC12细胞氧化应激损伤具有保护作用^[37], 同时还可以改善行为绝望小鼠抑郁样行为^[38]; 没食子酸能够缩短行为绝望模型小鼠强迫游泳和悬尾不动时间^[39]; 1, 2, 3, 4, 6-五没食子酰葡萄糖对1-甲基-4-苯基吡啶离子(MPP⁺) 诱导的PC12细胞损伤具有保护作用^[40]。因此, 推测单萜类及多酚类成分可能是BS-60E中主要的药效成分。后续实验将会采用血清药物化学、网络药理学等方法结合抑郁动物或细胞模型进一步挖掘白芍中发挥抗抑郁作用的成分, 为白芍药材功效成分的筛选提供科学依据。

作者贡献: 郑大华、于猛负责完成相关实验研究; 金朝、吴明负责数据分析的校对; 王平、邹忠梅负责对本课题实验设计思路进行指导。

利益冲突: 所有作者均声明不存在利益冲突。

基金

收起

国家自然科学基金项目(82073991)
中国医学科学院医学与健康科技创新工程项目(2022-I2M-1-017)

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2023年第58卷第5期

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doi: 10.16438/j.0513-4870.2022-1165

接收时间：2022-11-01
首发时间：2025-11-21
出版时间：2023-05-12

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出版历史

收稿日期：2022-11-01
修回日期：2023-03-01

基金

国家自然科学基金项目(82073991)

中国医学科学院医学与健康科技创新工程项目(2022-I2M-1-017)

作者信息

1.浙江工业大学药学院, 浙江杭州 310014

2.中国医学科学院、北京协和医学院药用植物研究所, 北京 100193

3.遵义医科大学药学院, 贵州遵义 563000

通讯作者:

*王平,Tel: 13634108877, E-mail: wangping45@zjut.edu.cn;

邹忠梅,Tel: 86-10-57833290, E-mail: zmzou@implad.ac.cn

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2种不同金属材料的力学参数

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

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Serial number	Retention time/min	Compound	Molecular formula	ES^-	ES⁺	Error/×10^-6	Classification	Ref.
1*	1.10	Sucrose*	C₁₂H₂₂O₁₁	341.108 3[M-H]^-	179	365.107 5[M+Na]⁺	325, 175, 145	-0.29	Oligosaccharide	[9]
2	1.31	Maltotriose	C₁₈H₃₂O₁₆	503.162 0[M-H]^-	341, 311, 179	527.158 3[M+Na]⁺	343, 325, 175, 163, 145	1.59	Oligosaccharide	[9]
3	1.41	Maltopentaose	C₃₀H₅₂O₂₆	827.267 4[M-H]^-	665, 503, 341, 311	-	-	0.60	Oligosaccharide	[9]
4	1.47	Maltohexaose	C₃₆H₆₂O₃₁	989.329 0[M-H]^-	827, 665	-	-	2.02	Oligosaccharide	[9]
5	1.54	Cyclomaltoheptaose	C₄₂H₇₀O₃₅	-	-	1 135.385 0[M+H]⁺	649, 487, 325, 163, 145	6.52	Oligosaccharide	[9]
6	1.55	Maltoheptaose	C₄₂H₇₂O₃₆	1 151.374 1 [M-H]^-	989, 827, 665, 503, 341	1 153.388 2[M+H]⁺	811, 649, 487, 325, 163, 145	1.39	Oligosaccharide	[9]
7*	1.74	Citric acid*	C₆H₈O₇	191.018 8[M-H]^-	111	-	-	-2.09	Other types	[10]
8	2.38	Desbenzoylpaeoniflorin	C₁₆H₂₄O₁₀	375.129 6[M-H]^-	345, 195, 165	399.123 0[M+Na]⁺	396, 331, 179, 151	1.30	Monoterpenoids	[10]
9	2.61	Oxiglutatione	C₂₀H₃₂N₆O₁₂S₂	611.142 7[M-H]^-	481, 331	613.160 0[M+H]⁺	487, 484	0.33	Other types	[11]
10	3.15	Galloylglucose	C₁₃H₁₆O₁₀	331.064 8[M-H]^-	169, 125	355.062 4[M+Na]⁺	325, 290, 208, 153, 145	-5.10	Polyphenols	[12]
11*	3.30	Adenosine*	C₁₀H₁₃N₅O₄	-	-	268.103 8[M+H]⁺	136, 153, 268	-2.98	Other types	[11]
12	3.35	Galloylglucose isomer	C₁₃H₁₆O₁₀	331.067 2[M-H]^-	169	-	-	2.11	Polyphenols	[12]
13	3.44	Galloylsucrose isomer	C₁₉H₂₆O₁₅	493.115 8[M-H]^-	331, 313, 283, 169	517.118 8[M+Na]⁺	325, 268, 153, 136	-7.09	Polyphenols	[13]
14	3.79	Desbenzoylpaeoniflorin isomer	C₁₆H₂₄O₁₀	-	-	399.123 0[M+Na]⁺	325, 215, 197, 151	5.60	Monoterpenoids	[10]
15	4.08	Glucopyranosyl paeonisuffrone	C₁₆H₂₄O₉	359.132 3[M-H]^-	311, 179	383.129 4[M+Na]⁺	325, 287, 163	-5.29	Monoterpenoids	[14]
16	4.48	Glucopyranosyl paeonisuffrone isomer	C₁₆H₂₄O₉	359.132 3[M-H]^-	311, 179	383.129 4[M+Na]⁺	325, 287, 163	-5.29	Monoterpenoids	[14]
17	5.36	Galloylsucrose isomer	C₁₉H₂₆O₁₅	493.115 8[M-H]^-	331, 313, 283	517.118 8[M+Na]⁺	433, 315, 153	-7.09	Polyphenols	[13]
18	5.72	Galloylsucrose isomer	C₁₉H₂₆O₁₅	493.115 8[M-H]^-	331, 313, 283	-	-	-7.09	Polyphenols	[13]
19	5.84	Galloylsucrose isomer	C₁₉H₂₆O₁₅	493.115 4[M-H]^-	331, 313, 283	517.118 8[M+Na]⁺	433, 315, 153	-7.91	Polyphenols	[13]
20	6.40	Digalloylglucose	C₂₀H₂₀O₁₄	483.073 8[M-H]^-	331, 313, 169	-	-	-7.66	Polyphenols	[15]
21	6.57	Galloyl desbenzoylpaeoniflorin	C₂₃H₂₈O₁₄	527.140 9[M-H]^-	169, 125	551.137 1[M+Na]⁺	496, 445, 345, 297, 164	1.52	Monoterpenoids	[16]
22	6.72	Glucopyranosyl lactinolide	C₁₆H₂₆O₉	361.151 6[M-H]^-	179	385.145 0[M+Na]⁺	205, 188, 144	4.71	Monoterpenoids	[17]
23	6.79	Digalloylglucose isomer	C₂₀H₂₀O₁₄	483.073 8[M-H]^-	331, 313, 169	-	-	-7.66	Polyphenols	[15]
24	6.92	Strictinin	C₂₇H₂₂O₁₈	633.073 5[M-H]^-	481, 301, 169	657.073 1[M+Na]⁺	367, 261	1.11	Polyphenols	[18]
25	7.00	Mudanpioside F	C₁₆H₂₄O₈	343.138 3[M-H]^-	181, 150	-	-	-2.91	Monoterpenoids	[19]
26	7.04	Galloyl desbenzoylpaeoniflorin isomer	C₂₃H₂₈O₁₄	527.142 1[M-H]^-	497, 169	551.137 1[M+Na]⁺	481, 365, 221, 281, 179	3.79	Monoterpenoids	[16]
27	7.18	Catechin glucoside	C₂₁H₂₄O₁₁	451.127 5[M-H]^-	289, 245, 169	475.117 7[M+Na]⁺	441, 291, 139	7.76	Polyphenols	[16]
28	7.23	Trigalloylglucose isomer	C₂₇H₂₄O₁₈	635.089 1[M-H]^-	465, 169, 313, 125	-	-	1.10	Polyphenols	[20]
29*	7.33	Procyanidin B1*	C₃₀H₂₆O₁₂	577.132 1[M-H]^-	289, 245, 203	579.150 9[M+H]⁺	409, 127	-4.30	Polyphenols	[21]
30	7.53	Oxypaeoniflorin isomer	C₂₃H₂₈O₁₂	495.149 8[M-H]^-	465, 345, 333, 281	519.150 9[M+Na]⁺	121	-1.01	Monoterpenoids	[22]
31	7.61	Procyanidin B2	C₃₀H₂₆O₁₂	577.132 1[M-H]^-	289, 245, 203	-	-	-4.30	Polyphenols	[21]
32	7.70	Trigalloylglucose isomer	C₂₇H₂₄O₁₈	635.089 1[M-H]^-	465, 169, 313, 125	-	-	1.10	Polyphenols	[20]
33*	7.76	Methyl gallate*	C₈H₈O₅	183.030 2[M-H]^-	168	-	-	4.92	Polyphenols	[23]
34*	7.82	Oxypaeoniflorin*	C₂₃H₂₈O₁₂	495.149 8[M-H]^-	465, 345, 333, 281	519.150 9[M+Na]⁺	291, 139	-1.01	Monoterpenoids	[22]
35	7.85	Trigalloylglucose isomer	C₂₇H₂₄O₁₈	635.089 1[M-H]^-	465, 169, 313, 125	-	-	1.10	Polyphenols	[20]
36*	7.89	Catechin*	C₁₅H₁₄O₆	289.072 2[M-H]^-	245, 203, 169	291.088 4[M+H]⁺	179, 147	3.50	Polyphenols	[24]
37	8.00	Procyanidin C	C₄₅H₃₈O₁₈	865.201 2[M-H]^-	577, 289, 245, 203	867.212 6[M+H]⁺	579, 245, 123	3.70	Polyphenols	[21]
38	8.35	Mudanpioside E	C₂₄H₃₀O₁₃	525.163 5[M-H]^-	495, 479	549.156 1[M+Na]⁺	349, 179	5.14	Monoterpenoids	[25]
39	8.45	Trigalloylglucose isomer	C₂₇H₂₄O₁₈	635.089 1[M-H]^-	465, 169, 313, 125	-	-	1.10	Polyphenols	[20]
40	8.52	Trigalloylglucose isomer	C₂₇H₂₄O₁₈	635.089 1[M-H]^-	465, 169, 313, 125	-	-	1.10	Polyphenols	[20]
41	8.65	Glucosylpaeoniflorin	C₂₉H₃₈O₁₆	641.209 0[M-H]^-	611, 489, 165 121	665.201 0[M+Na]⁺	483, 105	1.25	Monoterpenoids	[26]
42	8.94	Diglucosylpaeoniflorin	C₃₅H₄₈O₂₁	803.268 1[M-H]^-	773, 755, 641, 611, 489, 165	827.265 0[M+Na]⁺	409, 393, 371	-2.86	Monoterpenoids	[26]
43	9.06	Trigalloylglucose isomer	C₂₇H₂₄O₁₈	635.089 1[M-H]^-	465, 169, 313, 125	-	-	1.10	Polyphenols	[20]
44	9.30	Glucosylpaeoniflorin isomer	C₂₉H₃₈O₁₆	687.213 9 [M+COOH]^-	611, 489, 165, 121	665.201 0[M+Na]⁺	393, 153	1.31	Monoterpenoids	[26]
45*	9.50	1, 3, 6-Trigalloylglucose*	C₂₇H₂₄O₁₈	635.089 1[M-H]^-	465, 169, 313, 125	659.080 0[M+Na]⁺	619, 526, 467, 297, 153	1.10	Polyphenols	[27]
46*	9.60	Albiflorin*	C₂₃H₂₈O₁₁	525.162 5 [M+COOH]^-	525, 435, 449, 357, 327	481.174 9[M+H]⁺	319, 197, 105	3.24	Monoterpenoids	[28]
47	9.79	Glucosylpaeoniflorin isomer	C₂₉H₃₈O₁₆	641.209 0[M-H]^-	611, 489, 165, 121	655.156 1[M+Na]⁺	519	1.25	Monoterpenoids	[26]
48	10.06	Galloylpaeoniflorin	C₃₀H₃₂O₁₅	631.167 2[M-H]^-	481, 365, 221, 281, 179	655.160 2[M+Na]⁺	519, 503, 437, 153, 121	1.43	Monoterpenoids	[30]
49	10.20	Tetragalloylglucose isomer	C₃₄H₂₈O₂₂	787.103 5[M-H]^-	465, 169, 313, 125	-	-	5.21	Polyphenols	[27]
50*	10.20	Paeoniflorin*	C₂₃H₂₈O₁₁	479.155 0[M-H]^-	525, 449, 357, 327, 165 121, 77	503.153 1[M+Na]⁺	463, 179, 151	3.24	Monoterpenoids	[29]
51*	10.49	Ethyl gallate*	C₉H₁₀O₅	197.045 9[M-H]^-	169, 124	-	-	4.57	Polyphenols	[25]
52	11.34	Tetragalloylglucose isomer	C₃₄H₂₈O₂₂	787.097 9[M-H]^-	635, 617, 169	811.094 7[M+Na]⁺	641, 619, 525, 153	-1.91	Polyphenols	[31]
53*	11.78	1, 2, 3, 6-Tetragalloylglucose*	C₃₄H₂₈O₂₂	787.097 9[M-H]^-	787, 635, 617, 169	811.094 7[M+Na]⁺	641, 619, 525, 153	-1.91	Polyphenols	[27]
54*	12.30	Ellagic acid*	C₁₄H₆O₈	300.998 8[M-H]^-	245, 185, 175	-	-	1.33	Polyphenols	[23]
55*	12.98	6'-O-Galloylpaeoniflorin*	C₃₀H₃₂O₁₅	631.168 9[M-H]^-	481, 365, 221, 281, 179	655.160 2[M+Na]⁺	179, 153	1.43	Monoterpenoids	[30]
56	13.46	Galloylpaeoniflorin isomer	C₃₀H₃₂O₁₅	631.168 9[M-H]^-	481, 365, 221, 281, 179	655.167 4[M+Na]⁺	629, 613, 487, 153	1.43	Monoterpenoids	[30]
57*	13.58	1, 2, 3, 4, 6-Pentagalloylglucose*	C₄₁H₃₂O₂₆	939.113 6[M-H]^-	631, 469, 169	963.104 4[M+Na]⁺	771, 153	3.40	Polyphenols	[32]
58	13.84	Pentagalloylglucose isomer	C₄₁H₃₂O₂₆	939.116 9[M-H]^-	631, 469, 169	-	-	6.92	Polyphenols	[32]
59	14.00	Pentagalloylglucose isomer	C₄₁H₃₂O₂₆	-	-	963.104 4[M+Na]⁺	481, 365, 221, 281, 179	6.65	Polyphenols	[32]
60	14.22	Pentagalloylglucose isomer	C₄₁H₃₂O₂₆	-	-	963.104 4[M+Na]⁺	481, 365, 221, 281, 179	6.65	Polyphenols	[32]
61	14.28	Galloylpaeoniflorin isomer	C₃₀H₃₂O₁₅	631.168 9[M-H]^-	481, 365, 221, 281, 179	-	-	1.43	Monoterpenoids	[30]
62	14.80	Galloylpaeoniflorin isomer	C₃₀H₃₂O₁₅	631.168 9[M-H]^-	481, 365, 221, 281, 179	633.180 7[M+H]⁺	633, 267, 153, 105	-1.90	Monoterpenoids	[30]
63	15.11	Hexagalloylglucose	C₄₈H₃₆O₃₀	1 091.114 1[M-H]^-	939, 769, 169	1 115.110 8[M+Na]⁺	923, 771	-6.14	Polyphenols	[20]
64	15.60	Mudanpioside I	C₂₃H₂₈O₁₁	525.162 5[M+COOH]^-	357, 327, 283	481.174 9[M+H]⁺	503, 481, 319, 197, 133	3.24	Monoterpenoids	[33]
65	15.70	Hexagalloylglucose isomer	C₄₈H₃₆O₃₀	-	-	1 115.110 8[M+Na]⁺	923, 771	-7.26	Polyphenols	[20]
66	15.82	Hexagalloylglucose isomer	C₄₈H₃₆O₃₀	1 091.114 1[M-H]^-	939, 769, 169	1 115.110 8[M+Na]⁺	923, 771	-6.14	Polyphenols	[20]
67	17.13	Galloylpaeoniflorin isomer	C₃₀H₃₂O₁₅	631.167 2[M-H]^-	481, 365, 221, 281, 179	655.160 2[M+Na]⁺	613, 511, 153	1.43	Monoterpenoids	[30]
68	17.26	Digalloylpaeoniflorin	C₃₇H₃₆O₁₉	783.176 [M-H]^-	783, 643, 313, 169	-	-	-1.53	Monoterpenoids	[32]
69	17.55	Mudanpioside H	C₃₀H₃₂O₁₄	615.167 0[M-H]^-	493, 313	-	-	-7.15	Monoterpenoids	[34]
70	17.80	Pinane-10-yl vicianoside	C₂₁H₃₆O₁₀	447.222 3[M-H]^-	447, 315, 169	471.224 4[M+H]⁺	471, 349, 177	-1.57	Monoterpenoids	[35]
71*	17.61	Benzoyloxypaeoniflorin*	C₃₀H₃₂O₁₃	599.179 4[M-H]^-	165, 137, 121	-	-	4.84	Monoterpenoids	[28]
72	17.99	Galloylpaeoniflorin isomer	C₃₀H₃₂O₁₅	631.167 2[M-H]^-	481, 365, 221, 281, 179	-	-	1.11	Monoterpenoids	[30]
73	18.06	Pinen-10-yl vicianoside	C₂₁H₃₄O₁₀	445.205 7[M-H]^-	293, 149	-	-	-3.82	Monoterpenoids	[35]
74	18.31	Cineole rhamnosyl glucoside	C₂₂H₃₈O₁₀	461.239 0[M-H]^-	447, 163	485.234 3[M+H]⁺	355, 153	0.65	Monoterpenoids	[9]
75*	18.55	Benzoylpaeoniflorin*	C₃₀H₃₂O₁₂	583.182 9[M-H]^-	583, 553, 431, 165	607.179 4[M+Na]⁺	427, 267, 249, 179, 151	2.23	Monoterpenoids	[28]
76	18.63	Benzoylpaeoniflorin isomer	C₃₀H₃₂O₁₂	583.182 9[M-H]^-	629, 583	607.179 4[M+Na]⁺	427, 267, 249, 179, 151	5.09	Monoterpenoids	[28]
77	18.77	Paeonin D	C₃₇H₃₆O₁₆	735.192 5[M-H]^-	613, 583, 169	-	-	0.10	Monoterpenoids	[23]
78	18.98	Paeonin D isomer	C₃₇H₃₆O₁₆	735.192 5[M-H]^-	613, 583, 169	-	-	0.10	Monoterpenoids	[23]
79	19.07	Benzoylpaeoniflorin isomer	C₃₀H₃₂O₁₂	583.182 9[M-H]^-	463, 319, 267, 197	607.179 4[M+Na]⁺	427, 267, 249, 179, 151	2.23	Monoterpenoids	[28]

Serial number

Retention time/min

Compound

Molecular formula

ES^-

ES⁺

Error/×10^-6

Classification

Ref.

Observedmass m/z

Fragmention m/z

Observedmass m/z

Fragmention m/z

1.10

Sucrose*

C₁₂H₂₂O₁₁

341.108 3[M-H]^-

179

365.107 5[M+Na]⁺

325, 175, 145

-0.29

Oligosaccharide

[9]

1.31

Maltotriose

C₁₈H₃₂O₁₆

503.162 0[M-H]^-

341, 311, 179

527.158 3[M+Na]⁺

343, 325, 175, 163, 145

1.59

Oligosaccharide

[9]

1.41

Maltopentaose

C₃₀H₅₂O₂₆

827.267 4[M-H]^-

665, 503, 341, 311

0.60

Oligosaccharide

[9]

1.47

Maltohexaose

C₃₆H₆₂O₃₁

989.329 0[M-H]^-

827, 665

2.02

Oligosaccharide

[9]

1.54

Cyclomaltoheptaose

C₄₂H₇₀O₃₅

1 135.385 0[M+H]⁺

649, 487, 325, 163, 145

6.52

Oligosaccharide

[9]

1.55

Maltoheptaose

C₄₂H₇₂O₃₆

1 151.374 1
[M-H]^-

989, 827, 665, 503, 341

1 153.388 2[M+H]⁺

811, 649, 487, 325, 163, 145

1.39

Oligosaccharide

[9]

1.74

Citric acid*

C₆H₈O₇

191.018 8[M-H]^-

111

-2.09

Other types

[10]

2.38

Desbenzoylpaeoniflorin

C₁₆H₂₄O₁₀

375.129 6[M-H]^-

345, 195, 165

399.123 0[M+Na]⁺

396, 331, 179, 151

1.30

Monoterpenoids

[10]

2.61

Oxiglutatione

C₂₀H₃₂N₆O₁₂S₂

611.142 7[M-H]^-

481, 331

613.160 0[M+H]⁺

487, 484

0.33

Other types

[11]

3.15

Galloylglucose

C₁₃H₁₆O₁₀

331.064 8[M-H]^-

169, 125

355.062 4[M+Na]⁺

325, 290, 208, 153, 145

-5.10

Polyphenols

[12]

11*

3.30

Adenosine*

C₁₀H₁₃N₅O₄

268.103 8[M+H]⁺

136, 153, 268

-2.98

Other types

[11]

3.35

Galloylglucose isomer

C₁₃H₁₆O₁₀

331.067 2[M-H]^-

169

2.11

Polyphenols

[12]

3.44

Galloylsucrose isomer

C₁₉H₂₆O₁₅

493.115 8[M-H]^-

331, 313, 283, 169

517.118 8[M+Na]⁺

325, 268, 153, 136

-7.09

Polyphenols

[13]

3.79

Desbenzoylpaeoniflorin isomer

C₁₆H₂₄O₁₀

399.123 0[M+Na]⁺

325, 215, 197, 151

5.60

Monoterpenoids

[10]

4.08

Glucopyranosyl paeonisuffrone

C₁₆H₂₄O₉

359.132 3[M-H]^-

311, 179

383.129 4[M+Na]⁺

325, 287, 163

-5.29

Monoterpenoids

[14]

4.48

Glucopyranosyl paeonisuffrone isomer

C₁₆H₂₄O₉

359.132 3[M-H]^-

311, 179

383.129 4[M+Na]⁺

325, 287, 163

-5.29

Monoterpenoids

[14]

5.36

Galloylsucrose isomer

C₁₉H₂₆O₁₅

493.115 8[M-H]^-

331, 313, 283

517.118 8[M+Na]⁺

433, 315, 153

-7.09

Polyphenols

[13]

5.72

Galloylsucrose isomer

C₁₉H₂₆O₁₅

493.115 8[M-H]^-

331, 313, 283

-7.09

Polyphenols

[13]

5.84

Galloylsucrose isomer

C₁₉H₂₆O₁₅

493.115 4[M-H]^-

331, 313, 283

517.118 8[M+Na]⁺

433, 315, 153

-7.91

Polyphenols

[13]

6.40

Digalloylglucose

C₂₀H₂₀O₁₄

483.073 8[M-H]^-

331, 313, 169

-7.66

Polyphenols

[15]

6.57

Galloyl desbenzoylpaeoniflorin

C₂₃H₂₈O₁₄

527.140 9[M-H]^-

169, 125

551.137 1[M+Na]⁺

496, 445, 345, 297, 164

1.52

Monoterpenoids

[16]

6.72

Glucopyranosyl lactinolide

C₁₆H₂₆O₉

361.151 6[M-H]^-

179

385.145 0[M+Na]⁺

205, 188, 144

4.71

Monoterpenoids

[17]

6.79

Digalloylglucose isomer

C₂₀H₂₀O₁₄

483.073 8[M-H]^-

331, 313, 169

-7.66

Polyphenols

[15]

6.92

Strictinin

C₂₇H₂₂O₁₈

633.073 5[M-H]^-

481, 301, 169

657.073 1[M+Na]⁺

367, 261

1.11

Polyphenols

[18]

7.00

Mudanpioside F

C₁₆H₂₄O₈

343.138 3[M-H]^-

181, 150

-2.91

Monoterpenoids

[19]

7.04

Galloyl desbenzoylpaeoniflorin isomer

C₂₃H₂₈O₁₄

527.142 1[M-H]^-

497, 169

551.137 1[M+Na]⁺

481, 365, 221, 281, 179

3.79

Monoterpenoids

[16]

7.18

Catechin glucoside

C₂₁H₂₄O₁₁

451.127 5[M-H]^-

289, 245, 169

475.117 7[M+Na]⁺

441, 291, 139

7.76

Polyphenols

[16]

7.23

Trigalloylglucose isomer

C₂₇H₂₄O₁₈

635.089 1[M-H]^-

465, 169, 313, 125

1.10

Polyphenols

[20]

29*

7.33

Procyanidin B1*

C₃₀H₂₆O₁₂

577.132 1[M-H]^-

289, 245, 203

579.150 9[M+H]⁺

409, 127

-4.30

Polyphenols

[21]

7.53

Oxypaeoniflorin isomer

C₂₃H₂₈O₁₂

495.149 8[M-H]^-

465, 345, 333, 281

519.150 9[M+Na]⁺

121

-1.01

Monoterpenoids

[22]

7.61

Procyanidin B2

C₃₀H₂₆O₁₂

577.132 1[M-H]^-

289, 245, 203

-4.30

Polyphenols

[21]

7.70

Trigalloylglucose isomer

C₂₇H₂₄O₁₈

635.089 1[M-H]^-

465, 169, 313, 125

1.10

Polyphenols

[20]

33*

7.76

Methyl gallate*

C₈H₈O₅

183.030 2[M-H]^-

168

4.92

Polyphenols

[23]

34*

7.82

Oxypaeoniflorin*

C₂₃H₂₈O₁₂

495.149 8[M-H]^-

465, 345, 333, 281

519.150 9[M+Na]⁺

291, 139

-1.01

Monoterpenoids

[22]

7.85

Trigalloylglucose isomer

C₂₇H₂₄O₁₈

635.089 1[M-H]^-

465, 169, 313, 125

1.10

Polyphenols

[20]

36*

7.89

Catechin*

C₁₅H₁₄O₆

289.072 2[M-H]^-

245, 203, 169

291.088 4[M+H]⁺

179, 147

3.50

Polyphenols

[24]

8.00

Procyanidin C

C₄₅H₃₈O₁₈

865.201 2[M-H]^-

577, 289, 245, 203

867.212 6[M+H]⁺

579, 245, 123

3.70

Polyphenols

[21]

8.35

Mudanpioside E

C₂₄H₃₀O₁₃

525.163 5[M-H]^-

495, 479

549.156 1[M+Na]⁺

349, 179

5.14

Monoterpenoids

[25]

8.45

Trigalloylglucose isomer

C₂₇H₂₄O₁₈

635.089 1[M-H]^-

465, 169, 313, 125

1.10

Polyphenols

[20]

8.52

Trigalloylglucose isomer

C₂₇H₂₄O₁₈

635.089 1[M-H]^-

465, 169, 313, 125

1.10

Polyphenols

[20]

8.65

Glucosylpaeoniflorin

C₂₉H₃₈O₁₆

641.209 0[M-H]^-

611, 489, 165 121

665.201 0[M+Na]⁺

483, 105

1.25

Monoterpenoids

[26]

8.94

Diglucosylpaeoniflorin

C₃₅H₄₈O₂₁

803.268 1[M-H]^-

773, 755, 641, 611, 489, 165

827.265 0[M+Na]⁺

409, 393, 371

-2.86

Monoterpenoids

[26]

9.06

Trigalloylglucose isomer

C₂₇H₂₄O₁₈

635.089 1[M-H]^-

465, 169, 313, 125

1.10

Polyphenols

[20]

9.30

Glucosylpaeoniflorin isomer

C₂₉H₃₈O₁₆

687.213 9 [M+COOH]^-

611, 489, 165, 121

665.201 0[M+Na]⁺

393, 153

1.31

Monoterpenoids

[26]

45*

9.50

1, 3, 6-Trigalloylglucose*

C₂₇H₂₄O₁₈

635.089 1[M-H]^-

465, 169, 313, 125

659.080 0[M+Na]⁺

619, 526, 467, 297, 153

1.10

Polyphenols

[27]

46*

9.60

Albiflorin*

C₂₃H₂₈O₁₁

525.162 5 [M+COOH]^-

525, 435, 449, 357, 327

481.174 9[M+H]⁺

319, 197, 105

3.24

Monoterpenoids

[28]

9.79

Glucosylpaeoniflorin isomer

C₂₉H₃₈O₁₆

641.209 0[M-H]^-

611, 489, 165, 121

655.156 1[M+Na]⁺

519

1.25

Monoterpenoids

[26]

10.06

Galloylpaeoniflorin

C₃₀H₃₂O₁₅

631.167 2[M-H]^-

481, 365, 221, 281, 179

655.160 2[M+Na]⁺

519, 503, 437, 153, 121

1.43

Monoterpenoids

[30]

10.20

Tetragalloylglucose isomer

C₃₄H₂₈O₂₂

787.103 5[M-H]^-

465, 169, 313, 125

5.21

Polyphenols

[27]

50*

10.20

Paeoniflorin*

C₂₃H₂₈O₁₁

479.155 0[M-H]^-

525, 449, 357, 327, 165 121, 77

503.153 1[M+Na]⁺

463, 179, 151

3.24

Monoterpenoids

[29]

51*

10.49

Ethyl gallate*

C₉H₁₀O₅

197.045 9[M-H]^-

169, 124

4.57

Polyphenols

[25]

11.34

Tetragalloylglucose isomer

C₃₄H₂₈O₂₂

787.097 9[M-H]^-

635, 617, 169

811.094 7[M+Na]⁺

641, 619, 525, 153

-1.91

Polyphenols

[31]

53*

11.78

1, 2, 3, 6-Tetragalloylglucose*

C₃₄H₂₈O₂₂

787.097 9[M-H]^-

787, 635, 617, 169

811.094 7[M+Na]⁺

641, 619, 525, 153

-1.91

Polyphenols

[27]

54*

12.30

Ellagic acid*

C₁₄H₆O₈

300.998 8[M-H]^-

245, 185, 175

1.33

Polyphenols

[23]

55*

12.98

6'-O-Galloylpaeoniflorin*

C₃₀H₃₂O₁₅

631.168 9[M-H]^-

481, 365, 221, 281, 179

655.160 2[M+Na]⁺

179, 153

1.43

Monoterpenoids

[30]

13.46

Galloylpaeoniflorin isomer

C₃₀H₃₂O₁₅

631.168 9[M-H]^-

481, 365, 221, 281, 179

655.167 4[M+Na]⁺

629, 613, 487, 153

1.43

Monoterpenoids

[30]

57*

13.58

1, 2, 3, 4, 6-Pentagalloylglucose*

C₄₁H₃₂O₂₆

939.113 6[M-H]^-

631, 469, 169

963.104 4[M+Na]⁺

771, 153

3.40

Polyphenols

[32]

13.84

Pentagalloylglucose isomer

C₄₁H₃₂O₂₆

939.116 9[M-H]^-

631, 469, 169

6.92

Polyphenols

[32]

14.00

Pentagalloylglucose isomer

C₄₁H₃₂O₂₆

963.104 4[M+Na]⁺

481, 365, 221, 281, 179

6.65

Polyphenols

[32]

14.22

Pentagalloylglucose isomer

C₄₁H₃₂O₂₆

963.104 4[M+Na]⁺

481, 365, 221, 281, 179

6.65

Polyphenols

[32]

14.28

Galloylpaeoniflorin isomer

C₃₀H₃₂O₁₅

631.168 9[M-H]^-

481, 365, 221, 281, 179

1.43

Monoterpenoids

[30]

14.80

Galloylpaeoniflorin isomer

C₃₀H₃₂O₁₅

631.168 9[M-H]^-

481, 365, 221, 281, 179

633.180 7[M+H]⁺

633, 267, 153, 105

-1.90

Monoterpenoids

[30]

15.11

Hexagalloylglucose

C₄₈H₃₆O₃₀

1 091.114 1[M-H]^-

939, 769, 169

1 115.110 8[M+Na]⁺

923, 771

-6.14

Polyphenols

[20]

15.60

Mudanpioside I

C₂₃H₂₈O₁₁

525.162 5[M+COOH]^-

357, 327, 283

481.174 9[M+H]⁺

503, 481, 319, 197, 133

3.24

Monoterpenoids

[33]

15.70

Hexagalloylglucose isomer

C₄₈H₃₆O₃₀

1 115.110 8[M+Na]⁺

923, 771

-7.26

Polyphenols

[20]

15.82

Hexagalloylglucose isomer

C₄₈H₃₆O₃₀

1 091.114 1[M-H]^-

939, 769, 169

1 115.110 8[M+Na]⁺

923, 771

-6.14

Polyphenols

[20]

17.13

Galloylpaeoniflorin isomer

C₃₀H₃₂O₁₅

631.167 2[M-H]^-

481, 365, 221, 281, 179

655.160 2[M+Na]⁺

613, 511, 153

1.43

Monoterpenoids

[30]

17.26

Digalloylpaeoniflorin

C₃₇H₃₆O₁₉

783.176 [M-H]^-

783, 643, 313, 169

-1.53

Monoterpenoids

[32]

17.55

Mudanpioside H

C₃₀H₃₂O₁₄

615.167 0[M-H]^-

493, 313

-7.15

Monoterpenoids

[34]

17.80

Pinane-10-yl vicianoside

C₂₁H₃₆O₁₀

447.222 3[M-H]^-

447, 315, 169

471.224 4[M+H]⁺

471, 349, 177

-1.57

Monoterpenoids

[35]

71*

17.61

Benzoyloxypaeoniflorin*

C₃₀H₃₂O₁₃

599.179 4[M-H]^-

165, 137, 121

4.84

Monoterpenoids

[28]

17.99

Galloylpaeoniflorin isomer

C₃₀H₃₂O₁₅

631.167 2[M-H]^-

481, 365, 221, 281, 179

1.11

Monoterpenoids

[30]

18.06

Pinen-10-yl vicianoside

C₂₁H₃₄O₁₀

445.205 7[M-H]^-

293, 149

-3.82

Monoterpenoids

[35]

18.31

Cineole rhamnosyl glucoside

C₂₂H₃₈O₁₀

461.239 0[M-H]^-

447, 163

485.234 3[M+H]⁺

355, 153

0.65

Monoterpenoids

[9]

75*

18.55

Benzoylpaeoniflorin*

C₃₀H₃₂O₁₂

583.182 9[M-H]^-

583, 553, 431, 165

607.179 4[M+Na]⁺

427, 267, 249, 179, 151

2.23

Monoterpenoids

[28]

18.63

Benzoylpaeoniflorin isomer

C₃₀H₃₂O₁₂

583.182 9[M-H]^-

629, 583

607.179 4[M+Na]⁺

427, 267, 249, 179, 151

5.09

Monoterpenoids

[28]

18.77

Paeonin D

C₃₇H₃₆O₁₆

735.192 5[M-H]^-

613, 583, 169

0.10

Monoterpenoids

[23]

18.98

Paeonin D isomer

C₃₇H₃₆O₁₆

735.192 5[M-H]^-

613, 583, 169

0.10

Monoterpenoids

[23]

19.07

Benzoylpaeoniflorin isomer

C₃₀H₃₂O₁₂

583.182 9[M-H]^-

463, 319, 267, 197

607.179 4[M+Na]⁺

427, 267, 249, 179, 151

2.23

Monoterpenoids

[28]