药学学报

No.	t_R/min	Precursor ion	Response	Meas m/z	Error/ppm	Fragment ion	Molecular formula	Plausible identification	Source	Category	Reference
1	0.68	[M+HCOO]^－	5.3×10⁴	549.166 0	2.25	503.161 4, 341.109 1, 101.024 5	C₁₈H₃₂O₁₆	Maltotriose	SDH	Other	[30]
2	0.70	[M+H]⁺	1.2×10⁴	133.061 2	-3.24	91.053 6, 87.054 1	C₄H₈N₂O₃	L-Asparagine	DG	Other	[17]
3	0.70	[M-H]^－	2.1×10⁴	175.118 7	1.44	158.092 1, 116.071 3	C₆H₁₄N₄O₂	Arginine	DG	Other	[17]
4	0.71	[M-H]^－	1.1×10⁵	179.055 8	1.74	71.013 8, 63.024 5	C₆H₁₂O₆	Fructose	SDH	Other	[30]
5	0.71	[M-H]^－	5.3×10⁴	195.050 5	2.70	176.900 6, 159.895 2	C₆H₁₂O₇	Gluconic acid	DG	Other	[17]
6	0.93	[M-H]^－	3.3×10⁴	341.107 7	3.62	119.034 2, 89.023 3	C₁₂H₂₂O₁₁	Maltose	SDH	Other	[30]
7	1.00	[M-H]^－	1.3×10⁶	133.014 6	-2.65	115.004 1, 71.014 2	C₄H₆O₅	Malic acid	DG	Organic acid	[17]
8	1.11	[M-H]^－	5.1×10⁶	191.020 2	-2.48	111.002 9, 87.009 1	C₆H₈O₇	Citric acid^*	BS/SDH	Organic acid	[30]
9	1.26	[M+H]⁺	1.2×10⁴	245.077 1	-1.17	133.049 5, 113.034 5	C₉H₁₂N₂O₆	Uridine	SDH/RS	Alkaloid	[30]
10	1.48	[M+H]⁺	3.1×10⁶	268.104 7	-2.50	136.063 2, 119.035 6	C₁₀H₁₃N₅O₄	Adenosine	SDH/RS	Alkaloid	[31]
11	1.73	[M+H]⁺	5.2×10⁵	284.099 7	-2.66	152.056 3, 135.028 7, 85.027 7	C₁₀H₁₃N₅O₅	Guanosine	SDH	Alkaloid	[31]
12	1.91	[M-H]^－	1.7×10⁶	169.014 1	0.87	125.025 5, 97.028 8	C₇H₆O₅	Gallic acid^*	BS	Organic acid	[13]
13^#	2.02	[M-H]^－	3.7×10⁴	125.024 2	1.74	79.016 9	C₆H₆O₃	Pyrogallol	BS	Phenol	[13]
14	2.22	[M+HCOO]^－	1.4×10⁵	405.138 9	3.30	359.135 8, 254.074 6, 179.072 1	C₁₆H₂₄O₉	Peony ketone-1-O-β-D-glucoside	BS	Flavonoid	[28]
15^#	2.34	[M+HCOO]^－	8.8×10²	361.113 5	1.44	199.061 2, 169.050 3	C₁₅H₂₂O₁₀	Catalpol	SDH	Monoterpene	[30]
16	2.44	[M+H]⁺	1.5×10⁶	166.085 7	3.34	120.080 5, 103.054 3, 79.054 1	C₉H₁₁NO₂	L-Phenylalanine	DG	Other	[17]
17	2.75	[M+HCOO]^－	1.4×10⁵	731.223 4	2.39	685.223 3, 505.159 4, 341.110 7, 263.079 3, 179.057 9	C₂₇H₄₂O₂₀	Rehmannioside D^*	SDH	Monoterpene	[30]
18^#	2.75	[M-H]^－	6.3×10⁴	493.119 9	0	449.123 3, 313.057 4, 271.045 6, 169.013 4	C₁₉H₂₆O₁₅	1'-O-Galloylsucrose	SDH	Other	[30]
19	2.87	[M+HCOO]^－	9.5×10⁴	569.171 3	1.80	523.166 7, 463.143 4, 343.104 0, 228.058 5, 179.056 7	C₂₁H₃₂O₁₅	Rehmannioside A	SDH	Monoterpene	[30]
20	3.31	[M-H]^－	5.2×10⁴	153.019 3	0	109.029 2, 108.021 6	C₇H₆O₄	Protocatechuic acid	CX	Organic acid	[18]
21	3.46	[M-H]^－	3.3×10⁴	373.113 0	2.74	269.040 2, 211.059 4, 149.061 1, 123.046 4	C₁₆H₂₂O₁₀	Geniposidic acid	SDH	Monoterpene	[31]
22	3.51	[M+H]⁺	1.9×10⁴	384.114 7	0.75	252.072 2, 162.075 0, 136.060 9	C₁₄H₁₇N₅O₈	Succinyladenosine	SCP	Alkaloid	[32]
23^#	4.14	[M-H]^－	8.2×10³	183.029 9	0	169.013 8, 124.015 8	C₈H₈O₅	Methyl gallate	BS	Other	[28]
24^#	4.14	[M-H]^－	3.4×10³	205.097 7	-2.66	188.067 4, 146.059 3, 118.065 3	C₁₁H₁₂N₂O₂	Tryptophan	DG/CX	Organic acid	[17]
25	4.16	[M-H]^－	2.8×10⁵	353.087 6	0.58	191.055 8, 179.035 2, 173.044 2, 161.023 3, 135.044 7	C₁₆H₁₈O₉	Chlorogenic acid^*	DG/CX	Organic acid	[19]
26^#	4.19	[M-H]^－	7.9×10³	389.107 8	2.92	165.101 2, 139.552 1	C₁₆H₂₂O₁₁	Scandoside	SDH	Monoterpene	[31]
27^#	4.26	[M-H]^－	5.8×10³	347.133 2	4.48	167.071 2, 123.081 6	C₁₅H₂₄O₉	Ajugol	SDH	Monoterpene	[31]
28	4.42	[M+HCOO]^－	2.6×10⁴	389.144 0	3.39	343.139 8, 257.453 1, 181.088 2, 161.046 2	C₁₆H₂₄O₈	Mudanpioside F	BS	Monoterpene	[13]
29	4.47	[M-H]^－	6.1×10⁴	461.164 9	3.36	415.123 9, 294.122 7, 113.024 2	C₂₀H₃₀O₁₂	Forsythoside E	BS	Phenylethanoid	[28]
30	4.56	[M-H]^－	8.0×10⁴	375.128 3	3.65	314.306 6, 213.077 8, 169.087 0	C₁₆H₂₄O₁₀	8-Epiloganic acid	SDH	Monoterpene	[30]
31^#	4.66	[M-H]^－	1.2×10⁴	345.118 2	2.62	135.043 6, 123.043 5	C₁₅H₂₂O₉	Aucubin	SDH	Monoterpene	[30]
32^#	4.66	[M+HCOO]^－	1.2×10⁴	345.118 2	2.62	299.113 8, 179.057 5, 119.036 3	C₁₄H₂₀O₇	Salidroside	DG	Phenylethanoid	[17]
33	4.72	[M-H]^－	7.4×10⁴	461.128 7	2.96	266.043 6, 137.024 5, 93.035 5	C₁₉H₂₆O₁₃	Sibiricose A3	ZYZ	Oligosaccharide ester	[7]
34	5.35	[M+H]⁺	5.6×10³	389.144 7	-1.22	209.072 3, 149.063 1, 111.037 3	C₁₇H₂₄O₁₀	Geniposide	SDH	Monoterpene	[30]
35	5.55	[M+HCOO]^－	1.8×10⁵	391.159 7	3.25	345.157 4, 192.060 0, 161.046 8	C₁₆H₂₆O₈	Rehmapicroside	SDH	Monoterpene	[30]
36	5.62	[M-H]^－	6.5×10⁵	353.087 6	0.58	191.055 8, 179.035 2, 173.044 2, 161.023 3, 135.044 7	C₁₆H₁₈O₉	Neochlorogenic acid^*	DG/CX	Organic acid	[17]
37	5.67	[M+H]⁺	1.8×10³	291.085 1	4.17	167.034 5, 139.038 8, 127.034 2	C₁₅H₁₄O₆	Epicatechin	BS	Phenol	[33]
38	5.68	[M-H]^－	2.0×10⁵	123.045 1	0.43	105.271 4	C₇H₈O₂	Guaiacol	SDH	Phenol	[30]
39	5.82	[M-H]^－	2.1×10⁶	167.035 1	-0.70	123.046 1, 108.023 1	C₈H₈O₄	Vanillic acid^*	DG/CX	Organic acid	[17]
40	5.83	[M+H]⁺	4.2×10⁴	123.044 6	-4.42	105.033 6, 79.053 4, 77.038 6	C₇H₆O₂	Benzoic acid^*	DG	Organic acid	[18]
41^#	5.97	[M-H]^－	4.8×10³	593.149 0	3.70	287.054 3, 129.054 3	C₂₇H₃₀O₁₅	Nicotiflorin	BS	Flavonoid	[29]
42	5.98	[M-H]^－	2.4×10⁵	353.087 3	1.43	191.055 7, 179.035 1, 173.044 5, 161.023 4, 135.044 7	C₁₆H₁₈O₉	Cryptochlorogenic acid^*	DG/CX	Organic acid	[18]
43	5.98	[M+HCOO]^－	2.2×10⁵	563.161 0	1.35	517.159 6, 448.626 2, 341.110 0, 175.041 4	C₂₂H₃₀O₁₄	Sibiricose A5	ZYZ	Oligosaccharide ester	[7]
44	6.10	[M-H]^－	6.0×10⁵	179.035 4	-2.33	135.046 0, 79.056 2	C₉H₈O₄	Caffeic acid^*	DG	Organic acid	[18]
45	6.30	[M+HCOO]^－	2.8×10⁵	475.145 2	1.08	429.143 7, 307.104 0, 121.030 1	C₁₉H₂₆O₁₁	Polygalatenoside A	SDH	Other	[31]
46	6.35	[M-H]^－	2.2×10⁵	547.166 5	0.63	503.148 5, 341.109 5, 205.051 4	C₂₃H₃₂O₁₅	Sibiricose A6	ZYZ	Oligosaccharide ester	[7]
47	7.09	[M-H]^－	6.5×10³	323.124 0	2.66	203.080 5, 189.066 9, 161.071 2,	C₁₅H₂₀N₂O₆	Tatarine C	SCP	Alkaloid	[34]
48	7.32	[M+HCOO]^－	1.8×10⁶	525.161 9	1.65	449.153 2, 357.121 6, 283.079 3, 195.063 9, 121.029 4	C₂₃H₂₈O₁₁	Mudanpioside I	BS	Monoterpene	[13]
49	7.34	[M-H]^－	1.8×10⁶	525.161 9	1.65	449.147 2, 327.109 1, 165.056 9, 121.030 1	C₂₄H₃₀O₁₃	Mudanpioside E	BS	Monoterpene	[13]
50	7.62	[M+HCOO]^－	4.5×10⁴	541.155 4	1.62	465.138 7, 343.103 1, 193.050 7, 121.029 4	C₂₃H₂₈O₁₂	Oxypaeoniflorin^*	BS	Monoterpene	[14]
51	7.74	[M-H]^－	1.3×10⁴	785.248 2	3.52	707.224 3, 623.218 2, 545.172 6	C₃₅H₄₆O₂₀	Purpureaside B	SDH	Phenylethanoid	[31]
52	7.82	[M+HCOO]^－	2.0×10⁶	525.161 9	1.65	479.157 9, 449.147 8, 327.109 5, 121.020 3	C₂₃H₂₈O₁₁	Paeoniflorin^*	BS	Monoterpene	[15]
53	7.99	[M-H]^－	2.4×10⁵	183.102 5	0.92	139.112 1	C₁₀H₁₆O₃	Rehmapicrogenin	SDH	Monoterpene	[31]
54	8.20	[M+HCOO]^－	3.0×10⁵	537.125 0	0	493.163 4, 315.051 4, 210.603 9	C₂₄H₂₆O₁₄	Sibiricaxanthone B	ZYZ	Flavonoid	[7]
55	8.38	[M+HCOO]^－	5.9×10⁴	435.223 2	0.85	341.106 6, 193.050 9	C₁₉H₃₄O₈	Rehmaionoside A	SDH	Monoterpene	[31]
56^#	8.62	[M-H]^－	2.0×10⁴	787.098 1	2.35	617.080 2, 169.014 3, 125.025 2	C₃₄H₂₈O₂₂	Tetragalloylglucose	BS	Other	[15]
57	8.65	[M+HCOO]^－	3.0×10⁵	607.188 2	-0.37	561.185 1, 323.100 1, 237.078 6, 113.024 4	C₂₄H₃₄O₁₅	Sibiricose A2	ZYZ	Oligosaccharide ester	[7]
58^#	8.65	[M-H]^－	4.1×10⁴	799.265 8	1.02	623.219 1, 193.051 3, 175.039 3, 161.024 1	C₃₆H₄₈O₂₀	Cistanoside A	SDH	Phenylethanoid	[35]
59^#	8.70	[M-H]^－	1.3×10⁴	435.092 3	2.26	315.052 2, 287.018 6, 272.033 1	C₂₀H₂₀O₁₁	Irisxanthone	SDH	Flavonoid	[31]
60	8.73	[M-H]^－	9.8×10⁵	193.051 3	-3.46	178.027 6, 149.060 7, 134.037 4	C₁₀H₁₀O₄	Ferulic acid^*	DG/CX	Organic acid	[17]
61	8.73	[M+HCOO]^－	9.8×10⁵	193.051 3	-3.46	178.028 2, 149.060 7, 134.037 6,	C₉H₈O₂	5-Methoxy-1-benzofuran	BS	Other	[13]
62	8.78	[M-H]^－	2.6×10⁵	567.135 7	-0.28	417.081 7, 315.049 7, 179.030 9	C₂₅H₂₈O₁₅	Polygalaxanthone VIII	ZYZ	Flavonoid	[7]
63	8.85	[M-H]^－	2.6×10⁵	567.135 9	-0.63	435.095 5, 417.085 3, 345.063 5, 315.049 7, 297.040 1, 272.033 1	C₂₅H₂₈O₁₅	Polygalaxanthone III^*	ZYZ	Flavonoid	[29]
64	9.06	[M-H]^－	1.1×10³	577.155 9	0.66	270.047 2, 269.044 6	C₂₇H₃₀O₁₄	Rhoifolin	ZYZ	Flavonoid	[7]
65^#	9.10	[M+HCOO]^－	1.0×10³	609.143 9	3.63	519.145 7, 385.137 5, 253.061 7, 111.007 3	C₂₆H₂₈O₁₄	Isoschaftoside	BS	Flavonoid	[29]
66	9.18	[M+HCOO]^－	9.7×10⁴	435.223 0	1.31	341.106 6, 193.050 9	C₁₉H₃₄O₈	Rehmaionoside B	SDH	Monoterpene	[31]
67^#	9.38	[M+H]⁺	2.9×10³	146.044 9	4.08	117.059 5, 91.056 6	C₉H₇NO	Indole-3-carboxaldehyde	SCP	Alkaloid	[32]
68	9.38	[M-H]^－	1.6×10⁵	667.187 7	0.41	461.130 1, 299.079 1, 205.051 1, 137.024 6	C₃₀H₃₆O₁₇	Tenuifoliside B	ZYZ	Oligosaccharide ester	[7]
69	9.58	[M-H]^－	6.4×10⁵	631.167 8	-1.51	613.491 3, 491.119 0, 313.057 0, 211.171 9, 399.092 9, 169.014 9, 121.030 1	C₃₀H₃₂O₁₅	Galloylpaeoniflorin	BS	Monoterpene	[14]
70	9.61	[M+HCOO]^－	6.5×10⁵	631.167 1	-0.41	491.119 6, 313.057 0, 169.015 1	C₃₀H₃₂O₁₅	Galloylalbiflorin	BS	Monoterpene	[14]
71	9.64	[M+HCOO]^－	1.3×10⁴	328.117 6	4.41	175.038 4, 161.235 2, 147.044 0	C₁₈H₁₉NO₅	(S)-N-trans-Feruloyl-octopamine	DG	Alkaloid	[17]
72	9.68	[M-H]^－	1.2×10⁴	223.096 8	3.51	223.096 8, 205.087 2, 179.107 5, 161.098 1, 145.030 0, 117.035 2, 93.035 1	C₁₂H₁₆O₄	Senkyunolide I^*	DG/CX	Phthalide	[17]
73	9.71	[M-H]^－	1.4×10³	377.158 8	4.71	329.135 2, 165.056 7, 149.024 1	C₂₀H₂₆O₇	4, 7, 9, 9'-Tetrahydroxy-3, 3'-dimethoxy-8-O-4'-neolignan	BS	Other	[29]
74	9.86	[M-H]^－	3.4×10⁴	939.108 8	2.24	769.092 4, 617.080 1, 447.054 9, 169.013 4	C₄₁H₃₂O₂₆	Pentagalloylglucose	BS	Other	[29]
75	9.89	[M+H]⁺	7.9×10²	139.038 6	2.66	121.027 4, 95.048 2	C₇H₆O₃	p-Hydroxybenzoic acid	DG/CX	Organic acid	[18]
76	9.89	[M-H]^－	1.4×10⁴	813.280 1	2.67	637.232 2, 175.039 5	C₃₇H₅₀O₂₀	Jionoside B1	SDH	Phenylethanoid	[30]
77	10.17	[M-H]^－	1.3×10⁵	623.198 0	0.23	461.170 1, 315.110 9, 161.026 4, 135.045 0	C₂₉H₃₆O₁₅	Verbascoside^*	BS	Phenylethanoid	[36]
78	10.49	[M-H]^－	1.4×10³	447.094 2	-2.05	427.192 7, 271.059 3, 165.019 2	C₂₁H₂₀O₁₁	Kaempferol 3-O-D-glucopyranoside	SDH	Flavonoid	[30]
79	10.70	[M-H]^－	6.3×10⁵	753.224 9	-0.20	547.170 0, 367.105 3, 223.062 5, 205.052 7, 190.027 5	C₃₄H₄₂O₁₉	3, 6'-Disinapoyl sucrose^*	ZYZ	Oligosaccharide ester	[22]
80	10.80	[M-H]^－	1.7×10⁴	223.096 7	3.96	205.086 9, 179.107 2, 161.097 9, 145.032 8, 117.034 7, 93.035 5	C₁₂H₁₆O₄	Senkyunolide H^*	DG/CX	Phthalide	[18]
81^#	10.89	[M-H]^－	1.6×10⁴	225.113 0	1.03	181.123 7, 163.112 8, 124.052 8, 95.050 2	C₁₂H₁₈O₄	Senkyunolide N	DG/CX	Phthalide	[18]
82	10.90	[M-H]^－	1.5×10⁵	509.165 8	1.28	463.217 6, 306.077 7, 121.029 7	C₂₄H₃₀O₁₂	Mudanpioside D	BS	Monoterpene	[14]
83	10.93	[M-H]^－	1.7×10⁵	723.213 6	0.81	547.164 7, 430.141 2, 337.087 4, 175.039 8, 123.080 6	C₃₃H₄₀O₁₈	Arillanin A	ZYZ	Oligosaccharide ester	[7]
84	11.01	[M+Na]⁺	2.8×10³	263.088 1	3.40	223.096 3, 177.052 6, 165.053 1	C₁₂H₁₆O₅	Tatarinoids B	SCP	Monoterpene	[32]
85	11.18	[M+HCOO]^－	4.2×10³	345.097 0	2.83	217. 044 6, 187. 045 2	C₁₇H₁₆O₅	Cnidilin	CX	Other	[10]
86	11.42	[M+HCOO]^－	1.8×10⁵	507.150 5	0.59	461.145 6, 339.108 7, 179.054 2, 121.029 9	C₂₃H₂₆O₁₀	Lactiflorin	BS	Monoterpene	[14]
87	11.56	[M+H]⁺	6.8×10²	447.128 2	0.84	285.076 2, 270.052 3, 225.054 1, 137.023 1	C₂₂H₂₂O₁₀	Calycosin-7-O-β-D-glucoside^*	BS	Flavonoid	[28]
88	11.66	[M+HCOO]^－	6.0×10⁴	977.530 4	2.32	885.377 2, 799.496 1, 637.438 6, 475.384 9, 179.054 3	C₄₇H₈₀O₁₈	Notoginsenoside R1	RS	Saponin	[11]
89	11.70	[M-H]^－	7.2×10⁵	681.203 7	-0.11	443.119 6, 239.056 3, 137.024 2	C₃₁H₃₈O₁₇	Tenuifoliside A	ZYZ	Oligosaccharide Ester	[7]
90^#	12.04	[M-H]^－	3.3×10³	615.169 4	4.11	493.142 9, 273.033 8	C₃₀H₃₂O₁₄	Mudanpioside H	BS	Monoterpene	[14]
91^#	12.09	[M-H]^－	2.4×10³	599.174 5	4.20	551.255 2, 431.136 1, 165.058 6, 121.031 4	C₃₀H₃₂O₁₃	Benzoyloxypaeoniflorin	BS	Monoterpene	[14]
92	12.18	[M+HCOO]^－	3.2×10⁵	991.547 3	1.03	945.546 3, 799.486 8, 637.434 3, 475.379 6, 179.055 5	C₄₈H₈₂O₁₈	Ginsenoside Re	RS	Saponin	[11]
93	12.21	[M+HCOO]^－	6.6×10⁵	845.491 2	-0.93	799.490 8, 637.432 5, 475.379 5, 161.046 1	C₄₂H₇₂O₁₄	Pseudoginsenoside F11	RS	Saponin	[12]
94	12.36	[M+H]⁺	3.2×10⁴	314.138 4	0.91	297.100 7, 178.051 6, 148.053 5	C₁₈H₁₉NO₄	N-trans-Feruloyl-tyramine	SCP	Organic Acid	[32]
95	12.38	[M+HCOO]^－	5.7×10⁴	493.228 0	2.13	447.225 4, 315.181 3, 161.046 5	C₂₁H₃₆O₁₀	Shionoside A or isomer	CX	Monoterpene	[17]
96^#	12.38	[M-H]^－	1.2×10⁴	651.227 7	2.68	475.181 1, 193. 049 6, 175.039 3	C₃₁H₄₀O₁₅	Martynoside	SDH	Phenylethanoid	[30]
97	12.49	[M+HCOO]^－	2.4×10⁴	505.228 0	2.08	459.223 3, 417.175 2, 373.092 1, 149.024 1	C₂₂H₃₆O₁₀	Methyl oleate	DG	Other	[17]
98	12.56	[M-H]^－	5.8×10⁴	1 495.456 0	0.52	1 349.402 8, 1 203.363 6, 845.918 1, 655.182 0, 440.273 5, 307.086 1, 145.031 9	C₆₇H₈₄O₃₈	Tenuifoliose L	ZYZ	Oligosaccharide Ester	[7]
99^#	12.56	[M-H]^－	4.2×10⁴	1 525.466 5	0.55	1 379.400 2, 1 161.345 1, 673.198 2, 448.991 5, 218.635 7, 145.027 8	C₆₈H₈₆O₃₉	Tenuifoliose F	ZYZ	Oligosaccharide Ester	[7]
100	12.57	[M+HCOO]^－	3.9×10⁵	491.212 7	1.43	447.222 5, 293.088 3, 149.045 3	C₂₁H₃₄O₁₀	(Z)-(1S, 5R)-β-Pinen-10-yl-β-vicianoside	CX	Monoterpene	[10]
101	12.74	[M-H]^－	3.0×10⁴	1 265.375 7	1.62	1 119.338 8, 955.283 8, 719.713 1, 502.729 9, 306.080 8, 145.030 3	C₅₇H₇₀O₃₂	Tenuifoliose K	ZYZ	Oligosaccharide Ester	[7]
102	12.85	[M+H]⁺	1.2×10⁴	239.091 2	0.84	221.081 0, 190.063 3, 163.039 0	C₁₂H₁₄O₅	E-3, 4, 5-Trimethoxycinnamic acid	CX	Organic Acid	[10]
103	12.89	[M-H]^－	2.1×10⁵	767.240 4	0	529.157 8, 367.103 3, 205.051 2, 113.024 2	C₃₅H₄₄O₁₉	Tenuifoliside C	ZYZ	Oligosaccharide Ester	[7]
104^#	13.06	[M-H]^－	3.3×10³	309.086 3	2.21	263.081 4	C₁₇H₁₂N₂O₄	Flazin	SCP	Alkaloid	[32]
105	13.06	[M-H]^－	1.3×10⁵	1 295.387 6	0.55	1 119.344 2, 997.306 5, 753.221 8, 429.123 2, 307.084 3, 145.030 4	C₅₈H₇₂O₃₃	Tenuifoliose C	ZYZ	Oligosaccharide Ester	[7]
106	13.22	[M+HCOO]^－	1.1×10⁴	329.102 4	2.01	271.045 4, 203.031 2, 187.040 8	C₁₇H₁₆O₄	Pabulenol	SCP	Other	[34]
107	13.27	[M-H]^－	2.0×10⁴	1 397.621 3	1.26	1 308.382 7, 1 162.344 1, 960.932 7, 719.248 9, 425.301 1, 304.185 2, 173.691 6	C₆₄H₁₀₂O₃₃	Arillatanoside C	ZYZ	Saponin	[7]
108	13.34	[M+HCOO]^－	1.5×10⁵	1 353.393 9	-0.08	1 307.389 3, 1 161.3512, 1 015.313 6, 795.2312, 631.184 6, 528.951 4, 145.030 5	C₅₉H₇₂O₃₃	Tenuifoliose J	ZYZ	Oligosaccharide ester	[7]
109	13.55	[M-H]^－	1.8×10⁵	1 337.399 4	-0.39	1 161.350 0, 997.297 8, 731.222 3, 631.169 6, 307.081 2, 175.041 2	C₆₀H₇₄O₃₄	Tenuifoliose B	ZYZ	Oligosaccharide ester	[7]
110^#	13.68	[M+HCOO]^－	2.1×10³	971.481 6	4.24	731.478 1, 629.367 6, 455.354 4, 205.072 2, 163.060 2	C₄₇H₇₄O₁₈	Pseudoginsenoside Rt1	RS	Saponin	[6]
111	13.75	[M-H]^－	1.5×10⁴	203.071 4	0	174.032 9, 173.024 1, 160.016 9, 145.030 2, 132.022 8, 106.042 9	C₁₂H₁₂O₃	Senkyunolide B	DG/CX	Phthalide	[17]
112	13.78	[M-H]^－	1.4×10⁵	711.213 9	0.40	665.209 8, 543.173 7, 427.124 6, 237.078 0, 121.029 9	C₃₂H₄₀O₁₈	Telephiose C	SCP	Other	[34]
113^#	13.83	[M-H]^－	2.3×10⁴	1 235.568 2	-3.11	1 103.307 0, 879.462 6, 542.569 7, 337.112 4, 225.114 4	C₅₈H₉₂O₂₈	Arillatanoside A	ZYZ	Saponin	[7]
114^#	13.85	[M+HCOO]^－	5.1×10⁴	507.243 0	3.35	461.238 7, 368.996 9, 265.091 6, 163.061 8	C₂₂H₃₈O₁₀	Shionoside B	CX	Monoterpene	[10]
115	13.98	[M-H]^－	1.5×10⁵	221.081 9	0	177.093 3, 134.034 0, 77.039 6	C₁₂H₁₄O₄	Senkyunolide D or isomer	DG/CX	Phthalide	[17]
116	14.07	[M-H]^－	4.2×10⁵	1 103.527 5	0.43	879.475 4, 775.438 4, 598.524 1, 455.318 3, 337.114 3, 217.073 0	C₅₃H₈₄O₂₄	Polygalaxanthone XXVIII	ZYZ	Flavonoid	[27]
117	14.08	[M-H]^－	1.3×10⁵	221.081 7	1.05	177.093 3, 92.026 8	C₁₂H₁₄O₄	(E)-3-(2, 4, 5-Trimethoxyphenyl) acrylaldehyde	SCP	Other	[34]
118	14.09	[M+H]⁺	3.8×10⁵	189.091 7	-3.67	161.058 8, 143.086 1, 128.061 8, 105.068 9, 91.053 9	C₁₂H₁₂O₂	3-Butylidenephthalide	DG/CX	Phthalide	[18]
119	14.36	[M-H]^－	1.3×10⁵	1 349.399 8	-0.69	1 203.365 2, 1 040.317 1, 795.232 4, 673.201 8, 365.106 8, 145.029 7	C₆₁H₇₄O₃₄	Tenuifoliose H	ZYZ	Oligosaccharide ester	[7]
120	14.41	[M-H]^－	1.5×10⁴	1 367.407 6	1.34	1 191.363 9, 1 089.806 8, 909.287 4, 740.440 1, 383.473 1, 175.038 5	C₆₁H₇₆O₃₅	Tenuifoliose O	ZYZ	Oligosaccharide ester	[7]
121^#	14.48	[M-H]^－	3.3×10³	661.247 9	3.45	493.149 2, 417.212 5	C₃₃H₄₂O₁₄	Azadirachtin H	CX	Monoterpene	[10]
122	14.53	[M+HCOO]^－	8.7×10⁵	629.187 9	-0.51	553.174 9, 431.137 4, 165.056 6, 121.030 4	C₃₀H₃₂O₁₂	Benzoylpaeoniflorin^*	BS	Monoterpene	[36]
123	14.61	[M-H]^－	3.7×10⁵	1 379.411 2	-1.28	1 203.362 7, 1 029.496 5, 642.902 4, 501.774 3, 368.102 1, 274.081 9	C₆₂H₇₆O₃₅	Tenuifoliose A	ZYZ	Oligosaccharide Ester	[7]
124	14.81	[M-H]^－	2.5×10⁵	629.188 5	-1.46	553.173 0, 431.135 4, 267.073 4, 121.030 3	C₃₁H₃₄O₁₄	Mudanpioside B	BS	Monoterpene	[14]
125	15.01	[M+HCOO]^－	5.1×10⁵	845.4903	-0.13	799.489 2, 637.437 1, 475.382 0, 310.329 5, 161.046 8	C₄₂H₇₂O₁₄	Ginsenoside Rg₁^*	RS	Saponin	[11]
126	15.13	[M+H]⁺	4.8×10²	281.247 7	-0.69	245.225 8, 97.101 3	C₁₈H₃₂O₂	Linoleic acid	DG	Organic Acid	[17]
127	15.18	[M-H]^－	5.8×10⁴	355.118 2	1.44	296.108 2, 159.045 6	C₂₀H₂₀O₆	Coniferyl ferulate	DG/CX	Other	[18]
128	15.46	[M+HCOO]^－	2.6×10⁵	815.479 1	0.91	769.479 1, 637.434 4, 475.380 3, 366.176 7, 161.046 4	C₄₁H₇₀O₁₃	Ginsenoside F5	RS	Saponin	[6]
129^#	15.52	[M+HCOO]^－	1.9×10³	815.480 5	-0.80	769.475 9, 637.433 9, 475.380 3, 366.176 7, 161.046 4	C₄₁H₇₀O₁₃	Notoginsenoside R2	RS	Saponin	[12]
130^#	15.84	[M+HCOO]^－	4.8×10³	1 285.640 1	2.57	1 107.593 3, 945.540 7, 783.497 6, 621.436 8, 459.380 8	C₅₉H₁₀₀O₂₇	Ginsenoside Ra₃	RS	Saponin	[10]
131	15.92	[M-H]^－	1.8×10⁵	679.370 4	-0.73	635.384 8, 455.318 8, 425.3062	C₃₆H₅₆O₁₂	Tenuifolin^*	ZYZ	Saponin	[7]
132	15.92	[M+HCOO]^－	1.8×10⁵	1 153.600 6	0.47	1 107.601 2, 945.548 7, 783.487 2, 621.434 7, 459.384 5, 323.100 9, 179.056 6	C₅₄H₉₂O₂₃	Ginsenoside Rb₁	RS	Saponin	[12]
133	16.00	[M+HCOO]^－	2.1×10⁵	829.496 1	-0.73	783.491 0, 637.433 7, 475.378 9, 262.979 3, 161.046 3	C₄₂H₇₂O₁₃	Ginsenoside Rg₂^*	RS	Saponin	[11]
134	16.12	[M+HCOO]^－	1.7×10⁵	683.437 3	0.42	637.435 5, 475.379 6, 329.231 7, 101.023 5	C₃₆H₆₂O₉	Ginsenoside Rh₁	RS	Saponin	[12]
135	16.15	[M-H]^－	1.7×10⁵	1 193.595 6	0.38	1 149.608 8, 945.539 2, 783.489 1, 621.439 0, 323.09 44, 179.056 9	C₅₇H₉₄O₂₆	Malonyl-ginsenoside Rb₁	RS	Saponin	[12]
136	16.17	[M-H]^－	6.1×10⁵	329.233 6	-0.77	229.144 6, 211.134 2, 171.103 0, 139.112 5	C₁₈H₃₄O₅	Tianshic acid	CX	Organic Acid	[17]
137	16.29	[M+HCOO]^－	1.6×10⁵	1 123.590 1	0.42	1 077.588 4, 945.539 7, 783.489 5, 621.438 1, 149.045 4	C₅₃H₉₀O₂₂	Ginsenoside Rc	RS	Saponin	[12]
138^#	16.29	[M+HCOO]^－	9.4×10³	1 255.631 2	1.30	1 233.625 1, 467.136 3	C₅₈H₉₈O₂₆	Ginsenoside Ra₁	RS	Saponin	[12]
139	16.32	[M-H]^－	5.2×10⁵	207.103 1	-2.09	163.113 6, 161.094 4, 85.065 8	C₁₂H₁₆O₃	Senkyunolide G	DG/CX	Phthalide	[18]
140	16.42	[M-H]^－	3.4×10⁵	955.490 6	0.21	793.436 5, 731.437 3, 613.372 7 569.385 9, 455.351 3	C₄₈H₇₆O₁₉	Ginsenoside Ro	RS	Saponin	[12]
141	16.47	[M+H]⁺	1.4×10⁴	191.107 2	-2.85	173.095 6, 145.100 9, 135.043 8, 117.068 9, 91.053 8	C₁₂H₁₄O₂	n-Butylphthalide^*	DG/CX	Phthalide	[17]
142	16.48	[M+HCOO]^－	1.4×10⁵	683.437 8	-0.31	637.436 7, 475.379 3, 1161.046 4, 101.023 5	C₃₆H₆₂O₉	Ginsenoside F1	RS	Saponin	[12]
143	16.53	[M-H]^－	6.5×10⁴	1 163.583 2	1.97	1 119.601 7, 915.525 2, 783.490 0, 590.037 1, 376.585 9, 149.047 1	C₅₆H₉₂O₂₅	Malonylginsenoside Rc	RS	Saponin	[12]
144	16.65	[M+HCOO]^－	2.0×10⁵	1 123.590 1	0.42	1 077.587 7, 946.541 4, 783.494 5, 521.780 6, 459.384 5, 149.046 5	C₅₃H₉₀O₂₂	Ginsenoside Rb₂	RS	Saponin	[12]
145	17.10	[M-H]^－	6.2×10⁵	205.087 6	-2.84	161.092 8, 106.049 2, 83.050 9, 77.039 6	C₁₂H₁₄O₃	Senkyunolide F	DG/CX	Phthalide	[17]
146	17.21	[M-H]^－	2.8×10⁴	375.183 6	-6.10	245.086 3, 191.076 1	C₂₁H₂₈O₆	Ligraminol D	SCP	Other	[34]
147	17.23	[M-H]^－	3.2×10⁴	1 617.696 4	0.13	1 385.149 9, 1 048.084 7, 726.871 8, 419.879 0, 224.625 9	C₇₆H₁₁₄O₃₇	Onjisaponin R	ZYZ	Saponin	[7]
148	17.41	[M+HCOO]^－	2.5×10⁵	991.548 1	0.22	945.546 6, 783.489 5, 621.436 0, 511.699 6, 161.046 0	C₄₈H₈₂O₁₈	Ginsenoside Rd	RS	Saponin	[11]
149	17.54	[M+H]⁺	3.5×10³	251.164 0	0.47	233.154 3, 151.071 6, 135.042 4	C₁₅H₂₂O₃	Isocalamediol	SCP	Monoterpene	[32]
150	17.56	[M-H]^－	1.9×10⁴	1 031.541 1	2.07	987.557 0, 945.546 4, 765.478 6, 621.443 3, 395.521 2, 161.047 6	C₅₁H₈₄O₂₁	Malonyl-ginsenoside Rd	RS	Saponin	[12]
151	17.64	[M-H]^－	1.5×10⁴	891.254 7	1.96	811.208 1, 655.187 9, 551.137 1, 301.102 5	C₄₁H₄₈O₂₂	Tenuifoliside E	ZYZ	Oligosaccharide ester	[7]
152^#	17.69	[M-H]^－	4.6×10³	297.170 1	2.18	261.146 3, 253.180 2	C₁₆H₂₆O₅	2, 4, 5-Trimethoxyl-2′-butoxy-1, 2-phenyl propandiol	SCP	Other	[32]
153^#	17.91	[M-H]^－	4.0×10⁴	1 571.692 4	-0.80	1 253.118 4, 1 030.617 1, 701.769 5, 587.467 4, 439.649 9, 198.448 4	C₇₅H₁₁₂O₃₅	Onjisaponin B	ZYZ	Saponin	[7]
154	17.94	[M-H]^－	1.4×10⁵	203.072 0	-3.11	174.033 1, 173.025 0, 160.017 1, 145.032 9, 132.022 4, 117.035 1, 104.027 7, 92.028 0	C₁₂H₁₂O₃	Senkyunolide C	DG/CX	Phthalide	[17]
155	17.95	[M+H]⁺	6.1×10⁴	279.159 3	-0.77	261.146 2, 233.153 6, 191.106 7, 105.033 8, 71.048 8	C₁₆H₂₂O₄	Senkyunolide M	DG/CX	Phthalide	[18]
156^#	18.12	[M+HCOO]^－	3.5×10⁴	1 587.686 9	-0.53	1 455.641 4, 964.826 6, 676.245 8, 425.302 5, 237.078 2	C₇₄H₁₁₀O₃₄	Onjisaponin H	ZYZ	Saponin	[7]
157	18.17	[M-H]^－	3.5×10⁴	1 587.693 2	-4.5	1 455.641 4, 1 087.742 2, 676.245 8, 425.305 2, 237.078 2	C₇₅H₁₁₂O₃₆	Onjisaponin F	ZYZ	Saponin	[7]
158^#	18.32	[M-H]^－	4.3×10²	283.061 9	-2.48	268.037 2, 240.040 4, 135.007 8	C₁₆H₁₂O₅	Calycosin^*	BS	Flavonoid	[28]
159	18.36	[M-H]^－	2.2×10⁵	203.072 2	-4.10	174.032 9, 159.081 9, 131.051 1, 130.042 9, 91.021 1	C₁₂H₁₂O₃	Senkyunolide E	DG/CX	Phthalide	[17]
160	18.55	[M+H]⁺	7.4×10⁴	209.117 3	-0.38	194.091 2, 168.075 6, 153.051 5	C₁₂H₁₆O₃	β-Asarone	SCP	Other	[32]
161^#	18.60	[M-H]^－	5.3×10³	793.439 4	-1.79	613.376 9, 455.354 4, 311.220 2, 89.025 1	C₄₂H₆₆O₁₄	Zingibroside R1	RS	Saponin	[12]
162	18.64	[M+H]⁺	1.6×10⁶	193.123 1	-4.11	175.111 9, 147.117 1, 137.060 2, 93.069 8	C₁₂H₁₆O₂	Senkyunolide A^*	DG/CX	Phthalide	[24]
163	18.69	[M+HCOO]^－	1.6×10⁵	665.428 0	-1.47	619.422 4, 493.410 2, 327.752 8, 161.045 2	C₃₆H₆₀O₈	Ginsenoside Rh₄	RS	Saponin	[12]
164	18.79	[M+H]⁺	1.3×10⁵	209.117 3	-0.38	194.091 3, 179.067 4, 153.051 6	C₁₂H₁₆O₃	α-Asarone	SCP	Other	[32]
165	18.85	[M+HCOO]^－	5.2×10⁵	829.496 1	-0.73	783.491 0, 621.434 8, 459.381 7, 161.046 3	C₄₂H₇₂O₁₃	Ginsenoside Rg₃	RS	Saponin	[10]
166^#	18.90	[M+HCOO]^－	8.1×10³	323.185 5	2.78	239.128 6, 209.115 1, 171.100 8	C₁₇H₂₆O₃	2-Acetoxyacorenone	SCP	Monoterpene	[32]
167	19.14	[M+H]⁺	3.0×10⁵	191.106 9	-1.28	173.095 7, 163.111 5, 145.100 9, 117.070 1	C₁₂H₁₄O₂	(E)-Ligustilide	DG/CX	Phthalide	[17]
168	19.23	[M+H]⁺	9.1×10²	315.253 5	-1.63	185.117 3, 135.111 2, 121.101 0	C₁₈H₃₄O₄	Dibutyl sebacate or isomer	DG	Other	[17]
169	19.37	[M+HCOO]^－	1.7×10⁴	871.504 4	1.90	825.504 5, 783.491 4, 621.435 7, 447.037 8, 252.047 8	C₄₄H₇₄O₁₄	Ginsenoside Rs₃	RS	Saponin	[12]
170	19.39	[M+H]⁺	6.3×10⁵	191.107 2	-2.85	173.095 7, 145.100 9, 117.070 1, 105.070 2, 91.053 7, 79.053 8	C₁₂H₁₄O₂	(Z)-Ligustilide^*	DG/CX	Phthalide	[25]
171	19.69	[M+H]⁺	9.9×10³	165.090 8	1.59	137.059 3, 124.051 2, 105.069 2	C₁₀H₁₂O₂	Eugenol	BS	Phenylethanoid	[33]
172	19.76	[M+HCOO]^－	1.3×10⁵	811.483 8	1.39	619.422 9, 457.370 7	C₄₂H₇₀O₁₂	Ginsenoside Rg₆	RS	Saponin	[12]
173	19.86	[M+H]⁺	4.4×10³	401.194 5	3.40	371.185 0, 233.113 9, 203.104 4, 181.082 3	C₂₃H₂₈O₆	Ligraminol C	DG	Other	[17]
174	20.13	[M+HCOO]^－	4.8×10³	667.441 6	1.61	621.436 0, 459.387 2	C₃₆H₆₂O₈	Ginsenoside CK	RS	Saponin	[12]
175	20.33	[M+H]⁺	1.4×10⁵	209.117 3	-0.38	194.091 2, 168.075 6, 151.071 5	C₁₂H₁₆O₃	γ-Asarone	SCP	Other	[32]
176	20.44	[M+H]⁺	1.7×10³	277.144 1	1.56	261.146 1, 233.153 5, 191.106 7, 105.033 8, 71.048 8	C₁₆H₂₂O₄	Senkyunolide Q	DG/CX	Phthalide	[17]

No.	t_R/min	Precursor ion	Response	Meas m/z	Error/ppm	Fragment ion	Molecular formula	Plausible identification	Source	Category	Reference
1	0.68	[M+HCOO]^－	5.3×10⁴	549.166 0	2.25	503.161 4, 341.109 1, 101.024 5	C₁₈H₃₂O₁₆	Maltotriose	SDH	Other	[30]
2	0.70	[M+H]⁺	1.2×10⁴	133.061 2	-3.24	91.053 6, 87.054 1	C₄H₈N₂O₃	L-Asparagine	DG	Other	[17]
3	0.70	[M-H]^－	2.1×10⁴	175.118 7	1.44	158.092 1, 116.071 3	C₆H₁₄N₄O₂	Arginine	DG	Other	[17]
4	0.71	[M-H]^－	1.1×10⁵	179.055 8	1.74	71.013 8, 63.024 5	C₆H₁₂O₆	Fructose	SDH	Other	[30]
5	0.71	[M-H]^－	5.3×10⁴	195.050 5	2.70	176.900 6, 159.895 2	C₆H₁₂O₇	Gluconic acid	DG	Other	[17]
6	0.93	[M-H]^－	3.3×10⁴	341.107 7	3.62	119.034 2, 89.023 3	C₁₂H₂₂O₁₁	Maltose	SDH	Other	[30]
7	1.00	[M-H]^－	1.3×10⁶	133.014 6	-2.65	115.004 1, 71.014 2	C₄H₆O₅	Malic acid	DG	Organic acid	[17]
8	1.11	[M-H]^－	5.1×10⁶	191.020 2	-2.48	111.002 9, 87.009 1	C₆H₈O₇	Citric acid^*	BS/SDH	Organic acid	[30]
9	1.26	[M+H]⁺	1.2×10⁴	245.077 1	-1.17	133.049 5, 113.034 5	C₉H₁₂N₂O₆	Uridine	SDH/RS	Alkaloid	[30]
10	1.48	[M+H]⁺	3.1×10⁶	268.104 7	-2.50	136.063 2, 119.035 6	C₁₀H₁₃N₅O₄	Adenosine	SDH/RS	Alkaloid	[31]
11	1.73	[M+H]⁺	5.2×10⁵	284.099 7	-2.66	152.056 3, 135.028 7, 85.027 7	C₁₀H₁₃N₅O₅	Guanosine	SDH	Alkaloid	[31]
12	1.91	[M-H]^－	1.7×10⁶	169.014 1	0.87	125.025 5, 97.028 8	C₇H₆O₅	Gallic acid^*	BS	Organic acid	[13]
13^#	2.02	[M-H]^－	3.7×10⁴	125.024 2	1.74	79.016 9	C₆H₆O₃	Pyrogallol	BS	Phenol	[13]
14	2.22	[M+HCOO]^－	1.4×10⁵	405.138 9	3.30	359.135 8, 254.074 6, 179.072 1	C₁₆H₂₄O₉	Peony ketone-1-O-β-D-glucoside	BS	Flavonoid	[28]
15^#	2.34	[M+HCOO]^－	8.8×10²	361.113 5	1.44	199.061 2, 169.050 3	C₁₅H₂₂O₁₀	Catalpol	SDH	Monoterpene	[30]
16	2.44	[M+H]⁺	1.5×10⁶	166.085 7	3.34	120.080 5, 103.054 3, 79.054 1	C₉H₁₁NO₂	L-Phenylalanine	DG	Other	[17]
17	2.75	[M+HCOO]^－	1.4×10⁵	731.223 4	2.39	685.223 3, 505.159 4, 341.110 7, 263.079 3, 179.057 9	C₂₇H₄₂O₂₀	Rehmannioside D^*	SDH	Monoterpene	[30]
18^#	2.75	[M-H]^－	6.3×10⁴	493.119 9	0	449.123 3, 313.057 4, 271.045 6, 169.013 4	C₁₉H₂₆O₁₅	1'-O-Galloylsucrose	SDH	Other	[30]
19	2.87	[M+HCOO]^－	9.5×10⁴	569.171 3	1.80	523.166 7, 463.143 4, 343.104 0, 228.058 5, 179.056 7	C₂₁H₃₂O₁₅	Rehmannioside A	SDH	Monoterpene	[30]
20	3.31	[M-H]^－	5.2×10⁴	153.019 3	0	109.029 2, 108.021 6	C₇H₆O₄	Protocatechuic acid	CX	Organic acid	[18]
21	3.46	[M-H]^－	3.3×10⁴	373.113 0	2.74	269.040 2, 211.059 4, 149.061 1, 123.046 4	C₁₆H₂₂O₁₀	Geniposidic acid	SDH	Monoterpene	[31]
22	3.51	[M+H]⁺	1.9×10⁴	384.114 7	0.75	252.072 2, 162.075 0, 136.060 9	C₁₄H₁₇N₅O₈	Succinyladenosine	SCP	Alkaloid	[32]
23^#	4.14	[M-H]^－	8.2×10³	183.029 9	0	169.013 8, 124.015 8	C₈H₈O₅	Methyl gallate	BS	Other	[28]
24^#	4.14	[M-H]^－	3.4×10³	205.097 7	-2.66	188.067 4, 146.059 3, 118.065 3	C₁₁H₁₂N₂O₂	Tryptophan	DG/CX	Organic acid	[17]
25	4.16	[M-H]^－	2.8×10⁵	353.087 6	0.58	191.055 8, 179.035 2, 173.044 2, 161.023 3, 135.044 7	C₁₆H₁₈O₉	Chlorogenic acid^*	DG/CX	Organic acid	[19]
26^#	4.19	[M-H]^－	7.9×10³	389.107 8	2.92	165.101 2, 139.552 1	C₁₆H₂₂O₁₁	Scandoside	SDH	Monoterpene	[31]
27^#	4.26	[M-H]^－	5.8×10³	347.133 2	4.48	167.071 2, 123.081 6	C₁₅H₂₄O₉	Ajugol	SDH	Monoterpene	[31]
28	4.42	[M+HCOO]^－	2.6×10⁴	389.144 0	3.39	343.139 8, 257.453 1, 181.088 2, 161.046 2	C₁₆H₂₄O₈	Mudanpioside F	BS	Monoterpene	[13]
29	4.47	[M-H]^－	6.1×10⁴	461.164 9	3.36	415.123 9, 294.122 7, 113.024 2	C₂₀H₃₀O₁₂	Forsythoside E	BS	Phenylethanoid	[28]
30	4.56	[M-H]^－	8.0×10⁴	375.128 3	3.65	314.306 6, 213.077 8, 169.087 0	C₁₆H₂₄O₁₀	8-Epiloganic acid	SDH	Monoterpene	[30]
31^#	4.66	[M-H]^－	1.2×10⁴	345.118 2	2.62	135.043 6, 123.043 5	C₁₅H₂₂O₉	Aucubin	SDH	Monoterpene	[30]
32^#	4.66	[M+HCOO]^－	1.2×10⁴	345.118 2	2.62	299.113 8, 179.057 5, 119.036 3	C₁₄H₂₀O₇	Salidroside	DG	Phenylethanoid	[17]
33	4.72	[M-H]^－	7.4×10⁴	461.128 7	2.96	266.043 6, 137.024 5, 93.035 5	C₁₉H₂₆O₁₃	Sibiricose A3	ZYZ	Oligosaccharide ester	[7]
34	5.35	[M+H]⁺	5.6×10³	389.144 7	-1.22	209.072 3, 149.063 1, 111.037 3	C₁₇H₂₄O₁₀	Geniposide	SDH	Monoterpene	[30]
35	5.55	[M+HCOO]^－	1.8×10⁵	391.159 7	3.25	345.157 4, 192.060 0, 161.046 8	C₁₆H₂₆O₈	Rehmapicroside	SDH	Monoterpene	[30]
36	5.62	[M-H]^－	6.5×10⁵	353.087 6	0.58	191.055 8, 179.035 2, 173.044 2, 161.023 3, 135.044 7	C₁₆H₁₈O₉	Neochlorogenic acid^*	DG/CX	Organic acid	[17]
37	5.67	[M+H]⁺	1.8×10³	291.085 1	4.17	167.034 5, 139.038 8, 127.034 2	C₁₅H₁₄O₆	Epicatechin	BS	Phenol	[33]
38	5.68	[M-H]^－	2.0×10⁵	123.045 1	0.43	105.271 4	C₇H₈O₂	Guaiacol	SDH	Phenol	[30]
39	5.82	[M-H]^－	2.1×10⁶	167.035 1	-0.70	123.046 1, 108.023 1	C₈H₈O₄	Vanillic acid^*	DG/CX	Organic acid	[17]
40	5.83	[M+H]⁺	4.2×10⁴	123.044 6	-4.42	105.033 6, 79.053 4, 77.038 6	C₇H₆O₂	Benzoic acid^*	DG	Organic acid	[18]
41^#	5.97	[M-H]^－	4.8×10³	593.149 0	3.70	287.054 3, 129.054 3	C₂₇H₃₀O₁₅	Nicotiflorin	BS	Flavonoid	[29]
42	5.98	[M-H]^－	2.4×10⁵	353.087 3	1.43	191.055 7, 179.035 1, 173.044 5, 161.023 4, 135.044 7	C₁₆H₁₈O₉	Cryptochlorogenic acid^*	DG/CX	Organic acid	[18]
43	5.98	[M+HCOO]^－	2.2×10⁵	563.161 0	1.35	517.159 6, 448.626 2, 341.110 0, 175.041 4	C₂₂H₃₀O₁₄	Sibiricose A5	ZYZ	Oligosaccharide ester	[7]
44	6.10	[M-H]^－	6.0×10⁵	179.035 4	-2.33	135.046 0, 79.056 2	C₉H₈O₄	Caffeic acid^*	DG	Organic acid	[18]
45	6.30	[M+HCOO]^－	2.8×10⁵	475.145 2	1.08	429.143 7, 307.104 0, 121.030 1	C₁₉H₂₆O₁₁	Polygalatenoside A	SDH	Other	[31]
46	6.35	[M-H]^－	2.2×10⁵	547.166 5	0.63	503.148 5, 341.109 5, 205.051 4	C₂₃H₃₂O₁₅	Sibiricose A6	ZYZ	Oligosaccharide ester	[7]
47	7.09	[M-H]^－	6.5×10³	323.124 0	2.66	203.080 5, 189.066 9, 161.071 2,	C₁₅H₂₀N₂O₆	Tatarine C	SCP	Alkaloid	[34]
48	7.32	[M+HCOO]^－	1.8×10⁶	525.161 9	1.65	449.153 2, 357.121 6, 283.079 3, 195.063 9, 121.029 4	C₂₃H₂₈O₁₁	Mudanpioside I	BS	Monoterpene	[13]
49	7.34	[M-H]^－	1.8×10⁶	525.161 9	1.65	449.147 2, 327.109 1, 165.056 9, 121.030 1	C₂₄H₃₀O₁₃	Mudanpioside E	BS	Monoterpene	[13]
50	7.62	[M+HCOO]^－	4.5×10⁴	541.155 4	1.62	465.138 7, 343.103 1, 193.050 7, 121.029 4	C₂₃H₂₈O₁₂	Oxypaeoniflorin^*	BS	Monoterpene	[14]
51	7.74	[M-H]^－	1.3×10⁴	785.248 2	3.52	707.224 3, 623.218 2, 545.172 6	C₃₅H₄₆O₂₀	Purpureaside B	SDH	Phenylethanoid	[31]
52	7.82	[M+HCOO]^－	2.0×10⁶	525.161 9	1.65	479.157 9, 449.147 8, 327.109 5, 121.020 3	C₂₃H₂₈O₁₁	Paeoniflorin^*	BS	Monoterpene	[15]
53	7.99	[M-H]^－	2.4×10⁵	183.102 5	0.92	139.112 1	C₁₀H₁₆O₃	Rehmapicrogenin	SDH	Monoterpene	[31]
54	8.20	[M+HCOO]^－	3.0×10⁵	537.125 0	0	493.163 4, 315.051 4, 210.603 9	C₂₄H₂₆O₁₄	Sibiricaxanthone B	ZYZ	Flavonoid	[7]
55	8.38	[M+HCOO]^－	5.9×10⁴	435.223 2	0.85	341.106 6, 193.050 9	C₁₉H₃₄O₈	Rehmaionoside A	SDH	Monoterpene	[31]
56^#	8.62	[M-H]^－	2.0×10⁴	787.098 1	2.35	617.080 2, 169.014 3, 125.025 2	C₃₄H₂₈O₂₂	Tetragalloylglucose	BS	Other	[15]
57	8.65	[M+HCOO]^－	3.0×10⁵	607.188 2	-0.37	561.185 1, 323.100 1, 237.078 6, 113.024 4	C₂₄H₃₄O₁₅	Sibiricose A2	ZYZ	Oligosaccharide ester	[7]
58^#	8.65	[M-H]^－	4.1×10⁴	799.265 8	1.02	623.219 1, 193.051 3, 175.039 3, 161.024 1	C₃₆H₄₈O₂₀	Cistanoside A	SDH	Phenylethanoid	[35]
59^#	8.70	[M-H]^－	1.3×10⁴	435.092 3	2.26	315.052 2, 287.018 6, 272.033 1	C₂₀H₂₀O₁₁	Irisxanthone	SDH	Flavonoid	[31]
60	8.73	[M-H]^－	9.8×10⁵	193.051 3	-3.46	178.027 6, 149.060 7, 134.037 4	C₁₀H₁₀O₄	Ferulic acid^*	DG/CX	Organic acid	[17]
61	8.73	[M+HCOO]^－	9.8×10⁵	193.051 3	-3.46	178.028 2, 149.060 7, 134.037 6,	C₉H₈O₂	5-Methoxy-1-benzofuran	BS	Other	[13]
62	8.78	[M-H]^－	2.6×10⁵	567.135 7	-0.28	417.081 7, 315.049 7, 179.030 9	C₂₅H₂₈O₁₅	Polygalaxanthone VIII	ZYZ	Flavonoid	[7]
63	8.85	[M-H]^－	2.6×10⁵	567.135 9	-0.63	435.095 5, 417.085 3, 345.063 5, 315.049 7, 297.040 1, 272.033 1	C₂₅H₂₈O₁₅	Polygalaxanthone III^*	ZYZ	Flavonoid	[29]
64	9.06	[M-H]^－	1.1×10³	577.155 9	0.66	270.047 2, 269.044 6	C₂₇H₃₀O₁₄	Rhoifolin	ZYZ	Flavonoid	[7]
65^#	9.10	[M+HCOO]^－	1.0×10³	609.143 9	3.63	519.145 7, 385.137 5, 253.061 7, 111.007 3	C₂₆H₂₈O₁₄	Isoschaftoside	BS	Flavonoid	[29]
66	9.18	[M+HCOO]^－	9.7×10⁴	435.223 0	1.31	341.106 6, 193.050 9	C₁₉H₃₄O₈	Rehmaionoside B	SDH	Monoterpene	[31]
67^#	9.38	[M+H]⁺	2.9×10³	146.044 9	4.08	117.059 5, 91.056 6	C₉H₇NO	Indole-3-carboxaldehyde	SCP	Alkaloid	[32]
68	9.38	[M-H]^－	1.6×10⁵	667.187 7	0.41	461.130 1, 299.079 1, 205.051 1, 137.024 6	C₃₀H₃₆O₁₇	Tenuifoliside B	ZYZ	Oligosaccharide ester	[7]
69	9.58	[M-H]^－	6.4×10⁵	631.167 8	-1.51	613.491 3, 491.119 0, 313.057 0, 211.171 9, 399.092 9, 169.014 9, 121.030 1	C₃₀H₃₂O₁₅	Galloylpaeoniflorin	BS	Monoterpene	[14]
70	9.61	[M+HCOO]^－	6.5×10⁵	631.167 1	-0.41	491.119 6, 313.057 0, 169.015 1	C₃₀H₃₂O₁₅	Galloylalbiflorin	BS	Monoterpene	[14]
71	9.64	[M+HCOO]^－	1.3×10⁴	328.117 6	4.41	175.038 4, 161.235 2, 147.044 0	C₁₈H₁₉NO₅	(S)-N-trans-Feruloyl-octopamine	DG	Alkaloid	[17]
72	9.68	[M-H]^－	1.2×10⁴	223.096 8	3.51	223.096 8, 205.087 2, 179.107 5, 161.098 1, 145.030 0, 117.035 2, 93.035 1	C₁₂H₁₆O₄	Senkyunolide I^*	DG/CX	Phthalide	[17]
73	9.71	[M-H]^－	1.4×10³	377.158 8	4.71	329.135 2, 165.056 7, 149.024 1	C₂₀H₂₆O₇	4, 7, 9, 9'-Tetrahydroxy-3, 3'-dimethoxy-8-O-4'-neolignan	BS	Other	[29]
74	9.86	[M-H]^－	3.4×10⁴	939.108 8	2.24	769.092 4, 617.080 1, 447.054 9, 169.013 4	C₄₁H₃₂O₂₆	Pentagalloylglucose	BS	Other	[29]
75	9.89	[M+H]⁺	7.9×10²	139.038 6	2.66	121.027 4, 95.048 2	C₇H₆O₃	p-Hydroxybenzoic acid	DG/CX	Organic acid	[18]
76	9.89	[M-H]^－	1.4×10⁴	813.280 1	2.67	637.232 2, 175.039 5	C₃₇H₅₀O₂₀	Jionoside B1	SDH	Phenylethanoid	[30]
77	10.17	[M-H]^－	1.3×10⁵	623.198 0	0.23	461.170 1, 315.110 9, 161.026 4, 135.045 0	C₂₉H₃₆O₁₅	Verbascoside^*	BS	Phenylethanoid	[36]
78	10.49	[M-H]^－	1.4×10³	447.094 2	-2.05	427.192 7, 271.059 3, 165.019 2	C₂₁H₂₀O₁₁	Kaempferol 3-O-D-glucopyranoside	SDH	Flavonoid	[30]
79	10.70	[M-H]^－	6.3×10⁵	753.224 9	-0.20	547.170 0, 367.105 3, 223.062 5, 205.052 7, 190.027 5	C₃₄H₄₂O₁₉	3, 6'-Disinapoyl sucrose^*	ZYZ	Oligosaccharide ester	[22]
80	10.80	[M-H]^－	1.7×10⁴	223.096 7	3.96	205.086 9, 179.107 2, 161.097 9, 145.032 8, 117.034 7, 93.035 5	C₁₂H₁₆O₄	Senkyunolide H^*	DG/CX	Phthalide	[18]
81^#	10.89	[M-H]^－	1.6×10⁴	225.113 0	1.03	181.123 7, 163.112 8, 124.052 8, 95.050 2	C₁₂H₁₈O₄	Senkyunolide N	DG/CX	Phthalide	[18]
82	10.90	[M-H]^－	1.5×10⁵	509.165 8	1.28	463.217 6, 306.077 7, 121.029 7	C₂₄H₃₀O₁₂	Mudanpioside D	BS	Monoterpene	[14]
83	10.93	[M-H]^－	1.7×10⁵	723.213 6	0.81	547.164 7, 430.141 2, 337.087 4, 175.039 8, 123.080 6	C₃₃H₄₀O₁₈	Arillanin A	ZYZ	Oligosaccharide ester	[7]
84	11.01	[M+Na]⁺	2.8×10³	263.088 1	3.40	223.096 3, 177.052 6, 165.053 1	C₁₂H₁₆O₅	Tatarinoids B	SCP	Monoterpene	[32]
85	11.18	[M+HCOO]^－	4.2×10³	345.097 0	2.83	217. 044 6, 187. 045 2	C₁₇H₁₆O₅	Cnidilin	CX	Other	[10]
86	11.42	[M+HCOO]^－	1.8×10⁵	507.150 5	0.59	461.145 6, 339.108 7, 179.054 2, 121.029 9	C₂₃H₂₆O₁₀	Lactiflorin	BS	Monoterpene	[14]
87	11.56	[M+H]⁺	6.8×10²	447.128 2	0.84	285.076 2, 270.052 3, 225.054 1, 137.023 1	C₂₂H₂₂O₁₀	Calycosin-7-O-β-D-glucoside^*	BS	Flavonoid	[28]
88	11.66	[M+HCOO]^－	6.0×10⁴	977.530 4	2.32	885.377 2, 799.496 1, 637.438 6, 475.384 9, 179.054 3	C₄₇H₈₀O₁₈	Notoginsenoside R1	RS	Saponin	[11]
89	11.70	[M-H]^－	7.2×10⁵	681.203 7	-0.11	443.119 6, 239.056 3, 137.024 2	C₃₁H₃₈O₁₇	Tenuifoliside A	ZYZ	Oligosaccharide Ester	[7]
90^#	12.04	[M-H]^－	3.3×10³	615.169 4	4.11	493.142 9, 273.033 8	C₃₀H₃₂O₁₄	Mudanpioside H	BS	Monoterpene	[14]
91^#	12.09	[M-H]^－	2.4×10³	599.174 5	4.20	551.255 2, 431.136 1, 165.058 6, 121.031 4	C₃₀H₃₂O₁₃	Benzoyloxypaeoniflorin	BS	Monoterpene	[14]
92	12.18	[M+HCOO]^－	3.2×10⁵	991.547 3	1.03	945.546 3, 799.486 8, 637.434 3, 475.379 6, 179.055 5	C₄₈H₈₂O₁₈	Ginsenoside Re	RS	Saponin	[11]
93	12.21	[M+HCOO]^－	6.6×10⁵	845.491 2	-0.93	799.490 8, 637.432 5, 475.379 5, 161.046 1	C₄₂H₇₂O₁₄	Pseudoginsenoside F11	RS	Saponin	[12]
94	12.36	[M+H]⁺	3.2×10⁴	314.138 4	0.91	297.100 7, 178.051 6, 148.053 5	C₁₈H₁₉NO₄	N-trans-Feruloyl-tyramine	SCP	Organic Acid	[32]
95	12.38	[M+HCOO]^－	5.7×10⁴	493.228 0	2.13	447.225 4, 315.181 3, 161.046 5	C₂₁H₃₆O₁₀	Shionoside A or isomer	CX	Monoterpene	[17]
96^#	12.38	[M-H]^－	1.2×10⁴	651.227 7	2.68	475.181 1, 193. 049 6, 175.039 3	C₃₁H₄₀O₁₅	Martynoside	SDH	Phenylethanoid	[30]
97	12.49	[M+HCOO]^－	2.4×10⁴	505.228 0	2.08	459.223 3, 417.175 2, 373.092 1, 149.024 1	C₂₂H₃₆O₁₀	Methyl oleate	DG	Other	[17]
98	12.56	[M-H]^－	5.8×10⁴	1 495.456 0	0.52	1 349.402 8, 1 203.363 6, 845.918 1, 655.182 0, 440.273 5, 307.086 1, 145.031 9	C₆₇H₈₄O₃₈	Tenuifoliose L	ZYZ	Oligosaccharide Ester	[7]
99^#	12.56	[M-H]^－	4.2×10⁴	1 525.466 5	0.55	1 379.400 2, 1 161.345 1, 673.198 2, 448.991 5, 218.635 7, 145.027 8	C₆₈H₈₆O₃₉	Tenuifoliose F	ZYZ	Oligosaccharide Ester	[7]
100	12.57	[M+HCOO]^－	3.9×10⁵	491.212 7	1.43	447.222 5, 293.088 3, 149.045 3	C₂₁H₃₄O₁₀	(Z)-(1S, 5R)-β-Pinen-10-yl-β-vicianoside	CX	Monoterpene	[10]
101	12.74	[M-H]^－	3.0×10⁴	1 265.375 7	1.62	1 119.338 8, 955.283 8, 719.713 1, 502.729 9, 306.080 8, 145.030 3	C₅₇H₇₀O₃₂	Tenuifoliose K	ZYZ	Oligosaccharide Ester	[7]
102	12.85	[M+H]⁺	1.2×10⁴	239.091 2	0.84	221.081 0, 190.063 3, 163.039 0	C₁₂H₁₄O₅	E-3, 4, 5-Trimethoxycinnamic acid	CX	Organic Acid	[10]
103	12.89	[M-H]^－	2.1×10⁵	767.240 4	0	529.157 8, 367.103 3, 205.051 2, 113.024 2	C₃₅H₄₄O₁₉	Tenuifoliside C	ZYZ	Oligosaccharide Ester	[7]
104^#	13.06	[M-H]^－	3.3×10³	309.086 3	2.21	263.081 4	C₁₇H₁₂N₂O₄	Flazin	SCP	Alkaloid	[32]
105	13.06	[M-H]^－	1.3×10⁵	1 295.387 6	0.55	1 119.344 2, 997.306 5, 753.221 8, 429.123 2, 307.084 3, 145.030 4	C₅₈H₇₂O₃₃	Tenuifoliose C	ZYZ	Oligosaccharide Ester	[7]
106	13.22	[M+HCOO]^－	1.1×10⁴	329.102 4	2.01	271.045 4, 203.031 2, 187.040 8	C₁₇H₁₆O₄	Pabulenol	SCP	Other	[34]
107	13.27	[M-H]^－	2.0×10⁴	1 397.621 3	1.26	1 308.382 7, 1 162.344 1, 960.932 7, 719.248 9, 425.301 1, 304.185 2, 173.691 6	C₆₄H₁₀₂O₃₃	Arillatanoside C	ZYZ	Saponin	[7]
108	13.34	[M+HCOO]^－	1.5×10⁵	1 353.393 9	-0.08	1 307.389 3, 1 161.3512, 1 015.313 6, 795.2312, 631.184 6, 528.951 4, 145.030 5	C₅₉H₇₂O₃₃	Tenuifoliose J	ZYZ	Oligosaccharide ester	[7]
109	13.55	[M-H]^－	1.8×10⁵	1 337.399 4	-0.39	1 161.350 0, 997.297 8, 731.222 3, 631.169 6, 307.081 2, 175.041 2	C₆₀H₇₄O₃₄	Tenuifoliose B	ZYZ	Oligosaccharide ester	[7]
110^#	13.68	[M+HCOO]^－	2.1×10³	971.481 6	4.24	731.478 1, 629.367 6, 455.354 4, 205.072 2, 163.060 2	C₄₇H₇₄O₁₈	Pseudoginsenoside Rt1	RS	Saponin	[6]
111	13.75	[M-H]^－	1.5×10⁴	203.071 4	0	174.032 9, 173.024 1, 160.016 9, 145.030 2, 132.022 8, 106.042 9	C₁₂H₁₂O₃	Senkyunolide B	DG/CX	Phthalide	[17]
112	13.78	[M-H]^－	1.4×10⁵	711.213 9	0.40	665.209 8, 543.173 7, 427.124 6, 237.078 0, 121.029 9	C₃₂H₄₀O₁₈	Telephiose C	SCP	Other	[34]
113^#	13.83	[M-H]^－	2.3×10⁴	1 235.568 2	-3.11	1 103.307 0, 879.462 6, 542.569 7, 337.112 4, 225.114 4	C₅₈H₉₂O₂₈	Arillatanoside A	ZYZ	Saponin	[7]
114^#	13.85	[M+HCOO]^－	5.1×10⁴	507.243 0	3.35	461.238 7, 368.996 9, 265.091 6, 163.061 8	C₂₂H₃₈O₁₀	Shionoside B	CX	Monoterpene	[10]
115	13.98	[M-H]^－	1.5×10⁵	221.081 9	0	177.093 3, 134.034 0, 77.039 6	C₁₂H₁₄O₄	Senkyunolide D or isomer	DG/CX	Phthalide	[17]
116	14.07	[M-H]^－	4.2×10⁵	1 103.527 5	0.43	879.475 4, 775.438 4, 598.524 1, 455.318 3, 337.114 3, 217.073 0	C₅₃H₈₄O₂₄	Polygalaxanthone XXVIII	ZYZ	Flavonoid	[27]
117	14.08	[M-H]^－	1.3×10⁵	221.081 7	1.05	177.093 3, 92.026 8	C₁₂H₁₄O₄	(E)-3-(2, 4, 5-Trimethoxyphenyl) acrylaldehyde	SCP	Other	[34]
118	14.09	[M+H]⁺	3.8×10⁵	189.091 7	-3.67	161.058 8, 143.086 1, 128.061 8, 105.068 9, 91.053 9	C₁₂H₁₂O₂	3-Butylidenephthalide	DG/CX	Phthalide	[18]
119	14.36	[M-H]^－	1.3×10⁵	1 349.399 8	-0.69	1 203.365 2, 1 040.317 1, 795.232 4, 673.201 8, 365.106 8, 145.029 7	C₆₁H₇₄O₃₄	Tenuifoliose H	ZYZ	Oligosaccharide ester	[7]
120	14.41	[M-H]^－	1.5×10⁴	1 367.407 6	1.34	1 191.363 9, 1 089.806 8, 909.287 4, 740.440 1, 383.473 1, 175.038 5	C₆₁H₇₆O₃₅	Tenuifoliose O	ZYZ	Oligosaccharide ester	[7]
121^#	14.48	[M-H]^－	3.3×10³	661.247 9	3.45	493.149 2, 417.212 5	C₃₃H₄₂O₁₄	Azadirachtin H	CX	Monoterpene	[10]
122	14.53	[M+HCOO]^－	8.7×10⁵	629.187 9	-0.51	553.174 9, 431.137 4, 165.056 6, 121.030 4	C₃₀H₃₂O₁₂	Benzoylpaeoniflorin^*	BS	Monoterpene	[36]
123	14.61	[M-H]^－	3.7×10⁵	1 379.411 2	-1.28	1 203.362 7, 1 029.496 5, 642.902 4, 501.774 3, 368.102 1, 274.081 9	C₆₂H₇₆O₃₅	Tenuifoliose A	ZYZ	Oligosaccharide Ester	[7]
124	14.81	[M-H]^－	2.5×10⁵	629.188 5	-1.46	553.173 0, 431.135 4, 267.073 4, 121.030 3	C₃₁H₃₄O₁₄	Mudanpioside B	BS	Monoterpene	[14]
125	15.01	[M+HCOO]^－	5.1×10⁵	845.4903	-0.13	799.489 2, 637.437 1, 475.382 0, 310.329 5, 161.046 8	C₄₂H₇₂O₁₄	Ginsenoside Rg₁^*	RS	Saponin	[11]
126	15.13	[M+H]⁺	4.8×10²	281.247 7	-0.69	245.225 8, 97.101 3	C₁₈H₃₂O₂	Linoleic acid	DG	Organic Acid	[17]
127	15.18	[M-H]^－	5.8×10⁴	355.118 2	1.44	296.108 2, 159.045 6	C₂₀H₂₀O₆	Coniferyl ferulate	DG/CX	Other	[18]
128	15.46	[M+HCOO]^－	2.6×10⁵	815.479 1	0.91	769.479 1, 637.434 4, 475.380 3, 366.176 7, 161.046 4	C₄₁H₇₀O₁₃	Ginsenoside F5	RS	Saponin	[6]
129^#	15.52	[M+HCOO]^－	1.9×10³	815.480 5	-0.80	769.475 9, 637.433 9, 475.380 3, 366.176 7, 161.046 4	C₄₁H₇₀O₁₃	Notoginsenoside R2	RS	Saponin	[12]
130^#	15.84	[M+HCOO]^－	4.8×10³	1 285.640 1	2.57	1 107.593 3, 945.540 7, 783.497 6, 621.436 8, 459.380 8	C₅₉H₁₀₀O₂₇	Ginsenoside Ra₃	RS	Saponin	[10]
131	15.92	[M-H]^－	1.8×10⁵	679.370 4	-0.73	635.384 8, 455.318 8, 425.3062	C₃₆H₅₆O₁₂	Tenuifolin^*	ZYZ	Saponin	[7]
132	15.92	[M+HCOO]^－	1.8×10⁵	1 153.600 6	0.47	1 107.601 2, 945.548 7, 783.487 2, 621.434 7, 459.384 5, 323.100 9, 179.056 6	C₅₄H₉₂O₂₃	Ginsenoside Rb₁	RS	Saponin	[12]
133	16.00	[M+HCOO]^－	2.1×10⁵	829.496 1	-0.73	783.491 0, 637.433 7, 475.378 9, 262.979 3, 161.046 3	C₄₂H₇₂O₁₃	Ginsenoside Rg₂^*	RS	Saponin	[11]
134	16.12	[M+HCOO]^－	1.7×10⁵	683.437 3	0.42	637.435 5, 475.379 6, 329.231 7, 101.023 5	C₃₆H₆₂O₉	Ginsenoside Rh₁	RS	Saponin	[12]
135	16.15	[M-H]^－	1.7×10⁵	1 193.595 6	0.38	1 149.608 8, 945.539 2, 783.489 1, 621.439 0, 323.09 44, 179.056 9	C₅₇H₉₄O₂₆	Malonyl-ginsenoside Rb₁	RS	Saponin	[12]
136	16.17	[M-H]^－	6.1×10⁵	329.233 6	-0.77	229.144 6, 211.134 2, 171.103 0, 139.112 5	C₁₈H₃₄O₅	Tianshic acid	CX	Organic Acid	[17]
137	16.29	[M+HCOO]^－	1.6×10⁵	1 123.590 1	0.42	1 077.588 4, 945.539 7, 783.489 5, 621.438 1, 149.045 4	C₅₃H₉₀O₂₂	Ginsenoside Rc	RS	Saponin	[12]
138^#	16.29	[M+HCOO]^－	9.4×10³	1 255.631 2	1.30	1 233.625 1, 467.136 3	C₅₈H₉₈O₂₆	Ginsenoside Ra₁	RS	Saponin	[12]
139	16.32	[M-H]^－	5.2×10⁵	207.103 1	-2.09	163.113 6, 161.094 4, 85.065 8	C₁₂H₁₆O₃	Senkyunolide G	DG/CX	Phthalide	[18]
140	16.42	[M-H]^－	3.4×10⁵	955.490 6	0.21	793.436 5, 731.437 3, 613.372 7 569.385 9, 455.351 3	C₄₈H₇₆O₁₉	Ginsenoside Ro	RS	Saponin	[12]
141	16.47	[M+H]⁺	1.4×10⁴	191.107 2	-2.85	173.095 6, 145.100 9, 135.043 8, 117.068 9, 91.053 8	C₁₂H₁₄O₂	n-Butylphthalide^*	DG/CX	Phthalide	[17]
142	16.48	[M+HCOO]^－	1.4×10⁵	683.437 8	-0.31	637.436 7, 475.379 3, 1161.046 4, 101.023 5	C₃₆H₆₂O₉	Ginsenoside F1	RS	Saponin	[12]
143	16.53	[M-H]^－	6.5×10⁴	1 163.583 2	1.97	1 119.601 7, 915.525 2, 783.490 0, 590.037 1, 376.585 9, 149.047 1	C₅₆H₉₂O₂₅	Malonylginsenoside Rc	RS	Saponin	[12]
144	16.65	[M+HCOO]^－	2.0×10⁵	1 123.590 1	0.42	1 077.587 7, 946.541 4, 783.494 5, 521.780 6, 459.384 5, 149.046 5	C₅₃H₉₀O₂₂	Ginsenoside Rb₂	RS	Saponin	[12]
145	17.10	[M-H]^－	6.2×10⁵	205.087 6	-2.84	161.092 8, 106.049 2, 83.050 9, 77.039 6	C₁₂H₁₄O₃	Senkyunolide F	DG/CX	Phthalide	[17]
146	17.21	[M-H]^－	2.8×10⁴	375.183 6	-6.10	245.086 3, 191.076 1	C₂₁H₂₈O₆	Ligraminol D	SCP	Other	[34]
147	17.23	[M-H]^－	3.2×10⁴	1 617.696 4	0.13	1 385.149 9, 1 048.084 7, 726.871 8, 419.879 0, 224.625 9	C₇₆H₁₁₄O₃₇	Onjisaponin R	ZYZ	Saponin	[7]
148	17.41	[M+HCOO]^－	2.5×10⁵	991.548 1	0.22	945.546 6, 783.489 5, 621.436 0, 511.699 6, 161.046 0	C₄₈H₈₂O₁₈	Ginsenoside Rd	RS	Saponin	[11]
149	17.54	[M+H]⁺	3.5×10³	251.164 0	0.47	233.154 3, 151.071 6, 135.042 4	C₁₅H₂₂O₃	Isocalamediol	SCP	Monoterpene	[32]
150	17.56	[M-H]^－	1.9×10⁴	1 031.541 1	2.07	987.557 0, 945.546 4, 765.478 6, 621.443 3, 395.521 2, 161.047 6	C₅₁H₈₄O₂₁	Malonyl-ginsenoside Rd	RS	Saponin	[12]
151	17.64	[M-H]^－	1.5×10⁴	891.254 7	1.96	811.208 1, 655.187 9, 551.137 1, 301.102 5	C₄₁H₄₈O₂₂	Tenuifoliside E	ZYZ	Oligosaccharide ester	[7]
152^#	17.69	[M-H]^－	4.6×10³	297.170 1	2.18	261.146 3, 253.180 2	C₁₆H₂₆O₅	2, 4, 5-Trimethoxyl-2′-butoxy-1, 2-phenyl propandiol	SCP	Other	[32]
153^#	17.91	[M-H]^－	4.0×10⁴	1 571.692 4	-0.80	1 253.118 4, 1 030.617 1, 701.769 5, 587.467 4, 439.649 9, 198.448 4	C₇₅H₁₁₂O₃₅	Onjisaponin B	ZYZ	Saponin	[7]
154	17.94	[M-H]^－	1.4×10⁵	203.072 0	-3.11	174.033 1, 173.025 0, 160.017 1, 145.032 9, 132.022 4, 117.035 1, 104.027 7, 92.028 0	C₁₂H₁₂O₃	Senkyunolide C	DG/CX	Phthalide	[17]
155	17.95	[M+H]⁺	6.1×10⁴	279.159 3	-0.77	261.146 2, 233.153 6, 191.106 7, 105.033 8, 71.048 8	C₁₆H₂₂O₄	Senkyunolide M	DG/CX	Phthalide	[18]
156^#	18.12	[M+HCOO]^－	3.5×10⁴	1 587.686 9	-0.53	1 455.641 4, 964.826 6, 676.245 8, 425.302 5, 237.078 2	C₇₄H₁₁₀O₃₄	Onjisaponin H	ZYZ	Saponin	[7]
157	18.17	[M-H]^－	3.5×10⁴	1 587.693 2	-4.5	1 455.641 4, 1 087.742 2, 676.245 8, 425.305 2, 237.078 2	C₇₅H₁₁₂O₃₆	Onjisaponin F	ZYZ	Saponin	[7]
158^#	18.32	[M-H]^－	4.3×10²	283.061 9	-2.48	268.037 2, 240.040 4, 135.007 8	C₁₆H₁₂O₅	Calycosin^*	BS	Flavonoid	[28]
159	18.36	[M-H]^－	2.2×10⁵	203.072 2	-4.10	174.032 9, 159.081 9, 131.051 1, 130.042 9, 91.021 1	C₁₂H₁₂O₃	Senkyunolide E	DG/CX	Phthalide	[17]
160	18.55	[M+H]⁺	7.4×10⁴	209.117 3	-0.38	194.091 2, 168.075 6, 153.051 5	C₁₂H₁₆O₃	β-Asarone	SCP	Other	[32]
161^#	18.60	[M-H]^－	5.3×10³	793.439 4	-1.79	613.376 9, 455.354 4, 311.220 2, 89.025 1	C₄₂H₆₆O₁₄	Zingibroside R1	RS	Saponin	[12]
162	18.64	[M+H]⁺	1.6×10⁶	193.123 1	-4.11	175.111 9, 147.117 1, 137.060 2, 93.069 8	C₁₂H₁₆O₂	Senkyunolide A^*	DG/CX	Phthalide	[24]
163	18.69	[M+HCOO]^－	1.6×10⁵	665.428 0	-1.47	619.422 4, 493.410 2, 327.752 8, 161.045 2	C₃₆H₆₀O₈	Ginsenoside Rh₄	RS	Saponin	[12]
164	18.79	[M+H]⁺	1.3×10⁵	209.117 3	-0.38	194.091 3, 179.067 4, 153.051 6	C₁₂H₁₆O₃	α-Asarone	SCP	Other	[32]
165	18.85	[M+HCOO]^－	5.2×10⁵	829.496 1	-0.73	783.491 0, 621.434 8, 459.381 7, 161.046 3	C₄₂H₇₂O₁₃	Ginsenoside Rg₃	RS	Saponin	[10]
166^#	18.90	[M+HCOO]^－	8.1×10³	323.185 5	2.78	239.128 6, 209.115 1, 171.100 8	C₁₇H₂₆O₃	2-Acetoxyacorenone	SCP	Monoterpene	[32]
167	19.14	[M+H]⁺	3.0×10⁵	191.106 9	-1.28	173.095 7, 163.111 5, 145.100 9, 117.070 1	C₁₂H₁₄O₂	(E)-Ligustilide	DG/CX	Phthalide	[17]
168	19.23	[M+H]⁺	9.1×10²	315.253 5	-1.63	185.117 3, 135.111 2, 121.101 0	C₁₈H₃₄O₄	Dibutyl sebacate or isomer	DG	Other	[17]
169	19.37	[M+HCOO]^－	1.7×10⁴	871.504 4	1.90	825.504 5, 783.491 4, 621.435 7, 447.037 8, 252.047 8	C₄₄H₇₄O₁₄	Ginsenoside Rs₃	RS	Saponin	[12]
170	19.39	[M+H]⁺	6.3×10⁵	191.107 2	-2.85	173.095 7, 145.100 9, 117.070 1, 105.070 2, 91.053 7, 79.053 8	C₁₂H₁₄O₂	(Z)-Ligustilide^*	DG/CX	Phthalide	[25]
171	19.69	[M+H]⁺	9.9×10³	165.090 8	1.59	137.059 3, 124.051 2, 105.069 2	C₁₀H₁₂O₂	Eugenol	BS	Phenylethanoid	[33]
172	19.76	[M+HCOO]^－	1.3×10⁵	811.483 8	1.39	619.422 9, 457.370 7	C₄₂H₇₀O₁₂	Ginsenoside Rg₆	RS	Saponin	[12]
173	19.86	[M+H]⁺	4.4×10³	401.194 5	3.40	371.185 0, 233.113 9, 203.104 4, 181.082 3	C₂₃H₂₈O₆	Ligraminol C	DG	Other	[17]
174	20.13	[M+HCOO]^－	4.8×10³	667.441 6	1.61	621.436 0, 459.387 2	C₃₆H₆₂O₈	Ginsenoside CK	RS	Saponin	[12]
175	20.33	[M+H]⁺	1.4×10⁵	209.117 3	-0.38	194.091 2, 168.075 6, 151.071 5	C₁₂H₁₆O₃	γ-Asarone	SCP	Other	[32]
176	20.44	[M+H]⁺	1.7×10³	277.144 1	1.56	261.146 1, 233.153 5, 191.106 7, 105.033 8, 71.048 8	C₁₆H₂₂O₄	Senkyunolide Q	DG/CX	Phthalide	[17]

基于前离子选择的UHPLC-Q-TOF-MS/MS技术快速筛查加味定志丸中的化学成分

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魏祖英 ¹^,²^,^# , 方聪 ¹^,²^,³^,^# , 陈奎 ¹^,² , 杨浩澜 ¹^,² , 刘洁 ²^,⁴ , 贾志鑫 ²^,⁴ , 李月婷 ¹^,² , 肖红斌 ²^,⁴^,^*

药学学报 | 研究论文 2024,59(8): 2350-2364

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药学学报 | 研究论文 2024, 59(8): 2350-2364

基于前离子选择的UHPLC-Q-TOF-MS/MS技术快速筛查加味定志丸中的化学成分

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魏祖英¹^,²^,^#, 方聪¹^,²^,³^,^#, 陈奎¹^,², 杨浩澜¹^,², 刘洁²^,⁴, 贾志鑫²^,⁴, 李月婷¹^,², 肖红斌²^,⁴^,^*

作者信息

1.北京中医药大学中药学院, 北京 100029

2.北京中医药大学中药分析与转化研究中心, 北京 100029

3.江西中医药大学, 江西南昌 330000

4.北京中医药大学北京中医药研究院, 北京 100029

通讯作者:

^*肖红斌, Tel: 86-10-53911883, E-mail: hbxiao@163.com

Rapid screening the chemical components in Jiawei Dingzhi pills using precursor ion selection UHPLC-Q-TOF-MS/MS

Zu-ying WEI¹^,², Cong FANG¹^,²^,³, Kui CHEN¹^,², Hao-lan YANG¹^,², Jie LIU²^,⁴, Zhi-xin JIA²^,⁴, Yue-ting LI¹^,², Hong-bin XIAO²^,⁴^,^*

Affiliations

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

2. Research Center for Chinese Medicine Analysis and Transformation, Beijing University of Chinese Medicine, Beijing 100029, China

3. Jiangxi University of Chinese Medicine, Nanchang 330000, China

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

出版时间: 2024-08-12 doi: 10.16438/j.0513-4870.2024-0115

文章导航

摘要

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本研究建立一种基于前离子选择(precursor ion selection, PIS) 采集策略的超高效液相色谱-四极杆-飞行时间质谱(UHPLC-Q-TOF-MS) 分析方法, 全面快速筛查加味定志丸(Jiawei Dingzhi pills, JWDZP) 中成分。利用在线数据库和文献统计复方药味的化学成分, 共计1 921个, 经来源互证、统一成分名称、合并多药味归属成分、去掉弱极性分子后, 构建了包含450个成分的JWDZP化学成分数据库。采用Acquity UPLC HSS T3柱(100 mm × 2.1 mm, 1.8 μm), 以0.1%甲酸水(A)-乙腈(B) 为流动相, 流速0.35 mL·min^-1, 柱温35 ℃, 电喷雾离子源, 在正、负离子模式下基于PIS采集策略采集质谱数据, 通过精确分子量匹配筛查数据库中的化学成分, 利用其特征碎片离子、中性丢失、文献质谱数据比对进行结构确认, 部分化合物利用对照品进行确认。共从JWDZP提取物中筛查到176个化合物, 其中26个化合物经过对照品比对确认。这些化合物包含君药成分96个, 共流出离子强度低成分34个。本研究建立的PIS-UHPLC-Q-TOF-MS/MS方法能快速全面筛查JWDZP中的化学成分, 增强对共流出离子强度低成分的筛查, 为JWDZP物质基础研究提供依据。

关键词

加味定志丸 / UHPLC-Q-TOF-MS/MS / 化学成分 / 前离子选择采集 / 结构鉴定

Abstract

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A precursor ion selection (PIS) based ultra high performance liquid chromatography-quadrupole time of flight mass spectrometry (UHPLC-Q-TOF-MS) analytical method was used to screen the chemical components in Jiawei Dingzhi pills (JWDZP) comprehensively and rapidly. To compile the components of the compound medicine, a total of 1 921 components were found utilizing online databases and literature. After verifying the sources, unifying the component names, merging the multi-flavor attributed components, and removing the weak polar molecules, 450 components were successfully retained. The Acquity UPLC HSS T3 column (100 mm × 2.1 mm, 1.8 μm) was used, with a 0.1% formic acid water (A)-acetonitrile (B) as the mobile phase. The flow rate was 0.35 mL·min^-1, the column temperature was 35 ℃, and an electrospray ion source was used. Data was collected with the PIS strategy in both positive and negative ion modes. Compounds were screened through matching accurate molecular weight of the database, and identified according to MS/MS data (characteristic fragment ions and neutral loss), with comparison of reference. Some compounds were confirmed using standard products. A total of 176 compounds were screened out in the extract of JWDZP, among which 26 compounds were confirmed by standard products. These compounds include 96 components from the sovereign drug, and 34 coefflux components with low ion intensity. The PIS-UHPLC-Q-TOF-MS/MS method established in this study can quickly and comprehensively screen the chemical components of JWDZP, which enhanced the screening rate of components with co-elution compounds of low ion intensities and provided a basis for the study of the material foundation of JWDZP.

Key words

Jiawei Dingzhi pill / UHPLC-Q-TOF-MS/MS / chemical component / precursor ion selection / structural identification

引用本文

魏祖英, 方聪, 陈奎, 杨浩澜, 刘洁, 贾志鑫, 李月婷, 肖红斌. 基于前离子选择的UHPLC-Q-TOF-MS/MS技术快速筛查加味定志丸中的化学成分. 药学学报, 2024 , 59 (8) : 2350 -2364 . DOI: 10.16438/j.0513-4870.2024-0115

Zu-ying WEI, Cong FANG, Kui CHEN, Hao-lan YANG, Jie LIU, Zhi-xin JIA, Yue-ting LI, Hong-bin XIAO. Rapid screening the chemical components in Jiawei Dingzhi pills using precursor ion selection UHPLC-Q-TOF-MS/MS[J]. Acta Pharmaceutica Sinica, 2024 , 59 (8) : 2350 -2364 . DOI: 10.16438/j.0513-4870.2024-0115

正文

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加味定志丸(Jiawei Dingzhi pills, JWDZP) 出自《古今医鉴》 (陈白野方), 由当归、制远志、人参、川芎、白芍、熟地黄和石菖蒲7味药组成, 方中当归补养营血, 人参大补五脏元气兼有安神益智之效, 制远志安神益智, 三药共为君药; 川芎活血行气, 白芍养血敛阴, 熟地黄滋阴补血, 共为臣药; 石菖蒲开窍豁痰, 为佐药, 各药味相辅相成, 发挥养心益智、治健忘的功效^[1]。课题组前期研究表明, JWDZP具有显著改善脑缺血大鼠的学习记忆能力、脑血流量等效应, 具有深入研发的价值, 详见专利(专利号: 2021115851139)。但其发挥效应的药效物质基础尚不明确, 因此, 对JWDZP中的化学成分进行全面、准确分析具有必要性。

超高效液相色谱-高分辨质谱联用技术现已成为全面解析中药复杂成分的最常用手段, 其鉴定的全面性及准确度依赖于高质量的质谱数据采集和后处理策略。目前, 超高效液相色谱和细粒径的超高压色谱柱被广泛用于化合物的色谱分离, 以达到最优分离效果。此外, 自动的数据依赖型采集, 是最常见的数据采集技术^[2], 可以同时获得被测化合物的一级质谱数据信息及碎片信息, 且较窄的m/z窗口减少了干扰离子, 提供了较高质量的碎片信息。在这种模式下, 母离子的选择主要基于离子信号强度, 强度高的离子更容易被选中, 而分析复杂样品时, 一些含量低或电离强度低的离子与强度高的离子共流出, 这些有价值的离子未被选中, 造成漏检。因此, 为了获得足够多的质谱信息用于全面快速筛查JWDZP中的化学成分, 本研究提出基于PIS的采集策略, 对同一色谱峰中的多个母离子进行靶向的MS/MS采集。在质谱数据后处理方面, 已发展出非常多的数据鉴定策略, 广泛应用的主要有质量亏损过滤(mass defect filtering, MDF)^[3]、特征离子^[4]及中性丢失过滤(neutral loss filtering, NLF)^[5]。中药复方含有的成分数量繁多, 但成分类型的种类有限, 同类型成分具有相似的裂解规律。通过对照品二级质谱数据结合文献报道, 总结各类型化合物的质谱裂解规律(特征碎片离子及中性丢失), 实现化合物的结构解析。

综上, 本研究利用UHPLC-Q-TOF-MS/MS技术结合PIS采集策略, 对JWDZP中化学成分实现全面采集MS/MS质谱数据。在此基础上, 与自建化学成分数据库中的精确分子量匹配, 实现初步识别化合物, 进一步解析碎片归属结构, 辅以诊断特征规律(特征离子及中性丢失) 推测质谱碎裂、经对照品谱图对比和文献验证等确证结构, 实现全面、快速筛查JWDZP中的化学成分, 为其物质基础的阐明提供参考。

材料与方法

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仪器 UHPLC-Q-TOF-MS液质联用系统由美国Agilent公司的1290分析型高效液相色谱仪(自动进样器、柱温箱、二元泵、在线脱气设备、DAD检测器) 与6550四极杆-飞行时间质谱仪(配备Dual AJS ESI源) 组成; Milli Q超纯水机(美国Millipore公司); KQ-500E超声波清洗器(昆山市超声仪器有限公司); ME204万分之一电子天平[梅特勒-托利多仪器(上海) 有限公司]; XS105十万分之一电子天平[梅特勒-托利多仪器(上海) 有限公司]。

饮片人参(产地: 吉林, 批号: 2002085)、当归(产地: 甘肃, 批号: 2009025)、制远志(产地: 山西, 批号: 2001022)、白芍(产地: 安徽, 批号: 2103065)、石菖蒲(产地: 安徽, 批号: 2004044)、熟地黄(产地: 河南, 批号: 2001121)、川芎(产地: 四川, 批号: 2009002) 均购自北京太洋树康药业有限公司, 由北京中医药大学王学勇教授鉴定, 检验结果均符合中国药典(2020年版, 一部) 各药材饮片项下的有关规定, 存储于北京中医药大学中药分析与转化中心实验室。

试剂本实验共使用26个对照品, 柠檬酸(8, 批号: RFS-N01211812016)、没食子酸(12, 批号: RFS-M01711812016)、地黄苷D (17, 批号: RFS-D08402007022)、绿原酸(25, 批号: RFS-D08402007022)、新绿原酸(36, 批号: RFS-X01401903029)、香草酸(39, 批号: X-030-170322)、苯甲酸(40, 批号: RFS-B01311812016)、隐绿原酸(42, 批号: RFS-Y06701903029)、咖啡酸(44, 批号: RFS-K003-181216)、氧化芍药苷(50, 批号: MUST-17032810)、芍药苷(52, 批号: RFS-S01002101022)、阿魏酸(60, 批号: A-002-161216)、远志𠮿酮III (63, 批号: RFS-Y05511809007)、洋川芎内酯I (72, 批号: RFS-Y08501904030)、毛蕊花糖苷(77, 批号: RFS-M-01102103019)、3, 6′-二芥子酰基蔗糖(79, 批号: RFS-F01311804026)、洋川芎内酯H (80, 批号: RFS-Y08411905027)、毛蕊异黄酮苷(87, 批号: 111920-201606)、苯甲酰芍药苷(122, 批号: RFS-B02402011030)、人参皂苷Rg1 (125, 批号: RFS-R01502011030)、细叶远志皂苷(131, 批号: RFS-X00911801003)、人参皂苷Rg2 (133, 批号: RFS-R01602203015)、正丁基苯酞(141, 批号: RFS-Z03702008005)、毛蕊异黄酮(158, 批号: M-021-170517)、洋川芎内酯A (162, 批号: RFS-Y08301903021)、藁本内酯(170, 批号: RFS-G01001909016) 购自成都瑞芬思生物科技有限公司, 以上化合物经HPLC检测, 纯度均 > 98%。

质谱级甲醇、乙腈(美国Thermo Fisher公司); 甲酸(美国Honeywell公司); 超纯水由超纯水仪Milli-Q (美国Millipore公司) 制得。JWDZP样品为实验室制备得到。

JWDZP提取物及对照品溶液制备

JWDZP提取物制备取熟地黄120 g、当归120 g、川芎120 g、白芍120 g、人参120 g、石菖蒲80 g、制远志80 g, 合计760 g, 加入8倍量的水浸泡过夜后加热回流提取三次, 每次1 h, 合并滤液, 滤过, 减压浓缩至1 g (生药量)·mL^-1。移取JWDZP提取物10 mL, 加入50%甲醇100 mL, 即稀释至100 mg (生药量)·mL^-1, 经0.22 μm微孔滤膜过滤, 得续滤液。

26个对照品混合溶液制备称取各对照品适量, 精密称定, 加甲醇配制成1 mg·mL^-1的各对照品储备液, 分别移取各对照品储备液10 μL, 加入50%甲醇补足到1 mL, 即得10 μg·mL^-1的混合对照品溶液, -20 ℃保存, 备用。

色谱条件 色谱柱: ACQUITY UPLC HSS T3柱(100 mm × 2.1 mm, 1.8 μm, 美国Waters公司); 流动相: 0.1%甲酸水(A)-乙腈(B); 梯度洗脱: 0~3 min, 5%~10% B; 3~16 min, 10%~40% B; 16~20 min, 40%~90% B; 20~25 min, 90% B; 流速: 0.35 mL·min^-1; 柱温: 35 ℃; 进样体积: 2 µL。

质谱条件 干燥气温度: 150 ℃; 干燥气流速: 11 L·min^-1; 喷雾气压力: 35 psi; 鞘气温度: 250 ℃; 鞘气流速: 11 L·min^-1; 喷嘴电压: 500 V (ESI+)/1 000 V (ESI-); 毛细管出口电压: 380 V; 毛细管电压: 4 000 V (ESI+)/3 500 V (ESI-); 离子漏斗RF高电压150 V (ESI+)/90 V (ESI-); 离子漏斗RF低电压60 V (ESI+)/50 V (ESI-)。MS扫描范围: m/z 100~1 700, MS/MS扫描范围: m/z 50~1 500。

基于PIS的MS/MS数据采集策略的设置选择最大前离子数为3, 采用动态排除设置, 一个循环(32 ms) 中一个母离子只采集一张质谱图, 隔90 ms后释放该离子, 再进行第二次采集, 前离子电荷价态为1。设置碰撞能量分别为10、20、40 eV。

JWDZP化学成分数据构建及成分筛查流程

构建化学成分数据库从TCMSP (https://old.tcmsp-e.com/tcmsp.php)、ETCM (http://www.tcmip.cn/ETCM/index.php/)、HERB (http://herb.ac.cn/) 在线数据库和Web of Science (www.webofknowledge.com)、CNKI (http://www.cnki.net) 文献检索库中, 收集JWDZP复方中7味药材(即: 当归、制远志、人参、川芎、白芍、熟地黄和石菖蒲) 鉴定或分离的化学成分, 总计1 921个。对上述1 921个成分进行筛选与整理, 去掉单一来源的成分(即: 一个化合物至少同时出现在2种数据库或文献中)、整理同物异名成分(如: 3-butylphthalide、3-butylideneisobenzofuran-1 (3H)-one等都统一成n-butylphthalide)、合并本方不同药味来源成分(如: 当归和川芎两种药材含有许多相同的化学成分)、剔除极性小分子(如萜烯、烯醇等挥发油类成分不容易存在水提取物中) 后, 共得到450个成分, 导入PCDL (Personal Compound Database Library) Manager软件(Agilent Technologies, USA, Version B.07.00) 构建得到JWDZP化学成分数据库[包含化合物名称、化学结构、化学式、精确分子质量、CAS (Chemical Abstract Service) 号、质谱图信息、成分来源的文献等]。另外, 采用混合对照品溶液直接获取了26种化合物的色谱质谱信息, 利用PCDL Manager软件构建26个对照品的数据库, 所构建的对照品数据库包括上述提及的各项信息, 还重点关注对照品的结构特征及高分辨特征碎片离子信息, 将实验得到的结果与化学成分数据库进行对比, 验证化学成分数据库。

总结各类型化合物特征诊断规律 JWDZP复方含有的化合物类型主要为三萜皂苷类、单萜及其苷类、有机酸类、寡糖酯类、苯酞类以及黄酮类。基于对照品高分辨特征碎片离子信息及文献, 总结各类化合物的质谱裂解规律, 详细如下: 三萜皂苷类化合物, 按母核的不同主要分为3种类型: 原人参二醇型、原人参三醇型和齐敦果酸型。在负离子模式下, 原人参二醇型的母核特征碎片离子为m/z 459, 原人参三醇型的母核特征碎片离子为m/z 475, 齐墩果酸型的母核特征碎片离子为m/z 455和425^[6-10]。此外, 含有羧基的原人参二醇型皂苷(丙二酰基酸性人参皂苷) 还会发生中性丢失CO₂和丙二酰基, 也可以用于化学结构辅助分析^{[11, 12]}。单萜及其苷类化合物, 易丢失糖基, 形成高丰度的骨架离子, 同时中性丢失小分子基团如H₂O和CO₂等, 也是此类化合物的诊断特征^{[13, 14]}。芍药苷类似物在负离子模式下产生m/z 121苯甲酸碎片离子和m/z 165蒎烷碎片离子, 为此类化合物的特征离子^[15]。有机酸类化合物, 苯环上有1-2取代的羟基或者甲氧基, 容易中性丢失H₂O、OCH₃、CO^[16-18], 如咖啡酰奎宁酸类似物通常可产生诊断碎片离子m/z 191、173、179^[19]。寡糖酯类化合物以二糖或者五糖母核居多, 主要丢失酰基(乙酰基、苯甲酰基、阿魏酰基、肉桂酰基等)、糖基等^[20-22]。苯酞类化合物容易断裂侧链烯烃, 发生中性丢失CO、H₂O、C₃H₆、C₃H₇和C₄H₈等^[23-25]。黄酮类化合物主要包括远志𠮿酮类和异黄酮类, 远志𠮿酮类以糖苷键断裂为主^{[26, 27]}; 而异黄酮类似物会发生中性丢失CH₃、CO等, C环的RDA裂解也是此类化合物的重要鉴别特征^{[28, 29]}。

化合物初步识别与化学成分数据库中各化合物的精确分子量匹配, 设置筛选标准(mass error < 5 ppm), 初步识别化合物。

化合物鉴定及结构确证对于识别出的化合物, 进一步解析二级质谱碎片的结构信息, 结合文献报道, 推导结构并确定待核查化合物的名称和结构, 部分通过与对照品比对直接确定。另外, 采用诊断特征规律辅助鉴定, 如前文总结的特征离子m/z 459, 可作为原人参二醇型三萜皂苷类化合物的通用标准, 用于快速归属碎片和推测同类成分的裂解规律。在进行化合物推导时, 为尽可能准确, 还考虑了一些其他的质谱裂解规律, 如氮原子数量一般规律等。

本研究提出基于PIS数据采集结合化学成分数据库快速筛查成分的分析策略(图 1)。

结果

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1 化学成分的筛查

从在线数据库和文献中统计到1 921个化合物, 去掉单一来源成分、合并同物异名成分及不同药味来源成分、剔除弱极性小分子后, 最终构建了包含450个化合物的化学成分数据库, 包括以下10类成分, 即71个三萜皂苷、63个萜、41个有机酸、69个寡糖酯、55个苯酞、35个黄酮、17个酚、22个生物碱、13个苯乙醇苷和64个其他类。此外, 选取26个对照品化合物的高分辨质谱信息, 对比数据库筛查得到的结果, 验证了内部数据库的准确性。

本研究以成功筛查到的共流出离子强度低成分个数评估PIS采集方法的优势。对比PIS-MS/MS和auto-MS/MS两种采集方式的化合物数量, PIS-MS/MS采集策略可以多采集34个共流出离子强度低成分(化合物13、15、18、23、24、26、27、31、32、41、56、58、59、65、67、81、90、91、96、99、104、110、113、114、121、129、130、138、152、153、156、158、161、166), 验证了PIS-MS/MS策略在采集共流出色谱峰中低丰度化合物质谱数据的优势。

基于PIS-MS/MS采集数据, 共从JWDZP中快速筛查到176个化合物, 包括33个皂苷、33个单萜及其苷、19个寡糖酯、18个有机酸、16个苯酞、12个黄酮、8个生物碱、7个苯乙醇苷、4个酚和26个其他成分。其中26个化合物与对照品比对鉴定其化学结构。正、负离子模式下样品总离子流图, 见图 2, 最终筛查到的化合物结果和药材归属, 见表 1^{[6, 7, 10-15, 17-19, 22, 24, 25, 27-36]}。

2 三萜皂苷类化合物筛查

与化学成分数据库中化合物的准确分子质量匹配, 进一步解析二级碎片离子并进行结构归属, 与对照品和文献碎片离子对比等, 共从JWDZP中筛查出33个皂苷类化合物(其中8个为共流出离子强度低成分), 全部来自君药人参和制远志。如化合物129, 为共流出强度低成分之一, 保留时间为15.52 min, 负离子模式下检测得到准分子离子m/z 815.480 5 [M+HCOO]^－, 与数据库中人参的主要成分—三七皂苷R2最匹配(表 1, 分子质量匹配误差为0.80 ppm)。在MS/MS谱图中, 存在丢失一分子果糖残基(132 Da) 的碎片离子m/z 637.433 9 [M-H-fru]^－, 进一步丢失一分子葡萄糖残基(162 Da) 产生齐敦果烷型三萜皂苷的特征母核, 即碎片离子m/z 475.380 3 [M-H-fru-glc]^－, 通过文献^[12]对比确认其二级质谱与三七皂苷R2一致, 鉴定化合物129为三七皂苷R2。对照品对比鉴定化合物125和133分别为人参皂苷Rg₁和人参皂苷Rg₂。化合物165的准分子离子m/z 829.496 1 [M+HCOO]^－, 比化合物125少16 Da, 提示少一个O, 母离子丢失1分子葡萄糖残基, 产生碎片离子m/z 621.434 8 [M-H-glc]^－, 再丢失1分子葡萄糖残基, 产生特征母核碎片离子m/z 459.381 7 [M-H-glc-glc]^－, 对比化合物125的2个葡萄糖基缩合成二糖, 确定化合物165的2个葡萄糖基分别占据苷元的2个位置, 对比文献^[10]数据, 鉴定为人参皂苷Rg₃。化合物137的准分子离子m/z 1 123.590 1 [M+HCOO]^－, 主要存在母离子丢失1分子葡萄糖残基和1分子阿拉伯糖残基(132 Da) 的碎片离子m/z 783.489 5 [M-H-glc-ara]^－、碎片离子m/z 621.438 1 [M-H-glc-ara-glc-CH₃]^－、459.381 7 [M-H-glc-ara-glc-CH₃-glc]^－等, 对比文献^[12]数据, 鉴定化合物137为人参皂苷Rc。化合物113准分子离子m/z 1 235.568 2 [M-H]^－, 主要存在碎片离子m/z 1 103.307 0 [M-H-ara]^－、825.462 6 [M-H-ara-xyl]^－、特征碎片离子m/z 455.317 9 [M-H-ara-xyl-glc]^－、特征碎片离子m/z 425.301 1 [M-H-ara-xyl-glc-CH₂O]^－, 通过质谱数据分析及文献^[7], 鉴定化合物113为黄花远志皂苷A。

3 单萜及其苷类化合物筛查

共筛查得到33个单萜类化合物(其中9个为共流出离子强度低成分), 主要来自白芍和熟地黄。如化合物91, 保留时间为12.09 min (与化合物90、92为共流出成分, 图 1), 在负离子模式下检测得到准分子离子m/z 599.174 5 [M-H]^－, 与数据库中白芍的主要成分—苯甲酰氧化芍药苷最匹配(表 1, 分子质量匹配误差为4.20 ppm)。在MS/MS谱图中, 存在丢失一分子葡萄糖的碎片离子m/z 431.136 1 [M-H-glc]^－, 以及特征性蒎环骨架离子m/z 165.058 6和对羟基苯甲酰碎片离子m/z 121.031 4等, 经文献^[14]对比确认其二级质谱与苯甲酰氧化芍药苷一致, 鉴定化合物91为苯甲酰氧化芍药苷。化合物52和122经对照品对比鉴定为芍药苷和苯甲酰芍药苷, 化合物50的准分子离子m/z 541.155 4 [M-H]^－, 存在碎片离子m/z 137.023 1, 即对羟基苯甲酸去质子的碎片, 对比文献^[14], 鉴定为氧化芍药苷。化合物69的准分子离子m/z 631.167 8 [M-H]^－, 存在丢失水和苯甲酸的碎片离子m/z 491.119 0, 碎片离子m/z 169.014 9和121.030 1提示存在没食子酰基, 结合文献^[14]对比, 确定化合物69为没食子酰芍药苷。

4 有机酸类化合物筛查

共筛查得到18个有机酸类化合物(其中1个为共流出离子强度低成分), 主要来自当归和川芎。化合物25、36和42, 保留时间分别为4.16、5.62和5.98 min, 在负离子模式下检测得到准分子离子m/z 353.087 6 [M-H]^－, 与数据库中当归和川芎的主要成分—绿原酸及其异构体最为匹配(表 1, 分子质量匹配误差为0.58 ppm), 在MS/MS谱图中, 存在丢失一分子咖啡酸的特征碎片离子m/z 191.055 2 [M-H-C₉H₆O₃]^－, 丢失一分子奎宁酸的特征碎片离子m/z 179.034 6 [M-H-C₇H₁₀O₅]^－, 以及碎片m/z 173.045 3 [M-H-C₉H₆O₃-H₂O]^－、161.024 5 [M-H-C₇H₁₀O₅-H₂O]^－和135.044 9 [M-H-C₇H₁₀O₅-H₂O-CO₂]^－, 与对照品对比确定化合物25、36和42分别为绿原酸、新绿原酸和隐绿原酸。

5 寡糖酯类化合物筛查

共筛查得到19个寡糖酯类化合物(其中1个为共流出离子强度低成分), 全部来自制远志。如化合物99, 为共流出强度低成分, 保留时间为12.56 min, 在负离子模式下检测得到准分子离子m/z 1 525.466 5 [M-H]^－, 与数据库中制远志的主要成分—远志蔗糖酯F最匹配(表 1, 分子质量匹配误差为0.55 ppm), 在MS/MS谱图中, 主要存在丢失糖基的碎片离子m/z 1 379.400 2 [M-H-rha]^－、1 161.345 1 [M-H-rha-glc]^－、丢失香豆酰基碎片离子m/z 145.027 8 [C₁₀H₉O]^－, 与文献^[7]对比, 其二级质谱与远志蔗糖酯F一致, 鉴定化合物99为远志蔗糖酯F。化合物79的准分子离子m/z 753.224 9 [M-H]^－, 主要存在丢失芥子酸和水的碎片离子m/z 547.168 2 [M-H-C₁₁H₃₀O₄]^－、糖苷键断裂, 失去葡萄糖基和果糖残基的碎片离子m/z 223.062 5 [M-H-sinapic acid-H₂O-glc-fru]^－, 以及芥子酸丢失水的碎片离子m/z 205.052 7 [sinapic acid-H-H₂O]^－, 通过质谱数据分析并结合对照品比对, 鉴定化合物79为3, 6′-二芥子酰基蔗糖。

6 苯酞类化合物筛查

共筛查得到16个苯酞类化合物(其中1个为共流出离子强度低成分), 全部来自当归和川芎。如化合物81, 为共流出强度低成分, 保留时间为10.89 min, 在负离子模式下检测得到分子离子峰m/z 225.113 0 [M-H]^－, 与数据库中当归和川芎的主要成分—洋川芎内酯N最匹配(表 1, 分子质量匹配误差为1.03 ppm)。在MS/MS谱图中, 存在特征碎片离子m/z 181.123 7 [M-H-CO₂]^－、163.112 8 [M-H-H₂O]^－、124.052 8 [M-H-CO₂-C₄H₉]^－, 提示结构中有饱和正丁基, 与文献对比^[18]其二级质谱与洋川芎内酯N一致, 鉴定化合物81为洋川芎内酯N。化合物141、167与170的准分子离子均为m/z 191.106 7, 且产生相同碎片离子[M+H-H₂O]⁺、[M+H-CO]⁺和[M+H-C₄H₈]⁺, 说明三个化合物为立体异构体。经过标准品对比确定化合物141为正丁基苯酞、170为(Z)-藁本内酯, 而化合物167的保留时间比化合物170稍短, 鉴定167为(E)-藁本内酯^[17]。化合物162的母离子和碎片离子都比化合物170小2 Da (2H), 说明化合物162为饱和正丁基的烷基苯酞^[24], 鉴定为洋川芎内酯A。

7 黄酮类化合物筛查

共筛查得到12个黄酮类化合物(其中4个为共流出离子强度低成分), 主要来自白芍和制远志。如化合物158, 为共流出强度低成分之一, 保留时间为18.32 min, 在负离子模式下检测得到准分子离子m/z 283.061 9 [M-H]^－, 与数据库中白芍主要成分—毛蕊异黄酮最匹配(表 1, 分子质量匹配误差为2.48 ppm), 在MS/MS谱图中, 存在中性丢失CH₃、CO₂的碎片离子m/z 268.037 2 [M-H-CH₃]^－、240.040 4 [M-H-CO₂]^－, 而m/z 135.007 8为黄酮类化合物发生RDA裂解的特征碎片之一, 经过对照品对比, 鉴定化合物158为毛蕊异黄酮。化合物87的准分子离子m/z 447.128 4, 碎片离子m/z 285.067 2 [M+H-glc]⁺说明含有葡萄糖基, 经标准品确定化合物87为毛蕊异黄酮苷。

8 酚类化合物筛查

共筛查得到4个酚类化合物(其中1个为共流出离子强度低成分), 主要来自白芍、熟地黄。如化合物37, 在正离子模式下检测得到准分子离子m/z 291.085 1 [M+H]⁺, 与数据库中白芍主要成分—表儿茶素最匹配(表 1, 分子质量匹配误差为4.17 ppm), 在MS/MS谱图中, 碎片离子m/z 167.034 5 [M+H-C₇H₈O₂]⁺、139.038 8 [M+H-C₈H₈O₃]⁺, 提示C环发生了RDA裂解, 分别归属于B^{1, 3-}碎片和A^{1, 3-}碎片, 而碎片离子m/z 127.034 2 [M+H-C₉H₈O₃]⁺, 提示C环1, 4键断裂, 与文献^[33]对比, 其二级质谱与表儿茶素一致, 鉴定化合物37为表儿茶素。

9 生物碱类化合物筛查

生物碱类化合物结构中含N, 氮原子数量一般规律可用于辅助碎片解析与结构归属。共筛查得到8个生物碱类化合物(其中2个为共流出离子强度低成分), 来自熟地黄、人参和石菖蒲。如化合物67, 为共流出强度低成分之一, 保留时间为9.38 min, 在正离子模式下检测得到准分子离子m/z 146.044 9 [M+H]⁺, 与数据库中石菖蒲成分—3-吲哚甲醛最匹配(表 1, 分子质量匹配误差为4.08 ppm), 在MS/MS谱图中, 碎片离子m/z 117.059 5、91.056 6分别归属[M+H-CO]⁺、[M+H-CO-C₂H₂]⁺, 与文献^[32]对比, 其二级质谱与3-吲哚甲醛一致, 鉴定化合物67为3-吲哚甲醛。

10 苯乙醇苷类化合物筛查

共筛查得到7个苯乙醇类化合物(其中3个为共流出离子强度低成分), 主要来自白芍和熟地黄。如化合物58, 保留时间为8.65 min (与化合物56、57为共流出成分, 图 1), 在负离子模式下检测得到准分子离子m/z 799.265 8 [M-H]^－, 与数据库中熟地黄成分—肉苁蓉苷A最匹配(表 1, 分子质量匹配误差为1.02 ppm), 在MS/MS谱图中, 存在丢失甲基和咖啡酰基的碎片离子m/z 623.219 1 [M-H-C₁₀H₉O₃]^－, 咖啡酸脱水的碎片离子m/z 161.024 1 [C₉H₆O₃]^－等, 与文献^[35]对比, 其二级质谱与肉苁蓉苷A一致, 鉴定化合物58为肉苁蓉苷A。

11 其他类化合物筛查

对于碎片离子归属不强、种类较少的化合物, 根据成分数据库准确分子量匹配(mass error < 5 ppm)、文献碎片对比, 共从JWDZP中分析出26个其他类化合物(其中4个为共流出离子强度低成分), 包括氨基酸、没食子酰葡萄糖、细辛醚等, 以白芍和熟地黄成分居多。

讨论

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本研究采用PIS策略, 成功获取了重叠色谱峰中低含量或低电离强度成分的MS/MS数据。从图 2可见, 尽管经过UHPLC分离, 色谱峰重叠仍十分严重, 尽管质谱可以选择母离子并采集质谱裂解信息, 但母离子的选择依赖离子强度, 重叠峰中强度低的母离子可能未被选择。本研究采用的PIS数据采集策略可以有效改善这种情况, 让低丰度前离子被强行选择(高丰度离子被排除而不重复选择), 最终共从JWDZP中筛查出176个化合物, 包括了34个共流出离子强度低成分, 其中6个化合物来自人参、3个化合物来自制远志、5个化合物来自当归或者川芎、8个化合物来自白芍、8个化合物来自熟地黄、4个化合物来自石菖蒲。

JWDZP由当归、制远志、人参、川芎、白芍、熟地黄和石菖蒲组成, 各药材所含化学成分众多, 制剂的整体化学成分更为复杂, 目前尚无文献对其化学成分进行研究报道, 在一定程度上制约了JWDZP的基础研究与临床应用。本研究利用PIS-UHPLC-Q-TOF-MS/MS技术, 实现JWDZP化学成分快速、全面筛查与鉴定, 共筛查出176个成分, 对上述成分进行药材归属, 37个归属于当归(君药)、31个归属于制远志(君药)、28个归属于人参(君药)、归属于君药的成分共计96个, 其余30个归属于白芍、32个归属于川芎、29个归属于熟地黄、16个归属于石菖蒲, 27个为共有成分(其中24个成分为当归、川芎共有, 2个成分为熟地黄、人参共有, 1个成分为白芍、熟地黄共有)。JWDZP中的化学成分, 以君药人参和制远志中的三萜皂苷类成分最为丰富、其次是单萜类和寡糖酯类成分, 这些成分可以通过减轻缺血区小胶质细胞的活化^[37], 升高脑源性神经营养因子(BDNF) 的表达^[38], 提高脑内胆碱能系统功能、抗氧化、降低兴奋性氨基酸水平^[39]等多种途径, 发挥改善血管性痴呆大鼠的神经功能和记忆能力的药效作用, 可能是JWDZP的主要药效物质基础。

传统中药制剂化学物质基础复杂, 自动的数据依赖型采集模式容易遗漏有价值离子的质谱信息, 手动处理质谱原始数据费时费力, 难以挖掘有用的信息。本研究建立的PIS-MS/MS数据采集方法, 具有简便、高效、灵敏的优势, 采用动态排除设置解决了重叠峰中低含量或者低电离强度成分鉴定难的技术问题, 将PIS-MS/MS数据采集方法结合成分数据库匹配、特征碎片离子和中性丢失辅助推测碎裂规律等数据后处理方法, 快速、全面阐明了JWDZP的化学成分, 提供了全面、准确的JWDZP中化学成分信息, 为JWDZP药效物质基础发现及质量控制研究提供了充足的物质基础。

作者贡献: 魏祖英是本文第一作者, 负责数据库构建及文章撰写; 方聪为本文共同第一作者, 负责样品制备及结构鉴定; 陈奎、杨浩澜协助数据库资料收集及实验测试; 刘洁负责实验指导和文章修改; 贾志鑫负责设计实验; 李月婷负责文章修改; 肖红斌为本文通讯作者, 负责实验设计及把关、文章审阅等工作。

利益冲突: 所有作者均声明不存在利益冲突。

基金

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国家自然科学基金面上项目(82173957)
国家自然科学基金青年基金项目(82204599)
国家中医药管理局高水平中医药重点学科(中药分析学) 建设项目(zyyzdxk-2023265)

参考文献

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2024年第59卷第8期

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doi: 10.16438/j.0513-4870.2024-0115

接收时间：2024-02-04
首发时间：2025-11-26
出版时间：2024-08-12

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收稿日期：2024-02-04
修回日期：2024-04-29

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国家自然科学基金面上项目(82173957)

国家自然科学基金青年基金项目(82204599)

国家中医药管理局高水平中医药重点学科(中药分析学) 建设项目(zyyzdxk-2023265)

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1.北京中医药大学中药学院, 北京 100029

2.北京中医药大学中药分析与转化研究中心, 北京 100029

3.江西中医药大学, 江西南昌 330000

4.北京中医药大学北京中医药研究院, 北京 100029

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^*肖红斌, Tel: 86-10-53911883, E-mail: hbxiao@163.com

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2种不同金属材料的力学参数

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

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No.	t_R/min	Precursor ion	Response	Meas m/z	Error/ppm	Fragment ion	Molecular formula	Plausible identification	Source	Category	Reference
1	0.68	[M+HCOO]^－	5.3×10⁴	549.166 0	2.25	503.161 4, 341.109 1, 101.024 5	C₁₈H₃₂O₁₆	Maltotriose	SDH	Other	[30]
2	0.70	[M+H]⁺	1.2×10⁴	133.061 2	-3.24	91.053 6, 87.054 1	C₄H₈N₂O₃	L-Asparagine	DG	Other	[17]
3	0.70	[M-H]^－	2.1×10⁴	175.118 7	1.44	158.092 1, 116.071 3	C₆H₁₄N₄O₂	Arginine	DG	Other	[17]
4	0.71	[M-H]^－	1.1×10⁵	179.055 8	1.74	71.013 8, 63.024 5	C₆H₁₂O₆	Fructose	SDH	Other	[30]
5	0.71	[M-H]^－	5.3×10⁴	195.050 5	2.70	176.900 6, 159.895 2	C₆H₁₂O₇	Gluconic acid	DG	Other	[17]
6	0.93	[M-H]^－	3.3×10⁴	341.107 7	3.62	119.034 2, 89.023 3	C₁₂H₂₂O₁₁	Maltose	SDH	Other	[30]
7	1.00	[M-H]^－	1.3×10⁶	133.014 6	-2.65	115.004 1, 71.014 2	C₄H₆O₅	Malic acid	DG	Organic acid	[17]
8	1.11	[M-H]^－	5.1×10⁶	191.020 2	-2.48	111.002 9, 87.009 1	C₆H₈O₇	Citric acid^*	BS/SDH	Organic acid	[30]
9	1.26	[M+H]⁺	1.2×10⁴	245.077 1	-1.17	133.049 5, 113.034 5	C₉H₁₂N₂O₆	Uridine	SDH/RS	Alkaloid	[30]
10	1.48	[M+H]⁺	3.1×10⁶	268.104 7	-2.50	136.063 2, 119.035 6	C₁₀H₁₃N₅O₄	Adenosine	SDH/RS	Alkaloid	[31]
11	1.73	[M+H]⁺	5.2×10⁵	284.099 7	-2.66	152.056 3, 135.028 7, 85.027 7	C₁₀H₁₃N₅O₅	Guanosine	SDH	Alkaloid	[31]
12	1.91	[M-H]^－	1.7×10⁶	169.014 1	0.87	125.025 5, 97.028 8	C₇H₆O₅	Gallic acid^*	BS	Organic acid	[13]
13^#	2.02	[M-H]^－	3.7×10⁴	125.024 2	1.74	79.016 9	C₆H₆O₃	Pyrogallol	BS	Phenol	[13]
14	2.22	[M+HCOO]^－	1.4×10⁵	405.138 9	3.30	359.135 8, 254.074 6, 179.072 1	C₁₆H₂₄O₉	Peony ketone-1-O-β-D-glucoside	BS	Flavonoid	[28]
15^#	2.34	[M+HCOO]^－	8.8×10²	361.113 5	1.44	199.061 2, 169.050 3	C₁₅H₂₂O₁₀	Catalpol	SDH	Monoterpene	[30]
16	2.44	[M+H]⁺	1.5×10⁶	166.085 7	3.34	120.080 5, 103.054 3, 79.054 1	C₉H₁₁NO₂	L-Phenylalanine	DG	Other	[17]
17	2.75	[M+HCOO]^－	1.4×10⁵	731.223 4	2.39	685.223 3, 505.159 4, 341.110 7, 263.079 3, 179.057 9	C₂₇H₄₂O₂₀	Rehmannioside D^*	SDH	Monoterpene	[30]
18^#	2.75	[M-H]^－	6.3×10⁴	493.119 9	0	449.123 3, 313.057 4, 271.045 6, 169.013 4	C₁₉H₂₆O₁₅	1'-O-Galloylsucrose	SDH	Other	[30]
19	2.87	[M+HCOO]^－	9.5×10⁴	569.171 3	1.80	523.166 7, 463.143 4, 343.104 0, 228.058 5, 179.056 7	C₂₁H₃₂O₁₅	Rehmannioside A	SDH	Monoterpene	[30]
20	3.31	[M-H]^－	5.2×10⁴	153.019 3	0	109.029 2, 108.021 6	C₇H₆O₄	Protocatechuic acid	CX	Organic acid	[18]
21	3.46	[M-H]^－	3.3×10⁴	373.113 0	2.74	269.040 2, 211.059 4, 149.061 1, 123.046 4	C₁₆H₂₂O₁₀	Geniposidic acid	SDH	Monoterpene	[31]
22	3.51	[M+H]⁺	1.9×10⁴	384.114 7	0.75	252.072 2, 162.075 0, 136.060 9	C₁₄H₁₇N₅O₈	Succinyladenosine	SCP	Alkaloid	[32]
23^#	4.14	[M-H]^－	8.2×10³	183.029 9	0	169.013 8, 124.015 8	C₈H₈O₅	Methyl gallate	BS	Other	[28]
24^#	4.14	[M-H]^－	3.4×10³	205.097 7	-2.66	188.067 4, 146.059 3, 118.065 3	C₁₁H₁₂N₂O₂	Tryptophan	DG/CX	Organic acid	[17]
25	4.16	[M-H]^－	2.8×10⁵	353.087 6	0.58	191.055 8, 179.035 2, 173.044 2, 161.023 3, 135.044 7	C₁₆H₁₈O₉	Chlorogenic acid^*	DG/CX	Organic acid	[19]
26^#	4.19	[M-H]^－	7.9×10³	389.107 8	2.92	165.101 2, 139.552 1	C₁₆H₂₂O₁₁	Scandoside	SDH	Monoterpene	[31]
27^#	4.26	[M-H]^－	5.8×10³	347.133 2	4.48	167.071 2, 123.081 6	C₁₅H₂₄O₉	Ajugol	SDH	Monoterpene	[31]
28	4.42	[M+HCOO]^－	2.6×10⁴	389.144 0	3.39	343.139 8, 257.453 1, 181.088 2, 161.046 2	C₁₆H₂₄O₈	Mudanpioside F	BS	Monoterpene	[13]
29	4.47	[M-H]^－	6.1×10⁴	461.164 9	3.36	415.123 9, 294.122 7, 113.024 2	C₂₀H₃₀O₁₂	Forsythoside E	BS	Phenylethanoid	[28]
30	4.56	[M-H]^－	8.0×10⁴	375.128 3	3.65	314.306 6, 213.077 8, 169.087 0	C₁₆H₂₄O₁₀	8-Epiloganic acid	SDH	Monoterpene	[30]
31^#	4.66	[M-H]^－	1.2×10⁴	345.118 2	2.62	135.043 6, 123.043 5	C₁₅H₂₂O₉	Aucubin	SDH	Monoterpene	[30]
32^#	4.66	[M+HCOO]^－	1.2×10⁴	345.118 2	2.62	299.113 8, 179.057 5, 119.036 3	C₁₄H₂₀O₇	Salidroside	DG	Phenylethanoid	[17]
33	4.72	[M-H]^－	7.4×10⁴	461.128 7	2.96	266.043 6, 137.024 5, 93.035 5	C₁₉H₂₆O₁₃	Sibiricose A3	ZYZ	Oligosaccharide ester	[7]
34	5.35	[M+H]⁺	5.6×10³	389.144 7	-1.22	209.072 3, 149.063 1, 111.037 3	C₁₇H₂₄O₁₀	Geniposide	SDH	Monoterpene	[30]
35	5.55	[M+HCOO]^－	1.8×10⁵	391.159 7	3.25	345.157 4, 192.060 0, 161.046 8	C₁₆H₂₆O₈	Rehmapicroside	SDH	Monoterpene	[30]
36	5.62	[M-H]^－	6.5×10⁵	353.087 6	0.58	191.055 8, 179.035 2, 173.044 2, 161.023 3, 135.044 7	C₁₆H₁₈O₉	Neochlorogenic acid^*	DG/CX	Organic acid	[17]
37	5.67	[M+H]⁺	1.8×10³	291.085 1	4.17	167.034 5, 139.038 8, 127.034 2	C₁₅H₁₄O₆	Epicatechin	BS	Phenol	[33]
38	5.68	[M-H]^－	2.0×10⁵	123.045 1	0.43	105.271 4	C₇H₈O₂	Guaiacol	SDH	Phenol	[30]
39	5.82	[M-H]^－	2.1×10⁶	167.035 1	-0.70	123.046 1, 108.023 1	C₈H₈O₄	Vanillic acid^*	DG/CX	Organic acid	[17]
40	5.83	[M+H]⁺	4.2×10⁴	123.044 6	-4.42	105.033 6, 79.053 4, 77.038 6	C₇H₆O₂	Benzoic acid^*	DG	Organic acid	[18]
41^#	5.97	[M-H]^－	4.8×10³	593.149 0	3.70	287.054 3, 129.054 3	C₂₇H₃₀O₁₅	Nicotiflorin	BS	Flavonoid	[29]
42	5.98	[M-H]^－	2.4×10⁵	353.087 3	1.43	191.055 7, 179.035 1, 173.044 5, 161.023 4, 135.044 7	C₁₆H₁₈O₉	Cryptochlorogenic acid^*	DG/CX	Organic acid	[18]
43	5.98	[M+HCOO]^－	2.2×10⁵	563.161 0	1.35	517.159 6, 448.626 2, 341.110 0, 175.041 4	C₂₂H₃₀O₁₄	Sibiricose A5	ZYZ	Oligosaccharide ester	[7]
44	6.10	[M-H]^－	6.0×10⁵	179.035 4	-2.33	135.046 0, 79.056 2	C₉H₈O₄	Caffeic acid^*	DG	Organic acid	[18]
45	6.30	[M+HCOO]^－	2.8×10⁵	475.145 2	1.08	429.143 7, 307.104 0, 121.030 1	C₁₉H₂₆O₁₁	Polygalatenoside A	SDH	Other	[31]
46	6.35	[M-H]^－	2.2×10⁵	547.166 5	0.63	503.148 5, 341.109 5, 205.051 4	C₂₃H₃₂O₁₅	Sibiricose A6	ZYZ	Oligosaccharide ester	[7]
47	7.09	[M-H]^－	6.5×10³	323.124 0	2.66	203.080 5, 189.066 9, 161.071 2,	C₁₅H₂₀N₂O₆	Tatarine C	SCP	Alkaloid	[34]
48	7.32	[M+HCOO]^－	1.8×10⁶	525.161 9	1.65	449.153 2, 357.121 6, 283.079 3, 195.063 9, 121.029 4	C₂₃H₂₈O₁₁	Mudanpioside I	BS	Monoterpene	[13]
49	7.34	[M-H]^－	1.8×10⁶	525.161 9	1.65	449.147 2, 327.109 1, 165.056 9, 121.030 1	C₂₄H₃₀O₁₃	Mudanpioside E	BS	Monoterpene	[13]
50	7.62	[M+HCOO]^－	4.5×10⁴	541.155 4	1.62	465.138 7, 343.103 1, 193.050 7, 121.029 4	C₂₃H₂₈O₁₂	Oxypaeoniflorin^*	BS	Monoterpene	[14]
51	7.74	[M-H]^－	1.3×10⁴	785.248 2	3.52	707.224 3, 623.218 2, 545.172 6	C₃₅H₄₆O₂₀	Purpureaside B	SDH	Phenylethanoid	[31]
52	7.82	[M+HCOO]^－	2.0×10⁶	525.161 9	1.65	479.157 9, 449.147 8, 327.109 5, 121.020 3	C₂₃H₂₈O₁₁	Paeoniflorin^*	BS	Monoterpene	[15]
53	7.99	[M-H]^－	2.4×10⁵	183.102 5	0.92	139.112 1	C₁₀H₁₆O₃	Rehmapicrogenin	SDH	Monoterpene	[31]
54	8.20	[M+HCOO]^－	3.0×10⁵	537.125 0	0	493.163 4, 315.051 4, 210.603 9	C₂₄H₂₆O₁₄	Sibiricaxanthone B	ZYZ	Flavonoid	[7]
55	8.38	[M+HCOO]^－	5.9×10⁴	435.223 2	0.85	341.106 6, 193.050 9	C₁₉H₃₄O₈	Rehmaionoside A	SDH	Monoterpene	[31]
56^#	8.62	[M-H]^－	2.0×10⁴	787.098 1	2.35	617.080 2, 169.014 3, 125.025 2	C₃₄H₂₈O₂₂	Tetragalloylglucose	BS	Other	[15]
57	8.65	[M+HCOO]^－	3.0×10⁵	607.188 2	-0.37	561.185 1, 323.100 1, 237.078 6, 113.024 4	C₂₄H₃₄O₁₅	Sibiricose A2	ZYZ	Oligosaccharide ester	[7]
58^#	8.65	[M-H]^－	4.1×10⁴	799.265 8	1.02	623.219 1, 193.051 3, 175.039 3, 161.024 1	C₃₆H₄₈O₂₀	Cistanoside A	SDH	Phenylethanoid	[35]
59^#	8.70	[M-H]^－	1.3×10⁴	435.092 3	2.26	315.052 2, 287.018 6, 272.033 1	C₂₀H₂₀O₁₁	Irisxanthone	SDH	Flavonoid	[31]
60	8.73	[M-H]^－	9.8×10⁵	193.051 3	-3.46	178.027 6, 149.060 7, 134.037 4	C₁₀H₁₀O₄	Ferulic acid^*	DG/CX	Organic acid	[17]
61	8.73	[M+HCOO]^－	9.8×10⁵	193.051 3	-3.46	178.028 2, 149.060 7, 134.037 6,	C₉H₈O₂	5-Methoxy-1-benzofuran	BS	Other	[13]
62	8.78	[M-H]^－	2.6×10⁵	567.135 7	-0.28	417.081 7, 315.049 7, 179.030 9	C₂₅H₂₈O₁₅	Polygalaxanthone VIII	ZYZ	Flavonoid	[7]
63	8.85	[M-H]^－	2.6×10⁵	567.135 9	-0.63	435.095 5, 417.085 3, 345.063 5, 315.049 7, 297.040 1, 272.033 1	C₂₅H₂₈O₁₅	Polygalaxanthone III^*	ZYZ	Flavonoid	[29]
64	9.06	[M-H]^－	1.1×10³	577.155 9	0.66	270.047 2, 269.044 6	C₂₇H₃₀O₁₄	Rhoifolin	ZYZ	Flavonoid	[7]
65^#	9.10	[M+HCOO]^－	1.0×10³	609.143 9	3.63	519.145 7, 385.137 5, 253.061 7, 111.007 3	C₂₆H₂₈O₁₄	Isoschaftoside	BS	Flavonoid	[29]
66	9.18	[M+HCOO]^－	9.7×10⁴	435.223 0	1.31	341.106 6, 193.050 9	C₁₉H₃₄O₈	Rehmaionoside B	SDH	Monoterpene	[31]
67^#	9.38	[M+H]⁺	2.9×10³	146.044 9	4.08	117.059 5, 91.056 6	C₉H₇NO	Indole-3-carboxaldehyde	SCP	Alkaloid	[32]
68	9.38	[M-H]^－	1.6×10⁵	667.187 7	0.41	461.130 1, 299.079 1, 205.051 1, 137.024 6	C₃₀H₃₆O₁₇	Tenuifoliside B	ZYZ	Oligosaccharide ester	[7]
69	9.58	[M-H]^－	6.4×10⁵	631.167 8	-1.51	613.491 3, 491.119 0, 313.057 0, 211.171 9, 399.092 9, 169.014 9, 121.030 1	C₃₀H₃₂O₁₅	Galloylpaeoniflorin	BS	Monoterpene	[14]
70	9.61	[M+HCOO]^－	6.5×10⁵	631.167 1	-0.41	491.119 6, 313.057 0, 169.015 1	C₃₀H₃₂O₁₅	Galloylalbiflorin	BS	Monoterpene	[14]
71	9.64	[M+HCOO]^－	1.3×10⁴	328.117 6	4.41	175.038 4, 161.235 2, 147.044 0	C₁₈H₁₉NO₅	(S)-N-trans-Feruloyl-octopamine	DG	Alkaloid	[17]
72	9.68	[M-H]^－	1.2×10⁴	223.096 8	3.51	223.096 8, 205.087 2, 179.107 5, 161.098 1, 145.030 0, 117.035 2, 93.035 1	C₁₂H₁₆O₄	Senkyunolide I^*	DG/CX	Phthalide	[17]
73	9.71	[M-H]^－	1.4×10³	377.158 8	4.71	329.135 2, 165.056 7, 149.024 1	C₂₀H₂₆O₇	4, 7, 9, 9'-Tetrahydroxy-3, 3'-dimethoxy-8-O-4'-neolignan	BS	Other	[29]
74	9.86	[M-H]^－	3.4×10⁴	939.108 8	2.24	769.092 4, 617.080 1, 447.054 9, 169.013 4	C₄₁H₃₂O₂₆	Pentagalloylglucose	BS	Other	[29]
75	9.89	[M+H]⁺	7.9×10²	139.038 6	2.66	121.027 4, 95.048 2	C₇H₆O₃	p-Hydroxybenzoic acid	DG/CX	Organic acid	[18]
76	9.89	[M-H]^－	1.4×10⁴	813.280 1	2.67	637.232 2, 175.039 5	C₃₇H₅₀O₂₀	Jionoside B1	SDH	Phenylethanoid	[30]
77	10.17	[M-H]^－	1.3×10⁵	623.198 0	0.23	461.170 1, 315.110 9, 161.026 4, 135.045 0	C₂₉H₃₆O₁₅	Verbascoside^*	BS	Phenylethanoid	[36]
78	10.49	[M-H]^－	1.4×10³	447.094 2	-2.05	427.192 7, 271.059 3, 165.019 2	C₂₁H₂₀O₁₁	Kaempferol 3-O-D-glucopyranoside	SDH	Flavonoid	[30]
79	10.70	[M-H]^－	6.3×10⁵	753.224 9	-0.20	547.170 0, 367.105 3, 223.062 5, 205.052 7, 190.027 5	C₃₄H₄₂O₁₉	3, 6'-Disinapoyl sucrose^*	ZYZ	Oligosaccharide ester	[22]
80	10.80	[M-H]^－	1.7×10⁴	223.096 7	3.96	205.086 9, 179.107 2, 161.097 9, 145.032 8, 117.034 7, 93.035 5	C₁₂H₁₆O₄	Senkyunolide H^*	DG/CX	Phthalide	[18]
81^#	10.89	[M-H]^－	1.6×10⁴	225.113 0	1.03	181.123 7, 163.112 8, 124.052 8, 95.050 2	C₁₂H₁₈O₄	Senkyunolide N	DG/CX	Phthalide	[18]
82	10.90	[M-H]^－	1.5×10⁵	509.165 8	1.28	463.217 6, 306.077 7, 121.029 7	C₂₄H₃₀O₁₂	Mudanpioside D	BS	Monoterpene	[14]
83	10.93	[M-H]^－	1.7×10⁵	723.213 6	0.81	547.164 7, 430.141 2, 337.087 4, 175.039 8, 123.080 6	C₃₃H₄₀O₁₈	Arillanin A	ZYZ	Oligosaccharide ester	[7]
84	11.01	[M+Na]⁺	2.8×10³	263.088 1	3.40	223.096 3, 177.052 6, 165.053 1	C₁₂H₁₆O₅	Tatarinoids B	SCP	Monoterpene	[32]
85	11.18	[M+HCOO]^－	4.2×10³	345.097 0	2.83	217. 044 6, 187. 045 2	C₁₇H₁₆O₅	Cnidilin	CX	Other	[10]
86	11.42	[M+HCOO]^－	1.8×10⁵	507.150 5	0.59	461.145 6, 339.108 7, 179.054 2, 121.029 9	C₂₃H₂₆O₁₀	Lactiflorin	BS	Monoterpene	[14]
87	11.56	[M+H]⁺	6.8×10²	447.128 2	0.84	285.076 2, 270.052 3, 225.054 1, 137.023 1	C₂₂H₂₂O₁₀	Calycosin-7-O-β-D-glucoside^*	BS	Flavonoid	[28]
88	11.66	[M+HCOO]^－	6.0×10⁴	977.530 4	2.32	885.377 2, 799.496 1, 637.438 6, 475.384 9, 179.054 3	C₄₇H₈₀O₁₈	Notoginsenoside R1	RS	Saponin	[11]
89	11.70	[M-H]^－	7.2×10⁵	681.203 7	-0.11	443.119 6, 239.056 3, 137.024 2	C₃₁H₃₈O₁₇	Tenuifoliside A	ZYZ	Oligosaccharide Ester	[7]
90^#	12.04	[M-H]^－	3.3×10³	615.169 4	4.11	493.142 9, 273.033 8	C₃₀H₃₂O₁₄	Mudanpioside H	BS	Monoterpene	[14]
91^#	12.09	[M-H]^－	2.4×10³	599.174 5	4.20	551.255 2, 431.136 1, 165.058 6, 121.031 4	C₃₀H₃₂O₁₃	Benzoyloxypaeoniflorin	BS	Monoterpene	[14]
92	12.18	[M+HCOO]^－	3.2×10⁵	991.547 3	1.03	945.546 3, 799.486 8, 637.434 3, 475.379 6, 179.055 5	C₄₈H₈₂O₁₈	Ginsenoside Re	RS	Saponin	[11]
93	12.21	[M+HCOO]^－	6.6×10⁵	845.491 2	-0.93	799.490 8, 637.432 5, 475.379 5, 161.046 1	C₄₂H₇₂O₁₄	Pseudoginsenoside F11	RS	Saponin	[12]
94	12.36	[M+H]⁺	3.2×10⁴	314.138 4	0.91	297.100 7, 178.051 6, 148.053 5	C₁₈H₁₉NO₄	N-trans-Feruloyl-tyramine	SCP	Organic Acid	[32]
95	12.38	[M+HCOO]^－	5.7×10⁴	493.228 0	2.13	447.225 4, 315.181 3, 161.046 5	C₂₁H₃₆O₁₀	Shionoside A or isomer	CX	Monoterpene	[17]
96^#	12.38	[M-H]^－	1.2×10⁴	651.227 7	2.68	475.181 1, 193. 049 6, 175.039 3	C₃₁H₄₀O₁₅	Martynoside	SDH	Phenylethanoid	[30]
97	12.49	[M+HCOO]^－	2.4×10⁴	505.228 0	2.08	459.223 3, 417.175 2, 373.092 1, 149.024 1	C₂₂H₃₆O₁₀	Methyl oleate	DG	Other	[17]
98	12.56	[M-H]^－	5.8×10⁴	1 495.456 0	0.52	1 349.402 8, 1 203.363 6, 845.918 1, 655.182 0, 440.273 5, 307.086 1, 145.031 9	C₆₇H₈₄O₃₈	Tenuifoliose L	ZYZ	Oligosaccharide Ester	[7]
99^#	12.56	[M-H]^－	4.2×10⁴	1 525.466 5	0.55	1 379.400 2, 1 161.345 1, 673.198 2, 448.991 5, 218.635 7, 145.027 8	C₆₈H₈₆O₃₉	Tenuifoliose F	ZYZ	Oligosaccharide Ester	[7]
100	12.57	[M+HCOO]^－	3.9×10⁵	491.212 7	1.43	447.222 5, 293.088 3, 149.045 3	C₂₁H₃₄O₁₀	(Z)-(1S, 5R)-β-Pinen-10-yl-β-vicianoside	CX	Monoterpene	[10]
101	12.74	[M-H]^－	3.0×10⁴	1 265.375 7	1.62	1 119.338 8, 955.283 8, 719.713 1, 502.729 9, 306.080 8, 145.030 3	C₅₇H₇₀O₃₂	Tenuifoliose K	ZYZ	Oligosaccharide Ester	[7]
102	12.85	[M+H]⁺	1.2×10⁴	239.091 2	0.84	221.081 0, 190.063 3, 163.039 0	C₁₂H₁₄O₅	E-3, 4, 5-Trimethoxycinnamic acid	CX	Organic Acid	[10]
103	12.89	[M-H]^－	2.1×10⁵	767.240 4	0	529.157 8, 367.103 3, 205.051 2, 113.024 2	C₃₅H₄₄O₁₉	Tenuifoliside C	ZYZ	Oligosaccharide Ester	[7]
104^#	13.06	[M-H]^－	3.3×10³	309.086 3	2.21	263.081 4	C₁₇H₁₂N₂O₄	Flazin	SCP	Alkaloid	[32]
105	13.06	[M-H]^－	1.3×10⁵	1 295.387 6	0.55	1 119.344 2, 997.306 5, 753.221 8, 429.123 2, 307.084 3, 145.030 4	C₅₈H₇₂O₃₃	Tenuifoliose C	ZYZ	Oligosaccharide Ester	[7]
106	13.22	[M+HCOO]^－	1.1×10⁴	329.102 4	2.01	271.045 4, 203.031 2, 187.040 8	C₁₇H₁₆O₄	Pabulenol	SCP	Other	[34]
107	13.27	[M-H]^－	2.0×10⁴	1 397.621 3	1.26	1 308.382 7, 1 162.344 1, 960.932 7, 719.248 9, 425.301 1, 304.185 2, 173.691 6	C₆₄H₁₀₂O₃₃	Arillatanoside C	ZYZ	Saponin	[7]
108	13.34	[M+HCOO]^－	1.5×10⁵	1 353.393 9	-0.08	1 307.389 3, 1 161.3512, 1 015.313 6, 795.2312, 631.184 6, 528.951 4, 145.030 5	C₅₉H₇₂O₃₃	Tenuifoliose J	ZYZ	Oligosaccharide ester	[7]
109	13.55	[M-H]^－	1.8×10⁵	1 337.399 4	-0.39	1 161.350 0, 997.297 8, 731.222 3, 631.169 6, 307.081 2, 175.041 2	C₆₀H₇₄O₃₄	Tenuifoliose B	ZYZ	Oligosaccharide ester	[7]
110^#	13.68	[M+HCOO]^－	2.1×10³	971.481 6	4.24	731.478 1, 629.367 6, 455.354 4, 205.072 2, 163.060 2	C₄₇H₇₄O₁₈	Pseudoginsenoside Rt1	RS	Saponin	[6]
111	13.75	[M-H]^－	1.5×10⁴	203.071 4	0	174.032 9, 173.024 1, 160.016 9, 145.030 2, 132.022 8, 106.042 9	C₁₂H₁₂O₃	Senkyunolide B	DG/CX	Phthalide	[17]
112	13.78	[M-H]^－	1.4×10⁵	711.213 9	0.40	665.209 8, 543.173 7, 427.124 6, 237.078 0, 121.029 9	C₃₂H₄₀O₁₈	Telephiose C	SCP	Other	[34]
113^#	13.83	[M-H]^－	2.3×10⁴	1 235.568 2	-3.11	1 103.307 0, 879.462 6, 542.569 7, 337.112 4, 225.114 4	C₅₈H₉₂O₂₈	Arillatanoside A	ZYZ	Saponin	[7]
114^#	13.85	[M+HCOO]^－	5.1×10⁴	507.243 0	3.35	461.238 7, 368.996 9, 265.091 6, 163.061 8	C₂₂H₃₈O₁₀	Shionoside B	CX	Monoterpene	[10]
115	13.98	[M-H]^－	1.5×10⁵	221.081 9	0	177.093 3, 134.034 0, 77.039 6	C₁₂H₁₄O₄	Senkyunolide D or isomer	DG/CX	Phthalide	[17]
116	14.07	[M-H]^－	4.2×10⁵	1 103.527 5	0.43	879.475 4, 775.438 4, 598.524 1, 455.318 3, 337.114 3, 217.073 0	C₅₃H₈₄O₂₄	Polygalaxanthone XXVIII	ZYZ	Flavonoid	[27]
117	14.08	[M-H]^－	1.3×10⁵	221.081 7	1.05	177.093 3, 92.026 8	C₁₂H₁₄O₄	(E)-3-(2, 4, 5-Trimethoxyphenyl) acrylaldehyde	SCP	Other	[34]
118	14.09	[M+H]⁺	3.8×10⁵	189.091 7	-3.67	161.058 8, 143.086 1, 128.061 8, 105.068 9, 91.053 9	C₁₂H₁₂O₂	3-Butylidenephthalide	DG/CX	Phthalide	[18]
119	14.36	[M-H]^－	1.3×10⁵	1 349.399 8	-0.69	1 203.365 2, 1 040.317 1, 795.232 4, 673.201 8, 365.106 8, 145.029 7	C₆₁H₇₄O₃₄	Tenuifoliose H	ZYZ	Oligosaccharide ester	[7]
120	14.41	[M-H]^－	1.5×10⁴	1 367.407 6	1.34	1 191.363 9, 1 089.806 8, 909.287 4, 740.440 1, 383.473 1, 175.038 5	C₆₁H₇₆O₃₅	Tenuifoliose O	ZYZ	Oligosaccharide ester	[7]
121^#	14.48	[M-H]^－	3.3×10³	661.247 9	3.45	493.149 2, 417.212 5	C₃₃H₄₂O₁₄	Azadirachtin H	CX	Monoterpene	[10]
122	14.53	[M+HCOO]^－	8.7×10⁵	629.187 9	-0.51	553.174 9, 431.137 4, 165.056 6, 121.030 4	C₃₀H₃₂O₁₂	Benzoylpaeoniflorin^*	BS	Monoterpene	[36]
123	14.61	[M-H]^－	3.7×10⁵	1 379.411 2	-1.28	1 203.362 7, 1 029.496 5, 642.902 4, 501.774 3, 368.102 1, 274.081 9	C₆₂H₇₆O₃₅	Tenuifoliose A	ZYZ	Oligosaccharide Ester	[7]
124	14.81	[M-H]^－	2.5×10⁵	629.188 5	-1.46	553.173 0, 431.135 4, 267.073 4, 121.030 3	C₃₁H₃₄O₁₄	Mudanpioside B	BS	Monoterpene	[14]
125	15.01	[M+HCOO]^－	5.1×10⁵	845.4903	-0.13	799.489 2, 637.437 1, 475.382 0, 310.329 5, 161.046 8	C₄₂H₇₂O₁₄	Ginsenoside Rg₁^*	RS	Saponin	[11]
126	15.13	[M+H]⁺	4.8×10²	281.247 7	-0.69	245.225 8, 97.101 3	C₁₈H₃₂O₂	Linoleic acid	DG	Organic Acid	[17]
127	15.18	[M-H]^－	5.8×10⁴	355.118 2	1.44	296.108 2, 159.045 6	C₂₀H₂₀O₆	Coniferyl ferulate	DG/CX	Other	[18]
128	15.46	[M+HCOO]^－	2.6×10⁵	815.479 1	0.91	769.479 1, 637.434 4, 475.380 3, 366.176 7, 161.046 4	C₄₁H₇₀O₁₃	Ginsenoside F5	RS	Saponin	[6]
129^#	15.52	[M+HCOO]^－	1.9×10³	815.480 5	-0.80	769.475 9, 637.433 9, 475.380 3, 366.176 7, 161.046 4	C₄₁H₇₀O₁₃	Notoginsenoside R2	RS	Saponin	[12]
130^#	15.84	[M+HCOO]^－	4.8×10³	1 285.640 1	2.57	1 107.593 3, 945.540 7, 783.497 6, 621.436 8, 459.380 8	C₅₉H₁₀₀O₂₇	Ginsenoside Ra₃	RS	Saponin	[10]
131	15.92	[M-H]^－	1.8×10⁵	679.370 4	-0.73	635.384 8, 455.318 8, 425.3062	C₃₆H₅₆O₁₂	Tenuifolin^*	ZYZ	Saponin	[7]
132	15.92	[M+HCOO]^－	1.8×10⁵	1 153.600 6	0.47	1 107.601 2, 945.548 7, 783.487 2, 621.434 7, 459.384 5, 323.100 9, 179.056 6	C₅₄H₉₂O₂₃	Ginsenoside Rb₁	RS	Saponin	[12]
133	16.00	[M+HCOO]^－	2.1×10⁵	829.496 1	-0.73	783.491 0, 637.433 7, 475.378 9, 262.979 3, 161.046 3	C₄₂H₇₂O₁₃	Ginsenoside Rg₂^*	RS	Saponin	[11]
134	16.12	[M+HCOO]^－	1.7×10⁵	683.437 3	0.42	637.435 5, 475.379 6, 329.231 7, 101.023 5	C₃₆H₆₂O₉	Ginsenoside Rh₁	RS	Saponin	[12]
135	16.15	[M-H]^－	1.7×10⁵	1 193.595 6	0.38	1 149.608 8, 945.539 2, 783.489 1, 621.439 0, 323.09 44, 179.056 9	C₅₇H₉₄O₂₆	Malonyl-ginsenoside Rb₁	RS	Saponin	[12]
136	16.17	[M-H]^－	6.1×10⁵	329.233 6	-0.77	229.144 6, 211.134 2, 171.103 0, 139.112 5	C₁₈H₃₄O₅	Tianshic acid	CX	Organic Acid	[17]
137	16.29	[M+HCOO]^－	1.6×10⁵	1 123.590 1	0.42	1 077.588 4, 945.539 7, 783.489 5, 621.438 1, 149.045 4	C₅₃H₉₀O₂₂	Ginsenoside Rc	RS	Saponin	[12]
138^#	16.29	[M+HCOO]^－	9.4×10³	1 255.631 2	1.30	1 233.625 1, 467.136 3	C₅₈H₉₈O₂₆	Ginsenoside Ra₁	RS	Saponin	[12]
139	16.32	[M-H]^－	5.2×10⁵	207.103 1	-2.09	163.113 6, 161.094 4, 85.065 8	C₁₂H₁₆O₃	Senkyunolide G	DG/CX	Phthalide	[18]
140	16.42	[M-H]^－	3.4×10⁵	955.490 6	0.21	793.436 5, 731.437 3, 613.372 7 569.385 9, 455.351 3	C₄₈H₇₆O₁₉	Ginsenoside Ro	RS	Saponin	[12]
141	16.47	[M+H]⁺	1.4×10⁴	191.107 2	-2.85	173.095 6, 145.100 9, 135.043 8, 117.068 9, 91.053 8	C₁₂H₁₄O₂	n-Butylphthalide^*	DG/CX	Phthalide	[17]
142	16.48	[M+HCOO]^－	1.4×10⁵	683.437 8	-0.31	637.436 7, 475.379 3, 1161.046 4, 101.023 5	C₃₆H₆₂O₉	Ginsenoside F1	RS	Saponin	[12]
143	16.53	[M-H]^－	6.5×10⁴	1 163.583 2	1.97	1 119.601 7, 915.525 2, 783.490 0, 590.037 1, 376.585 9, 149.047 1	C₅₆H₉₂O₂₅	Malonylginsenoside Rc	RS	Saponin	[12]
144	16.65	[M+HCOO]^－	2.0×10⁵	1 123.590 1	0.42	1 077.587 7, 946.541 4, 783.494 5, 521.780 6, 459.384 5, 149.046 5	C₅₃H₉₀O₂₂	Ginsenoside Rb₂	RS	Saponin	[12]
145	17.10	[M-H]^－	6.2×10⁵	205.087 6	-2.84	161.092 8, 106.049 2, 83.050 9, 77.039 6	C₁₂H₁₄O₃	Senkyunolide F	DG/CX	Phthalide	[17]
146	17.21	[M-H]^－	2.8×10⁴	375.183 6	-6.10	245.086 3, 191.076 1	C₂₁H₂₈O₆	Ligraminol D	SCP	Other	[34]
147	17.23	[M-H]^－	3.2×10⁴	1 617.696 4	0.13	1 385.149 9, 1 048.084 7, 726.871 8, 419.879 0, 224.625 9	C₇₆H₁₁₄O₃₇	Onjisaponin R	ZYZ	Saponin	[7]
148	17.41	[M+HCOO]^－	2.5×10⁵	991.548 1	0.22	945.546 6, 783.489 5, 621.436 0, 511.699 6, 161.046 0	C₄₈H₈₂O₁₈	Ginsenoside Rd	RS	Saponin	[11]
149	17.54	[M+H]⁺	3.5×10³	251.164 0	0.47	233.154 3, 151.071 6, 135.042 4	C₁₅H₂₂O₃	Isocalamediol	SCP	Monoterpene	[32]
150	17.56	[M-H]^－	1.9×10⁴	1 031.541 1	2.07	987.557 0, 945.546 4, 765.478 6, 621.443 3, 395.521 2, 161.047 6	C₅₁H₈₄O₂₁	Malonyl-ginsenoside Rd	RS	Saponin	[12]
151	17.64	[M-H]^－	1.5×10⁴	891.254 7	1.96	811.208 1, 655.187 9, 551.137 1, 301.102 5	C₄₁H₄₈O₂₂	Tenuifoliside E	ZYZ	Oligosaccharide ester	[7]
152^#	17.69	[M-H]^－	4.6×10³	297.170 1	2.18	261.146 3, 253.180 2	C₁₆H₂₆O₅	2, 4, 5-Trimethoxyl-2′-butoxy-1, 2-phenyl propandiol	SCP	Other	[32]
153^#	17.91	[M-H]^－	4.0×10⁴	1 571.692 4	-0.80	1 253.118 4, 1 030.617 1, 701.769 5, 587.467 4, 439.649 9, 198.448 4	C₇₅H₁₁₂O₃₅	Onjisaponin B	ZYZ	Saponin	[7]
154	17.94	[M-H]^－	1.4×10⁵	203.072 0	-3.11	174.033 1, 173.025 0, 160.017 1, 145.032 9, 132.022 4, 117.035 1, 104.027 7, 92.028 0	C₁₂H₁₂O₃	Senkyunolide C	DG/CX	Phthalide	[17]
155	17.95	[M+H]⁺	6.1×10⁴	279.159 3	-0.77	261.146 2, 233.153 6, 191.106 7, 105.033 8, 71.048 8	C₁₆H₂₂O₄	Senkyunolide M	DG/CX	Phthalide	[18]
156^#	18.12	[M+HCOO]^－	3.5×10⁴	1 587.686 9	-0.53	1 455.641 4, 964.826 6, 676.245 8, 425.302 5, 237.078 2	C₇₄H₁₁₀O₃₄	Onjisaponin H	ZYZ	Saponin	[7]
157	18.17	[M-H]^－	3.5×10⁴	1 587.693 2	-4.5	1 455.641 4, 1 087.742 2, 676.245 8, 425.305 2, 237.078 2	C₇₅H₁₁₂O₃₆	Onjisaponin F	ZYZ	Saponin	[7]
158^#	18.32	[M-H]^－	4.3×10²	283.061 9	-2.48	268.037 2, 240.040 4, 135.007 8	C₁₆H₁₂O₅	Calycosin^*	BS	Flavonoid	[28]
159	18.36	[M-H]^－	2.2×10⁵	203.072 2	-4.10	174.032 9, 159.081 9, 131.051 1, 130.042 9, 91.021 1	C₁₂H₁₂O₃	Senkyunolide E	DG/CX	Phthalide	[17]
160	18.55	[M+H]⁺	7.4×10⁴	209.117 3	-0.38	194.091 2, 168.075 6, 153.051 5	C₁₂H₁₆O₃	β-Asarone	SCP	Other	[32]
161^#	18.60	[M-H]^－	5.3×10³	793.439 4	-1.79	613.376 9, 455.354 4, 311.220 2, 89.025 1	C₄₂H₆₆O₁₄	Zingibroside R1	RS	Saponin	[12]
162	18.64	[M+H]⁺	1.6×10⁶	193.123 1	-4.11	175.111 9, 147.117 1, 137.060 2, 93.069 8	C₁₂H₁₆O₂	Senkyunolide A^*	DG/CX	Phthalide	[24]
163	18.69	[M+HCOO]^－	1.6×10⁵	665.428 0	-1.47	619.422 4, 493.410 2, 327.752 8, 161.045 2	C₃₆H₆₀O₈	Ginsenoside Rh₄	RS	Saponin	[12]
164	18.79	[M+H]⁺	1.3×10⁵	209.117 3	-0.38	194.091 3, 179.067 4, 153.051 6	C₁₂H₁₆O₃	α-Asarone	SCP	Other	[32]
165	18.85	[M+HCOO]^－	5.2×10⁵	829.496 1	-0.73	783.491 0, 621.434 8, 459.381 7, 161.046 3	C₄₂H₇₂O₁₃	Ginsenoside Rg₃	RS	Saponin	[10]
166^#	18.90	[M+HCOO]^－	8.1×10³	323.185 5	2.78	239.128 6, 209.115 1, 171.100 8	C₁₇H₂₆O₃	2-Acetoxyacorenone	SCP	Monoterpene	[32]
167	19.14	[M+H]⁺	3.0×10⁵	191.106 9	-1.28	173.095 7, 163.111 5, 145.100 9, 117.070 1	C₁₂H₁₄O₂	(E)-Ligustilide	DG/CX	Phthalide	[17]
168	19.23	[M+H]⁺	9.1×10²	315.253 5	-1.63	185.117 3, 135.111 2, 121.101 0	C₁₈H₃₄O₄	Dibutyl sebacate or isomer	DG	Other	[17]
169	19.37	[M+HCOO]^－	1.7×10⁴	871.504 4	1.90	825.504 5, 783.491 4, 621.435 7, 447.037 8, 252.047 8	C₄₄H₇₄O₁₄	Ginsenoside Rs₃	RS	Saponin	[12]
170	19.39	[M+H]⁺	6.3×10⁵	191.107 2	-2.85	173.095 7, 145.100 9, 117.070 1, 105.070 2, 91.053 7, 79.053 8	C₁₂H₁₄O₂	(Z)-Ligustilide^*	DG/CX	Phthalide	[25]
171	19.69	[M+H]⁺	9.9×10³	165.090 8	1.59	137.059 3, 124.051 2, 105.069 2	C₁₀H₁₂O₂	Eugenol	BS	Phenylethanoid	[33]
172	19.76	[M+HCOO]^－	1.3×10⁵	811.483 8	1.39	619.422 9, 457.370 7	C₄₂H₇₀O₁₂	Ginsenoside Rg₆	RS	Saponin	[12]
173	19.86	[M+H]⁺	4.4×10³	401.194 5	3.40	371.185 0, 233.113 9, 203.104 4, 181.082 3	C₂₃H₂₈O₆	Ligraminol C	DG	Other	[17]
174	20.13	[M+HCOO]^－	4.8×10³	667.441 6	1.61	621.436 0, 459.387 2	C₃₆H₆₂O₈	Ginsenoside CK	RS	Saponin	[12]
175	20.33	[M+H]⁺	1.4×10⁵	209.117 3	-0.38	194.091 2, 168.075 6, 151.071 5	C₁₂H₁₆O₃	γ-Asarone	SCP	Other	[32]
176	20.44	[M+H]⁺	1.7×10³	277.144 1	1.56	261.146 1, 233.153 5, 191.106 7, 105.033 8, 71.048 8	C₁₆H₂₂O₄	Senkyunolide Q	DG/CX	Phthalide	[17]

No.

t_R/min

Precursor ion

Response

Meas
m/z

Error/ppm

Fragment ion

Molecular formula

Plausible identification

Source