药学学报

No.	t_R/min	Identification	Molecularformula	[M–H]^–/[M+HCOO]^–	Error/ppm	Fragmentaion	Source
1^b	1.19	Rehmannioside D^[11]	C₂₇H₄₂O₁₀	685.218 2/–	–0.6	667.215 9, 523.161 2, 179.055 4, 361.110 4	D
2^c	1.23	D-Glucosamine	C₆H₁₃NO₅	178.071 4/–	2.8	160.060 7, 142.050 1, 124.039 5	G, M, Z, C, X
3^d	1.26	Stachyose	C₂₄H₄₂O₂₁	665.214 1/–	0.9	545.175 5, 503.159 2, 485.149 7	D
4^c	1.27	D-Raffinose	C₁₈H₃₂O₁₆	503.161 5/–	1.8	485.162 6, 443.140 3, 383.119 4, 341.108 5, 323.098 6	D, S
5^c	1.29	D-(+)-Mannose	C₆H₁₂O₆	179.055 5/–	2.8	161.044 8, 131.033 8, 113.023 7, 89.023 4	All
6^c	1.32	Gluconic acid	C₆H₁₂O₇	195.050 5/–	3.0	177.039 7, 159.029 2, 141.018 5, 129.018 5	D, S, Z, M, G, X
7^c	1.34	D-(–)-Quinic acid	C₇H₁₂O₆	191.055 5/–	2.6	173.044 8, 155.034 1, 147.029 3, 137.023 4	G, S, X, M, C
8^d	1.35	Sucrose	C₁₂H₂₂O₁₁	341.108 6/–	2.3	179.055 5, 161.044 9, 143.034 1, 89.023 4	All
9^c	1.69	2-Furoic acid	C₅H₄O₃	111.007 8/–	1.8	83.012 9, 67.017 9	All
10^{b, c}	1.71	Citric acid^[11]	C₆H₈O₇	191.019 1/–	–0.5	173.008 4, 129.018 4, 111.007 8, 147.029 0	All
11^{a, b}	1.78	Catalpol^[11]	C₁₅H₂₂O₁₀	361.113 9/–	2.8	199.060 5, 169.050 0, 331.066 9	D
12^{b, c}	1.86	Succinic acid^[22]	C₄H₆O₄	117.018 4/–	1.7	99.007 8, 73.028 5, 55.017 9	All
13^b	1.89	Galloyl-glucose^[17]	C₁₃H₁₆O₁₀	331.066 7/–	2.1	271.045 8, 211.024 3, 191.019 1, 169.013 5	M
14^b	2.03	RehmanniosideA^[11]	C₂₁H₃₂O₁₅	523.166 7/–	1.9	505.167 3, 361.131 3, 323.096 8, 199.060 8	D
15^{a, b, c}	2.14	Gallic acid^[17]	C₇H₆O₅	169.013 5/–	2.4	125.023 6, 97.028 4	Z, M
16^b	2.25	Danmelittoside^[11]	C₁₅H₂₂O₁₀	361.114 0/–	3.0	199.060 8, 179.055 6, 161.044 9	D
17^b	2.44	Peony glucoside B^[17]	C₁₈H₂₄O₁₄	463.109 1/–	1.9	463.109 1, 403.088 0, 373.077 7, 343.066 9, 301.056 4	M
18^b	2.88	Aucubin^[11]	C₁₅H₂₂O₉	345.118 7/–	2.0	327.128 0, 309.108 9, 183.066 1, 165.055 2	D
19^b	3.06	Vanillic acid^[18]	C₈H₈O₄	167.034 2/–	1.8	152.010 8, 137.023 0, 139.039 3, 123.044 3	X, Z, S, G, B
20^b	3.06	Pseudolaroside B^[15]	C₁₄H₁₈O₉	329.087 6/–	2.7	167.034 2, 152.010 7	Z, B, R
21^b	3.10	Tanshinol^[21]	C₉H₉O₅	197.045 0/–	3.0	179.034 4, 151.039 4, 135.044 3, 123.044 2	S
22^b	3.13	HA^[23]	C₈H₈O₃	151.039 3/–	2.0	133.028 5, 123.044 3, 107.049 3, 93.033 7	R, S, X, G, B
23^d	3.43	Dihydrocatalpol	C₁₅H₂₄O₁₀	363.128 8/–	0.8		D
24^b	3.51	Protocatechuic acid^[21]	C₇H₆O₄	153.018 6/–	2.6	141.911 7, 109.028 6, 123.901 0, 110.031 9	S, X, G, C, F, B, R, L
25^{a, b}	4.41	Neochlorogenic acid^[24]	C₁₆H₁₈O₉	353.087 7/–	2.8	353.087 6, 191.055 6, 179.034 3, 173.045 0	Z, X, G
26^c	4.99	DHA	C₉H₁₀O₄	181.050 0/–	2.8	163.039 3, 135.044 3	S, Z
27^d	5.22	Leonuride	C₁₅H₂₄O₉	347.134 7/–	3.2		D
28^b	5.62	Protocatechuic aldehyde^[21]	C₇H₆O₃	137.023 6/–	2.2	119.013 0, 109.028 5, 108.020 6	All
29^b	6.79	Geniposide^[11]	C₁₇H₂₄O₁₀	387.129 5/–	2.3	225.076 0	D, R
30^{a, b}	7.05	Chlorogenic acid^{[18, 24]}	C₁₆H₁₈O₉	353.087 7/–	2.8	353.087 6, 191.055 7, 179.034 0, 173.045 4	X, Z, G, C
31^b	7.20	Oxypaeoniflorin^[17]	C₂₃H₂₈O₁₂	495.150 6/–	1.8	465.141 1, 333.098 0, 165.055 0, 137.023 6	M
32^{a, b}	7.52	Cryptochlorogenic acid^[24]	C₁₆H₁₈O₉	353.087 7/–	2.8	353.087 4, 191.055 6, 179.034 3, 173.044 8	X, G
33^{a, b, c}	7.52	Caffeic acid^[21]	C₉H₈O₄	179.034 3/–	2.2	143.864 7, 135.044 3, 104.927 0, 89.023 4	S, D, C, Z, R
34^c	7.55	Isophthalic acid	C₈H₆O₄	165.018 6/–	2.4	121.028 6	G, Z, X, C
35^{b, c}	7.82	Benzoic acid^[18]	C₇H₆O₂	121.028 6/–	1.6	93.033 7, 77.038 5	Z, M, C, F, B, Z, L
36^d	7.87	Ajugoside	C₁₇H₂₅O₁₀	389.144 8/–	1.5		D
37^c	7.97	6-Methoxysalicylic acid	C₈H₈O₄	167.034 3/–	2.4	123.044 3, 121.028 9	G, X, C
38^c	8.80	2-Hydroxycaproic acid	C₆H₁₂O₃	131.070 5/–	1.5	85.064 8	X, G
39^b	8.85	Paeonolide^[17]	C₂₀H₂₈O₁₂	–/505.159 9	1.4	459.150 8, 293.087 8, 165.055 0	M
40^c	8.88	Apocynin	C₉H₁₀O₃	165.054 4/–	–1.2		M
41^b	8.89	Vicenin Ⅱ^[16]	C₂₇H₃₀O₁₅	593.151 2/–	1.8	503.120 0, 473.108 8, 413.087 1, 383.077 1, 353.066 6	S
42^b	9.26	Paeonolide^[17]	C₂₀H₂₈O₁₂	–/505.154 4	–1.6	459.150 9, 293.088 0, 165.055 0, 233.066 1	M
43^b	9.36	Galloyl-oxypaeoniflorin^[17]	C₃₀H₃₂O₁₆	647.161 9/–	1.8	509.128 8, 399.093 1, 313.056 7, 271.045 2, 211.024 3	M
44^b	9.44	p-Coumaric acid^{[18, 23]}	C₉H₈O₃	163.039 3/–	1.8	162.838 4, 159.859 2, 145.861 5, 123.945 5, 119.049 3	R, Z, S, G, C, R, L
45^d	9.50	Purpureaside C	C₃₅H₄₆O₂₀	785.250 4/–	0.6		D
46^b	9.81	Salvianolic acid F^[21]	C₁₇H₁₄O₆	313.071 9/–	4.1	269.081 7, 159.044 4	S
47^{a, b}	9.95	Paeoniflorin^[17]	C₂₃H₂₈O₁₁	–/525.161 1	1.5	525.161 2, 479.155 6, 449.154 5, 327.108 9, 165.054 9	M
48^c	10.21	3-Phenyllactic acid	C₉H₁₀O₃	165.055 0/–	2.4	147.044 4, 127.869 9, 119.049 3, 101.038 8	Z, D, M, X, C
49^d	10.42	Jionoside A	C₃₆H₄₈O₂₀	799.266 2/–	0.8		D
50^{a, b, c}	10.54	Ferulic acid^{[12, 24]}	C₁₀H₁₀O₄	193.050 1/–	3.1	193.050 1, 178.026 5, 149.060 0, 134.036 5	G, X, S, G, C
51^b	10.65	Isoferulic acid^[12]	C₁₀H₁₀O₄	193.050 3/–	4.1	178.026 5, 149.060 1, 134.036 5	G, X, S, G, C
52^{a, b}	10.72	Spinosin^[19]	C₂₈H₃₂O₁₅	607.166 8/–	1.8	607.167 0, 487.126 2, 445.114 6, 427.103 2, 325.071 8	Z
53^b	10.84	Suffruticoside B/D^[17]	C₂₇H₃₂O₁₆	611.161 9/–	2.1	445.098 5, 343.067 7, 169.013 6	M
54^b	11.35	Acteoside^[11]	C₂₉H₃₆O₁₅	623.198 0/–	1.6	461.166 5, 161.023 7	D
55^b	11.36	Galloyl-paeoniflorin^[17]	C₃₀H₃₂O₁₅	631.166 9/–	1.9	509.131 3, 479.119 4, 399.092 4, 313.056 5, 169.013 6	M
56^b	11.65	Salvianolic acid H/I^[21]	C₂₇H₂₂O₁₂	537.101 2/–	–2.8	339.050 9, 295.061 1	S
57^d	11.68	Jionoside B	C₃₇H₅₀O₂₀	813.282 5/–	1.7		D
58^b	11.72	Rehmaionoside A/B^[11]	C₁₉H₃₄O₈	389.218 2/–	3.1	435.223 44	D
59^b	11.75	Salvianolic acid D^[21]	C₂₀H₁₈O₁₀	417.082 7/–	2.6	417.082 8, 197.045 1, 175.039 4, 157.028 7	S
60^b	11.90	Isoacteoside^[11]	C₂₉H₃₆O₁₅	623.197 5/–	0.8	461.166 8, 161.023 7	D
61^c	12.35	Salicylic acid	C₇H₆O₃	137.023 6/–	2.2	109.028 4, 93.033 6	G, D, M, X, C
62^b	12.45	Rehmannia bitterglycosides^[11]	C₁₆H₂₆O₈	345.155 7/–	3.8	183.102 0, 179.055 5, 165.091 4	D
63^b	12.60	Rosmarinic acid^[21]	C₁₈H₁₆O₈	359.077 0/–	2.5	359.077 5, 197.045 0, 179.034 4, 161.023 7, 133.028 7	S
64^c	12.71	Azelaic acid	C₉H₁₆O₄	187.097 0/–	2.7	169.086 3, 125.096 3	All
65^b	12.71	Salvianolic acid A^[21]	C₂₆H₂₂O₁₀	493.113 9/–	2.0	493.114 0, 313.071 5, 295.061 1, 185.023 9	S
66^b	12.74	Lithospermic acid^[21]	C₂₇H₂₂O₁₂	[M+M–H]^–:1 075.216 9	2.8	537.103 6, 340.898 9, 295.060 6	S
67^b	13.15	HOG^[17]	C₂₂H₂₄O₁₁	463.124 6/–	2.4	301.071 6, 271.064 5, 229.024 9	C
68^{b, c}	13.30	Salvianolic acid B^[21]	C₃₆H₃₀O₁₆	717.146 3/–	1.8	519.092 8, 339.050 5, 321.040 0, 295.060 5, 279.029 6	S
69^b	13.55	BOHD^[25]	C₁₉H₁₈O₈	373.092 4/–	1.6	345.098 5, 358.069 5, 343.082 4, 313.072 8	C
70^b	13.78	CMGC^[17]	C₃₀H₃₂O₁₃	599.176 9/–	1.7	551.152 2, 477.139 7, 447.129 9, 431.135 5, 281.066 7	M
71^b	13.92	Salvianolic acid E/Isosalvianolic acid B^[21]	C₃₆H₃₀O₁₆	717.146 1/–	1.5	717.145 8, 519.093 3, 339.050 9, 321.040 5, 295.061 2, 279.029 8	S
72^b	14.15	Salvianolic acid C^[21]	C₂₆H₂₀O₁₀	491.098 4/–	2.2	311.056 1, 293.045 7, 265.050 6	S
73^b	14.45	Benzoyloxypaeoniflorin^[17]	C₃₀H₃₂O₁₃	599.176 9/–	1.7	569.164 7, 477.138 5, 137.023 6, 121.028 6, 165.055 0	M
74^c	14.83	3-tert-Butyladipic acid	C₁₀H₁₈O₄	201.112 8/–	3.5	183.102 1, 157.122 6, 139.112 1	All
75^b	14.89	RI^[11]	C₃₁H₄₀O₁₅	651.229 6/–	2.0	475.183 9, 193.050 3, 175.039 4	D
76^b	16.35	GSPLLPT^[25]	C₃₆H₅₃N₇O₉	726.382 9/–	1.1	726.383 8, 696.372 0, 697.378 7, 590.330 5	C
77^b	16.50	Benzoyl paeoniflorin^[17]	C₃₀H₃₂O₁₂	–/629.188 0	2.4	583.182 3, 553.171 5, 431.135 3, 165.055 1	M
78^b	17.78	ATTPLI^[25]	C₃₄H₅₃N₇O₉	702.383 0/–	1.3	702.381 3, 658.356 0, 615.333 9, 614.330 6	C
79^{a, b}	17.85	Jujuboside A^[7]	C₅₈H₉₄O₂₆	–/1 251.601 1	0.6		Z
80^{a, b}	18.36	Jujuboside B^[7]	C₅₂H₈₄O₂₁	–/1 089.547 5	–0.1		Z
81^c	20.48	α-Estrdiol	C₁₈H₂₄O₂	271.170 2/–	3.7		S

No.

t_R/min

Identification

Molecularformula

[M–H]^–/[M+HCOO]^–

Error/ppm

Fragmentaion

Source

1^b

1.19

Rehmannioside D^[11]

C₂₇H₄₂O₁₀

685.218 2/–

–0.6

667.215 9, 523.161 2, 179.055 4, 361.110 4

2^c

1.23

D-Glucosamine

C₆H₁₃NO₅

178.071 4/–

2.8

160.060 7, 142.050 1, 124.039 5

G, M, Z, C, X

3^d

1.26

Stachyose

C₂₄H₄₂O₂₁

665.214 1/–

0.9

545.175 5, 503.159 2, 485.149 7

4^c

1.27

D-Raffinose

C₁₈H₃₂O₁₆

503.161 5/–

1.8

485.162 6, 443.140 3, 383.119 4, 341.108 5, 323.098 6

D, S

5^c

1.29

D-(+)-Mannose

C₆H₁₂O₆

179.055 5/–

2.8

161.044 8, 131.033 8, 113.023 7, 89.023 4

All

6^c

1.32

Gluconic acid

C₆H₁₂O₇

195.050 5/–

3.0

177.039 7, 159.029 2, 141.018 5, 129.018 5

D, S, Z, M, G, X

7^c

1.34

D-(–)-Quinic acid

C₇H₁₂O₆

191.055 5/–

2.6

173.044 8, 155.034 1, 147.029 3, 137.023 4

G, S, X, M, C

8^d

1.35

Sucrose

C₁₂H₂₂O₁₁

341.108 6/–

2.3

179.055 5, 161.044 9, 143.034 1, 89.023 4

All

9^c

1.69

2-Furoic acid

C₅H₄O₃

111.007 8/–

1.8

83.012 9, 67.017 9

All

10^{b, c}

1.71

Citric acid^[11]

C₆H₈O₇

191.019 1/–

–0.5

173.008 4, 129.018 4, 111.007 8, 147.029 0

All

11^{a, b}

1.78

Catalpol^[11]

C₁₅H₂₂O₁₀

361.113 9/–

2.8

199.060 5, 169.050 0, 331.066 9

12^{b, c}

1.86

Succinic acid^[22]

C₄H₆O₄

117.018 4/–

1.7

99.007 8, 73.028 5, 55.017 9

All

13^b

1.89

Galloyl-glucose^[17]

C₁₃H₁₆O₁₀

331.066 7/–

2.1

271.045 8, 211.024 3, 191.019 1, 169.013 5

14^b

2.03

RehmanniosideA^[11]

C₂₁H₃₂O₁₅

523.166 7/–

1.9

505.167 3, 361.131 3, 323.096 8, 199.060 8

15^{a, b, c}

2.14

Gallic acid^[17]

C₇H₆O₅

169.013 5/–

2.4

125.023 6, 97.028 4

Z, M

16^b

2.25

Danmelittoside^[11]

C₁₅H₂₂O₁₀

361.114 0/–

3.0

199.060 8, 179.055 6, 161.044 9

17^b

2.44

Peony glucoside B^[17]

C₁₈H₂₄O₁₄

463.109 1/–

1.9

463.109 1, 403.088 0, 373.077 7, 343.066 9, 301.056 4

18^b

2.88

Aucubin^[11]

C₁₅H₂₂O₉

345.118 7/–

2.0

327.128 0, 309.108 9, 183.066 1, 165.055 2

19^b

3.06

Vanillic acid^[18]

C₈H₈O₄

167.034 2/–

1.8

152.010 8, 137.023 0, 139.039 3, 123.044 3

X, Z, S, G, B

20^b

3.06

Pseudolaroside B^[15]

C₁₄H₁₈O₉

329.087 6/–

2.7

167.034 2, 152.010 7

Z, B, R

21^b

3.10

Tanshinol^[21]

C₉H₉O₅

197.045 0/–

3.0

179.034 4, 151.039 4, 135.044 3, 123.044 2

22^b

3.13

HA^[23]

C₈H₈O₃

151.039 3/–

2.0

133.028 5, 123.044 3, 107.049 3, 93.033 7

R, S, X, G, B

23^d

3.43

Dihydrocatalpol

C₁₅H₂₄O₁₀

363.128 8/–

0.8

24^b

3.51

Protocatechuic acid^[21]

C₇H₆O₄

153.018 6/–

2.6

141.911 7, 109.028 6, 123.901 0, 110.031 9

S, X, G, C, F, B, R, L

25^{a, b}

4.41

Neochlorogenic acid^[24]

C₁₆H₁₈O₉

353.087 7/–

2.8

353.087 6, 191.055 6, 179.034 3, 173.045 0

Z, X, G

26^c

4.99

DHA

C₉H₁₀O₄

181.050 0/–

2.8

163.039 3, 135.044 3

S, Z

27^d

5.22

Leonuride

C₁₅H₂₄O₉

347.134 7/–

3.2

28^b

5.62

Protocatechuic aldehyde^[21]

C₇H₆O₃

137.023 6/–

2.2

119.013 0, 109.028 5, 108.020 6

All

29^b

6.79

Geniposide^[11]

C₁₇H₂₄O₁₀

387.129 5/–

2.3

225.076 0

D, R

30^{a, b}

7.05

Chlorogenic acid^{[18, 24]}

C₁₆H₁₈O₉

353.087 7/–

2.8

353.087 6, 191.055 7, 179.034 0, 173.045 4

X, Z, G, C

31^b

7.20

Oxypaeoniflorin^[17]

C₂₃H₂₈O₁₂

495.150 6/–

1.8

465.141 1, 333.098 0, 165.055 0, 137.023 6

32^{a, b}

7.52

Cryptochlorogenic acid^[24]

C₁₆H₁₈O₉

353.087 7/–

2.8

353.087 4, 191.055 6, 179.034 3, 173.044 8

X, G

33^{a, b, c}

7.52

Caffeic acid^[21]

C₉H₈O₄

179.034 3/–

2.2

143.864 7, 135.044 3, 104.927 0, 89.023 4

S, D, C, Z, R

34^c

7.55

Isophthalic acid

C₈H₆O₄

165.018 6/–

2.4

121.028 6

G, Z, X, C

35^{b, c}

7.82

Benzoic acid^[18]

C₇H₆O₂

121.028 6/–

1.6

93.033 7, 77.038 5

Z, M, C, F, B, Z, L

36^d

7.87

Ajugoside

C₁₇H₂₅O₁₀

389.144 8/–

1.5

37^c

7.97

6-Methoxysalicylic acid

C₈H₈O₄

167.034 3/–

2.4

123.044 3, 121.028 9

G, X, C

38^c

8.80

2-Hydroxycaproic acid

C₆H₁₂O₃

131.070 5/–

1.5

85.064 8

X, G

39^b

8.85

Paeonolide^[17]

C₂₀H₂₈O₁₂

–/505.159 9

1.4

459.150 8, 293.087 8, 165.055 0

40^c

8.88

Apocynin

C₉H₁₀O₃

165.054 4/–

–1.2

41^b

8.89

Vicenin Ⅱ^[16]

C₂₇H₃₀O₁₅

593.151 2/–

1.8

503.120 0, 473.108 8, 413.087 1, 383.077 1, 353.066 6

42^b

9.26

Paeonolide^[17]

C₂₀H₂₈O₁₂

–/505.154 4

–1.6

459.150 9, 293.088 0, 165.055 0, 233.066 1

43^b

9.36

Galloyl-oxypaeoniflorin^[17]

C₃₀H₃₂O₁₆

647.161 9/–

1.8

509.128 8, 399.093 1, 313.056 7, 271.045 2, 211.024 3

44^b

9.44

p-Coumaric acid^{[18, 23]}

C₉H₈O₃

163.039 3/–

1.8

162.838 4, 159.859 2, 145.861 5, 123.945 5, 119.049 3

R, Z, S, G, C, R, L

45^d

9.50

Purpureaside C

C₃₅H₄₆O₂₀

785.250 4/–

0.6

46^b

9.81

Salvianolic acid F^[21]

C₁₇H₁₄O₆

313.071 9/–

4.1

269.081 7, 159.044 4

47^{a, b}

9.95

Paeoniflorin^[17]

C₂₃H₂₈O₁₁

–/525.161 1

1.5

525.161 2, 479.155 6, 449.154 5, 327.108 9, 165.054 9

48^c

10.21

3-Phenyllactic acid

C₉H₁₀O₃

165.055 0/–

2.4

147.044 4, 127.869 9, 119.049 3, 101.038 8

Z, D, M, X, C

49^d

10.42

Jionoside A

C₃₆H₄₈O₂₀

799.266 2/–

0.8

50^{a, b, c}

10.54

Ferulic acid^{[12, 24]}

C₁₀H₁₀O₄

193.050 1/–

3.1

193.050 1, 178.026 5, 149.060 0, 134.036 5

G, X, S, G, C

51^b

10.65

Isoferulic acid^[12]

C₁₀H₁₀O₄

193.050 3/–

4.1

178.026 5, 149.060 1, 134.036 5

G, X, S, G, C

52^{a, b}

10.72

Spinosin^[19]

C₂₈H₃₂O₁₅

607.166 8/–

1.8

607.167 0, 487.126 2, 445.114 6, 427.103 2, 325.071 8

53^b

10.84

Suffruticoside B/D^[17]

C₂₇H₃₂O₁₆

611.161 9/–

2.1

445.098 5, 343.067 7, 169.013 6

54^b

11.35

Acteoside^[11]

C₂₉H₃₆O₁₅

623.198 0/–

1.6

461.166 5, 161.023 7

55^b

11.36

Galloyl-paeoniflorin^[17]

C₃₀H₃₂O₁₅

631.166 9/–

1.9

509.131 3, 479.119 4, 399.092 4, 313.056 5, 169.013 6

56^b

11.65

Salvianolic acid H/I^[21]

C₂₇H₂₂O₁₂

537.101 2/–

–2.8

339.050 9, 295.061 1

57^d

11.68

Jionoside B

C₃₇H₅₀O₂₀

813.282 5/–

1.7

58^b

11.72

Rehmaionoside A/B^[11]

C₁₉H₃₄O₈

389.218 2/–

3.1

435.223 44

59^b

11.75

Salvianolic acid D^[21]

C₂₀H₁₈O₁₀

417.082 7/–

2.6

417.082 8, 197.045 1, 175.039 4, 157.028 7

60^b

11.90

Isoacteoside^[11]

C₂₉H₃₆O₁₅

623.197 5/–

0.8

461.166 8, 161.023 7

61^c

12.35

Salicylic acid

C₇H₆O₃

137.023 6/–

2.2

109.028 4, 93.033 6

G, D, M, X, C

62^b

12.45

Rehmannia bitterglycosides^[11]

C₁₆H₂₆O₈

345.155 7/–

3.8

183.102 0, 179.055 5, 165.091 4

63^b

12.60

Rosmarinic acid^[21]

C₁₈H₁₆O₈

359.077 0/–

2.5

359.077 5, 197.045 0, 179.034 4, 161.023 7, 133.028 7

64^c

12.71

Azelaic acid

C₉H₁₆O₄

187.097 0/–

2.7

169.086 3, 125.096 3

All

65^b

12.71

Salvianolic acid A^[21]

C₂₆H₂₂O₁₀

493.113 9/–

2.0

493.114 0, 313.071 5, 295.061 1, 185.023 9

66^b

12.74

Lithospermic acid^[21]

C₂₇H₂₂O₁₂

[M+M–H]^–:1 075.216 9

2.8

537.103 6, 340.898 9, 295.060 6

67^b

13.15

HOG^[17]

C₂₂H₂₄O₁₁

463.124 6/–

2.4

301.071 6, 271.064 5, 229.024 9

68^{b, c}

13.30

Salvianolic acid B^[21]

C₃₆H₃₀O₁₆

717.146 3/–

1.8

519.092 8, 339.050 5, 321.040 0, 295.060 5, 279.029 6

69^b

13.55

BOHD^[25]

C₁₉H₁₈O₈

373.092 4/–

1.6

345.098 5, 358.069 5, 343.082 4, 313.072 8

70^b

13.78

CMGC^[17]

C₃₀H₃₂O₁₃

599.176 9/–

1.7

551.152 2, 477.139 7, 447.129 9, 431.135 5, 281.066 7

71^b

13.92

Salvianolic acid E/Isosalvianolic acid B^[21]

C₃₆H₃₀O₁₆

717.146 1/–

1.5

717.145 8, 519.093 3, 339.050 9, 321.040 5, 295.061 2, 279.029 8

72^b

14.15

Salvianolic acid C^[21]

C₂₆H₂₀O₁₀

491.098 4/–

2.2

311.056 1, 293.045 7, 265.050 6

73^b

14.45

Benzoyloxypaeoniflorin^[17]

C₃₀H₃₂O₁₃

599.176 9/–

1.7

569.164 7, 477.138 5, 137.023 6, 121.028 6, 165.055 0

74^c

14.83

3-tert-Butyladipic acid

C₁₀H₁₈O₄

201.112 8/–

3.5

183.102 1, 157.122 6, 139.112 1

All

75^b

14.89

RI^[11]

C₃₁H₄₀O₁₅

651.229 6/–

2.0

475.183 9, 193.050 3, 175.039 4

76^b

16.35

GSPLLPT^[25]

C₃₆H₅₃N₇O₉

726.382 9/–

1.1

726.383 8, 696.372 0, 697.378 7, 590.330 5

77^b

16.50

Benzoyl paeoniflorin^[17]

C₃₀H₃₂O₁₂

–/629.188 0

2.4

583.182 3, 553.171 5, 431.135 3, 165.055 1

78^b

17.78

ATTPLI^[25]

C₃₄H₅₃N₇O₉

702.383 0/–

1.3

702.381 3, 658.356 0, 615.333 9, 614.330 6

79^{a, b}

17.85

Jujuboside A^[7]

C₅₈H₉₄O₂₆

–/1 251.601 1

0.6

80^{a, b}

18.36

Jujuboside B^[7]

C₅₂H₈₄O₂₁

–/1 089.547 5

–0.1

81^c

20.48

α-Estrdiol

C₁₈H₂₄O₂

271.170 2/–

3.7

No.	t_R/min	Identification	Molecularformula	[M–H]^–/[M+HCOO]^–	Error/ppm	Fragmentaion	Source
1^b	1.19	Rehmannioside D^[11]	C₂₇H₄₂O₁₀	685.218 2/–	–0.6	667.215 9, 523.161 2, 179.055 4, 361.110 4	D
2^c	1.23	D-Glucosamine	C₆H₁₃NO₅	178.071 4/–	2.8	160.060 7, 142.050 1, 124.039 5	G, M, Z, C, X
3^d	1.26	Stachyose	C₂₄H₄₂O₂₁	665.214 1/–	0.9	545.175 5, 503.159 2, 485.149 7	D
4^c	1.27	D-Raffinose	C₁₈H₃₂O₁₆	503.161 5/–	1.8	485.162 6, 443.140 3, 383.119 4, 341.108 5, 323.098 6	D, S
5^c	1.29	D-(+)-Mannose	C₆H₁₂O₆	179.055 5/–	2.8	161.044 8, 131.033 8, 113.023 7, 89.023 4	All
6^c	1.32	Gluconic acid	C₆H₁₂O₇	195.050 5/–	3.0	177.039 7, 159.029 2, 141.018 5, 129.018 5	D, S, Z, M, G, X
7^c	1.34	D-(–)-Quinic acid	C₇H₁₂O₆	191.055 5/–	2.6	173.044 8, 155.034 1, 147.029 3, 137.023 4	G, S, X, M, C
8^d	1.35	Sucrose	C₁₂H₂₂O₁₁	341.108 6/–	2.3	179.055 5, 161.044 9, 143.034 1, 89.023 4	All
9^c	1.69	2-Furoic acid	C₅H₄O₃	111.007 8/–	1.8	83.012 9, 67.017 9	All
10^{b, c}	1.71	Citric acid^[11]	C₆H₈O₇	191.019 1/–	–0.5	173.008 4, 129.018 4, 111.007 8, 147.029 0	All
11^{a, b}	1.78	Catalpol^[11]	C₁₅H₂₂O₁₀	361.113 9/–	2.8	199.060 5, 169.050 0, 331.066 9	D
12^{b, c}	1.86	Succinic acid^[22]	C₄H₆O₄	117.018 4/–	1.7	99.007 8, 73.028 5, 55.017 9	All
13^b	1.89	Galloyl-glucose^[17]	C₁₃H₁₆O₁₀	331.066 7/–	2.1	271.045 8, 211.024 3, 191.019 1, 169.013 5	M
14^b	2.03	RehmanniosideA^[11]	C₂₁H₃₂O₁₅	523.166 7/–	1.9	505.167 3, 361.131 3, 323.096 8, 199.060 8	D
15^{a, b, c}	2.14	Gallic acid^[17]	C₇H₆O₅	169.013 5/–	2.4	125.023 6, 97.028 4	Z, M
16^b	2.25	Danmelittoside^[11]	C₁₅H₂₂O₁₀	361.114 0/–	3.0	199.060 8, 179.055 6, 161.044 9	D
17^b	2.44	Peony glucoside B^[17]	C₁₈H₂₄O₁₄	463.109 1/–	1.9	463.109 1, 403.088 0, 373.077 7, 343.066 9, 301.056 4	M
18^b	2.88	Aucubin^[11]	C₁₅H₂₂O₉	345.118 7/–	2.0	327.128 0, 309.108 9, 183.066 1, 165.055 2	D
19^b	3.06	Vanillic acid^[18]	C₈H₈O₄	167.034 2/–	1.8	152.010 8, 137.023 0, 139.039 3, 123.044 3	X, Z, S, G, B
20^b	3.06	Pseudolaroside B^[15]	C₁₄H₁₈O₉	329.087 6/–	2.7	167.034 2, 152.010 7	Z, B, R
21^b	3.10	Tanshinol^[21]	C₉H₉O₅	197.045 0/–	3.0	179.034 4, 151.039 4, 135.044 3, 123.044 2	S
22^b	3.13	HA^[23]	C₈H₈O₃	151.039 3/–	2.0	133.028 5, 123.044 3, 107.049 3, 93.033 7	R, S, X, G, B
23^d	3.43	Dihydrocatalpol	C₁₅H₂₄O₁₀	363.128 8/–	0.8		D
24^b	3.51	Protocatechuic acid^[21]	C₇H₆O₄	153.018 6/–	2.6	141.911 7, 109.028 6, 123.901 0, 110.031 9	S, X, G, C, F, B, R, L
25^{a, b}	4.41	Neochlorogenic acid^[24]	C₁₆H₁₈O₉	353.087 7/–	2.8	353.087 6, 191.055 6, 179.034 3, 173.045 0	Z, X, G
26^c	4.99	DHA	C₉H₁₀O₄	181.050 0/–	2.8	163.039 3, 135.044 3	S, Z
27^d	5.22	Leonuride	C₁₅H₂₄O₉	347.134 7/–	3.2		D
28^b	5.62	Protocatechuic aldehyde^[21]	C₇H₆O₃	137.023 6/–	2.2	119.013 0, 109.028 5, 108.020 6	All
29^b	6.79	Geniposide^[11]	C₁₇H₂₄O₁₀	387.129 5/–	2.3	225.076 0	D, R
30^{a, b}	7.05	Chlorogenic acid^{[18, 24]}	C₁₆H₁₈O₉	353.087 7/–	2.8	353.087 6, 191.055 7, 179.034 0, 173.045 4	X, Z, G, C
31^b	7.20	Oxypaeoniflorin^[17]	C₂₃H₂₈O₁₂	495.150 6/–	1.8	465.141 1, 333.098 0, 165.055 0, 137.023 6	M
32^{a, b}	7.52	Cryptochlorogenic acid^[24]	C₁₆H₁₈O₉	353.087 7/–	2.8	353.087 4, 191.055 6, 179.034 3, 173.044 8	X, G
33^{a, b, c}	7.52	Caffeic acid^[21]	C₉H₈O₄	179.034 3/–	2.2	143.864 7, 135.044 3, 104.927 0, 89.023 4	S, D, C, Z, R
34^c	7.55	Isophthalic acid	C₈H₆O₄	165.018 6/–	2.4	121.028 6	G, Z, X, C
35^{b, c}	7.82	Benzoic acid^[18]	C₇H₆O₂	121.028 6/–	1.6	93.033 7, 77.038 5	Z, M, C, F, B, Z, L
36^d	7.87	Ajugoside	C₁₇H₂₅O₁₀	389.144 8/–	1.5		D
37^c	7.97	6-Methoxysalicylic acid	C₈H₈O₄	167.034 3/–	2.4	123.044 3, 121.028 9	G, X, C
38^c	8.80	2-Hydroxycaproic acid	C₆H₁₂O₃	131.070 5/–	1.5	85.064 8	X, G
39^b	8.85	Paeonolide^[17]	C₂₀H₂₈O₁₂	–/505.159 9	1.4	459.150 8, 293.087 8, 165.055 0	M
40^c	8.88	Apocynin	C₉H₁₀O₃	165.054 4/–	–1.2		M
41^b	8.89	Vicenin Ⅱ^[16]	C₂₇H₃₀O₁₅	593.151 2/–	1.8	503.120 0, 473.108 8, 413.087 1, 383.077 1, 353.066 6	S
42^b	9.26	Paeonolide^[17]	C₂₀H₂₈O₁₂	–/505.154 4	–1.6	459.150 9, 293.088 0, 165.055 0, 233.066 1	M
43^b	9.36	Galloyl-oxypaeoniflorin^[17]	C₃₀H₃₂O₁₆	647.161 9/–	1.8	509.128 8, 399.093 1, 313.056 7, 271.045 2, 211.024 3	M
44^b	9.44	p-Coumaric acid^{[18, 23]}	C₉H₈O₃	163.039 3/–	1.8	162.838 4, 159.859 2, 145.861 5, 123.945 5, 119.049 3	R, Z, S, G, C, R, L
45^d	9.50	Purpureaside C	C₃₅H₄₆O₂₀	785.250 4/–	0.6		D
46^b	9.81	Salvianolic acid F^[21]	C₁₇H₁₄O₆	313.071 9/–	4.1	269.081 7, 159.044 4	S
47^{a, b}	9.95	Paeoniflorin^[17]	C₂₃H₂₈O₁₁	–/525.161 1	1.5	525.161 2, 479.155 6, 449.154 5, 327.108 9, 165.054 9	M
48^c	10.21	3-Phenyllactic acid	C₉H₁₀O₃	165.055 0/–	2.4	147.044 4, 127.869 9, 119.049 3, 101.038 8	Z, D, M, X, C
49^d	10.42	Jionoside A	C₃₆H₄₈O₂₀	799.266 2/–	0.8		D
50^{a, b, c}	10.54	Ferulic acid^{[12, 24]}	C₁₀H₁₀O₄	193.050 1/–	3.1	193.050 1, 178.026 5, 149.060 0, 134.036 5	G, X, S, G, C
51^b	10.65	Isoferulic acid^[12]	C₁₀H₁₀O₄	193.050 3/–	4.1	178.026 5, 149.060 1, 134.036 5	G, X, S, G, C
52^{a, b}	10.72	Spinosin^[19]	C₂₈H₃₂O₁₅	607.166 8/–	1.8	607.167 0, 487.126 2, 445.114 6, 427.103 2, 325.071 8	Z
53^b	10.84	Suffruticoside B/D^[17]	C₂₇H₃₂O₁₆	611.161 9/–	2.1	445.098 5, 343.067 7, 169.013 6	M
54^b	11.35	Acteoside^[11]	C₂₉H₃₆O₁₅	623.198 0/–	1.6	461.166 5, 161.023 7	D
55^b	11.36	Galloyl-paeoniflorin^[17]	C₃₀H₃₂O₁₅	631.166 9/–	1.9	509.131 3, 479.119 4, 399.092 4, 313.056 5, 169.013 6	M
56^b	11.65	Salvianolic acid H/I^[21]	C₂₇H₂₂O₁₂	537.101 2/–	–2.8	339.050 9, 295.061 1	S
57^d	11.68	Jionoside B	C₃₇H₅₀O₂₀	813.282 5/–	1.7		D
58^b	11.72	Rehmaionoside A/B^[11]	C₁₉H₃₄O₈	389.218 2/–	3.1	435.223 44	D
59^b	11.75	Salvianolic acid D^[21]	C₂₀H₁₈O₁₀	417.082 7/–	2.6	417.082 8, 197.045 1, 175.039 4, 157.028 7	S
60^b	11.90	Isoacteoside^[11]	C₂₉H₃₆O₁₅	623.197 5/–	0.8	461.166 8, 161.023 7	D
61^c	12.35	Salicylic acid	C₇H₆O₃	137.023 6/–	2.2	109.028 4, 93.033 6	G, D, M, X, C
62^b	12.45	Rehmannia bitterglycosides^[11]	C₁₆H₂₆O₈	345.155 7/–	3.8	183.102 0, 179.055 5, 165.091 4	D
63^b	12.60	Rosmarinic acid^[21]	C₁₈H₁₆O₈	359.077 0/–	2.5	359.077 5, 197.045 0, 179.034 4, 161.023 7, 133.028 7	S
64^c	12.71	Azelaic acid	C₉H₁₆O₄	187.097 0/–	2.7	169.086 3, 125.096 3	All
65^b	12.71	Salvianolic acid A^[21]	C₂₆H₂₂O₁₀	493.113 9/–	2.0	493.114 0, 313.071 5, 295.061 1, 185.023 9	S
66^b	12.74	Lithospermic acid^[21]	C₂₇H₂₂O₁₂	[M+M–H]^–:1 075.216 9	2.8	537.103 6, 340.898 9, 295.060 6	S
67^b	13.15	HOG^[17]	C₂₂H₂₄O₁₁	463.124 6/–	2.4	301.071 6, 271.064 5, 229.024 9	C
68^{b, c}	13.30	Salvianolic acid B^[21]	C₃₆H₃₀O₁₆	717.146 3/–	1.8	519.092 8, 339.050 5, 321.040 0, 295.060 5, 279.029 6	S
69^b	13.55	BOHD^[25]	C₁₉H₁₈O₈	373.092 4/–	1.6	345.098 5, 358.069 5, 343.082 4, 313.072 8	C
70^b	13.78	CMGC^[17]	C₃₀H₃₂O₁₃	599.176 9/–	1.7	551.152 2, 477.139 7, 447.129 9, 431.135 5, 281.066 7	M
71^b	13.92	Salvianolic acid E/Isosalvianolic acid B^[21]	C₃₆H₃₀O₁₆	717.146 1/–	1.5	717.145 8, 519.093 3, 339.050 9, 321.040 5, 295.061 2, 279.029 8	S
72^b	14.15	Salvianolic acid C^[21]	C₂₆H₂₀O₁₀	491.098 4/–	2.2	311.056 1, 293.045 7, 265.050 6	S
73^b	14.45	Benzoyloxypaeoniflorin^[17]	C₃₀H₃₂O₁₃	599.176 9/–	1.7	569.164 7, 477.138 5, 137.023 6, 121.028 6, 165.055 0	M
74^c	14.83	3-tert-Butyladipic acid	C₁₀H₁₈O₄	201.112 8/–	3.5	183.102 1, 157.122 6, 139.112 1	All
75^b	14.89	RI^[11]	C₃₁H₄₀O₁₅	651.229 6/–	2.0	475.183 9, 193.050 3, 175.039 4	D
76^b	16.35	GSPLLPT^[25]	C₃₆H₅₃N₇O₉	726.382 9/–	1.1	726.383 8, 696.372 0, 697.378 7, 590.330 5	C
77^b	16.50	Benzoyl paeoniflorin^[17]	C₃₀H₃₂O₁₂	–/629.188 0	2.4	583.182 3, 553.171 5, 431.135 3, 165.055 1	M
78^b	17.78	ATTPLI^[25]	C₃₄H₅₃N₇O₉	702.383 0/–	1.3	702.381 3, 658.356 0, 615.333 9, 614.330 6	C
79^{a, b}	17.85	Jujuboside A^[7]	C₅₈H₉₄O₂₆	–/1 251.601 1	0.6		Z
80^{a, b}	18.36	Jujuboside B^[7]	C₅₂H₈₄O₂₁	–/1 089.547 5	–0.1		Z
81^c	20.48	α-Estrdiol	C₁₈H₂₄O₂	271.170 2/–	3.7		S

No.

t_R/min

Identification

Molecularformula

[M–H]^–/[M+HCOO]^–

Error/ppm

Fragmentaion

Source

1^b

1.19

Rehmannioside D^[11]

C₂₇H₄₂O₁₀

685.218 2/–

–0.6

667.215 9, 523.161 2, 179.055 4, 361.110 4

2^c

1.23

D-Glucosamine

C₆H₁₃NO₅

178.071 4/–

2.8

160.060 7, 142.050 1, 124.039 5

G, M, Z, C, X

3^d

1.26

Stachyose

C₂₄H₄₂O₂₁

665.214 1/–

0.9

545.175 5, 503.159 2, 485.149 7

4^c

1.27

D-Raffinose

C₁₈H₃₂O₁₆

503.161 5/–

1.8

485.162 6, 443.140 3, 383.119 4, 341.108 5, 323.098 6

D, S

5^c

1.29

D-(+)-Mannose

C₆H₁₂O₆

179.055 5/–

2.8

161.044 8, 131.033 8, 113.023 7, 89.023 4

All

6^c

1.32

Gluconic acid

C₆H₁₂O₇

195.050 5/–

3.0

177.039 7, 159.029 2, 141.018 5, 129.018 5

D, S, Z, M, G, X

7^c

1.34

D-(–)-Quinic acid

C₇H₁₂O₆

191.055 5/–

2.6

173.044 8, 155.034 1, 147.029 3, 137.023 4

G, S, X, M, C

8^d

1.35

Sucrose

C₁₂H₂₂O₁₁

341.108 6/–

2.3

179.055 5, 161.044 9, 143.034 1, 89.023 4

All

9^c

1.69

2-Furoic acid

C₅H₄O₃

111.007 8/–

1.8

83.012 9, 67.017 9

All

10^{b, c}

1.71

Citric acid^[11]

C₆H₈O₇

191.019 1/–

–0.5

173.008 4, 129.018 4, 111.007 8, 147.029 0

All

11^{a, b}

1.78

Catalpol^[11]

C₁₅H₂₂O₁₀

361.113 9/–

2.8

199.060 5, 169.050 0, 331.066 9

12^{b, c}

1.86

Succinic acid^[22]

C₄H₆O₄

117.018 4/–

1.7

99.007 8, 73.028 5, 55.017 9

All

13^b

1.89

Galloyl-glucose^[17]

C₁₃H₁₆O₁₀

331.066 7/–

2.1

271.045 8, 211.024 3, 191.019 1, 169.013 5

14^b

2.03

RehmanniosideA^[11]

C₂₁H₃₂O₁₅

523.166 7/–

1.9

505.167 3, 361.131 3, 323.096 8, 199.060 8

15^{a, b, c}

2.14

Gallic acid^[17]

C₇H₆O₅

169.013 5/–

2.4

125.023 6, 97.028 4

Z, M

16^b

2.25

Danmelittoside^[11]

C₁₅H₂₂O₁₀

361.114 0/–

3.0

199.060 8, 179.055 6, 161.044 9

17^b

2.44

Peony glucoside B^[17]

C₁₈H₂₄O₁₄

463.109 1/–

1.9

463.109 1, 403.088 0, 373.077 7, 343.066 9, 301.056 4

18^b

2.88

Aucubin^[11]

C₁₅H₂₂O₉

345.118 7/–

2.0

327.128 0, 309.108 9, 183.066 1, 165.055 2

19^b

3.06

Vanillic acid^[18]

C₈H₈O₄

167.034 2/–

1.8

152.010 8, 137.023 0, 139.039 3, 123.044 3

X, Z, S, G, B

20^b

3.06

Pseudolaroside B^[15]

C₁₄H₁₈O₉

329.087 6/–

2.7

167.034 2, 152.010 7

Z, B, R

21^b

3.10

Tanshinol^[21]

C₉H₉O₅

197.045 0/–

3.0

179.034 4, 151.039 4, 135.044 3, 123.044 2

22^b

3.13

HA^[23]

C₈H₈O₃

151.039 3/–

2.0

133.028 5, 123.044 3, 107.049 3, 93.033 7

R, S, X, G, B

23^d

3.43

Dihydrocatalpol

C₁₅H₂₄O₁₀

363.128 8/–

0.8

24^b

3.51

Protocatechuic acid^[21]

C₇H₆O₄

153.018 6/–

2.6

141.911 7, 109.028 6, 123.901 0, 110.031 9

S, X, G, C, F, B, R, L

25^{a, b}

4.41

Neochlorogenic acid^[24]

C₁₆H₁₈O₉

353.087 7/–

2.8

353.087 6, 191.055 6, 179.034 3, 173.045 0

Z, X, G

26^c

4.99

DHA

C₉H₁₀O₄

181.050 0/–

2.8

163.039 3, 135.044 3

S, Z

27^d

5.22

Leonuride

C₁₅H₂₄O₉

347.134 7/–

3.2

28^b

5.62

Protocatechuic aldehyde^[21]

C₇H₆O₃

137.023 6/–

2.2

119.013 0, 109.028 5, 108.020 6

All

29^b

6.79

Geniposide^[11]

C₁₇H₂₄O₁₀

387.129 5/–

2.3

225.076 0

D, R

30^{a, b}

7.05

Chlorogenic acid^{[18, 24]}

C₁₆H₁₈O₉

353.087 7/–

2.8

353.087 6, 191.055 7, 179.034 0, 173.045 4

X, Z, G, C

31^b

7.20

Oxypaeoniflorin^[17]

C₂₃H₂₈O₁₂

495.150 6/–

1.8

465.141 1, 333.098 0, 165.055 0, 137.023 6

32^{a, b}

7.52

Cryptochlorogenic acid^[24]

C₁₆H₁₈O₉

353.087 7/–

2.8

353.087 4, 191.055 6, 179.034 3, 173.044 8

X, G

33^{a, b, c}

7.52

Caffeic acid^[21]

C₉H₈O₄

179.034 3/–

2.2

143.864 7, 135.044 3, 104.927 0, 89.023 4

S, D, C, Z, R

34^c

7.55

Isophthalic acid

C₈H₆O₄

165.018 6/–

2.4

121.028 6

G, Z, X, C

35^{b, c}

7.82

Benzoic acid^[18]

C₇H₆O₂

121.028 6/–

1.6

93.033 7, 77.038 5

Z, M, C, F, B, Z, L

36^d

7.87

Ajugoside

C₁₇H₂₅O₁₀

389.144 8/–

1.5

37^c

7.97

6-Methoxysalicylic acid

C₈H₈O₄

167.034 3/–

2.4

123.044 3, 121.028 9

G, X, C

38^c

8.80

2-Hydroxycaproic acid

C₆H₁₂O₃

131.070 5/–

1.5

85.064 8

X, G

39^b

8.85

Paeonolide^[17]

C₂₀H₂₈O₁₂

–/505.159 9

1.4

459.150 8, 293.087 8, 165.055 0

40^c

8.88

Apocynin

C₉H₁₀O₃

165.054 4/–

–1.2

41^b

8.89

Vicenin Ⅱ^[16]

C₂₇H₃₀O₁₅

593.151 2/–

1.8

503.120 0, 473.108 8, 413.087 1, 383.077 1, 353.066 6

42^b

9.26

Paeonolide^[17]

C₂₀H₂₈O₁₂

–/505.154 4

–1.6

459.150 9, 293.088 0, 165.055 0, 233.066 1

43^b

9.36

Galloyl-oxypaeoniflorin^[17]

C₃₀H₃₂O₁₆

647.161 9/–

1.8

509.128 8, 399.093 1, 313.056 7, 271.045 2, 211.024 3

44^b

9.44

p-Coumaric acid^{[18, 23]}

C₉H₈O₃

163.039 3/–

1.8

162.838 4, 159.859 2, 145.861 5, 123.945 5, 119.049 3

R, Z, S, G, C, R, L

45^d

9.50

Purpureaside C

C₃₅H₄₆O₂₀

785.250 4/–

0.6

46^b

9.81

Salvianolic acid F^[21]

C₁₇H₁₄O₆

313.071 9/–

4.1

269.081 7, 159.044 4

47^{a, b}

9.95

Paeoniflorin^[17]

C₂₃H₂₈O₁₁

–/525.161 1

1.5

525.161 2, 479.155 6, 449.154 5, 327.108 9, 165.054 9

48^c

10.21

3-Phenyllactic acid

C₉H₁₀O₃

165.055 0/–

2.4

147.044 4, 127.869 9, 119.049 3, 101.038 8

Z, D, M, X, C

49^d

10.42

Jionoside A

C₃₆H₄₈O₂₀

799.266 2/–

0.8

50^{a, b, c}

10.54

Ferulic acid^{[12, 24]}

C₁₀H₁₀O₄

193.050 1/–

3.1

193.050 1, 178.026 5, 149.060 0, 134.036 5

G, X, S, G, C

51^b

10.65

Isoferulic acid^[12]

C₁₀H₁₀O₄

193.050 3/–

4.1

178.026 5, 149.060 1, 134.036 5

G, X, S, G, C

52^{a, b}

10.72

Spinosin^[19]

C₂₈H₃₂O₁₅

607.166 8/–

1.8

607.167 0, 487.126 2, 445.114 6, 427.103 2, 325.071 8

53^b

10.84

Suffruticoside B/D^[17]

C₂₇H₃₂O₁₆

611.161 9/–

2.1

445.098 5, 343.067 7, 169.013 6

54^b

11.35

Acteoside^[11]

C₂₉H₃₆O₁₅

623.198 0/–

1.6

461.166 5, 161.023 7

55^b

11.36

Galloyl-paeoniflorin^[17]

C₃₀H₃₂O₁₅

631.166 9/–

1.9

509.131 3, 479.119 4, 399.092 4, 313.056 5, 169.013 6

56^b

11.65

Salvianolic acid H/I^[21]

C₂₇H₂₂O₁₂

537.101 2/–

–2.8

339.050 9, 295.061 1

57^d

11.68

Jionoside B

C₃₇H₅₀O₂₀

813.282 5/–

1.7

58^b

11.72

Rehmaionoside A/B^[11]

C₁₉H₃₄O₈

389.218 2/–

3.1

435.223 44

59^b

11.75

Salvianolic acid D^[21]

C₂₀H₁₈O₁₀

417.082 7/–

2.6

417.082 8, 197.045 1, 175.039 4, 157.028 7

60^b

11.90

Isoacteoside^[11]

C₂₉H₃₆O₁₅

623.197 5/–

0.8

461.166 8, 161.023 7

61^c

12.35

Salicylic acid

C₇H₆O₃

137.023 6/–

2.2

109.028 4, 93.033 6

G, D, M, X, C

62^b

12.45

Rehmannia bitterglycosides^[11]

C₁₆H₂₆O₈

345.155 7/–

3.8

183.102 0, 179.055 5, 165.091 4

63^b

12.60

Rosmarinic acid^[21]

C₁₈H₁₆O₈

359.077 0/–

2.5

359.077 5, 197.045 0, 179.034 4, 161.023 7, 133.028 7

64^c

12.71

Azelaic acid

C₉H₁₆O₄

187.097 0/–

2.7

169.086 3, 125.096 3

All

65^b

12.71

Salvianolic acid A^[21]

C₂₆H₂₂O₁₀

493.113 9/–

2.0

493.114 0, 313.071 5, 295.061 1, 185.023 9

66^b

12.74

Lithospermic acid^[21]

C₂₇H₂₂O₁₂

[M+M–H]^–:1 075.216 9

2.8

537.103 6, 340.898 9, 295.060 6

67^b

13.15

HOG^[17]

C₂₂H₂₄O₁₁

463.124 6/–

2.4

301.071 6, 271.064 5, 229.024 9

68^{b, c}

13.30

Salvianolic acid B^[21]

C₃₆H₃₀O₁₆

717.146 3/–

1.8

519.092 8, 339.050 5, 321.040 0, 295.060 5, 279.029 6

69^b

13.55

BOHD^[25]

C₁₉H₁₈O₈

373.092 4/–

1.6

345.098 5, 358.069 5, 343.082 4, 313.072 8

70^b

13.78

CMGC^[17]

C₃₀H₃₂O₁₃

599.176 9/–

1.7

551.152 2, 477.139 7, 447.129 9, 431.135 5, 281.066 7

71^b

13.92

Salvianolic acid E/Isosalvianolic acid B^[21]

C₃₆H₃₀O₁₆

717.146 1/–

1.5

717.145 8, 519.093 3, 339.050 9, 321.040 5, 295.061 2, 279.029 8

72^b

14.15

Salvianolic acid C^[21]

C₂₆H₂₀O₁₀

491.098 4/–

2.2

311.056 1, 293.045 7, 265.050 6

73^b

14.45

Benzoyloxypaeoniflorin^[17]

C₃₀H₃₂O₁₃

599.176 9/–

1.7

569.164 7, 477.138 5, 137.023 6, 121.028 6, 165.055 0

74^c

14.83

3-tert-Butyladipic acid

C₁₀H₁₈O₄

201.112 8/–

3.5

183.102 1, 157.122 6, 139.112 1

All

75^b

14.89

RI^[11]

C₃₁H₄₀O₁₅

651.229 6/–

2.0

475.183 9, 193.050 3, 175.039 4

76^b

16.35

GSPLLPT^[25]

C₃₆H₅₃N₇O₉

726.382 9/–

1.1

726.383 8, 696.372 0, 697.378 7, 590.330 5

77^b

16.50

Benzoyl paeoniflorin^[17]

C₃₀H₃₂O₁₂

–/629.188 0

2.4

583.182 3, 553.171 5, 431.135 3, 165.055 1

78^b

17.78

ATTPLI^[25]

C₃₄H₅₃N₇O₉

702.383 0/–

1.3

702.381 3, 658.356 0, 615.333 9, 614.330 6

79^{a, b}

17.85

Jujuboside A^[7]

C₅₈H₉₄O₂₆

–/1 251.601 1

0.6

80^{a, b}

18.36

Jujuboside B^[7]

C₅₂H₈₄O₂₁

–/1 089.547 5

–0.1

81^c

20.48

α-Estrdiol

C₁₈H₂₄O₂

271.170 2/–

3.7

No.	t_R/min	Identification	Molecularformula	[M+H]⁺/[M+Na]⁺	Error/ppm	Fragmentaion	Source
1^b	1.21	Lysine^[22]	C₆H₁₄N₂O₂	147.112 9/–	0.7	130.086 5	All
2^b	1.24	Arginine^[22]	C₆H₁₄N₄O₂	175.119 0/–	0.6	116.070 8	All
3^c	1.26	Choline	C₅H₁₃NO	104.107 3/–	2.9	87.044 4, 69.034 0	All
4^c	1.32	Proline	C₅H₉NO₂	116.070 8/–	1.7	98.984 4, 70.065 7	All
5^b	1.34	Glutamate^[22]	C₅H₉NO₄	148.060 4/–	0	135.050 0	All
6^c	1.34	DL-Stachydrine	C₇H₁₃NO₂	144.101 9/–	0	102.150 0, 84.081 2	All
7^c	1.42	DF	C₉H₁₁NO	150.091 4/–	0.6	135.067 9, 132.080 8, 117.057 8	G, S, D, X, C
8^c	1.67	Phenylephrine	C₉H₁₃NO₂	168.102 0/–	1.2	150.091 5
9^c	1.68	L-Pyroglutamic acid	C₅H₇NO₃	130.050 1/–	2.3	102.055 3, 84.044 9	All
10^b	1.70	Adenosine^[22]	C₁₀H₁₃N₅O₄	268.104 0/–	0	136.061 8, 119.035 6	All
11^b	1.70	Hypoxanthine^[22]	C₅H₄N₄O	137.045 9/–	0.7	119.035 7, 110.035 1	L, S, X, R
12^c	1.71	L-Tyrosine	C₉H₁₁NO₃	182.081 3/–	0.5	165.054 6, 147.044 0, 136.075 7	All
13^b	1.74	Tyrosine^[22]	C₉H₁₁NO₃	182.081 2/–	0	165.054 6, 136.075 7, 119.049 3, 107.049 7, 95.049 6	All
14^b	1.77	Guanine^[22]	C₅H₅N₅O	152.056 8/–	0.6	135.030 2, 110.035 3, 55.029 9	All
15^b	1.91	Glutarylcarnitine^[22]	C₁₂H₂₁NO₆	276.144 0/–	–0.7	258.133 5, 230.138 6, 212.127 9, 170.117 8, 144.101 9	All
16^b	2.05	ANDA^[22]	C₁₂H₂₁NO₆	276.143 9/–	–1.0	258.133 5, 230.138 6, 212.128 2, 170.117 3, 161.068 3	All
17^{b, c}	2.13	L-Norleucine^[22]	C₆H₁₃NO₂	132.101 9/–	0	86.096 9, 69.070 4	All
18^c	2.10	Pyrogallol	C₆H₆O₃	127.039 1/–	0.8	109.028 6	All
19^b	2.83	GHIA^[15]	C₁₆H₁₉NO₉	370.113 8/–	1.4	352.100 6, 308.113 1, 290.101 8, 272.114 3, 232.071 6	Z
20^{b, c}	2.94	L-Phenylalanine^[22]	C₉H₁₁NO₂	166.086 2/–	–1.2	149.059 5, 120.081 0, 103.054 5, 91.054 4, 77.039 2	All
21^c	3.01	5-Hydroxymethyl-2-furaldehyde	C₆H₆O₃	127.039 1/–	0.8	109.028 7, 99.044 3	All
22^b	3.02	Fructose phenylalanine^[22]	C₁₅H₂₁NO₇	328.138 9/–	–0.6	310.128 3, 292.117 6, 282.134 2, 264.122 7, 178.086 1	L, S, D, M, X, C, R
23^b	3.02	AEOA^[22]	C₁₅H₁₉NO₆	310.127 7/–	–2.6	292.117 7, 264.122 9, 178.086 1, 166.086 2	L, S, D, X, G
24^c	3.05	Isovanillic acid	C₈H₈O₄	169.049 5/–	0		X, Z, S, G, B
25^b	3.08	GHIA^[15]	C₁₆H₁₉NO₉	370.113 0/–	–0.8	352.100 7, 308.112 9, 290.100 2, 272.112 6, 208.060 5	Z
26^{b, c}	5.39	L-Tryptophan^[22]	C₁₁H₁₂N₂O₂	205.097 5/–	2.0	188.070 6, 159.091 7, 132.080 7, 130.065 1, 118.065 3	L, Z, S, M, X, G, C
27^c	5.62	2, 5-Dihydroxybenzaldehyde	C₇H₆O₃	139.039 1/–	0.7	121.028 6, 111.044 3, 102.948 4	All
28^b	5.85	N-Glc-indoleaceticacid^[15]	C₁₆H₁₉NO₈	354.118 3/–	0	188.070 6, 174.054 9, 146.060 2, 128.049 6	Z
29^b	6.75	6-Glc-coclaurine^[15]	C₂₃H₂₉NO₈	448.196 3/–	–0.7	286.143 7, 269.117 0, 237.090 8, 219.081 4, 209.095 9	Z
30^b	6.81	N-Glc-indoleaceticacid^[15]	C₁₆H₁₉NO₈	354.118 3/–	0	188.070 6, 146.060 1, 128.049 7	Z
31^c	7.72	6-Methylquinoline	C₁₀H₉N	144.080 9/–	0.7	128.950 9, 126.955 2	Z
32^b	8.64	Coclaurine^[15]	C₁₇H₁₉NO₃	286.143 6/–	–0.7	269.117 0, 254.094 1, 237.090 8, 219.080 6, 209.096 1	Z
33^c	8.67	Morphine	C₁₇H₁₉NO₃	286.143 6/–	–0.7	269.117 0, 254.094 1, 237.090 8, 209.096 1	Z
34^b	8.86	Juzirine^[15]	C₁₇H₁₅NO₃	282.112 5/–	0	238.038 7, 188.070 8	Z
35^b	8.90	Meloside A^[15]	C₂₇H₃₀O₁₅	595.165 3/–	–0.7	379.080 8, 367.084 0, 337.070 6, 313.071 5, 283.061 0	Z
36^b	9.20	Zizyphusine^[15]	C₂₀H₂₄NO₄⁺	[M]⁺:342.169 9	–0.3	297.112 0, 282.088 6, 265.085 8, 237.090 9, 222.067 4	Z, B
37^b	9.27	Magnoflorine^[19]	C₂₀H₂₃NO₄	342.170 1/–	0.3	342.169 9, 311.127 0, 299.127 7, 297.112 0, 282.088 6	Z, B
38^c	9.56	Naringenin	C₁₅H₁₂O₅	273.075 7/–	0	171.028 7, 153.018 3, 147.044 1, 119.049 3	C
39^b	10.11	Lotusine^[15]	C₁₉H₂₄NO₃⁺	[M]⁺: 314.175 0	–0.3	237.091 6, 209.096 3, 165.069 9, 137.059 8, 107.049 5	Z
40^b	10.44	Camelliaside B^[15]	C₃₂H₃₈O₁₉	727.208 3/–	0.4	595.163 0, 449.114 4, 287.054 7	Z
41^d	10.59	Quercetin	C₁₅H₁₀O₇	303.049 9/–	0		M
42^c	10.69	Neodiosmin	C₂₈H₃₂O₁₅	609.180 8/–	0.8	591.166 0, 447.128 3, 327.086 1, 285.075 3	Z
43^b	10.81	Senkyunolide H/I^{[12, 13]}	C₁₂H₁₆O₄	225.111 8/–	–1.3	207.101 8, 189.091 2, 164.042 3, 161.096 1	G, X
44^{a, b, c}	11.85	Naringin^[14]	C₂₇H₃₂O₁₄	581.186 8/ 603.168 4	0.7/ 0.3	435.128 1, 401.123 0, 383.111 7, 273.075 6	C
45^c	11.85	Prunin	C₂₁H₂₂O₁₀	435.128 5/–	0	399.107 1, 273.075 7, 147.044 1, 119.019 2	C
46^d	11.95	Perlolyrine	C₁₆H₁₂N₂O₂	265.097 3/–	0.7		X
47^d	12.32	Senkyunolide-N	C₁₂H₁₈O₄	227.127 7/–	0		X
48^{a, b, c,}	12.62	Hesperidin^[14]	C₂₈H₃₄O₁₅	611.197 7/633.179 6	1.1/ 1.1	557.158 6, 465.139 1, 449.144 4, 303.086 3, 177.054 6, 151.075 1	C
49^c	12.62	Hesperetin	C₁₆H₁₄O₆	303.086 3/–	0	177.054 6, 153.018 2	C
50^c	12.65	Obacunoic acid	C₂₆H₃₂O₈	473.217 3/–	0.6	455.205 1, 427.211 5, 413.194 5, 395.183 9	C
51^{a, b}	12.69	Swertisin^[15]	C₂₂H₂₂O₁₀	447.130 8/–	4.9	411.107 0, 327.085 9, 297.075 7	Z
52^c	13.31	1, 4-Dimethoxyanthraquinone	C₁₆H₁₂O₄	269.080 7/–	–0.4		S
53^b	13.68	Senkyunolide H/I^{[12, 13]}	C₁₂H₁₆O₄	225.112 0/–	–0.4	207.101 7, 164.042 3, 161.096 1, 179.106 2	G, X
54^b	13.94	Mucronine J^[15]	C₂₇H₄₀N₄O₄	485.311 7/–	–1.0	221.080 6, 207.065 4, 114.124 9	Z
55^d	14.82	6'-p-coumaroylspinosin	C₃₈H₄₀O₁₇	769.230 8/–	–3.9		Z
56^b	15.12	Poncirin^[14]	C₂₈H₃₄O₁₄	595.202 1/617.183 8	0	433.148 9, 415.138 1, 397.128 3, 353.100 9	C
57^c	15.13	Sakuranetin	C₁₆H₁₄O₅	287.091 1/–	–1.0	171.028 6, 161.059 6, 153.018 1	C
58^{a, b}	16.26	E-Butylidenephthalide^{[12, 13]}	C₁₂H₁₂O₂	189.091 1/–	0.5	189.091 0, 171.080 4, 143.085 6, 105.033 8, 153.069 5	X, G
59^b	16.58	Narirutin^[13]	C₂₇H₃₂O₁₄	581.186 5/603.168 4	0	419.133 5, 404.110 1, 389.086 5, 371.076 2	C
60^d	16.92	Sanjoinine A	C₃₁H₄₂N₄O₄	535.327 8/–	0		Z
61^b	17.21	Paeonol^[17]	C₉H₁₀O₃	167.030 3/–	0	167.030 3, 149.059 8	M, X, S, G
62^b	17.72	Sinensetin/Isosinensetin^[14]	C₂₀H₂₀O₇	373.128 2/–	0	373.128 0, 358.104 0, 343.081 2, 328.058 8, 313.069 9	C
63^d	17.76	Jioglutin A	C₁₀H₁₅ClO₅	251.068 1/–	0		D
64^c	17.87	ODDA	C₁₈H₃₀O₃	295.226 5/–	–0.7	277.216 1, 259.204 9	All
65^{a, b}	17.98	Z-Butylidenephthalide^{[12, 13]}	C₁₂H₁₂O₂	189.091 1/–	0.5	189.090 9, 153.069 9, 143.085 6, 105.033 8	X, G
66^b	18.12	E-Ligustilide^{[12, 13]}	C₁₂H₁₄O₂	191.106 8/–	0.5	191.106 3, 173.096 1, 163.111 5	X, G
67^b	18.24	Butylphthalide^[12]	C₁₂H₁₄O₂	191.106 3/–	–2.1	173.096 1, 145.101 1, 117.069 7	X, G
68^b	18.34	Sinensetin/Isosinensetin^[14]	C₂₀H₂₀O₇	373.128 3/–	0.3	358.103 7, 343.081 0, 328.056 8, 313.070 4, 315.085 9	C
69^b	18.39	5, 6, 7, 4'-Tetramethoxyflavone^[14]	C₁₉H₁₈O₆	343.117 6/–	0	328.094 1, 313.070 6, 285.075 6, 153.043 6, 181.012 9	C
70^c	18.42	Limonin	C₂₆H₃₀O₈	471.201 4/–	0.2	471.201 3, 453.190 2, 425.196 0, 367.191 9	C
71^b	18.74	3, 5, 6, 7, 3', 4'-Hexamethoxyflavone^[14]	C₂₁H₂₂O₈	403.138 7/425.120 5	0/ –0.5	388.112 9, 373.091 7, 358.068 1, 343.043 2, 327.085 8, 165.055 0	C
72^{b, c}	18.93	Nobiletin^[14]	C₂₁H₂₂O₈	403.139 0/425.120 8	0.7/ –0.2	403.138 7, 388.115 1, 373.091 8, 358.068 3, 343.044 7, 327.086 4, 165.054 7, 345.097 0	C
73^b	18.97	5, 6, 7, 4'-Tetramethoxybaicalein^[14]	C₁₉H₁₈O₆	343.117 6/–	0	328.093 8, 313.070 4, 285.075 9, 282.088 4, 327.085 8	C
74^d	19.11	Sanjoinine B	C₃₀H₄₀N₄O₄	521.312 0/–	–0.4		Z
75^b	19.47	Senkyunolide A^{[12, 13]}	C₁₂H₁₆O₂	193.122 5/–	1.0	175.111 7, 147.116 9, 137.059 8, 119.085 7	G, X
76^{b, c}	19.47	Tangeritin	C₂₀H₂₀O₇	373.128 4/–	0.5	358.104 3, 343.081 1, 328.057 9, 313.071 4, 315.085 1, 299.055 1, 271.060 2, 211.023 4	C
77^b	19.96	Linolenic acid^{[22, 26]}	C₁₈H₃₀O₂	279.231 6/–	–0.7	149.023 3, 137.132 4, 135.116 4, 123.116 9, 121.028 5	L, Z
78^b	20.25	Z-Ligustilide^{[12, 13]}	C₁₂H₁₄O₂	191.106 7/–	0	191.106 6, 173.096 1, 163.111 7	X, G
79^c	20.58	1-Tetradecylamine	C₁₄H₃₁N	214.252 9/–	0	195.535 0, 171.091 8, 149.940 3	B
80^c	21.08	Cryptotanshinone	C₁₉H₂₀O₃	297.148 7/–	0.7	297.148 5, 279.137 9, 264.112 7, 251.142 9	S

No.

t_R/min

Identification

Molecularformula

[M+H]⁺/[M+Na]⁺

Error/ppm

Fragmentaion

Source

1^b

1.21

Lysine^[22]

C₆H₁₄N₂O₂

147.112 9/–

0.7

130.086 5

All

2^b

1.24

Arginine^[22]

C₆H₁₄N₄O₂

175.119 0/–

0.6

116.070 8

All

3^c

1.26

Choline

C₅H₁₃NO

104.107 3/–

2.9

87.044 4, 69.034 0

All

4^c

1.32

Proline

C₅H₉NO₂

116.070 8/–

1.7

98.984 4, 70.065 7

All

5^b

1.34

Glutamate^[22]

C₅H₉NO₄

148.060 4/–

135.050 0

All

6^c

1.34

DL-Stachydrine

C₇H₁₃NO₂

144.101 9/–

102.150 0, 84.081 2

All

7^c

1.42

C₉H₁₁NO

150.091 4/–

0.6

135.067 9, 132.080 8, 117.057 8

G, S, D, X, C

8^c

1.67

Phenylephrine

C₉H₁₃NO₂

168.102 0/–

1.2

150.091 5

9^c

1.68

L-Pyroglutamic acid

C₅H₇NO₃

130.050 1/–

2.3

102.055 3, 84.044 9

All

10^b

1.70

Adenosine^[22]

C₁₀H₁₃N₅O₄

268.104 0/–

136.061 8, 119.035 6

All

11^b

1.70

Hypoxanthine^[22]

C₅H₄N₄O

137.045 9/–

0.7

119.035 7, 110.035 1

L, S, X, R

12^c

1.71

L-Tyrosine

C₉H₁₁NO₃

182.081 3/–

0.5

165.054 6, 147.044 0, 136.075 7

All

13^b

1.74

Tyrosine^[22]

C₉H₁₁NO₃

182.081 2/–

165.054 6, 136.075 7, 119.049 3, 107.049 7, 95.049 6

All

14^b

1.77

Guanine^[22]

C₅H₅N₅O

152.056 8/–

0.6

135.030 2, 110.035 3, 55.029 9

All

15^b

1.91

Glutarylcarnitine^[22]

C₁₂H₂₁NO₆

276.144 0/–

–0.7

258.133 5, 230.138 6, 212.127 9, 170.117 8, 144.101 9

All

16^b

2.05

ANDA^[22]

C₁₂H₂₁NO₆

276.143 9/–

–1.0

258.133 5, 230.138 6, 212.128 2, 170.117 3, 161.068 3

All

17^{b, c}

2.13

L-Norleucine^[22]

C₆H₁₃NO₂

132.101 9/–

86.096 9, 69.070 4

All

18^c

2.10

Pyrogallol

C₆H₆O₃

127.039 1/–

0.8

109.028 6

All

19^b

2.83

GHIA^[15]

C₁₆H₁₉NO₉

370.113 8/–

1.4

352.100 6, 308.113 1, 290.101 8, 272.114 3, 232.071 6

20^{b, c}

2.94

L-Phenylalanine^[22]

C₉H₁₁NO₂

166.086 2/–

–1.2

149.059 5, 120.081 0, 103.054 5, 91.054 4, 77.039 2

All

21^c

3.01

5-Hydroxymethyl-2-furaldehyde

C₆H₆O₃

127.039 1/–

0.8

109.028 7, 99.044 3

All

22^b

3.02

Fructose phenylalanine^[22]

C₁₅H₂₁NO₇

328.138 9/–

–0.6

310.128 3, 292.117 6, 282.134 2, 264.122 7, 178.086 1

L, S, D, M, X, C, R

23^b

3.02

AEOA^[22]

C₁₅H₁₉NO₆

310.127 7/–

–2.6

292.117 7, 264.122 9, 178.086 1, 166.086 2

L, S, D, X, G

24^c

3.05

Isovanillic acid

C₈H₈O₄

169.049 5/–

X, Z, S, G, B

25^b

3.08

GHIA^[15]

C₁₆H₁₉NO₉

370.113 0/–

–0.8

352.100 7, 308.112 9, 290.100 2, 272.112 6, 208.060 5

26^{b, c}

5.39

L-Tryptophan^[22]

C₁₁H₁₂N₂O₂

205.097 5/–

2.0

188.070 6, 159.091 7, 132.080 7, 130.065 1, 118.065 3

L, Z, S, M, X, G, C

27^c

5.62

2, 5-Dihydroxybenzaldehyde

C₇H₆O₃

139.039 1/–

0.7

121.028 6, 111.044 3, 102.948 4

All

28^b

5.85

N-Glc-indoleaceticacid^[15]

C₁₆H₁₉NO₈

354.118 3/–

188.070 6, 174.054 9, 146.060 2, 128.049 6

29^b

6.75

6-Glc-coclaurine^[15]

C₂₃H₂₉NO₈

448.196 3/–

–0.7

286.143 7, 269.117 0, 237.090 8, 219.081 4, 209.095 9

30^b

6.81

N-Glc-indoleaceticacid^[15]

C₁₆H₁₉NO₈

354.118 3/–

188.070 6, 146.060 1, 128.049 7

31^c

7.72

6-Methylquinoline

C₁₀H₉N

144.080 9/–

0.7

128.950 9, 126.955 2

32^b

8.64

Coclaurine^[15]

C₁₇H₁₉NO₃

286.143 6/–

–0.7

269.117 0, 254.094 1, 237.090 8, 219.080 6, 209.096 1

33^c

8.67

Morphine

C₁₇H₁₉NO₃

286.143 6/–

–0.7

269.117 0, 254.094 1, 237.090 8, 209.096 1

34^b

8.86

Juzirine^[15]

C₁₇H₁₅NO₃

282.112 5/–

238.038 7, 188.070 8

35^b

8.90

Meloside A^[15]

C₂₇H₃₀O₁₅

595.165 3/–

–0.7

379.080 8, 367.084 0, 337.070 6, 313.071 5, 283.061 0

36^b

9.20

Zizyphusine^[15]

C₂₀H₂₄NO₄⁺

[M]⁺:342.169 9

–0.3

297.112 0, 282.088 6, 265.085 8, 237.090 9, 222.067 4

Z, B

37^b

9.27

Magnoflorine^[19]

C₂₀H₂₃NO₄

342.170 1/–

0.3

342.169 9, 311.127 0, 299.127 7, 297.112 0, 282.088 6

Z, B

38^c

9.56

Naringenin

C₁₅H₁₂O₅

273.075 7/–

171.028 7, 153.018 3, 147.044 1, 119.049 3

39^b

10.11

Lotusine^[15]

C₁₉H₂₄NO₃⁺

[M]⁺: 314.175 0

–0.3

237.091 6, 209.096 3, 165.069 9, 137.059 8, 107.049 5

40^b

10.44

Camelliaside B^[15]

C₃₂H₃₈O₁₉

727.208 3/–

0.4

595.163 0, 449.114 4, 287.054 7

41^d

10.59

Quercetin

C₁₅H₁₀O₇

303.049 9/–

42^c

10.69

Neodiosmin

C₂₈H₃₂O₁₅

609.180 8/–

0.8

591.166 0, 447.128 3, 327.086 1, 285.075 3

43^b

10.81

Senkyunolide H/I^{[12, 13]}

C₁₂H₁₆O₄

225.111 8/–

–1.3

207.101 8, 189.091 2, 164.042 3, 161.096 1

G, X

44^{a, b, c}

11.85

Naringin^[14]

C₂₇H₃₂O₁₄

581.186 8/ 603.168 4

0.7/ 0.3

435.128 1, 401.123 0, 383.111 7, 273.075 6

45^c

11.85

Prunin

C₂₁H₂₂O₁₀

435.128 5/–

399.107 1, 273.075 7, 147.044 1, 119.019 2

46^d

11.95

Perlolyrine

C₁₆H₁₂N₂O₂

265.097 3/–

0.7

47^d

12.32

Senkyunolide-N

C₁₂H₁₈O₄

227.127 7/–

48^{a, b, c,}

12.62

Hesperidin^[14]

C₂₈H₃₄O₁₅

611.197 7/633.179 6

1.1/ 1.1

557.158 6, 465.139 1, 449.144 4, 303.086 3, 177.054 6, 151.075 1

49^c

12.62

Hesperetin

C₁₆H₁₄O₆

303.086 3/–

177.054 6, 153.018 2

50^c

12.65

Obacunoic acid

C₂₆H₃₂O₈

473.217 3/–

0.6

455.205 1, 427.211 5, 413.194 5, 395.183 9

51^{a, b}

12.69

Swertisin^[15]

C₂₂H₂₂O₁₀

447.130 8/–

4.9

411.107 0, 327.085 9, 297.075 7

52^c

13.31

1, 4-Dimethoxyanthraquinone

C₁₆H₁₂O₄

269.080 7/–

–0.4

53^b

13.68

Senkyunolide H/I^{[12, 13]}

C₁₂H₁₆O₄

225.112 0/–

–0.4

207.101 7, 164.042 3, 161.096 1, 179.106 2

G, X

54^b

13.94

Mucronine J^[15]

C₂₇H₄₀N₄O₄

485.311 7/–

–1.0

221.080 6, 207.065 4, 114.124 9

55^d

14.82

6'-p-coumaroylspinosin

C₃₈H₄₀O₁₇

769.230 8/–

–3.9

56^b

15.12

Poncirin^[14]

C₂₈H₃₄O₁₄

595.202 1/617.183 8

433.148 9, 415.138 1, 397.128 3, 353.100 9

57^c

15.13

Sakuranetin

C₁₆H₁₄O₅

287.091 1/–

–1.0

171.028 6, 161.059 6, 153.018 1

58^{a, b}

16.26

E-Butylidenephthalide^{[12, 13]}

C₁₂H₁₂O₂

189.091 1/–

0.5

189.091 0, 171.080 4, 143.085 6, 105.033 8, 153.069 5

X, G

59^b

16.58

Narirutin^[13]

C₂₇H₃₂O₁₄

581.186 5/603.168 4

419.133 5, 404.110 1, 389.086 5, 371.076 2

60^d

16.92

Sanjoinine A

C₃₁H₄₂N₄O₄

535.327 8/–

61^b

17.21

Paeonol^[17]

C₉H₁₀O₃

167.030 3/–

167.030 3, 149.059 8

M, X, S, G

62^b

17.72

Sinensetin/Isosinensetin^[14]

C₂₀H₂₀O₇

373.128 2/–

373.128 0, 358.104 0, 343.081 2, 328.058 8, 313.069 9

63^d

17.76

Jioglutin A

C₁₀H₁₅ClO₅

251.068 1/–

64^c

17.87

ODDA

C₁₈H₃₀O₃

295.226 5/–

–0.7

277.216 1, 259.204 9

All

65^{a, b}

17.98

Z-Butylidenephthalide^{[12, 13]}

C₁₂H₁₂O₂

189.091 1/–

0.5

189.090 9, 153.069 9, 143.085 6, 105.033 8

X, G

66^b

18.12

E-Ligustilide^{[12, 13]}

C₁₂H₁₄O₂

191.106 8/–

0.5

191.106 3, 173.096 1, 163.111 5

X, G

67^b

18.24

Butylphthalide^[12]

C₁₂H₁₄O₂

191.106 3/–

–2.1

173.096 1, 145.101 1, 117.069 7

X, G

68^b

18.34

Sinensetin/Isosinensetin^[14]

C₂₀H₂₀O₇

373.128 3/–

0.3

358.103 7, 343.081 0, 328.056 8, 313.070 4, 315.085 9

69^b

18.39

5, 6, 7, 4'-Tetramethoxyflavone^[14]

C₁₉H₁₈O₆

343.117 6/–

328.094 1, 313.070 6, 285.075 6, 153.043 6, 181.012 9

70^c

18.42

Limonin

C₂₆H₃₀O₈

471.201 4/–

0.2

471.201 3, 453.190 2, 425.196 0, 367.191 9

71^b

18.74

3, 5, 6, 7, 3', 4'-Hexamethoxyflavone^[14]

C₂₁H₂₂O₈

403.138 7/425.120 5

0/ –0.5

388.112 9, 373.091 7, 358.068 1, 343.043 2, 327.085 8, 165.055 0

72^{b, c}

18.93

Nobiletin^[14]

C₂₁H₂₂O₈

403.139 0/425.120 8

0.7/ –0.2

403.138 7, 388.115 1, 373.091 8, 358.068 3, 343.044 7, 327.086 4, 165.054 7, 345.097 0

73^b

18.97

5, 6, 7, 4'-Tetramethoxybaicalein^[14]

C₁₉H₁₈O₆

343.117 6/–

328.093 8, 313.070 4, 285.075 9, 282.088 4, 327.085 8

74^d

19.11

Sanjoinine B

C₃₀H₄₀N₄O₄

521.312 0/–

–0.4

75^b

19.47

Senkyunolide A^{[12, 13]}

C₁₂H₁₆O₂

193.122 5/–

1.0

175.111 7, 147.116 9, 137.059 8, 119.085 7

G, X

76^{b, c}

19.47

Tangeritin

C₂₀H₂₀O₇

373.128 4/–

0.5

358.104 3, 343.081 1, 328.057 9, 313.071 4, 315.085 1, 299.055 1, 271.060 2, 211.023 4

77^b

19.96

Linolenic acid^{[22, 26]}

C₁₈H₃₀O₂

279.231 6/–

–0.7

149.023 3, 137.132 4, 135.116 4, 123.116 9, 121.028 5

L, Z

78^b

20.25

Z-Ligustilide^{[12, 13]}

C₁₂H₁₄O₂

191.106 7/–

191.106 6, 173.096 1, 163.111 7

X, G

79^c

20.58

1-Tetradecylamine

C₁₄H₃₁N

214.252 9/–

195.535 0, 171.091 8, 149.940 3

80^c

21.08

Cryptotanshinone

C₁₉H₂₀O₃

297.148 7/–

0.7

297.148 5, 279.137 9, 264.112 7, 251.142 9

No.	t_R/min	Identification	Molecularformula	[M+H]⁺/[M+Na]⁺	Error/ppm	Fragmentaion	Source
1^b	1.21	Lysine^[22]	C₆H₁₄N₂O₂	147.112 9/–	0.7	130.086 5	All
2^b	1.24	Arginine^[22]	C₆H₁₄N₄O₂	175.119 0/–	0.6	116.070 8	All
3^c	1.26	Choline	C₅H₁₃NO	104.107 3/–	2.9	87.044 4, 69.034 0	All
4^c	1.32	Proline	C₅H₉NO₂	116.070 8/–	1.7	98.984 4, 70.065 7	All
5^b	1.34	Glutamate^[22]	C₅H₉NO₄	148.060 4/–	0	135.050 0	All
6^c	1.34	DL-Stachydrine	C₇H₁₃NO₂	144.101 9/–	0	102.150 0, 84.081 2	All
7^c	1.42	DF	C₉H₁₁NO	150.091 4/–	0.6	135.067 9, 132.080 8, 117.057 8	G, S, D, X, C
8^c	1.67	Phenylephrine	C₉H₁₃NO₂	168.102 0/–	1.2	150.091 5
9^c	1.68	L-Pyroglutamic acid	C₅H₇NO₃	130.050 1/–	2.3	102.055 3, 84.044 9	All
10^b	1.70	Adenosine^[22]	C₁₀H₁₃N₅O₄	268.104 0/–	0	136.061 8, 119.035 6	All
11^b	1.70	Hypoxanthine^[22]	C₅H₄N₄O	137.045 9/–	0.7	119.035 7, 110.035 1	L, S, X, R
12^c	1.71	L-Tyrosine	C₉H₁₁NO₃	182.081 3/–	0.5	165.054 6, 147.044 0, 136.075 7	All
13^b	1.74	Tyrosine^[22]	C₉H₁₁NO₃	182.081 2/–	0	165.054 6, 136.075 7, 119.049 3, 107.049 7, 95.049 6	All
14^b	1.77	Guanine^[22]	C₅H₅N₅O	152.056 8/–	0.6	135.030 2, 110.035 3, 55.029 9	All
15^b	1.91	Glutarylcarnitine^[22]	C₁₂H₂₁NO₆	276.144 0/–	–0.7	258.133 5, 230.138 6, 212.127 9, 170.117 8, 144.101 9	All
16^b	2.05	ANDA^[22]	C₁₂H₂₁NO₆	276.143 9/–	–1.0	258.133 5, 230.138 6, 212.128 2, 170.117 3, 161.068 3	All
17^{b, c}	2.13	L-Norleucine^[22]	C₆H₁₃NO₂	132.101 9/–	0	86.096 9, 69.070 4	All
18^c	2.10	Pyrogallol	C₆H₆O₃	127.039 1/–	0.8	109.028 6	All
19^b	2.83	GHIA^[15]	C₁₆H₁₉NO₉	370.113 8/–	1.4	352.100 6, 308.113 1, 290.101 8, 272.114 3, 232.071 6	Z
20^{b, c}	2.94	L-Phenylalanine^[22]	C₉H₁₁NO₂	166.086 2/–	–1.2	149.059 5, 120.081 0, 103.054 5, 91.054 4, 77.039 2	All
21^c	3.01	5-Hydroxymethyl-2-furaldehyde	C₆H₆O₃	127.039 1/–	0.8	109.028 7, 99.044 3	All
22^b	3.02	Fructose phenylalanine^[22]	C₁₅H₂₁NO₇	328.138 9/–	–0.6	310.128 3, 292.117 6, 282.134 2, 264.122 7, 178.086 1	L, S, D, M, X, C, R
23^b	3.02	AEOA^[22]	C₁₅H₁₉NO₆	310.127 7/–	–2.6	292.117 7, 264.122 9, 178.086 1, 166.086 2	L, S, D, X, G
24^c	3.05	Isovanillic acid	C₈H₈O₄	169.049 5/–	0		X, Z, S, G, B
25^b	3.08	GHIA^[15]	C₁₆H₁₉NO₉	370.113 0/–	–0.8	352.100 7, 308.112 9, 290.100 2, 272.112 6, 208.060 5	Z
26^{b, c}	5.39	L-Tryptophan^[22]	C₁₁H₁₂N₂O₂	205.097 5/–	2.0	188.070 6, 159.091 7, 132.080 7, 130.065 1, 118.065 3	L, Z, S, M, X, G, C
27^c	5.62	2, 5-Dihydroxybenzaldehyde	C₇H₆O₃	139.039 1/–	0.7	121.028 6, 111.044 3, 102.948 4	All
28^b	5.85	N-Glc-indoleaceticacid^[15]	C₁₆H₁₉NO₈	354.118 3/–	0	188.070 6, 174.054 9, 146.060 2, 128.049 6	Z
29^b	6.75	6-Glc-coclaurine^[15]	C₂₃H₂₉NO₈	448.196 3/–	–0.7	286.143 7, 269.117 0, 237.090 8, 219.081 4, 209.095 9	Z
30^b	6.81	N-Glc-indoleaceticacid^[15]	C₁₆H₁₉NO₈	354.118 3/–	0	188.070 6, 146.060 1, 128.049 7	Z
31^c	7.72	6-Methylquinoline	C₁₀H₉N	144.080 9/–	0.7	128.950 9, 126.955 2	Z
32^b	8.64	Coclaurine^[15]	C₁₇H₁₉NO₃	286.143 6/–	–0.7	269.117 0, 254.094 1, 237.090 8, 219.080 6, 209.096 1	Z
33^c	8.67	Morphine	C₁₇H₁₉NO₃	286.143 6/–	–0.7	269.117 0, 254.094 1, 237.090 8, 209.096 1	Z
34^b	8.86	Juzirine^[15]	C₁₇H₁₅NO₃	282.112 5/–	0	238.038 7, 188.070 8	Z
35^b	8.90	Meloside A^[15]	C₂₇H₃₀O₁₅	595.165 3/–	–0.7	379.080 8, 367.084 0, 337.070 6, 313.071 5, 283.061 0	Z
36^b	9.20	Zizyphusine^[15]	C₂₀H₂₄NO₄⁺	[M]⁺:342.169 9	–0.3	297.112 0, 282.088 6, 265.085 8, 237.090 9, 222.067 4	Z, B
37^b	9.27	Magnoflorine^[19]	C₂₀H₂₃NO₄	342.170 1/–	0.3	342.169 9, 311.127 0, 299.127 7, 297.112 0, 282.088 6	Z, B
38^c	9.56	Naringenin	C₁₅H₁₂O₅	273.075 7/–	0	171.028 7, 153.018 3, 147.044 1, 119.049 3	C
39^b	10.11	Lotusine^[15]	C₁₉H₂₄NO₃⁺	[M]⁺: 314.175 0	–0.3	237.091 6, 209.096 3, 165.069 9, 137.059 8, 107.049 5	Z
40^b	10.44	Camelliaside B^[15]	C₃₂H₃₈O₁₉	727.208 3/–	0.4	595.163 0, 449.114 4, 287.054 7	Z
41^d	10.59	Quercetin	C₁₅H₁₀O₇	303.049 9/–	0		M
42^c	10.69	Neodiosmin	C₂₈H₃₂O₁₅	609.180 8/–	0.8	591.166 0, 447.128 3, 327.086 1, 285.075 3	Z
43^b	10.81	Senkyunolide H/I^{[12, 13]}	C₁₂H₁₆O₄	225.111 8/–	–1.3	207.101 8, 189.091 2, 164.042 3, 161.096 1	G, X
44^{a, b, c}	11.85	Naringin^[14]	C₂₇H₃₂O₁₄	581.186 8/ 603.168 4	0.7/ 0.3	435.128 1, 401.123 0, 383.111 7, 273.075 6	C
45^c	11.85	Prunin	C₂₁H₂₂O₁₀	435.128 5/–	0	399.107 1, 273.075 7, 147.044 1, 119.019 2	C
46^d	11.95	Perlolyrine	C₁₆H₁₂N₂O₂	265.097 3/–	0.7		X
47^d	12.32	Senkyunolide-N	C₁₂H₁₈O₄	227.127 7/–	0		X
48^{a, b, c,}	12.62	Hesperidin^[14]	C₂₈H₃₄O₁₅	611.197 7/633.179 6	1.1/ 1.1	557.158 6, 465.139 1, 449.144 4, 303.086 3, 177.054 6, 151.075 1	C
49^c	12.62	Hesperetin	C₁₆H₁₄O₆	303.086 3/–	0	177.054 6, 153.018 2	C
50^c	12.65	Obacunoic acid	C₂₆H₃₂O₈	473.217 3/–	0.6	455.205 1, 427.211 5, 413.194 5, 395.183 9	C
51^{a, b}	12.69	Swertisin^[15]	C₂₂H₂₂O₁₀	447.130 8/–	4.9	411.107 0, 327.085 9, 297.075 7	Z
52^c	13.31	1, 4-Dimethoxyanthraquinone	C₁₆H₁₂O₄	269.080 7/–	–0.4		S
53^b	13.68	Senkyunolide H/I^{[12, 13]}	C₁₂H₁₆O₄	225.112 0/–	–0.4	207.101 7, 164.042 3, 161.096 1, 179.106 2	G, X
54^b	13.94	Mucronine J^[15]	C₂₇H₄₀N₄O₄	485.311 7/–	–1.0	221.080 6, 207.065 4, 114.124 9	Z
55^d	14.82	6'-p-coumaroylspinosin	C₃₈H₄₀O₁₇	769.230 8/–	–3.9		Z
56^b	15.12	Poncirin^[14]	C₂₈H₃₄O₁₄	595.202 1/617.183 8	0	433.148 9, 415.138 1, 397.128 3, 353.100 9	C
57^c	15.13	Sakuranetin	C₁₆H₁₄O₅	287.091 1/–	–1.0	171.028 6, 161.059 6, 153.018 1	C
58^{a, b}	16.26	E-Butylidenephthalide^{[12, 13]}	C₁₂H₁₂O₂	189.091 1/–	0.5	189.091 0, 171.080 4, 143.085 6, 105.033 8, 153.069 5	X, G
59^b	16.58	Narirutin^[13]	C₂₇H₃₂O₁₄	581.186 5/603.168 4	0	419.133 5, 404.110 1, 389.086 5, 371.076 2	C
60^d	16.92	Sanjoinine A	C₃₁H₄₂N₄O₄	535.327 8/–	0		Z
61^b	17.21	Paeonol^[17]	C₉H₁₀O₃	167.030 3/–	0	167.030 3, 149.059 8	M, X, S, G
62^b	17.72	Sinensetin/Isosinensetin^[14]	C₂₀H₂₀O₇	373.128 2/–	0	373.128 0, 358.104 0, 343.081 2, 328.058 8, 313.069 9	C
63^d	17.76	Jioglutin A	C₁₀H₁₅ClO₅	251.068 1/–	0		D
64^c	17.87	ODDA	C₁₈H₃₀O₃	295.226 5/–	–0.7	277.216 1, 259.204 9	All
65^{a, b}	17.98	Z-Butylidenephthalide^{[12, 13]}	C₁₂H₁₂O₂	189.091 1/–	0.5	189.090 9, 153.069 9, 143.085 6, 105.033 8	X, G
66^b	18.12	E-Ligustilide^{[12, 13]}	C₁₂H₁₄O₂	191.106 8/–	0.5	191.106 3, 173.096 1, 163.111 5	X, G
67^b	18.24	Butylphthalide^[12]	C₁₂H₁₄O₂	191.106 3/–	–2.1	173.096 1, 145.101 1, 117.069 7	X, G
68^b	18.34	Sinensetin/Isosinensetin^[14]	C₂₀H₂₀O₇	373.128 3/–	0.3	358.103 7, 343.081 0, 328.056 8, 313.070 4, 315.085 9	C
69^b	18.39	5, 6, 7, 4'-Tetramethoxyflavone^[14]	C₁₉H₁₈O₆	343.117 6/–	0	328.094 1, 313.070 6, 285.075 6, 153.043 6, 181.012 9	C
70^c	18.42	Limonin	C₂₆H₃₀O₈	471.201 4/–	0.2	471.201 3, 453.190 2, 425.196 0, 367.191 9	C
71^b	18.74	3, 5, 6, 7, 3', 4'-Hexamethoxyflavone^[14]	C₂₁H₂₂O₈	403.138 7/425.120 5	0/ –0.5	388.112 9, 373.091 7, 358.068 1, 343.043 2, 327.085 8, 165.055 0	C
72^{b, c}	18.93	Nobiletin^[14]	C₂₁H₂₂O₈	403.139 0/425.120 8	0.7/ –0.2	403.138 7, 388.115 1, 373.091 8, 358.068 3, 343.044 7, 327.086 4, 165.054 7, 345.097 0	C
73^b	18.97	5, 6, 7, 4'-Tetramethoxybaicalein^[14]	C₁₉H₁₈O₆	343.117 6/–	0	328.093 8, 313.070 4, 285.075 9, 282.088 4, 327.085 8	C
74^d	19.11	Sanjoinine B	C₃₀H₄₀N₄O₄	521.312 0/–	–0.4		Z
75^b	19.47	Senkyunolide A^{[12, 13]}	C₁₂H₁₆O₂	193.122 5/–	1.0	175.111 7, 147.116 9, 137.059 8, 119.085 7	G, X
76^{b, c}	19.47	Tangeritin	C₂₀H₂₀O₇	373.128 4/–	0.5	358.104 3, 343.081 1, 328.057 9, 313.071 4, 315.085 1, 299.055 1, 271.060 2, 211.023 4	C
77^b	19.96	Linolenic acid^{[22, 26]}	C₁₈H₃₀O₂	279.231 6/–	–0.7	149.023 3, 137.132 4, 135.116 4, 123.116 9, 121.028 5	L, Z
78^b	20.25	Z-Ligustilide^{[12, 13]}	C₁₂H₁₄O₂	191.106 7/–	0	191.106 6, 173.096 1, 163.111 7	X, G
79^c	20.58	1-Tetradecylamine	C₁₄H₃₁N	214.252 9/–	0	195.535 0, 171.091 8, 149.940 3	B
80^c	21.08	Cryptotanshinone	C₁₉H₂₀O₃	297.148 7/–	0.7	297.148 5, 279.137 9, 264.112 7, 251.142 9	S

No.

t_R/min

Identification

Molecularformula

[M+H]⁺/[M+Na]⁺

Error/ppm

Fragmentaion

Source

1^b

1.21

Lysine^[22]

C₆H₁₄N₂O₂

147.112 9/–

0.7

130.086 5

All

2^b

1.24

Arginine^[22]

C₆H₁₄N₄O₂

175.119 0/–

0.6

116.070 8

All

3^c

1.26

Choline

C₅H₁₃NO

104.107 3/–

2.9

87.044 4, 69.034 0

All

4^c

1.32

Proline

C₅H₉NO₂

116.070 8/–

1.7

98.984 4, 70.065 7

All

5^b

1.34

Glutamate^[22]

C₅H₉NO₄

148.060 4/–

135.050 0

All

6^c

1.34

DL-Stachydrine

C₇H₁₃NO₂

144.101 9/–

102.150 0, 84.081 2

All

7^c

1.42

C₉H₁₁NO

150.091 4/–

0.6

135.067 9, 132.080 8, 117.057 8

G, S, D, X, C

8^c

1.67

Phenylephrine

C₉H₁₃NO₂

168.102 0/–

1.2

150.091 5

9^c

1.68

L-Pyroglutamic acid

C₅H₇NO₃

130.050 1/–

2.3

102.055 3, 84.044 9

All

10^b

1.70

Adenosine^[22]

C₁₀H₁₃N₅O₄

268.104 0/–

136.061 8, 119.035 6

All

11^b

1.70

Hypoxanthine^[22]

C₅H₄N₄O

137.045 9/–

0.7

119.035 7, 110.035 1

L, S, X, R

12^c

1.71

L-Tyrosine

C₉H₁₁NO₃

182.081 3/–

0.5

165.054 6, 147.044 0, 136.075 7

All

13^b

1.74

Tyrosine^[22]

C₉H₁₁NO₃

182.081 2/–

165.054 6, 136.075 7, 119.049 3, 107.049 7, 95.049 6

All

14^b

1.77

Guanine^[22]

C₅H₅N₅O

152.056 8/–

0.6

135.030 2, 110.035 3, 55.029 9

All

15^b

1.91

Glutarylcarnitine^[22]

C₁₂H₂₁NO₆

276.144 0/–

–0.7

258.133 5, 230.138 6, 212.127 9, 170.117 8, 144.101 9

All

16^b

2.05

ANDA^[22]

C₁₂H₂₁NO₆

276.143 9/–

–1.0

258.133 5, 230.138 6, 212.128 2, 170.117 3, 161.068 3

All

17^{b, c}

2.13

L-Norleucine^[22]

C₆H₁₃NO₂

132.101 9/–

86.096 9, 69.070 4

All

18^c

2.10

Pyrogallol

C₆H₆O₃

127.039 1/–

0.8

109.028 6

All

19^b

2.83

GHIA^[15]

C₁₆H₁₉NO₉

370.113 8/–

1.4

352.100 6, 308.113 1, 290.101 8, 272.114 3, 232.071 6

20^{b, c}

2.94

L-Phenylalanine^[22]

C₉H₁₁NO₂

166.086 2/–

–1.2

149.059 5, 120.081 0, 103.054 5, 91.054 4, 77.039 2

All

21^c

3.01

5-Hydroxymethyl-2-furaldehyde

C₆H₆O₃

127.039 1/–

0.8

109.028 7, 99.044 3

All

22^b

3.02

Fructose phenylalanine^[22]

C₁₅H₂₁NO₇

328.138 9/–

–0.6

310.128 3, 292.117 6, 282.134 2, 264.122 7, 178.086 1

L, S, D, M, X, C, R

23^b

3.02

AEOA^[22]

C₁₅H₁₉NO₆

310.127 7/–

–2.6

292.117 7, 264.122 9, 178.086 1, 166.086 2

L, S, D, X, G

24^c

3.05

Isovanillic acid

C₈H₈O₄

169.049 5/–

X, Z, S, G, B

25^b

3.08

GHIA^[15]

C₁₆H₁₉NO₉

370.113 0/–

–0.8

352.100 7, 308.112 9, 290.100 2, 272.112 6, 208.060 5

26^{b, c}

5.39

L-Tryptophan^[22]

C₁₁H₁₂N₂O₂

205.097 5/–

2.0

188.070 6, 159.091 7, 132.080 7, 130.065 1, 118.065 3

L, Z, S, M, X, G, C

27^c

5.62

2, 5-Dihydroxybenzaldehyde

C₇H₆O₃

139.039 1/–

0.7

121.028 6, 111.044 3, 102.948 4

All

28^b

5.85

N-Glc-indoleaceticacid^[15]

C₁₆H₁₉NO₈

354.118 3/–

188.070 6, 174.054 9, 146.060 2, 128.049 6

29^b

6.75

6-Glc-coclaurine^[15]

C₂₃H₂₉NO₈

448.196 3/–

–0.7

286.143 7, 269.117 0, 237.090 8, 219.081 4, 209.095 9

30^b

6.81

N-Glc-indoleaceticacid^[15]

C₁₆H₁₉NO₈

354.118 3/–

188.070 6, 146.060 1, 128.049 7

31^c

7.72

6-Methylquinoline

C₁₀H₉N

144.080 9/–

0.7

128.950 9, 126.955 2

32^b

8.64

Coclaurine^[15]

C₁₇H₁₉NO₃

286.143 6/–

–0.7

269.117 0, 254.094 1, 237.090 8, 219.080 6, 209.096 1

33^c

8.67

Morphine

C₁₇H₁₉NO₃

286.143 6/–

–0.7

269.117 0, 254.094 1, 237.090 8, 209.096 1

34^b

8.86

Juzirine^[15]

C₁₇H₁₅NO₃

282.112 5/–

238.038 7, 188.070 8

35^b

8.90

Meloside A^[15]

C₂₇H₃₀O₁₅

595.165 3/–

–0.7

379.080 8, 367.084 0, 337.070 6, 313.071 5, 283.061 0

36^b

9.20

Zizyphusine^[15]

C₂₀H₂₄NO₄⁺

[M]⁺:342.169 9

–0.3

297.112 0, 282.088 6, 265.085 8, 237.090 9, 222.067 4

Z, B

37^b

9.27

Magnoflorine^[19]

C₂₀H₂₃NO₄

342.170 1/–

0.3

342.169 9, 311.127 0, 299.127 7, 297.112 0, 282.088 6

Z, B

38^c

9.56

Naringenin

C₁₅H₁₂O₅

273.075 7/–

171.028 7, 153.018 3, 147.044 1, 119.049 3

39^b

10.11

Lotusine^[15]

C₁₉H₂₄NO₃⁺

[M]⁺: 314.175 0

–0.3

237.091 6, 209.096 3, 165.069 9, 137.059 8, 107.049 5

40^b

10.44

Camelliaside B^[15]

C₃₂H₃₈O₁₉

727.208 3/–

0.4

595.163 0, 449.114 4, 287.054 7

41^d

10.59

Quercetin

C₁₅H₁₀O₇

303.049 9/–

42^c

10.69

Neodiosmin

C₂₈H₃₂O₁₅

609.180 8/–

0.8

591.166 0, 447.128 3, 327.086 1, 285.075 3

43^b

10.81

Senkyunolide H/I^{[12, 13]}

C₁₂H₁₆O₄

225.111 8/–

–1.3

207.101 8, 189.091 2, 164.042 3, 161.096 1

G, X

44^{a, b, c}

11.85

Naringin^[14]

C₂₇H₃₂O₁₄

581.186 8/ 603.168 4

0.7/ 0.3

435.128 1, 401.123 0, 383.111 7, 273.075 6

45^c

11.85

Prunin

C₂₁H₂₂O₁₀

435.128 5/–

399.107 1, 273.075 7, 147.044 1, 119.019 2

46^d

11.95

Perlolyrine

C₁₆H₁₂N₂O₂

265.097 3/–

0.7

47^d

12.32

Senkyunolide-N

C₁₂H₁₈O₄

227.127 7/–

48^{a, b, c,}

12.62

Hesperidin^[14]

C₂₈H₃₄O₁₅

611.197 7/633.179 6

1.1/ 1.1

557.158 6, 465.139 1, 449.144 4, 303.086 3, 177.054 6, 151.075 1

49^c

12.62

Hesperetin

C₁₆H₁₄O₆

303.086 3/–

177.054 6, 153.018 2

50^c

12.65

Obacunoic acid

C₂₆H₃₂O₈

473.217 3/–

0.6

455.205 1, 427.211 5, 413.194 5, 395.183 9

51^{a, b}

12.69

Swertisin^[15]

C₂₂H₂₂O₁₀

447.130 8/–

4.9

411.107 0, 327.085 9, 297.075 7

52^c

13.31

1, 4-Dimethoxyanthraquinone

C₁₆H₁₂O₄

269.080 7/–

–0.4

53^b

13.68

Senkyunolide H/I^{[12, 13]}

C₁₂H₁₆O₄

225.112 0/–

–0.4

207.101 7, 164.042 3, 161.096 1, 179.106 2

G, X

54^b

13.94

Mucronine J^[15]

C₂₇H₄₀N₄O₄

485.311 7/–

–1.0

221.080 6, 207.065 4, 114.124 9

55^d

14.82

6'-p-coumaroylspinosin

C₃₈H₄₀O₁₇

769.230 8/–

–3.9

56^b

15.12

Poncirin^[14]

C₂₈H₃₄O₁₄

595.202 1/617.183 8

433.148 9, 415.138 1, 397.128 3, 353.100 9

57^c

15.13

Sakuranetin

C₁₆H₁₄O₅

287.091 1/–

–1.0

171.028 6, 161.059 6, 153.018 1

58^{a, b}

16.26

E-Butylidenephthalide^{[12, 13]}

C₁₂H₁₂O₂

189.091 1/–

0.5

189.091 0, 171.080 4, 143.085 6, 105.033 8, 153.069 5

X, G

59^b

16.58

Narirutin^[13]

C₂₇H₃₂O₁₄

581.186 5/603.168 4

419.133 5, 404.110 1, 389.086 5, 371.076 2

60^d

16.92

Sanjoinine A

C₃₁H₄₂N₄O₄

535.327 8/–

61^b

17.21

Paeonol^[17]

C₉H₁₀O₃

167.030 3/–

167.030 3, 149.059 8

M, X, S, G

62^b

17.72

Sinensetin/Isosinensetin^[14]

C₂₀H₂₀O₇

373.128 2/–

373.128 0, 358.104 0, 343.081 2, 328.058 8, 313.069 9

63^d

17.76

Jioglutin A

C₁₀H₁₅ClO₅

251.068 1/–

64^c

17.87

ODDA

C₁₈H₃₀O₃

295.226 5/–

–0.7

277.216 1, 259.204 9

All

65^{a, b}

17.98

Z-Butylidenephthalide^{[12, 13]}

C₁₂H₁₂O₂

189.091 1/–

0.5

189.090 9, 153.069 9, 143.085 6, 105.033 8

X, G

66^b

18.12

E-Ligustilide^{[12, 13]}

C₁₂H₁₄O₂

191.106 8/–

0.5

191.106 3, 173.096 1, 163.111 5

X, G

67^b

18.24

Butylphthalide^[12]

C₁₂H₁₄O₂

191.106 3/–

–2.1

173.096 1, 145.101 1, 117.069 7

X, G

68^b

18.34

Sinensetin/Isosinensetin^[14]

C₂₀H₂₀O₇

373.128 3/–

0.3

358.103 7, 343.081 0, 328.056 8, 313.070 4, 315.085 9

69^b

18.39

5, 6, 7, 4'-Tetramethoxyflavone^[14]

C₁₉H₁₈O₆

343.117 6/–

328.094 1, 313.070 6, 285.075 6, 153.043 6, 181.012 9

70^c

18.42

Limonin

C₂₆H₃₀O₈

471.201 4/–

0.2

471.201 3, 453.190 2, 425.196 0, 367.191 9

71^b

18.74

3, 5, 6, 7, 3', 4'-Hexamethoxyflavone^[14]

C₂₁H₂₂O₈

403.138 7/425.120 5

0/ –0.5

388.112 9, 373.091 7, 358.068 1, 343.043 2, 327.085 8, 165.055 0

72^{b, c}

18.93

Nobiletin^[14]

C₂₁H₂₂O₈

403.139 0/425.120 8

0.7/ –0.2

403.138 7, 388.115 1, 373.091 8, 358.068 3, 343.044 7, 327.086 4, 165.054 7, 345.097 0

73^b

18.97

5, 6, 7, 4'-Tetramethoxybaicalein^[14]

C₁₉H₁₈O₆

343.117 6/–

328.093 8, 313.070 4, 285.075 9, 282.088 4, 327.085 8

74^d

19.11

Sanjoinine B

C₃₀H₄₀N₄O₄

521.312 0/–

–0.4

75^b

19.47

Senkyunolide A^{[12, 13]}

C₁₂H₁₆O₂

193.122 5/–

1.0

175.111 7, 147.116 9, 137.059 8, 119.085 7

G, X

76^{b, c}

19.47

Tangeritin

C₂₀H₂₀O₇

373.128 4/–

0.5

358.104 3, 343.081 1, 328.057 9, 313.071 4, 315.085 1, 299.055 1, 271.060 2, 211.023 4

77^b

19.96

Linolenic acid^{[22, 26]}

C₁₈H₃₀O₂

279.231 6/–

–0.7

149.023 3, 137.132 4, 135.116 4, 123.116 9, 121.028 5

L, Z

78^b

20.25

Z-Ligustilide^{[12, 13]}

C₁₂H₁₄O₂

191.106 7/–

191.106 6, 173.096 1, 163.111 7

X, G

79^c

20.58

1-Tetradecylamine

C₁₄H₃₁N

214.252 9/–

195.535 0, 171.091 8, 149.940 3

80^c

21.08

Cryptotanshinone

C₁₉H₂₀O₃

297.148 7/–

0.7

297.148 5, 279.137 9, 264.112 7, 251.142 9

Negative mode
2	94.5	4	73.9	3	90.5	4	90.0	6	99.0
5	65.8	6	89.8	7	65.8	8	88.9	9	86.8
7	90.9	9	86.0	12	84.1	17	75.7	18	78.4
10	79.8	12	72.9	20	88.4	21	85.2	24	83.8
15	84.9	26	63.2	26	71.2	27	88.9	31	74.1
33	83.6	34	59.7	33	62.7	38	94.6	42	51.6
35	82.1	37	85.0	44	79.2	45	82.4	48	89.2
38	67.4	40	71.8	49	94.8	50	65.9	52	70.6
48	84.7	50	79.0	57	62.2	65	81.2	70	83.7
61	65.4	64	88.3	72	89.9	76	89.4	79	82.2
68	79.9	74	79.7	80	91.2
81	84.7

Negative mode

Positive mode

No.

Best match/%

No.

Best match/%

No.

Best match/%

No.

Best match/%

No.

Best match/%

94.5

73.9

90.5

90.0

99.0

65.8

89.8

65.8

88.9

86.8

90.9

86.0

84.1

75.7

78.4

79.8

72.9

88.4

85.2

83.8

84.9

63.2

71.2

88.9

74.1

83.6

59.7

62.7

94.6

51.6

82.1

85.0

79.2

82.4

89.2

67.4

71.8

94.8

65.9

70.6

84.7

79.0

62.2

81.2

83.7

65.4

88.3

89.9

89.4

82.2

79.9

79.7

91.2

84.7

Negative mode
2	94.5	4	73.9	3	90.5	4	90.0	6	99.0
5	65.8	6	89.8	7	65.8	8	88.9	9	86.8
7	90.9	9	86.0	12	84.1	17	75.7	18	78.4
10	79.8	12	72.9	20	88.4	21	85.2	24	83.8
15	84.9	26	63.2	26	71.2	27	88.9	31	74.1
33	83.6	34	59.7	33	62.7	38	94.6	42	51.6
35	82.1	37	85.0	44	79.2	45	82.4	48	89.2
38	67.4	40	71.8	49	94.8	50	65.9	52	70.6
48	84.7	50	79.0	57	62.2	65	81.2	70	83.7
61	65.4	64	88.3	72	89.9	76	89.4	79	82.2
68	79.9	74	79.7	80	91.2
81	84.7

Negative mode

Positive mode

No.

Best match/%

No.

Best match/%

No.

Best match/%

No.

Best match/%

No.

Best match/%

94.5

73.9

90.5

90.0

99.0

65.8

89.8

65.8

88.9

86.8

90.9

86.0

84.1

75.7

78.4

79.8

72.9

88.4

85.2

83.8

84.9

63.2

71.2

88.9

74.1

83.6

59.7

62.7

94.6

51.6

82.1

85.0

79.2

82.4

89.2

67.4

71.8

94.8

65.9

70.6

84.7

79.0

62.2

81.2

83.7

65.4

88.3

89.9

89.4

82.2

79.9

79.7

91.2

84.7

采用UHPLC-Q Exactive轨道肼高分辨质谱快速识别脑震宁颗粒的化学成分

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于舒婷 ¹^,³ , 刘海霞 ² , 李昆 ² , 秦正国 ² , 秦雪梅 ¹ , 朱平 ²^,^* , 李震宇 ¹^,^*

药学学报 | 研究论文·药物分析 2018,53(4): 609-620

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药学学报 | 研究论文·药物分析 2018, 53(4): 609-620

采用UHPLC-Q Exactive轨道肼高分辨质谱快速识别脑震宁颗粒的化学成分

全屏

于舒婷¹^,³, 刘海霞², 李昆², 秦正国², 秦雪梅¹, 朱平²^,^*, 李震宇¹^,^*

作者信息

1.山西大学中医药现代研究中心, 山西太原 030006

2.山西振东安特生物制药有限公司, 山西晋中 030600

3.山西大学化学化工学院, 山西太原 030006

通讯作者:

* 朱平, Tel/Fax:86-354-2467991, 86-351-7018379, E-mail:zp8236@sohu.com;

李震宇, E-mail:lizhenyu@sxu.edu.cn

Identification of chemical constituents in Naozhenning granule by UHPLC coupled with hybrid quadrupole-orbitrap MS

Shu-ting YU¹^,³, Hai-xia LIU², Kun LI², Zheng-guo QIN², Xue-mei QIN¹, Ping ZHU²^,^*, Zhen-yu LI¹^,^*

Affiliations

1. Modern Research Center for Traditional Chinese Medicine of Shanxi University, Taiyuan 030006, China

2. Shanxi Zhendong Ante Biological Pharmaceutical Co., Ltd., Jinzhong 030600, China

3. College of Chemistry and Chemical Engineering of Shanxi University, Taiyuan 030006, China

出版时间: 2018-04-12 doi: 10.16438/j.0513-4870.2017-1190

文章导航

摘要

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脑震宁颗粒是由11味中药组成的复方制剂，临床主要用于治疗脑震荡、脑外伤综合征等。针对其复杂的物质组成，本研究采用UHPLC-Q Exactive轨道肼高分辨质谱建立了脑震宁颗粒化学成分的快速识别方法，通过分析色谱保留行为、精确分子质量、裂解碎片信息，结合文献及对照品数据对照，并借助Compound Discover 2.0自动指认，共鉴定出脑震宁颗粒中161个化合物，并对这些成分的来源进行了归属。所鉴定的成分包括环烯醚萜苷类9个、丁基苯酞类8个、黄酮及黄酮苷类26个、酚酸类8个、单萜苷类8个、生物碱类9个，以及有机酸、氨基酸、糖类等中药材共性成分。本研究首次对脑震宁颗粒的化学组成进行了全面表征，所构建的脑震宁化学成分物质组为其进一步的质量控制和药效物质基础研究奠定了基础。

关键词

脑震宁颗粒 / 化学成分 / UHPLC-Q Exactive轨道肼高分辨质谱

Abstract

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Naozhenning granule, which is composed of 11 herbal drugs, is mainly used in the treatment of concussion, cerebral post-traumatic syndrome. As the chemical composition of Naozhenning was complex, the ultrahigh performance liquid chromatography coupled with hybrid quadrupole-orbitrap mass spectrometry was applied to identify the chemical constituents rapidly in the Naozhenning granule. By analyzing the retention behaviors, accurate molecular weight, the fragmentation pathway, and comparison with the MS data from the standards and references, as well as the automatic identification by the Compound Discover 2.0, a total of 161 compounds were identified or tentatively deduced, and the sources of constituents were also confirmed. The compounds identified in Naozhenning granule included 9 iridoids, 8 butylphthalides, 26 flavonoids and flavonoid glycosides, 8 phenolic acids, 8 monoterpenoid glycosides and 9 alkaloids, as well as the common compounds in the herbal drugs, such as organic acids, amino acids, and sugars. The chemical composition of Naozhenning was studied for the first time, which provides a scientific basis for the quality control and document of effective materials of Naozhenning granule.

Key words

Naozhenning granule / chemical constituent / UHPLC-Q Exactive quadrupole-orbitrap MS

引用本文

于舒婷, 刘海霞, 李昆, 秦正国, 秦雪梅, 朱平, 李震宇. 采用UHPLC-Q Exactive轨道肼高分辨质谱快速识别脑震宁颗粒的化学成分. 药学学报, 2018 , 53 (4) : 609 -620 . DOI: 10.16438/j.0513-4870.2017-1190

Shu-ting YU, Hai-xia LIU, Kun LI, Zheng-guo QIN, Xue-mei QIN, Ping ZHU, Zhen-yu LI. Identification of chemical constituents in Naozhenning granule by UHPLC coupled with hybrid quadrupole-orbitrap MS[J]. Acta Pharmaceutica Sinica, 2018 , 53 (4) : 609 -620 . DOI: 10.16438/j.0513-4870.2017-1190

正文

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脑震宁颗粒是由当归、地黄、牡丹皮、川芎、地龙、丹参、茯苓、陈皮、炒酸枣仁、竹茹和柏子仁共11味中药经科学提取加工制成的一种中药复方制剂。临床常用于治疗颅脑损伤后遗症、血管神经性头痛^[1], 具有凉血活血、化瘀通络、补血安神、宁心定智、除烦止呕之功效^[2], 是一种改善中轻型颅脑外伤症状, 促进功能恢复, 纠正植物神经功能紊乱的有效药物^[1]。目前关于脑震宁颗粒的研究多是药理药效^[3]以及基于阿魏酸^[4]、橙皮苷^{[4, 5]}、丹酚酸B^[5]等指标成分的含量测定。由于脑震宁颗粒组方中含有11味中药材, 导致其化学成分非常复杂。然而其化学成分和物质基础研究目前未见报道, 明确其化学成分对于进一步阐明脑震宁颗粒药效物质基础以及作用机制是非常必要的。

液质联用技术具有高分离能力、高灵敏度和专属性强的特点, 在天然产物的定性鉴别中发挥着重要的作用。UHPLC-Q Exactive轨道高分辨质谱将四级杆母离子选择性与高分辨率和准确质量数(HRAM) Orbitrap检测相结合, 具有高灵敏度, 在一次扫描中同时检测痕量级和高丰度化合物, 可用于中药复杂体系的快速分析和成分识别, 如金钗石斛^[6]、酸枣仁^[7]、酸枣叶^[8]、中华苦荬菜与苣荬菜^[9]、黄芪建中汤^[10]等。本研究拟采用UHPLC-Q Exactive轨道肼高分辨质谱对脑震宁颗粒的化学成分进行分析鉴定, 得到所含成分的准分子离子峰及蕴含丰富结构信息的碎片离子峰, 从而对其结构进行准确、快速的鉴定, 为脑震宁颗粒质量控制和药效物质基础研究奠定依据。

材料与方法

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仪器与试剂 Thermo fisher U3000超高效液相色谱仪, 配置在线脱气机、四元梯度泵、柱温箱、自动进样器(美国Thermo Fisher Scientific公司), Thermo Scientific^TMQ Exactive^TM组合型四极杆Orbitrap质谱仪; 十万分之一天平(梅特勒−托利多仪器有限公司); 数据分析采用Xcalibur 3.2软件, Compound Discover 2.0软件。超纯水由Milli-Q Integral Water Purification System (美国Millipore公司)制备, 甲酸、乙腈为色谱纯(美国Thermo公司), 甲醇(分析纯)购于天津市大茂化学试剂厂。

对照品与药材 对照品斯皮诺素(批号: 131217, 质量分数≥98%)、酸枣仁皂苷A (批号: A0274, 质量分数≥98%)、酸枣仁皂苷B (批号: A0275, 质量分数≥98%)、梓醇(批号: 0808-9803, 质量分数≥98%)、柚皮苷(批号: 110722-200309, 质量分数≥98%)、丹皮酚(批号: 110708-200506, 质量分数≥98%)、芍药苷(批号: 110736-201640, 质量分数≥98%)购自中国食品药品检定研究院; 当药黄素(批号: 140516, 质量分数≥98%)购自四川省维克奇生物科技有限公司; 咖啡酸(批号: YJ-141119, 质量分数≥98%)、绿原酸(批号: YJ-141004, 质量分数≥98%)、新绿原酸(批号: YJ-140925, 质量分数≥98%)、隐绿原酸(批号: YJ-141020, 质量分数≥98%)、橙皮苷(批号: YJ-141108, 质量分数≥98%)购自江苏永健医药有限公司; 没食子酸(批号: 20130729, 质量分数≥98%)购自上海源叶生物科技有限公司; 亚正丁基苯酞内酯, (E)+(Z) (批号: 10153545, 质量分数≥95%), 购自阿法埃莎(中国)化学有限公司。脑震宁颗粒(批号: 20151202, 20160501, 20160609)以及当归、地黄、牡丹皮、川芎、地龙、丹参、茯苓、陈皮、炒酸枣仁、竹茹和柏子仁药材由山西振东安特生物制药有限公司提供, 药材均经山西大学秦雪梅教授鉴定, 当归为伞形科植物当归[Angelica sinensis (Oliv.) Diels]的干燥根, 地黄为玄参科植物地黄(Rehmannia glutinosa Libosch.)干燥块根, 牡丹皮为毛茛科植物牡丹[Paeonia suffruticosa Andr.]的干燥根皮, 川芎为伞形科植物川芎[Ligusticum chuanxiong Hort.]的干燥根茎, 地龙为钜蚓科环毛属参环毛蚓[Pheretima aspergillum (E. Perrier)]的干燥虫体, 丹参为唇形科植物丹参[Salvia miltiorrhiza Bge.]的干燥根及根茎, 茯苓为多孔菌科真菌茯苓[Poria cocos (Schw.) Wolf]的干燥菌核, 陈皮为芸香科柑橘属植物橘[Citrus reticulata Blanco]及其栽培变种的干燥成熟果皮, 酸枣仁为鼠李科植物酸枣[Ziziphus jujuba Mill. var. spinosa (Bunge) Hu ex H.F.Chou]的干燥成熟种子, 竹茹为禾本科植物淡竹[Phyllostachys nigra (Lodd.) Munro var. henonis (Mitf.) Stapf ex Rendle]的茎秆的干燥中间层, 柏子仁为柏科植物侧柏[Platycladus orientalis (L.) Franco]的干燥成熟种仁。

供试品溶液的制备 取三批脑震宁颗粒混匀, 称取1 g, 研细, 置于具塞锥形瓶中, 加入50 mL 50%甲醇溶液, 超声提取30 min, 放至室温, 用定性滤纸过滤, 取上清液经0.22 µm微孔滤膜滤过, 置4 ℃冰箱备用。

单味药材样品溶液的制备 分别称取各单味药当归、地黄、牡丹皮、川芎、地龙、丹参、茯苓、陈皮、炒酸枣仁、竹茹和柏子仁各10 g, 分别加水100 mL煎煮1.5 h, 滤过, 浓缩后分别置于50 mL锥形瓶, 加50%甲醇溶液50 mL, 超声提取30 min, 用定性滤纸过滤, 取上清液经0.22 µm微孔滤膜滤过, 置4 ℃冰箱备用。

对照品溶液的配制 分别取各对照品适量, 精密称定, 用甲醇制备斯皮诺素(1.220 mg·mL⁻¹)、酸枣仁皂苷A (1.240 mg·mL⁻¹)、酸枣仁皂苷B (1.260 mg·mL⁻¹)、当药黄素(1.130 mg·mL⁻¹)、梓醇(1.230 mg·mL⁻¹)、柚皮苷(1.250 mg·mL⁻¹)、丹皮酚(1.240 mg·mL⁻¹)、橙皮苷(1.210 mg·mL⁻¹)、绿原酸(1.350 mg·mL⁻¹)、新绿原酸(1.510 mg·mL⁻¹)、隐绿原酸(1.420 mg·mL⁻¹)、阿魏酸(1.020 mg·mL⁻¹)、没食子酸(1.550 mg·mL⁻¹)、咖啡酸(1.270 mg·mL⁻¹)、芍药苷(1.250 mg·mL⁻¹)、亚正丁基苯酞内酯(1.550 mg·mL⁻¹)对照品储备液, 各取200 µL到5 mL量瓶, 用50%甲醇溶液定容, 制备成混合对照品溶液。

超高效液相色谱条件 色谱柱为Waters Acquity UPLC BEH C₁₈液相色谱柱(2.1 mm × 100 mm, 1.7 µm), 流动相为A: 0.1%甲酸水溶液; B:乙腈。梯度洗脱, 0~15 min, 5%~20% B; 15~20 min, 20%~35% B; 20~30 min, 35%~55% B。检测波长为290 nm, 柱温为45 ℃, 流速为0.2 mL·min⁻¹, 进样量为1 μL。

质谱条件 Full MS/DD MS² (TOPN); 离子源:电喷雾离子源(HESI); 扫描方式:正负离子同时扫描; 毛细管温度: 320 ℃; 鞘气体积流量为35 psi (1 psi ≈ 6.9 kPa), 辅助气体积流量为10 psi; 喷雾电压:正离子模式为3.5 kV, 负离子模式为2.5 kV, 透镜电压55 kPa; 探头加温器温度: 300 ℃; 最大喷雾电流: 100 V; NEC: 10, 30, 50;质量扫描范围均为m/z 100~1 500, 质量分辨率70 000。

数据处理分析 将采集到的原始质谱数据运用Xcalibur 3.2数据软件进行峰提取、峰匹配分析处理。将采集到的原始质谱数据导入Compound Discover 2.0软件, 与数据库进行计算匹配, 导出样品名称、保留时间、分子式、质荷比、以及对应的离子强度组成的数据集, 主要参数设置如下:保留时间范围0~25 min; 质荷比范围为100~1 500 Da; 偏差为5 ppm; 信噪比为3;保留时间漂移值为0.1 min。

结果

收起

采用UHPLC-Q Exactive轨道肼高分辨质谱对脑震宁颗粒进行分析, 同时获得正负离子模式下多级质谱数据, 然后运用Xcalibur 3.2数据软件进行分析处理。正、负总离子流分别如图 1所示。

1 基于质谱裂解途径的定性鉴别

1.1 环烯醚萜苷类

脑震宁颗粒中的环烯醚萜苷类化合物来源于地黄, 其中梓醇是代表性成分。在负离子模式下化合物11得到准分子离子峰m/z 361.112 9 [M–H]^–, 然后失去一分子葡萄糖(Glu)得到m/z 199.060 5 [M–H–Glu]^–, 进一步失去一分子–CH₂O得到m/z 169.050 0 [M–H–Glu–CH₂O]^–; 此外, 准分子离子峰还可失去一分子–CH₂O得到m/z 331.066 9 [M– H–CH₂O]^–。进一步通过与梓醇对照品的质谱行为进行比对后确定化合物11为梓醇。

负离子模式下化合物18的准分子离子峰m/z 345.118 0 [M–H]^–, 一方面失去一分子Glu得到m/z 183.066 1 [M–H–Glu]^–, 随后再失去一分子H₂O得到m/z 165.055 2 [M–H–Glu–H₂O]^–。另一方面准分子离子峰失去一分子H₂O得到m/z 327.128 0 [M–H–H₂O]^–, 再失去一分子H₂O得到m/z 309.108 9 [M–H–2H₂O]^–, 与文献中桃叶珊瑚苷的质谱碎片一致^[11]。脑震宁颗粒中鉴定的环烯醚萜苷类化合物还包括地黄苷A^[11]、地黄苷D^[11]、单密力特苷^[11]、京尼平苷^[11], 该类成分均为负离子模式下鉴定。环烯醚萜苷类化合物裂解途径有一定的共性规律, 大多会失去H₂O、–CH₂O等中性碎片, 或是失去糖得到苷元后再失去H₂O、–CH₂O等。

1.2 丁基苯酞类

当归和川芎均含有丁基苯酞类化合物。在正离子模式下, 化合物58、65具有相同的准分子离子峰m/z 189.091 1 [M+H]⁺, 保留时间分别为16.26和17.98 min。在正离子二级质谱图中, 化合物58准分子离子峰失去一分子H₂O得到m/z 171.080 4 [M+H–H₂O]⁺, 再失去一分子H₂O, 得到m/z 153.069 5 [M+H–2H₂O]⁺, 准分子离子峰还可同时失去H₂O和CO得到m/z 143.085 6 [M+H–H₂O–CO]⁺, 另外还观察到m/z 105.033 8 [M+H–C₅H₈O]^–的碎片峰; 化合物65产生的碎片离子包括m/z 153.069 9 [M+H–2H₂O]⁺、m/z 143.085 6 [M+H–H₂O–CO]⁺、m/z 105.033 8 [M+H– C₅H₈O]^–。通过和对照品的保留时间和质谱碎片相比对, 结合文献^{[12, 13]}报道确认化合物58、65分别为E-丁烯基苯酞和Z-丁烯基苯酞。

在正离子模式下, 化合物66的保留时间为18.12 min, 准分子离子峰为m/z 191.106 8 [M+H]⁺, 在二级质谱中失去一分子H₂O得到m/z 173.096 1 [M+ H–H₂O]⁺, 失去一分子CO得到m/z 163.111 5 [M+H– CO]⁺; 化合物78的保留时间为20.25 min, 准分子离子峰为m/z 191.106 7 [M+H]⁺, 在二级质谱中失去一分子H₂O得到m/z 173.096 1 [M+H–H₂O]⁺, 失去一分子CO得到m/z 163.111 7 [M+H–CO]⁺; 结合文献^{[12, 13]}报道, 推测保留时间较小的化合物66为E-蒿本内酯, 化合物78为Z-蒿本内酯。此外, 脑震宁颗粒中鉴定的丁基苯酞类化合物还包括senkyunolide H/I^{[12, 13]}、butylphthalide^{[12, 13]}、senkyunolide A^{[12, 13]}, 该类成分均为正离子模式下鉴定。丁基苯酞类化合物在正离子模式下一般会失去一分子CO形成四元环, 进一步电子转移再失去一分子H₂O; 或内酯环电子转移失去一分子H₂O, 进一步电子转移再失去一分子H₂O。

1.3 黄酮氧苷类

在正离子模式下, 化合物44的准分子离子峰为m/z 581.186 8 [M+H]⁺, 并通过m/z 603.168 6 [M+Na]⁺进一步确认其为准分子离子峰。在二级质谱中, 准分子离子峰失去鼠李糖(rhamnose, Rha)得到m/z 435.128 1 [M+H–Rha]⁺, 进一步失去一分子Glu则得到二氢黄酮苷元, 其m/z 273.075 6 [M+ H–Rha–Glu]⁺。该苷元可发生裂解得到m/z 147.044 1, 并进一步失去CO得到m/z 119.049 3。在正离子模式下化合物48产生m/z 611.197 7 [M+H]⁺的准分子离子峰和m/z 633.179 6 [M+Na]⁺, 准分子离子峰失去3分子H₂O产生m/z 557.158 6, 同时裂解产生m/z 465.139 1 [M+H–Rha]⁺, 进一步失去一分子Glu得到m/z 303.086 3 [M+H–Rha–Glu]⁺, 柚皮苷和橙皮苷的质谱行为均与对照品一致。

在正离子模式下, 化合物56的准分子离子峰为m/z 595.202 1 [M+H]⁺, 并找到m/z 617.183 8 [M+Na]⁺, 准分子离子峰失去Rha得到m/z 449.144 2 [M+H– Rha]⁺, 进一步失去O得到m/z 433.148 9 [M+H–Rha–O]⁺, 继续失去H₂O得到m/z 415.138 1 [M+H–Rha–O–H₂O]⁺、m/z 397.128 3 [M+H–Rha–O–2H₂O]⁺; 准分子离子峰失去一分子Rha、一分子Glu得到m/z 287.091 2 [M+ H–Rha–Glu]⁺, 与文献^[14]报道的枸橘苷质谱裂解碎片一致。脑震宁中鉴定的黄酮氧苷类化合物还包括陈皮中的芸香柚皮苷^[14], 炒酸枣仁中的当药黄素^[15]。该类成分均为正离子模式下鉴定, 质谱碎片主要是氧苷键断裂和脱水产生。

1.4 黄酮碳苷类

酸枣仁中含有斯皮诺素等黄酮碳苷类化合物。在负离子模式下化合物52产生m/z 607.166 8 [M–H]^–准分子离子峰, 失去一分子Glu得到m/z 445.114 6 [M–H–Glu]^–, 继续失去一分子H₂O得到m/z 427.103 2 [M–H–Glu–H₂O]^–, 失去C₄H₈O₄则产生m/z 325.071 8 [M–H–Glu–C₄H₈O₄]^–。其质谱行为与斯皮诺素对照品一致。

在负离子模式下化合物41产生m/z 593.151 2 [M–H]^–的准分子离子峰, 失去一分子H₂O得到m/z 445.114 6 [M–H–H₂O]^–, 失去C₄H₈O₄产生m/z 473.108 8 [M–H–C₄H₈O₄]^–, 失去两个C₄H₈O₄产生m/z 353.066 6 [M–H–2C₄H₈O₄]^–, 再失去一分子CO得到m/z 325.071 3 [M–H–2C₄H₈O₄–CO]^–, 与黄酮碳苷的裂解途径相一致, 参考文献^[16]报道的裂解规律, 可以推测化合物41为vicenin Ⅱ。在负离子模式下该类化合物的碳苷键难以断裂, 首先出现丢失C₄H₈O₄的碎片。

1.5 单萜苷类

牡丹皮中含有以芍药苷为代表的单萜苷类化合物。在负离子模式下化合物47产生准分子离子峰m/z 479.155 6 [M–H]^–、m/z 525.161 1 [M+ HCOO^–]^–。准分子离子峰失去CH₂O得到m/z 449.145 4 [M–H–CH₂O]^–, 酯键断裂再脱水得到m/z 327.108 9 [M–H–CH₂O–C₇H₆O₂]^–, 进一步脱去C₆H₁₀O₅得到m/z 165.054 9 [M–H–CH₂O–C₇H₆O₂–C₆H₁₀O₅]^–。通过和对照品质谱数据比较, 可以确定化合物47为芍药苷。

在负离子模式下化合物31产生准分子离子峰m/z 495.150 6 [M–H]^–, 准分子离子峰失去CH₂O得到m/z 465.150 6 [M–H–CH₂O]^–, 苯甲酰酯键断裂同时脱掉1分子H₂O得到m/z 327.107 0 [M–H–CH₂O– C₇H₆O₃]^–, 最后再脱去C₆H₁₀O₅得到m/z 165.055 0 [M–H–CH₂O–C₇H₆O₃–C₆H₁₀O₅]^–, 另外还有酯键断裂产生的m/z 137.023 6。通过与文献报道的裂解碎片^[17]比较推测化合物31为氧化芍药苷(图 2)。通过分析该类化合物的质谱裂解规律, 从脑震宁中鉴定的该类成分还包括没食子酰芍药苷^[17]、没食子酰芍氧化药苷^[17]、苯甲酰芍药苷^[17]、苯甲酰氧化芍药苷^[17]、牡丹皮苷C^[17], 该类成分均为负离子模式下鉴定。单萜苷类化合物在负离子模式下裂解途径相近, 通常是丢失–CH₂O后酯键或糖苷键断裂, 最后都会得到m/z 165的碎片峰。

1.6 咖啡酰基奎尼酸类

新绿原酸、绿原酸、隐绿原酸互为同分异构体, 其分子式均为C₁₆H₁₈O₉。在负离子模式下均产生准分子离子峰m/z 353.087 7 [M– H]^–, 保留时间分别为4.41、7.05、7.52 min (化合物25、30、32)。进一步分析二级质谱数据, 化合物25酯键断裂, 准分子离子峰失去C₉H₇O₃, 得到m/z 191.055 6 [M–C₉H₇O₃]^–, 进一步失去一分子H₂O, 得到m/z 173.045 0 [M–C₉H₇O₃–H₂O]^–, 另外还有脱掉奎尼酸产生的m/z 179.034 3 [M–C₇H₁₁O₅]^–碎片峰, 而化合物30、32也产生相同的碎片峰, 与对照品和文献^{[18, 19]}中报道的碎片峰相一致。通过与对照品保留时间对照, 可以确定化合物25、30、32分别为新绿原酸、绿原酸、隐绿原酸。

1.7 丹酚酸类

丹酚酸类化合物是丹参的特征成分。在负离子模式下化合物68得到准分子离子峰m/z 717.146 3 [M–H]^–, 分子离子峰进行电子转移, 失去C₉H₁₀O₅得到m/z 519.092 8 [M–H–C₉H₁₀O₅]^–, 然后进一步裂解得到m/z 339.050 5 [M–H–C₁₈H₁₈O₉]^–、m/z 321.040 0 [M–H–C₁₈H₂₀O₁₀]^–、m/z 295.060 5 [M–H– C₁₉H₁₈O₁₁]^–, 与文献^[20]报道质谱碎片裂解途径相一致, 所以推测化合物68为丹酚酸B (图 3)。

在负离子模式下化合物65下产生m/z 493.113 9 [M–H]^–准分子离子峰, 可进一步裂解得到m/z 313.071 5 [M–H–C₉H₈O₄]^–, 或酯键断裂失去C₉H₁₀O₅得到m/z 295.061 1 [M–H–C₉H₁₀O₅]^–, 然后再失去一分子H₂O得到m/z 277.050 4 [M–H–C₉H₁₀O₅–H₂O]^–, 参考文献^[21]报道的裂解特征推测化合物65为丹酚酸A。通过分析该类化合物的共性裂解特征, 从脑震宁颗粒中鉴定的丹酚酸类化合物还包括丹酚酸C^[21]、丹酚酸D^[21]、丹酚酸E^[21]、丹酚酸F^[21]、丹酚酸H/I^[21], 该类成分均为负离子模式下鉴定。

1.8 生物碱类

在正离子模式下, 化合物32产生m/z 286.143 6 [M+H]⁺准分子离子峰, 二级质谱中产生碎片m/z 269.117 0 [M+H–NH₃]⁺、m/z 254.096 1 [M+ H–NH₃–CH₃]⁺、m/z 237.090 8 [M+H–CH₃O–H₂O]⁺, 参照文献报道的质谱碎片推测其为乌药碱^[15]。化合物37在正离子模式下产生m/z 342.170 1 [M+H]⁺准分子离子峰, 二级质谱产生m/z 311.127 0 [M+H–CH₃O]⁺和311.127 0 [M+H–C₂H₆N]⁺, 推测其为木兰花碱^[19]。脑震宁中鉴定的生物碱类化合物还包括酸李碱^[15]、N-glc-indoleaceticacid^[15]、juzirine^[15]、lotusine^[15], 这些成分均来源于酸枣仁, 且均在正离子模式下鉴定。

1.9 其他类化合物

通过与对照品比对保留时间和精确分子量还鉴定了酸枣仁皂苷A、B, 由于酸枣仁皂苷类成分分子量大, 难以电离, 仅提取到酸枣仁皂苷A、B的准分子离子峰, 未检测到其碎片峰及其同类成分。

此外, 脑震宁中还含有氨基酸、小分子有机酸等化合物, 这些化合物的鉴定主要通过裂解碎片分析并结合文献对照完成。在负离子模式下化合物50产生准分子离子峰m/z 193.050 1 [M–H]^–, 裂解失去CH₃得到m/z 178.026 5 [M–H–CH₃]^–, 或失去一分子CO₂得到m/z 149.060 0 [M–H–CO₂]^–, 与对照品质谱行为相一致。脑震宁中鉴定的小分子有机酸类化合物还包括柠檬酸^[11]、琥珀酸^[22]、没食子酸^[17]、香草酸^[18]、原儿茶酸^[21]、对香豆酸^{[18, 23]}、对羟基苯乙酸^[23]、原儿茶酸^[21]和咖啡酸^[21], 这些成分均在负离子模式下鉴定。

在正离子模式下, 化合物13产生准分子离子峰m/z 182.081 2 [M+H]⁺, 二级质谱中产生碎片m/z 165.054 6 [M+H–NH₃]⁺、m/z 136.061 8 [M–COOH]⁺、m/z 119.049 3 [M+H–NH₃–COOH]⁺和m/z 107.049 7 [M+H–NH₃–COOH–NH]⁺, 通过参照文献报道的质谱碎片推测其为酪氨酸^[22]。脑震宁中鉴定的氨基酸类化合物还包括亮氨酸^[22]、苯丙氨酸^[22]、色氨酸^[22]、赖氨酸^[22]、精氨酸^[22]和谷氨酸^[22], 均在正离子模式下鉴定。

2 Compound Discover 2.0指认

将样品和空白溶剂的谱图导入Compound Discover 2.0中, 设置预测化合物的分子组成为C、H、O、N, 并将化合物碎片匹配值设置在50%以上, 通过CD数据库进行自动结构指认, 鉴定出93个可能的结构, 手动去除非天然产物、未提取到准分子离子峰的化合物、匹配度低于70%且未在二级质谱图中找到碎片的化合物后, 共指认53个化合物, 其中包括上述手动鉴定的化合物12个, 新鉴定化合物41个, 主要包括隐丹参酮、柠檬苦素、neodiosmin、prunin等次级代谢物, 以及葡萄糖醛酸、甘露糖、棉子糖等初级代谢物。

3 药材中特征化合物的鉴定

通过TCMSP数据库(http://ibts.hkbu.edu.hk/LSP/tcmsp.php )进一步查询单味药材中含有的特征成分, 并从中筛选出上述裂解规律分析和CD自动鉴定过程中均未得到鉴定的成分, 分别列出分子式, 在Xcalibur 3.2软件中提取这些化合物可能产生的准分子离子峰, 共有14个成分检测到准分子离子峰, 但无二级碎片或仅有少量裂解途径未知的碎片, 包括水苏糖、二氢梓醇、槲皮素等。

综上, 采用上述指认策略从脑震宁颗粒中共指认出161个化合物, 其中负离子模式下鉴定成分81个(表 1^{[7, 1, 12, 15−19, 21−25]}), 正离子模式下鉴定成分80个(表 2^{[12−15, 17, 19, 22, 26]})。按照结构鉴定的可靠性, 将定性分析结果由高到低分为4个不同层次。a为与对照品比对鉴定, 包括16个化合物; b为分析精确分子质量、裂解碎片结合文献数据对照鉴定, 包括106个化合物; c为Compound Discover 2.0自动鉴定, 包括54个化合物, 见表 3; d为仅检测到准分子离子峰的药材特征性成分, 包括14个化合物。

4 脑震宁颗粒主要色谱峰归属

通过比较脑震宁颗粒与单味药总离子流图保留时间初步判断峰来源, 然后通过保留时间下的质谱图比对进一步确定峰的归属。脑震宁中鉴定的161个成分中, 有42个来源于地黄, 54个来源于当归, 58个来源于川芎, 62个来源于陈皮, 50个来源于丹参, 49个来源于牡丹皮, 64个来源于酸枣仁, 36个来源于竹茹, 37个来源于柏子仁, 32个来源于地龙, 28个来源于茯苓。上述鉴定和归属的化合物中包括部分共有成分, 如氨基酸类, 糖类, 以及柠檬酸、琥珀酸、原儿茶酸、阿魏酸、咖啡酸、对香豆酸等小分子有机酸类, 在多种药材中均有发现。

讨论

收起

通过分析裂解碎片信息、结合文献及对照品MS数据对照, 并借助Compound Discover 2.0自动指认, 共鉴定出脑震宁颗粒中161个化合物, 包括环烯醚萜苷类、丁基苯酞类、黄酮苷类、酚酸类、单萜苷类等, 所构建的脑震宁化学成分物质组为其质量控制和药效物质基础研究奠定了基础。

柏子仁主要成分是脂肪油^[26], 茯苓主要成分是三萜类化合物^[27], 竹茹的主要化学成分是木脂素类^[28]和三萜类^[29], 这些极性较低的化学成分在本研究中检出较少, 原因可能在于脑震宁颗粒的生产工艺中这些药材均为水煎煮提取。脑震宁颗粒化学成分复杂, 对于在液质联用中难以电离或存在离子抑制的成分, 还需要进一步采用核磁共振等非选择性技术进行分析。此外, 脑震宁颗粒生产过程中包括当归、牡丹皮、陈皮、川芎的挥发油成分提取, 因此该中成药还含有丰富的挥发性成分, 下一步还将采用气质联用对其挥发性成分进行系统分析。

基金

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山西省中药现代化振东专项基金：基于功能主治的脑震宁工艺优化和标准提升(2106ZD0404)
山西省重点研发计划：山西名优中成药脑震宁颗粒大品种二次开发(201603D3113003)

参考文献

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文献

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2018年第53卷第4期

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doi: 10.16438/j.0513-4870.2017-1190

接收时间：2017-11-30
首发时间：2026-01-15
出版时间：2018-04-12

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收稿日期：2017-11-30
修回日期：2018-01-10

基金

山西省中药现代化振东专项基金：基于功能主治的脑震宁工艺优化和标准提升(2106ZD0404)

山西省重点研发计划：山西名优中成药脑震宁颗粒大品种二次开发(201603D3113003)

作者信息

1.山西大学中医药现代研究中心, 山西太原 030006

2.山西振东安特生物制药有限公司, 山西晋中 030600

3.山西大学化学化工学院, 山西太原 030006

通讯作者:

* 朱平, Tel/Fax:86-354-2467991, 86-351-7018379, E-mail:zp8236@sohu.com;

李震宇, E-mail:lizhenyu@sxu.edu.cn

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2种不同金属材料的力学参数

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

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No.	t_R/min	Identification	Molecularformula	[M–H]^–/[M+HCOO]^–	Error/ppm	Fragmentaion	Source
1^b	1.19	Rehmannioside D^[11]	C₂₇H₄₂O₁₀	685.218 2/–	–0.6	667.215 9, 523.161 2, 179.055 4, 361.110 4	D
2^c	1.23	D-Glucosamine	C₆H₁₃NO₅	178.071 4/–	2.8	160.060 7, 142.050 1, 124.039 5	G, M, Z, C, X
3^d	1.26	Stachyose	C₂₄H₄₂O₂₁	665.214 1/–	0.9	545.175 5, 503.159 2, 485.149 7	D
4^c	1.27	D-Raffinose	C₁₈H₃₂O₁₆	503.161 5/–	1.8	485.162 6, 443.140 3, 383.119 4, 341.108 5, 323.098 6	D, S
5^c	1.29	D-(+)-Mannose	C₆H₁₂O₆	179.055 5/–	2.8	161.044 8, 131.033 8, 113.023 7, 89.023 4	All
6^c	1.32	Gluconic acid	C₆H₁₂O₇	195.050 5/–	3.0	177.039 7, 159.029 2, 141.018 5, 129.018 5	D, S, Z, M, G, X
7^c	1.34	D-(–)-Quinic acid	C₇H₁₂O₆	191.055 5/–	2.6	173.044 8, 155.034 1, 147.029 3, 137.023 4	G, S, X, M, C
8^d	1.35	Sucrose	C₁₂H₂₂O₁₁	341.108 6/–	2.3	179.055 5, 161.044 9, 143.034 1, 89.023 4	All
9^c	1.69	2-Furoic acid	C₅H₄O₃	111.007 8/–	1.8	83.012 9, 67.017 9	All
10^{b, c}	1.71	Citric acid^[11]	C₆H₈O₇	191.019 1/–	–0.5	173.008 4, 129.018 4, 111.007 8, 147.029 0	All
11^{a, b}	1.78	Catalpol^[11]	C₁₅H₂₂O₁₀	361.113 9/–	2.8	199.060 5, 169.050 0, 331.066 9	D
12^{b, c}	1.86	Succinic acid^[22]	C₄H₆O₄	117.018 4/–	1.7	99.007 8, 73.028 5, 55.017 9	All
13^b	1.89	Galloyl-glucose^[17]	C₁₃H₁₆O₁₀	331.066 7/–	2.1	271.045 8, 211.024 3, 191.019 1, 169.013 5	M
14^b	2.03	RehmanniosideA^[11]	C₂₁H₃₂O₁₅	523.166 7/–	1.9	505.167 3, 361.131 3, 323.096 8, 199.060 8	D
15^{a, b, c}	2.14	Gallic acid^[17]	C₇H₆O₅	169.013 5/–	2.4	125.023 6, 97.028 4	Z, M
16^b	2.25	Danmelittoside^[11]	C₁₅H₂₂O₁₀	361.114 0/–	3.0	199.060 8, 179.055 6, 161.044 9	D
17^b	2.44	Peony glucoside B^[17]	C₁₈H₂₄O₁₄	463.109 1/–	1.9	463.109 1, 403.088 0, 373.077 7, 343.066 9, 301.056 4	M
18^b	2.88	Aucubin^[11]	C₁₅H₂₂O₉	345.118 7/–	2.0	327.128 0, 309.108 9, 183.066 1, 165.055 2	D
19^b	3.06	Vanillic acid^[18]	C₈H₈O₄	167.034 2/–	1.8	152.010 8, 137.023 0, 139.039 3, 123.044 3	X, Z, S, G, B
20^b	3.06	Pseudolaroside B^[15]	C₁₄H₁₈O₉	329.087 6/–	2.7	167.034 2, 152.010 7	Z, B, R
21^b	3.10	Tanshinol^[21]	C₉H₉O₅	197.045 0/–	3.0	179.034 4, 151.039 4, 135.044 3, 123.044 2	S
22^b	3.13	HA^[23]	C₈H₈O₃	151.039 3/–	2.0	133.028 5, 123.044 3, 107.049 3, 93.033 7	R, S, X, G, B
23^d	3.43	Dihydrocatalpol	C₁₅H₂₄O₁₀	363.128 8/–	0.8		D
24^b	3.51	Protocatechuic acid^[21]	C₇H₆O₄	153.018 6/–	2.6	141.911 7, 109.028 6, 123.901 0, 110.031 9	S, X, G, C, F, B, R, L
25^{a, b}	4.41	Neochlorogenic acid^[24]	C₁₆H₁₈O₉	353.087 7/–	2.8	353.087 6, 191.055 6, 179.034 3, 173.045 0	Z, X, G
26^c	4.99	DHA	C₉H₁₀O₄	181.050 0/–	2.8	163.039 3, 135.044 3	S, Z
27^d	5.22	Leonuride	C₁₅H₂₄O₉	347.134 7/–	3.2		D
28^b	5.62	Protocatechuic aldehyde^[21]	C₇H₆O₃	137.023 6/–	2.2	119.013 0, 109.028 5, 108.020 6	All
29^b	6.79	Geniposide^[11]	C₁₇H₂₄O₁₀	387.129 5/–	2.3	225.076 0	D, R
30^{a, b}	7.05	Chlorogenic acid^{[18, 24]}	C₁₆H₁₈O₉	353.087 7/–	2.8	353.087 6, 191.055 7, 179.034 0, 173.045 4	X, Z, G, C
31^b	7.20	Oxypaeoniflorin^[17]	C₂₃H₂₈O₁₂	495.150 6/–	1.8	465.141 1, 333.098 0, 165.055 0, 137.023 6	M
32^{a, b}	7.52	Cryptochlorogenic acid^[24]	C₁₆H₁₈O₉	353.087 7/–	2.8	353.087 4, 191.055 6, 179.034 3, 173.044 8	X, G
33^{a, b, c}	7.52	Caffeic acid^[21]	C₉H₈O₄	179.034 3/–	2.2	143.864 7, 135.044 3, 104.927 0, 89.023 4	S, D, C, Z, R
34^c	7.55	Isophthalic acid	C₈H₆O₄	165.018 6/–	2.4	121.028 6	G, Z, X, C
35^{b, c}	7.82	Benzoic acid^[18]	C₇H₆O₂	121.028 6/–	1.6	93.033 7, 77.038 5	Z, M, C, F, B, Z, L
36^d	7.87	Ajugoside	C₁₇H₂₅O₁₀	389.144 8/–	1.5		D
37^c	7.97	6-Methoxysalicylic acid	C₈H₈O₄	167.034 3/–	2.4	123.044 3, 121.028 9	G, X, C
38^c	8.80	2-Hydroxycaproic acid	C₆H₁₂O₃	131.070 5/–	1.5	85.064 8	X, G
39^b	8.85	Paeonolide^[17]	C₂₀H₂₈O₁₂	–/505.159 9	1.4	459.150 8, 293.087 8, 165.055 0	M
40^c	8.88	Apocynin	C₉H₁₀O₃	165.054 4/–	–1.2		M
41^b	8.89	Vicenin Ⅱ^[16]	C₂₇H₃₀O₁₅	593.151 2/–	1.8	503.120 0, 473.108 8, 413.087 1, 383.077 1, 353.066 6	S
42^b	9.26	Paeonolide^[17]	C₂₀H₂₈O₁₂	–/505.154 4	–1.6	459.150 9, 293.088 0, 165.055 0, 233.066 1	M
43^b	9.36	Galloyl-oxypaeoniflorin^[17]	C₃₀H₃₂O₁₆	647.161 9/–	1.8	509.128 8, 399.093 1, 313.056 7, 271.045 2, 211.024 3	M
44^b	9.44	p-Coumaric acid^{[18, 23]}	C₉H₈O₃	163.039 3/–	1.8	162.838 4, 159.859 2, 145.861 5, 123.945 5, 119.049 3	R, Z, S, G, C, R, L
45^d	9.50	Purpureaside C	C₃₅H₄₆O₂₀	785.250 4/–	0.6		D
46^b	9.81	Salvianolic acid F^[21]	C₁₇H₁₄O₆	313.071 9/–	4.1	269.081 7, 159.044 4	S
47^{a, b}	9.95	Paeoniflorin^[17]	C₂₃H₂₈O₁₁	–/525.161 1	1.5	525.161 2, 479.155 6, 449.154 5, 327.108 9, 165.054 9	M
48^c	10.21	3-Phenyllactic acid	C₉H₁₀O₃	165.055 0/–	2.4	147.044 4, 127.869 9, 119.049 3, 101.038 8	Z, D, M, X, C
49^d	10.42	Jionoside A	C₃₆H₄₈O₂₀	799.266 2/–	0.8		D
50^{a, b, c}	10.54	Ferulic acid^{[12, 24]}	C₁₀H₁₀O₄	193.050 1/–	3.1	193.050 1, 178.026 5, 149.060 0, 134.036 5	G, X, S, G, C
51^b	10.65	Isoferulic acid^[12]	C₁₀H₁₀O₄	193.050 3/–	4.1	178.026 5, 149.060 1, 134.036 5	G, X, S, G, C
52^{a, b}	10.72	Spinosin^[19]	C₂₈H₃₂O₁₅	607.166 8/–	1.8	607.167 0, 487.126 2, 445.114 6, 427.103 2, 325.071 8	Z
53^b	10.84	Suffruticoside B/D^[17]	C₂₇H₃₂O₁₆	611.161 9/–	2.1	445.098 5, 343.067 7, 169.013 6	M
54^b	11.35	Acteoside^[11]	C₂₉H₃₆O₁₅	623.198 0/–	1.6	461.166 5, 161.023 7	D
55^b	11.36	Galloyl-paeoniflorin^[17]	C₃₀H₃₂O₁₅	631.166 9/–	1.9	509.131 3, 479.119 4, 399.092 4, 313.056 5, 169.013 6	M
56^b	11.65	Salvianolic acid H/I^[21]	C₂₇H₂₂O₁₂	537.101 2/–	–2.8	339.050 9, 295.061 1	S
57^d	11.68	Jionoside B	C₃₇H₅₀O₂₀	813.282 5/–	1.7		D
58^b	11.72	Rehmaionoside A/B^[11]	C₁₉H₃₄O₈	389.218 2/–	3.1	435.223 44	D
59^b	11.75	Salvianolic acid D^[21]	C₂₀H₁₈O₁₀	417.082 7/–	2.6	417.082 8, 197.045 1, 175.039 4, 157.028 7	S
60^b	11.90	Isoacteoside^[11]	C₂₉H₃₆O₁₅	623.197 5/–	0.8	461.166 8, 161.023 7	D
61^c	12.35	Salicylic acid	C₇H₆O₃	137.023 6/–	2.2	109.028 4, 93.033 6	G, D, M, X, C
62^b	12.45	Rehmannia bitterglycosides^[11]	C₁₆H₂₆O₈	345.155 7/–	3.8	183.102 0, 179.055 5, 165.091 4	D
63^b	12.60	Rosmarinic acid^[21]	C₁₈H₁₆O₈	359.077 0/–	2.5	359.077 5, 197.045 0, 179.034 4, 161.023 7, 133.028 7	S
64^c	12.71	Azelaic acid	C₉H₁₆O₄	187.097 0/–	2.7	169.086 3, 125.096 3	All
65^b	12.71	Salvianolic acid A^[21]	C₂₆H₂₂O₁₀	493.113 9/–	2.0	493.114 0, 313.071 5, 295.061 1, 185.023 9	S
66^b	12.74	Lithospermic acid^[21]	C₂₇H₂₂O₁₂	[M+M–H]^–:1 075.216 9	2.8	537.103 6, 340.898 9, 295.060 6	S
67^b	13.15	HOG^[17]	C₂₂H₂₄O₁₁	463.124 6/–	2.4	301.071 6, 271.064 5, 229.024 9	C
68^{b, c}	13.30	Salvianolic acid B^[21]	C₃₆H₃₀O₁₆	717.146 3/–	1.8	519.092 8, 339.050 5, 321.040 0, 295.060 5, 279.029 6	S
69^b	13.55	BOHD^[25]	C₁₉H₁₈O₈	373.092 4/–	1.6	345.098 5, 358.069 5, 343.082 4, 313.072 8	C
70^b	13.78	CMGC^[17]	C₃₀H₃₂O₁₃	599.176 9/–	1.7	551.152 2, 477.139 7, 447.129 9, 431.135 5, 281.066 7	M
71^b	13.92	Salvianolic acid E/Isosalvianolic acid B^[21]	C₃₆H₃₀O₁₆	717.146 1/–	1.5	717.145 8, 519.093 3, 339.050 9, 321.040 5, 295.061 2, 279.029 8	S
72^b	14.15	Salvianolic acid C^[21]	C₂₆H₂₀O₁₀	491.098 4/–	2.2	311.056 1, 293.045 7, 265.050 6	S
73^b	14.45	Benzoyloxypaeoniflorin^[17]	C₃₀H₃₂O₁₃	599.176 9/–	1.7	569.164 7, 477.138 5, 137.023 6, 121.028 6, 165.055 0	M
74^c	14.83	3-tert-Butyladipic acid	C₁₀H₁₈O₄	201.112 8/–	3.5	183.102 1, 157.122 6, 139.112 1	All
75^b	14.89	RI^[11]	C₃₁H₄₀O₁₅	651.229 6/–	2.0	475.183 9, 193.050 3, 175.039 4	D
76^b	16.35	GSPLLPT^[25]	C₃₆H₅₃N₇O₉	726.382 9/–	1.1	726.383 8, 696.372 0, 697.378 7, 590.330 5	C
77^b	16.50	Benzoyl paeoniflorin^[17]	C₃₀H₃₂O₁₂	–/629.188 0	2.4	583.182 3, 553.171 5, 431.135 3, 165.055 1	M
78^b	17.78	ATTPLI^[25]	C₃₄H₅₃N₇O₉	702.383 0/–	1.3	702.381 3, 658.356 0, 615.333 9, 614.330 6	C
79^{a, b}	17.85	Jujuboside A^[7]	C₅₈H₉₄O₂₆	–/1 251.601 1	0.6		Z
80^{a, b}	18.36	Jujuboside B^[7]	C₅₂H₈₄O₂₁	–/1 089.547 5	–0.1		Z
81^c	20.48	α-Estrdiol	C₁₈H₂₄O₂	271.170 2/–	3.7		S

No.

t_R/min

Identification

Molecularformula

[M–H]^–/[M+HCOO]^–

Error/ppm

Fragmentaion

Source

1^b

1.19

Rehmannioside D^[11]

C₂₇H₄₂O₁₀

685.218 2/–

–0.6

667.215 9, 523.161 2, 179.055 4, 361.110 4

2^c

1.23

D-Glucosamine

C₆H₁₃NO₅

178.071 4/–

2.8

160.060 7, 142.050 1, 124.039 5

G, M, Z, C, X

3^d

1.26

Stachyose

C₂₄H₄₂O₂₁

665.214 1/–

0.9

545.175 5, 503.159 2, 485.149 7

4^c

1.27

D-Raffinose

C₁₈H₃₂O₁₆

503.161 5/–

1.8

485.162 6, 443.140 3, 383.119 4, 341.108 5, 323.098 6

D, S

5^c

1.29

D-(+)-Mannose

C₆H₁₂O₆

179.055 5/–

2.8

161.044 8, 131.033 8, 113.023 7, 89.023 4

All

6^c

1.32

Gluconic acid

C₆H₁₂O₇

195.050 5/–

3.0

177.039 7, 159.029 2, 141.018 5, 129.018 5

D, S, Z, M, G, X

7^c

1.34

D-(–)-Quinic acid

C₇H₁₂O₆

191.055 5/–

2.6

173.044 8, 155.034 1, 147.029 3, 137.023 4

G, S, X, M, C

8^d

1.35

Sucrose

C₁₂H₂₂O₁₁

341.108 6/–

2.3

179.055 5, 161.044 9, 143.034 1, 89.023 4

All

9^c

1.69

2-Furoic acid

C₅H₄O₃

111.007 8/–

1.8

83.012 9, 67.017 9

All

10^{b, c}

1.71

Citric acid^[11]

C₆H₈O₇

191.019 1/–

–0.5

173.008 4, 129.018 4, 111.007 8, 147.029 0

All

11^{a, b}

1.78

Catalpol^[11]

C₁₅H₂₂O₁₀

361.113 9/–

2.8

199.060 5, 169.050 0, 331.066 9

12^{b, c}

1.86

Succinic acid^[22]

C₄H₆O₄

117.018 4/–

1.7

99.007 8, 73.028 5, 55.017 9

All

13^b

1.89

Galloyl-glucose^[17]

C₁₃H₁₆O₁₀

331.066 7/–

2.1

271.045 8, 211.024 3, 191.019 1, 169.013 5

14^b

2.03

RehmanniosideA^[11]

C₂₁H₃₂O₁₅

523.166 7/–

1.9

505.167 3, 361.131 3, 323.096 8, 199.060 8

15^{a, b, c}

2.14

Gallic acid^[17]

C₇H₆O₅

169.013 5/–

2.4

125.023 6, 97.028 4

Z, M

16^b

2.25

Danmelittoside^[11]

C₁₅H₂₂O₁₀

361.114 0/–

3.0

199.060 8, 179.055 6, 161.044 9

17^b

2.44

Peony glucoside B^[17]

C₁₈H₂₄O₁₄

463.109 1/–

1.9

463.109 1, 403.088 0, 373.077 7, 343.066 9, 301.056 4

18^b

2.88

Aucubin^[11]

C₁₅H₂₂O₉

345.118 7/–

2.0

327.128 0, 309.108 9, 183.066 1, 165.055 2

19^b

3.06

Vanillic acid^[18]

C₈H₈O₄

167.034 2/–

1.8

152.010 8, 137.023 0, 139.039 3, 123.044 3

X, Z, S, G, B

20^b

3.06

Pseudolaroside B^[15]

C₁₄H₁₈O₉

329.087 6/–

2.7

167.034 2, 152.010 7

Z, B, R

21^b

3.10

Tanshinol^[21]

C₉H₉O₅

197.045 0/–

3.0

179.034 4, 151.039 4, 135.044 3, 123.044 2

22^b

3.13

HA^[23]

C₈H₈O₃

151.039 3/–

2.0

133.028 5, 123.044 3, 107.049 3, 93.033 7

R, S, X, G, B

23^d

3.43

Dihydrocatalpol

C₁₅H₂₄O₁₀

363.128 8/–

0.8

24^b

3.51

Protocatechuic acid^[21]

C₇H₆O₄

153.018 6/–

2.6

141.911 7, 109.028 6, 123.901 0, 110.031 9

S, X, G, C, F, B, R, L

25^{a, b}

4.41

Neochlorogenic acid^[24]

C₁₆H₁₈O₉

353.087 7/–

2.8

353.087 6, 191.055 6, 179.034 3, 173.045 0

Z, X, G

26^c

4.99

DHA

C₉H₁₀O₄

181.050 0/–

2.8

163.039 3, 135.044 3

S, Z

27^d

5.22

Leonuride

C₁₅H₂₄O₉

347.134 7/–

3.2

28^b

5.62

Protocatechuic aldehyde^[21]

C₇H₆O₃

137.023 6/–

2.2

119.013 0, 109.028 5, 108.020 6

All

29^b

6.79

Geniposide^[11]

C₁₇H₂₄O₁₀

387.129 5/–

2.3

225.076 0

D, R

30^{a, b}

7.05

Chlorogenic acid^{[18, 24]}

C₁₆H₁₈O₉

353.087 7/–

2.8

353.087 6, 191.055 7, 179.034 0, 173.045 4

X, Z, G, C

31^b

7.20

Oxypaeoniflorin^[17]

C₂₃H₂₈O₁₂

495.150 6/–

1.8

465.141 1, 333.098 0, 165.055 0, 137.023 6

32^{a, b}

7.52

Cryptochlorogenic acid^[24]

C₁₆H₁₈O₉

353.087 7/–

2.8

353.087 4, 191.055 6, 179.034 3, 173.044 8

X, G

33^{a, b, c}

7.52

Caffeic acid^[21]

C₉H₈O₄

179.034 3/–

2.2

143.864 7, 135.044 3, 104.927 0, 89.023 4

S, D, C, Z, R

34^c

7.55

Isophthalic acid

C₈H₆O₄

165.018 6/–

2.4

121.028 6

G, Z, X, C

35^{b, c}

7.82

Benzoic acid^[18]

C₇H₆O₂

121.028 6/–

1.6

93.033 7, 77.038 5

Z, M, C, F, B, Z, L

36^d

7.87

Ajugoside

C₁₇H₂₅O₁₀

389.144 8/–

1.5

37^c

7.97

6-Methoxysalicylic acid

C₈H₈O₄

167.034 3/–

2.4

123.044 3, 121.028 9

G, X, C

38^c

8.80

2-Hydroxycaproic acid

C₆H₁₂O₃

131.070 5/–

1.5

85.064 8

X, G

39^b

8.85

Paeonolide^[17]

C₂₀H₂₈O₁₂

–/505.159 9

1.4

459.150 8, 293.087 8, 165.055 0

40^c

8.88

Apocynin

C₉H₁₀O₃

165.054 4/–

–1.2

41^b

8.89

Vicenin Ⅱ^[16]

C₂₇H₃₀O₁₅

593.151 2/–

1.8

503.120 0, 473.108 8, 413.087 1, 383.077 1, 353.066 6

42^b

9.26

Paeonolide^[17]

C₂₀H₂₈O₁₂

–/505.154 4

–1.6

459.150 9, 293.088 0, 165.055 0, 233.066 1

43^b

9.36

Galloyl-oxypaeoniflorin^[17]

C₃₀H₃₂O₁₆

647.161 9/–

1.8

509.128 8, 399.093 1, 313.056 7, 271.045 2, 211.024 3

44^b

9.44

p-Coumaric acid^{[18, 23]}

C₉H₈O₃

163.039 3/–

1.8

162.838 4, 159.859 2, 145.861 5, 123.945 5, 119.049 3

R, Z, S, G, C, R, L

45^d

9.50

Purpureaside C

C₃₅H₄₆O₂₀

785.250 4/–

0.6

46^b

9.81

Salvianolic acid F^[21]

C₁₇H₁₄O₆

313.071 9/–

4.1

269.081 7, 159.044 4

47^{a, b}

9.95

Paeoniflorin^[17]

C₂₃H₂₈O₁₁

–/525.161 1

1.5

525.161 2, 479.155 6, 449.154 5, 327.108 9, 165.054 9

48^c

10.21

3-Phenyllactic acid

C₉H₁₀O₃

165.055 0/–

2.4

147.044 4, 127.869 9, 119.049 3, 101.038 8

Z, D, M, X, C

49^d

10.42

Jionoside A

C₃₆H₄₈O₂₀

799.266 2/–

0.8

50^{a, b, c}

10.54

Ferulic acid^{[12, 24]}

C₁₀H₁₀O₄

193.050 1/–

3.1

193.050 1, 178.026 5, 149.060 0, 134.036 5

G, X, S, G, C

51^b

10.65

Isoferulic acid^[12]

C₁₀H₁₀O₄

193.050 3/–

4.1

178.026 5, 149.060 1, 134.036 5

G, X, S, G, C

52^{a, b}

10.72

Spinosin^[19]

C₂₈H₃₂O₁₅

607.166 8/–

1.8

607.167 0, 487.126 2, 445.114 6, 427.103 2, 325.071 8

53^b

10.84

Suffruticoside B/D^[17]

C₂₇H₃₂O₁₆

611.161 9/–

2.1

445.098 5, 343.067 7, 169.013 6

54^b

11.35

Acteoside^[11]

C₂₉H₃₆O₁₅

623.198 0/–

1.6

461.166 5, 161.023 7

55^b

11.36

Galloyl-paeoniflorin^[17]

C₃₀H₃₂O₁₅

631.166 9/–

1.9

509.131 3, 479.119 4, 399.092 4, 313.056 5, 169.013 6

56^b

11.65

Salvianolic acid H/I^[21]

C₂₇H₂₂O₁₂

537.101 2/–

–2.8

339.050 9, 295.061 1

57^d

11.68

Jionoside B

C₃₇H₅₀O₂₀

813.282 5/–

1.7

58^b

11.72

Rehmaionoside A/B^[11]

C₁₉H₃₄O₈

389.218 2/–

3.1

435.223 44

59^b

11.75

Salvianolic acid D^[21]

C₂₀H₁₈O₁₀

417.082 7/–

2.6

417.082 8, 197.045 1, 175.039 4, 157.028 7

60^b

11.90

Isoacteoside^[11]

C₂₉H₃₆O₁₅

623.197 5/–

0.8

461.166 8, 161.023 7

61^c

12.35

Salicylic acid

C₇H₆O₃

137.023 6/–

2.2

109.028 4, 93.033 6

G, D, M, X, C

62^b

12.45

Rehmannia bitterglycosides^[11]

C₁₆H₂₆O₈

345.155 7/–

3.8

183.102 0, 179.055 5, 165.091 4

63^b

12.60

Rosmarinic acid^[21]

C₁₈H₁₆O₈

359.077 0/–

2.5

359.077 5, 197.045 0, 179.034 4, 161.023 7, 133.028 7

64^c

12.71

Azelaic acid

C₉H₁₆O₄

187.097 0/–

2.7

169.086 3, 125.096 3

All

65^b

12.71

Salvianolic acid A^[21]

C₂₆H₂₂O₁₀

493.113 9/–

2.0

493.114 0, 313.071 5, 295.061 1, 185.023 9

66^b

12.74

Lithospermic acid^[21]

C₂₇H₂₂O₁₂

[M+M–H]^–:1 075.216 9

2.8

537.103 6, 340.898 9, 295.060 6

67^b

13.15

HOG^[17]

C₂₂H₂₄O₁₁

463.124 6/–

2.4

301.071 6, 271.064 5, 229.024 9

68^{b, c}

13.30

Salvianolic acid B^[21]

C₃₆H₃₀O₁₆

717.146 3/–

1.8

519.092 8, 339.050 5, 321.040 0, 295.060 5, 279.029 6

69^b

13.55

BOHD^[25]

C₁₉H₁₈O₈

373.092 4/–

1.6

345.098 5, 358.069 5, 343.082 4, 313.072 8

70^b

13.78

CMGC^[17]

C₃₀H₃₂O₁₃

599.176 9/–

1.7

551.152 2, 477.139 7, 447.129 9, 431.135 5, 281.066 7

71^b

13.92

Salvianolic acid E/Isosalvianolic acid B^[21]

C₃₆H₃₀O₁₆

717.146 1/–

1.5

717.145 8, 519.093 3, 339.050 9, 321.040 5, 295.061 2, 279.029 8

72^b

14.15

Salvianolic acid C^[21]

C₂₆H₂₀O₁₀

491.098 4/–

2.2

311.056 1, 293.045 7, 265.050 6

73^b

14.45

Benzoyloxypaeoniflorin^[17]

C₃₀H₃₂O₁₃

599.176 9/–

1.7

569.164 7, 477.138 5, 137.023 6, 121.028 6, 165.055 0

74^c

14.83

3-tert-Butyladipic acid

C₁₀H₁₈O₄

201.112 8/–

3.5

183.102 1, 157.122 6, 139.112 1

All

75^b

14.89

RI^[11]

C₃₁H₄₀O₁₅

651.229 6/–

2.0

475.183 9, 193.050 3, 175.039 4

76^b

16.35

GSPLLPT^[25]

C₃₆H₅₃N₇O₉

726.382 9/–

1.1

726.383 8, 696.372 0, 697.378 7, 590.330 5

77^b

16.50

Benzoyl paeoniflorin^[17]

C₃₀H₃₂O₁₂

–/629.188 0

2.4

583.182 3, 553.171 5, 431.135 3, 165.055 1

78^b

17.78

ATTPLI^[25]

C₃₄H₅₃N₇O₉

702.383 0/–

1.3

702.381 3, 658.356 0, 615.333 9, 614.330 6

79^{a, b}

17.85

Jujuboside A^[7]

C₅₈H₉₄O₂₆

–/1 251.601 1

0.6

80^{a, b}

18.36

Jujuboside B^[7]

C₅₂H₈₄O₂₁

–/1 089.547 5

–0.1

81^c

20.48

α-Estrdiol

C₁₈H₂₄O₂

271.170 2/–

3.7

No.	t_R/min	Identification	Molecularformula	[M+H]⁺/[M+Na]⁺	Error/ppm	Fragmentaion	Source
1^b	1.21	Lysine^[22]	C₆H₁₄N₂O₂	147.112 9/–	0.7	130.086 5	All
2^b	1.24	Arginine^[22]	C₆H₁₄N₄O₂	175.119 0/–	0.6	116.070 8	All
3^c	1.26	Choline	C₅H₁₃NO	104.107 3/–	2.9	87.044 4, 69.034 0	All
4^c	1.32	Proline	C₅H₉NO₂	116.070 8/–	1.7	98.984 4, 70.065 7	All
5^b	1.34	Glutamate^[22]	C₅H₉NO₄	148.060 4/–	0	135.050 0	All
6^c	1.34	DL-Stachydrine	C₇H₁₃NO₂	144.101 9/–	0	102.150 0, 84.081 2	All
7^c	1.42	DF	C₉H₁₁NO	150.091 4/–	0.6	135.067 9, 132.080 8, 117.057 8	G, S, D, X, C
8^c	1.67	Phenylephrine	C₉H₁₃NO₂	168.102 0/–	1.2	150.091 5
9^c	1.68	L-Pyroglutamic acid	C₅H₇NO₃	130.050 1/–	2.3	102.055 3, 84.044 9	All
10^b	1.70	Adenosine^[22]	C₁₀H₁₃N₅O₄	268.104 0/–	0	136.061 8, 119.035 6	All
11^b	1.70	Hypoxanthine^[22]	C₅H₄N₄O	137.045 9/–	0.7	119.035 7, 110.035 1	L, S, X, R
12^c	1.71	L-Tyrosine	C₉H₁₁NO₃	182.081 3/–	0.5	165.054 6, 147.044 0, 136.075 7	All
13^b	1.74	Tyrosine^[22]	C₉H₁₁NO₃	182.081 2/–	0	165.054 6, 136.075 7, 119.049 3, 107.049 7, 95.049 6	All
14^b	1.77	Guanine^[22]	C₅H₅N₅O	152.056 8/–	0.6	135.030 2, 110.035 3, 55.029 9	All
15^b	1.91	Glutarylcarnitine^[22]	C₁₂H₂₁NO₆	276.144 0/–	–0.7	258.133 5, 230.138 6, 212.127 9, 170.117 8, 144.101 9	All
16^b	2.05	ANDA^[22]	C₁₂H₂₁NO₆	276.143 9/–	–1.0	258.133 5, 230.138 6, 212.128 2, 170.117 3, 161.068 3	All
17^{b, c}	2.13	L-Norleucine^[22]	C₆H₁₃NO₂	132.101 9/–	0	86.096 9, 69.070 4	All
18^c	2.10	Pyrogallol	C₆H₆O₃	127.039 1/–	0.8	109.028 6	All
19^b	2.83	GHIA^[15]	C₁₆H₁₉NO₉	370.113 8/–	1.4	352.100 6, 308.113 1, 290.101 8, 272.114 3, 232.071 6	Z
20^{b, c}	2.94	L-Phenylalanine^[22]	C₉H₁₁NO₂	166.086 2/–	–1.2	149.059 5, 120.081 0, 103.054 5, 91.054 4, 77.039 2	All
21^c	3.01	5-Hydroxymethyl-2-furaldehyde	C₆H₆O₃	127.039 1/–	0.8	109.028 7, 99.044 3	All
22^b	3.02	Fructose phenylalanine^[22]	C₁₅H₂₁NO₇	328.138 9/–	–0.6	310.128 3, 292.117 6, 282.134 2, 264.122 7, 178.086 1	L, S, D, M, X, C, R
23^b	3.02	AEOA^[22]	C₁₅H₁₉NO₆	310.127 7/–	–2.6	292.117 7, 264.122 9, 178.086 1, 166.086 2	L, S, D, X, G
24^c	3.05	Isovanillic acid	C₈H₈O₄	169.049 5/–	0		X, Z, S, G, B
25^b	3.08	GHIA^[15]	C₁₆H₁₉NO₉	370.113 0/–	–0.8	352.100 7, 308.112 9, 290.100 2, 272.112 6, 208.060 5	Z
26^{b, c}	5.39	L-Tryptophan^[22]	C₁₁H₁₂N₂O₂	205.097 5/–	2.0	188.070 6, 159.091 7, 132.080 7, 130.065 1, 118.065 3	L, Z, S, M, X, G, C
27^c	5.62	2, 5-Dihydroxybenzaldehyde	C₇H₆O₃	139.039 1/–	0.7	121.028 6, 111.044 3, 102.948 4	All
28^b	5.85	N-Glc-indoleaceticacid^[15]	C₁₆H₁₉NO₈	354.118 3/–	0	188.070 6, 174.054 9, 146.060 2, 128.049 6	Z
29^b	6.75	6-Glc-coclaurine^[15]	C₂₃H₂₉NO₈	448.196 3/–	–0.7	286.143 7, 269.117 0, 237.090 8, 219.081 4, 209.095 9	Z
30^b	6.81	N-Glc-indoleaceticacid^[15]	C₁₆H₁₉NO₈	354.118 3/–	0	188.070 6, 146.060 1, 128.049 7	Z
31^c	7.72	6-Methylquinoline	C₁₀H₉N	144.080 9/–	0.7	128.950 9, 126.955 2	Z
32^b	8.64	Coclaurine^[15]	C₁₇H₁₉NO₃	286.143 6/–	–0.7	269.117 0, 254.094 1, 237.090 8, 219.080 6, 209.096 1	Z
33^c	8.67	Morphine	C₁₇H₁₉NO₃	286.143 6/–	–0.7	269.117 0, 254.094 1, 237.090 8, 209.096 1	Z
34^b	8.86	Juzirine^[15]	C₁₇H₁₅NO₃	282.112 5/–	0	238.038 7, 188.070 8	Z
35^b	8.90	Meloside A^[15]	C₂₇H₃₀O₁₅	595.165 3/–	–0.7	379.080 8, 367.084 0, 337.070 6, 313.071 5, 283.061 0	Z
36^b	9.20	Zizyphusine^[15]	C₂₀H₂₄NO₄⁺	[M]⁺:342.169 9	–0.3	297.112 0, 282.088 6, 265.085 8, 237.090 9, 222.067 4	Z, B
37^b	9.27	Magnoflorine^[19]	C₂₀H₂₃NO₄	342.170 1/–	0.3	342.169 9, 311.127 0, 299.127 7, 297.112 0, 282.088 6	Z, B
38^c	9.56	Naringenin	C₁₅H₁₂O₅	273.075 7/–	0	171.028 7, 153.018 3, 147.044 1, 119.049 3	C
39^b	10.11	Lotusine^[15]	C₁₉H₂₄NO₃⁺	[M]⁺: 314.175 0	–0.3	237.091 6, 209.096 3, 165.069 9, 137.059 8, 107.049 5	Z
40^b	10.44	Camelliaside B^[15]	C₃₂H₃₈O₁₉	727.208 3/–	0.4	595.163 0, 449.114 4, 287.054 7	Z
41^d	10.59	Quercetin	C₁₅H₁₀O₇	303.049 9/–	0		M
42^c	10.69	Neodiosmin	C₂₈H₃₂O₁₅	609.180 8/–	0.8	591.166 0, 447.128 3, 327.086 1, 285.075 3	Z
43^b	10.81	Senkyunolide H/I^{[12, 13]}	C₁₂H₁₆O₄	225.111 8/–	–1.3	207.101 8, 189.091 2, 164.042 3, 161.096 1	G, X
44^{a, b, c}	11.85	Naringin^[14]	C₂₇H₃₂O₁₄	581.186 8/ 603.168 4	0.7/ 0.3	435.128 1, 401.123 0, 383.111 7, 273.075 6	C
45^c	11.85	Prunin	C₂₁H₂₂O₁₀	435.128 5/–	0	399.107 1, 273.075 7, 147.044 1, 119.019 2	C
46^d	11.95	Perlolyrine	C₁₆H₁₂N₂O₂	265.097 3/–	0.7		X
47^d	12.32	Senkyunolide-N	C₁₂H₁₈O₄	227.127 7/–	0		X
48^{a, b, c,}	12.62	Hesperidin^[14]	C₂₈H₃₄O₁₅	611.197 7/633.179 6	1.1/ 1.1	557.158 6, 465.139 1, 449.144 4, 303.086 3, 177.054 6, 151.075 1	C
49^c	12.62	Hesperetin	C₁₆H₁₄O₆	303.086 3/–	0	177.054 6, 153.018 2	C
50^c	12.65	Obacunoic acid	C₂₆H₃₂O₈	473.217 3/–	0.6	455.205 1, 427.211 5, 413.194 5, 395.183 9	C
51^{a, b}	12.69	Swertisin^[15]	C₂₂H₂₂O₁₀	447.130 8/–	4.9	411.107 0, 327.085 9, 297.075 7	Z
52^c	13.31	1, 4-Dimethoxyanthraquinone	C₁₆H₁₂O₄	269.080 7/–	–0.4		S
53^b	13.68	Senkyunolide H/I^{[12, 13]}	C₁₂H₁₆O₄	225.112 0/–	–0.4	207.101 7, 164.042 3, 161.096 1, 179.106 2	G, X
54^b	13.94	Mucronine J^[15]	C₂₇H₄₀N₄O₄	485.311 7/–	–1.0	221.080 6, 207.065 4, 114.124 9	Z
55^d	14.82	6'-p-coumaroylspinosin	C₃₈H₄₀O₁₇	769.230 8/–	–3.9		Z
56^b	15.12	Poncirin^[14]	C₂₈H₃₄O₁₄	595.202 1/617.183 8	0	433.148 9, 415.138 1, 397.128 3, 353.100 9	C
57^c	15.13	Sakuranetin	C₁₆H₁₄O₅	287.091 1/–	–1.0	171.028 6, 161.059 6, 153.018 1	C
58^{a, b}	16.26	E-Butylidenephthalide^{[12, 13]}	C₁₂H₁₂O₂	189.091 1/–	0.5	189.091 0, 171.080 4, 143.085 6, 105.033 8, 153.069 5	X, G
59^b	16.58	Narirutin^[13]	C₂₇H₃₂O₁₄	581.186 5/603.168 4	0	419.133 5, 404.110 1, 389.086 5, 371.076 2	C
60^d	16.92	Sanjoinine A	C₃₁H₄₂N₄O₄	535.327 8/–	0		Z
61^b	17.21	Paeonol^[17]	C₉H₁₀O₃	167.030 3/–	0	167.030 3, 149.059 8	M, X, S, G
62^b	17.72	Sinensetin/Isosinensetin^[14]	C₂₀H₂₀O₇	373.128 2/–	0	373.128 0, 358.104 0, 343.081 2, 328.058 8, 313.069 9	C
63^d	17.76	Jioglutin A	C₁₀H₁₅ClO₅	251.068 1/–	0		D
64^c	17.87	ODDA	C₁₈H₃₀O₃	295.226 5/–	–0.7	277.216 1, 259.204 9	All
65^{a, b}	17.98	Z-Butylidenephthalide^{[12, 13]}	C₁₂H₁₂O₂	189.091 1/–	0.5	189.090 9, 153.069 9, 143.085 6, 105.033 8	X, G
66^b	18.12	E-Ligustilide^{[12, 13]}	C₁₂H₁₄O₂	191.106 8/–	0.5	191.106 3, 173.096 1, 163.111 5	X, G
67^b	18.24	Butylphthalide^[12]	C₁₂H₁₄O₂	191.106 3/–	–2.1	173.096 1, 145.101 1, 117.069 7	X, G
68^b	18.34	Sinensetin/Isosinensetin^[14]	C₂₀H₂₀O₇	373.128 3/–	0.3	358.103 7, 343.081 0, 328.056 8, 313.070 4, 315.085 9	C
69^b	18.39	5, 6, 7, 4'-Tetramethoxyflavone^[14]	C₁₉H₁₈O₆	343.117 6/–	0	328.094 1, 313.070 6, 285.075 6, 153.043 6, 181.012 9	C
70^c	18.42	Limonin	C₂₆H₃₀O₈	471.201 4/–	0.2	471.201 3, 453.190 2, 425.196 0, 367.191 9	C
71^b	18.74	3, 5, 6, 7, 3', 4'-Hexamethoxyflavone^[14]	C₂₁H₂₂O₈	403.138 7/425.120 5	0/ –0.5	388.112 9, 373.091 7, 358.068 1, 343.043 2, 327.085 8, 165.055 0	C
72^{b, c}	18.93	Nobiletin^[14]	C₂₁H₂₂O₈	403.139 0/425.120 8	0.7/ –0.2	403.138 7, 388.115 1, 373.091 8, 358.068 3, 343.044 7, 327.086 4, 165.054 7, 345.097 0	C
73^b	18.97	5, 6, 7, 4'-Tetramethoxybaicalein^[14]	C₁₉H₁₈O₆	343.117 6/–	0	328.093 8, 313.070 4, 285.075 9, 282.088 4, 327.085 8	C
74^d	19.11	Sanjoinine B	C₃₀H₄₀N₄O₄	521.312 0/–	–0.4		Z
75^b	19.47	Senkyunolide A^{[12, 13]}	C₁₂H₁₆O₂	193.122 5/–	1.0	175.111 7, 147.116 9, 137.059 8, 119.085 7	G, X
76^{b, c}	19.47	Tangeritin	C₂₀H₂₀O₇	373.128 4/–	0.5	358.104 3, 343.081 1, 328.057 9, 313.071 4, 315.085 1, 299.055 1, 271.060 2, 211.023 4	C
77^b	19.96	Linolenic acid^{[22, 26]}	C₁₈H₃₀O₂	279.231 6/–	–0.7	149.023 3, 137.132 4, 135.116 4, 123.116 9, 121.028 5	L, Z
78^b	20.25	Z-Ligustilide^{[12, 13]}	C₁₂H₁₄O₂	191.106 7/–	0	191.106 6, 173.096 1, 163.111 7	X, G
79^c	20.58	1-Tetradecylamine	C₁₄H₃₁N	214.252 9/–	0	195.535 0, 171.091 8, 149.940 3	B
80^c	21.08	Cryptotanshinone	C₁₉H₂₀O₃	297.148 7/–	0.7	297.148 5, 279.137 9, 264.112 7, 251.142 9	S

No.

t_R/min

Identification

Molecularformula

[M+H]⁺/[M+Na]⁺

Error/ppm

Fragmentaion

Source

1^b

1.21

Lysine^[22]

C₆H₁₄N₂O₂

147.112 9/–

0.7

130.086 5

All

2^b

1.24

Arginine^[22]

C₆H₁₄N₄O₂

175.119 0/–

0.6

116.070 8

All

3^c

1.26

Choline

C₅H₁₃NO

104.107 3/–

2.9

87.044 4, 69.034 0

All

4^c

1.32

Proline

C₅H₉NO₂

116.070 8/–

1.7

98.984 4, 70.065 7

All

5^b

1.34

Glutamate^[22]

C₅H₉NO₄

148.060 4/–

135.050 0

All

6^c

1.34

DL-Stachydrine

C₇H₁₃NO₂

144.101 9/–

102.150 0, 84.081 2

All

7^c

1.42

C₉H₁₁NO

150.091 4/–

0.6

135.067 9, 132.080 8, 117.057 8

G, S, D, X, C

8^c

1.67

Phenylephrine

C₉H₁₃NO₂

168.102 0/–

1.2

150.091 5

9^c

1.68

L-Pyroglutamic acid

C₅H₇NO₃

130.050 1/–

2.3

102.055 3, 84.044 9

All

10^b

1.70

Adenosine^[22]

C₁₀H₁₃N₅O₄

268.104 0/–

136.061 8, 119.035 6

All

11^b

1.70

Hypoxanthine^[22]

C₅H₄N₄O

137.045 9/–

0.7

119.035 7, 110.035 1

L, S, X, R

12^c

1.71

L-Tyrosine

C₉H₁₁NO₃

182.081 3/–

0.5

165.054 6, 147.044 0, 136.075 7

All

13^b

1.74

Tyrosine^[22]

C₉H₁₁NO₃

182.081 2/–

165.054 6, 136.075 7, 119.049 3, 107.049 7, 95.049 6

All

14^b

1.77

Guanine^[22]

C₅H₅N₅O

152.056 8/–

0.6

135.030 2, 110.035 3, 55.029 9

All

15^b

1.91

Glutarylcarnitine^[22]

C₁₂H₂₁NO₆

276.144 0/–

–0.7

258.133 5, 230.138 6, 212.127 9, 170.117 8, 144.101 9

All

16^b

2.05

ANDA^[22]

C₁₂H₂₁NO₆

276.143 9/–

–1.0

258.133 5, 230.138 6, 212.128 2, 170.117 3, 161.068 3

All

17^{b, c}

2.13

L-Norleucine^[22]

C₆H₁₃NO₂

132.101 9/–

86.096 9, 69.070 4

All

18^c

2.10

Pyrogallol

C₆H₆O₃

127.039 1/–

0.8

109.028 6

All

19^b

2.83

GHIA^[15]

C₁₆H₁₉NO₉

370.113 8/–

1.4

352.100 6, 308.113 1, 290.101 8, 272.114 3, 232.071 6

20^{b, c}

2.94

L-Phenylalanine^[22]

C₉H₁₁NO₂

166.086 2/–

–1.2

149.059 5, 120.081 0, 103.054 5, 91.054 4, 77.039 2

All

21^c

3.01

5-Hydroxymethyl-2-furaldehyde

C₆H₆O₃

127.039 1/–

0.8

109.028 7, 99.044 3

All

22^b

3.02

Fructose phenylalanine^[22]

C₁₅H₂₁NO₇

328.138 9/–

–0.6

310.128 3, 292.117 6, 282.134 2, 264.122 7, 178.086 1

L, S, D, M, X, C, R

23^b

3.02

AEOA^[22]

C₁₅H₁₉NO₆

310.127 7/–

–2.6

292.117 7, 264.122 9, 178.086 1, 166.086 2

L, S, D, X, G

24^c

3.05

Isovanillic acid

C₈H₈O₄

169.049 5/–

X, Z, S, G, B

25^b

3.08

GHIA^[15]

C₁₆H₁₉NO₉

370.113 0/–

–0.8

352.100 7, 308.112 9, 290.100 2, 272.112 6, 208.060 5

26^{b, c}

5.39

L-Tryptophan^[22]

C₁₁H₁₂N₂O₂

205.097 5/–

2.0

188.070 6, 159.091 7, 132.080 7, 130.065 1, 118.065 3

L, Z, S, M, X, G, C

27^c

5.62

2, 5-Dihydroxybenzaldehyde

C₇H₆O₃

139.039 1/–

0.7

121.028 6, 111.044 3, 102.948 4

All

28^b

5.85

N-Glc-indoleaceticacid^[15]

C₁₆H₁₉NO₈

354.118 3/–

188.070 6, 174.054 9, 146.060 2, 128.049 6

29^b

6.75

6-Glc-coclaurine^[15]

C₂₃H₂₉NO₈

448.196 3/–

–0.7

286.143 7, 269.117 0, 237.090 8, 219.081 4, 209.095 9

30^b

6.81

N-Glc-indoleaceticacid^[15]

C₁₆H₁₉NO₈

354.118 3/–

188.070 6, 146.060 1, 128.049 7

31^c

7.72

6-Methylquinoline

C₁₀H₉N

144.080 9/–

0.7

128.950 9, 126.955 2

32^b

8.64

Coclaurine^[15]

C₁₇H₁₉NO₃

286.143 6/–

–0.7

269.117 0, 254.094 1, 237.090 8, 219.080 6, 209.096 1

33^c

8.67

Morphine

C₁₇H₁₉NO₃

286.143 6/–

–0.7

269.117 0, 254.094 1, 237.090 8, 209.096 1

34^b

8.86

Juzirine^[15]

C₁₇H₁₅NO₃

282.112 5/–

238.038 7, 188.070 8

35^b

8.90

Meloside A^[15]

C₂₇H₃₀O₁₅

595.165 3/–

–0.7

379.080 8, 367.084 0, 337.070 6, 313.071 5, 283.061 0

36^b

9.20

Zizyphusine^[15]

C₂₀H₂₄NO₄⁺

[M]⁺:342.169 9

–0.3

297.112 0, 282.088 6, 265.085 8, 237.090 9, 222.067 4

Z, B

37^b

9.27

Magnoflorine^[19]

C₂₀H₂₃NO₄

342.170 1/–

0.3

342.169 9, 311.127 0, 299.127 7, 297.112 0, 282.088 6

Z, B

38^c

9.56

Naringenin

C₁₅H₁₂O₅

273.075 7/–

171.028 7, 153.018 3, 147.044 1, 119.049 3

39^b

10.11

Lotusine^[15]

C₁₉H₂₄NO₃⁺

[M]⁺: 314.175 0

–0.3

237.091 6, 209.096 3, 165.069 9, 137.059 8, 107.049 5

40^b

10.44

Camelliaside B^[15]

C₃₂H₃₈O₁₉

727.208 3/–

0.4

595.163 0, 449.114 4, 287.054 7

41^d

10.59

Quercetin

C₁₅H₁₀O₇

303.049 9/–

42^c

10.69

Neodiosmin

C₂₈H₃₂O₁₅

609.180 8/–

0.8

591.166 0, 447.128 3, 327.086 1, 285.075 3

43^b

10.81

Senkyunolide H/I^{[12, 13]}

C₁₂H₁₆O₄

225.111 8/–

–1.3

207.101 8, 189.091 2, 164.042 3, 161.096 1

G, X

44^{a, b, c}

11.85

Naringin^[14]

C₂₇H₃₂O₁₄

581.186 8/ 603.168 4

0.7/ 0.3

435.128 1, 401.123 0, 383.111 7, 273.075 6

45^c

11.85

Prunin

C₂₁H₂₂O₁₀

435.128 5/–

399.107 1, 273.075 7, 147.044 1, 119.019 2

46^d

11.95

Perlolyrine

C₁₆H₁₂N₂O₂

265.097 3/–

0.7

47^d

12.32

Senkyunolide-N

C₁₂H₁₈O₄

227.127 7/–

48^{a, b, c,}

12.62

Hesperidin^[14]

C₂₈H₃₄O₁₅

611.197 7/633.179 6

1.1/ 1.1

557.158 6, 465.139 1, 449.144 4, 303.086 3, 177.054 6, 151.075 1

49^c

12.62

Hesperetin

C₁₆H₁₄O₆

303.086 3/–

177.054 6, 153.018 2

50^c

12.65

Obacunoic acid

C₂₆H₃₂O₈

473.217 3/–

0.6

455.205 1, 427.211 5, 413.194 5, 395.183 9

51^{a, b}

12.69

Swertisin^[15]

C₂₂H₂₂O₁₀

447.130 8/–

4.9

411.107 0, 327.085 9, 297.075 7

52^c

13.31

1, 4-Dimethoxyanthraquinone

C₁₆H₁₂O₄

269.080 7/–

–0.4

53^b

13.68

Senkyunolide H/I^{[12, 13]}

C₁₂H₁₆O₄

225.112 0/–

–0.4

207.101 7, 164.042 3, 161.096 1, 179.106 2

G, X

54^b

13.94

Mucronine J^[15]

C₂₇H₄₀N₄O₄

485.311 7/–

–1.0

221.080 6, 207.065 4, 114.124 9

55^d

14.82

6'-p-coumaroylspinosin

C₃₈H₄₀O₁₇

769.230 8/–

–3.9

56^b

15.12

Poncirin^[14]

C₂₈H₃₄O₁₄

595.202 1/617.183 8

433.148 9, 415.138 1, 397.128 3, 353.100 9

57^c

15.13

Sakuranetin

C₁₆H₁₄O₅

287.091 1/–

–1.0

171.028 6, 161.059 6, 153.018 1

58^{a, b}

16.26

E-Butylidenephthalide^{[12, 13]}

C₁₂H₁₂O₂

189.091 1/–

0.5

189.091 0, 171.080 4, 143.085 6, 105.033 8, 153.069 5

X, G

59^b

16.58

Narirutin^[13]

C₂₇H₃₂O₁₄

581.186 5/603.168 4

419.133 5, 404.110 1, 389.086 5, 371.076 2

60^d

16.92

Sanjoinine A

C₃₁H₄₂N₄O₄

535.327 8/–

61^b

17.21

Paeonol^[17]

C₉H₁₀O₃

167.030 3/–

167.030 3, 149.059 8

M, X, S, G

62^b

17.72

Sinensetin/Isosinensetin^[14]

C₂₀H₂₀O₇

373.128 2/–

373.128 0, 358.104 0, 343.081 2, 328.058 8, 313.069 9

63^d

17.76

Jioglutin A

C₁₀H₁₅ClO₅

251.068 1/–

64^c

17.87

ODDA

C₁₈H₃₀O₃

295.226 5/–

–0.7

277.216 1, 259.204 9

All

65^{a, b}

17.98

Z-Butylidenephthalide^{[12, 13]}

C₁₂H₁₂O₂

189.091 1/–

0.5

189.090 9, 153.069 9, 143.085 6, 105.033 8

X, G

66^b

18.12

E-Ligustilide^{[12, 13]}

C₁₂H₁₄O₂

191.106 8/–

0.5

191.106 3, 173.096 1, 163.111 5

X, G

67^b

18.24

Butylphthalide^[12]

C₁₂H₁₄O₂

191.106 3/–

–2.1

173.096 1, 145.101 1, 117.069 7

X, G

68^b

18.34

Sinensetin/Isosinensetin^[14]

C₂₀H₂₀O₇

373.128 3/–

0.3

358.103 7, 343.081 0, 328.056 8, 313.070 4, 315.085 9

69^b

18.39

5, 6, 7, 4'-Tetramethoxyflavone^[14]

C₁₉H₁₈O₆

343.117 6/–

328.094 1, 313.070 6, 285.075 6, 153.043 6, 181.012 9

70^c

18.42

Limonin

C₂₆H₃₀O₈

471.201 4/–

0.2

471.201 3, 453.190 2, 425.196 0, 367.191 9

71^b

18.74

3, 5, 6, 7, 3', 4'-Hexamethoxyflavone^[14]

C₂₁H₂₂O₈

403.138 7/425.120 5

0/ –0.5

388.112 9, 373.091 7, 358.068 1, 343.043 2, 327.085 8, 165.055 0

72^{b, c}

18.93

Nobiletin^[14]

C₂₁H₂₂O₈

403.139 0/425.120 8

0.7/ –0.2

403.138 7, 388.115 1, 373.091 8, 358.068 3, 343.044 7, 327.086 4, 165.054 7, 345.097 0

73^b

18.97

5, 6, 7, 4'-Tetramethoxybaicalein^[14]

C₁₉H₁₈O₆

343.117 6/–

328.093 8, 313.070 4, 285.075 9, 282.088 4, 327.085 8

74^d

19.11

Sanjoinine B

C₃₀H₄₀N₄O₄

521.312 0/–

–0.4

75^b

19.47

Senkyunolide A^{[12, 13]}

C₁₂H₁₆O₂

193.122 5/–

1.0

175.111 7, 147.116 9, 137.059 8, 119.085 7

G, X

76^{b, c}

19.47

Tangeritin

C₂₀H₂₀O₇

373.128 4/–

0.5

358.104 3, 343.081 1, 328.057 9, 313.071 4, 315.085 1, 299.055 1, 271.060 2, 211.023 4

77^b

19.96

Linolenic acid^{[22, 26]}

C₁₈H₃₀O₂

279.231 6/–

–0.7

149.023 3, 137.132 4, 135.116 4, 123.116 9, 121.028 5

L, Z

78^b

20.25

Z-Ligustilide^{[12, 13]}

C₁₂H₁₄O₂

191.106 7/–

191.106 6, 173.096 1, 163.111 7

X, G

79^c

20.58

1-Tetradecylamine

C₁₄H₃₁N

214.252 9/–

195.535 0, 171.091 8, 149.940 3

80^c

21.08

Cryptotanshinone

C₁₉H₂₀O₃

297.148 7/–

0.7

297.148 5, 279.137 9, 264.112 7, 251.142 9

Negative mode
2	94.5	4	73.9	3	90.5	4	90.0	6	99.0
5	65.8	6	89.8	7	65.8	8	88.9	9	86.8
7	90.9	9	86.0	12	84.1	17	75.7	18	78.4
10	79.8	12	72.9	20	88.4	21	85.2	24	83.8
15	84.9	26	63.2	26	71.2	27	88.9	31	74.1
33	83.6	34	59.7	33	62.7	38	94.6	42	51.6
35	82.1	37	85.0	44	79.2	45	82.4	48	89.2
38	67.4	40	71.8	49	94.8	50	65.9	52	70.6
48	84.7	50	79.0	57	62.2	65	81.2	70	83.7
61	65.4	64	88.3	72	89.9	76	89.4	79	82.2
68	79.9	74	79.7	80	91.2
81	84.7

Negative mode

Positive mode

No.

Best match/%

No.

Best match/%

No.

Best match/%

No.

Best match/%

No.

Best match/%

94.5

73.9

90.5

90.0

99.0

65.8

89.8

65.8

88.9

86.8

90.9

86.0

84.1

75.7

78.4

79.8

72.9

88.4

85.2

83.8

84.9

63.2

71.2

88.9

74.1

83.6

59.7

62.7

94.6

51.6

82.1

85.0

79.2

82.4

89.2

67.4

71.8

94.8

65.9

70.6

84.7

79.0

62.2

81.2

83.7

65.4

88.3

89.9

89.4

82.2

79.9

79.7

91.2

84.7