中国药学杂志

No.	Name	Formula	t_R/min	ESI^+/-	m/z(MS)	m/z(MS/MS)	Error/×10^-6	Structure class
1	Arginine¹⁾	C₆H₁₄N₄O₂	1.21	[M+H]⁺	175.119 9	158.090 0, 116.064 8	-5.40	Amino acid
2	Anthranilic acid^[13]	C₇H₇NO₂	1.31	[M+H]⁺	138.055 5	94.066 2, 93.056 1, 92.050 4	-3.98	Organic acid
3	Proline¹⁾	C₅H₉NO₂	1.39	[M+H]⁺	116.069 9	70.065 8	6.13	Amino acid
4	L-Valine^[14]	C₅H₁₁NO₂	1.62	[M+H]⁺	118.085 3	72.081 8, 55.055 0	8.16	Amino acid
5	Adenine^[13]	C₅H₅N₅	1.69	[M+H]⁺	136.062 4	119.036 3, 92.025 3, 67.030 1	-4.56	Amino acid
6	Citric acid or isomer^[15]	C₆H₈O₇	1.69	[M-H]^-	191.021 2	387.009 8, 129.020 0, 111.010 2	-7.68	Organic acid
7	Nicotinic acid¹⁾	C₆H₅NO₂	1.74	[M+H]⁺	124.040 0	78.034 9, 53.039 2	-5.65	Vitamin
8	Citric acid or isomer^[15]	C₆H₈O₇	1.75	[M-H]^-	191.021 1	387.009 0, 129.020 5, 111.011 5	-7.47	Organic acid
9	Uracil¹⁾	C₄H₄N₂O₂	2.17	[M+H]⁺	113.034 7	96.008 2, 95.023 5	-1.3	Nucleoside
10	Uridine^[16]	C₉H₁₂N₂O₆	2.25	[M+H]⁺	245.078 1	113.035 4, 96.009 1, 70.029 2	-5.27	Nucleoside
11	L-Tyrosine^[14]	C₉H₁₁NO₃	2.4	[M+H]⁺	182.082 5	165.055 1, 147.044 7, 136.076 6, 123.045 1, 91.055 1, 77.039 2	-7.35	Amino acid
12	L-isoleucine^[14]	C₆H₁₃NO₂	2.62	[M+H]⁺	132.102 9	86.097 7, 69.070 9, 57.058 0	-7.59	Amino acid
13	L-leucine¹⁾	C₆H₁₃NO₂	2.80	[M+H]⁺	132.102 8	86.097 5, 69.071 4, 57.058 3	-6.83	Amino acid
14	Adenosine¹⁾	C₁₀H₁₃N₅O₄	2.87	[M+H]⁺	268.105 6	136.062 4, 57.034 3	-5.88	Nucleoside
15	Pyridoxine^[14]	C₈H₁₁NO₃	2.94	[M+H]⁺	170.081 8	152.071 6, 134.061 2, 124.077 0, 106.066 6, 77.039 7, 65.038 7	-3.73	Vitamin
16	Guanosine^[16]	C₁₀H₁₃N₅O₅	3.06	[M+H]⁺	284.100 3	152.057 2, 135.031 0, 98.060 8	-4.79	Nucleoside
17	5'-Deoxyadenosine^[13]	C₁₀H₁₃N₅O₃	3.08	[M+H]⁺	252.110 4	136.062 2, 117.054 7	-5.11	Nucleoside
18	Phenylalanine^[13]	C₉H₁₁NO₂	4.10	[M+H]⁺	166.087 0	120.081 9, 103.055 2, 93.070 7, 77.039 6	-4.51	Amino acid
19	Protocatechuic acid¹⁾	C₇H₆O₄	5.05	[M-H]^-	153.020 3	109.030 8, 108.022 9, 65.003 7, 53.030 9,	-6.28	Organic acid
20	6-O-caffeoyl-α-D-fructofuranosyl- (2→1)-α-D-glucopyranoside^[17]	C₂₁H₂₈O₁₄	5.76	[M-H]^-	503.143 5	485.134 2, 341.111 6, 323.079 9, 281.073 5, 221.047 6, 179.034 9, 161.024 6	-5.69	Phenylpropanoids
21	5'-Deoxy-5'-methylthio adeno- sine^[18]	C₁₁H₁₅N₅O₃S	6.58	[M+H]⁺	298.098 1	136.062 6, 127.021 1, 119.106 4, 97.029 5	-4.25	Nucleoside
22	Aesculetin¹⁾	C₉H₆O₄	8.35	[M+H]⁺	179.034 5	151.039 2, 123.044 9, 105.034 6, 77.039 5	-3.45	Coumarin
23	Caffeic acid¹⁾	C₉H₈O₄	8.87	[M-H]^-	179.034 8	135.046 3, 107.051 3	1.01	Organic acid
24	Acretoside^[17]	C₂₁H₂₈O₁₃	9.59	[M-H]^-	487.148 2	307.080 6, 163.040 5, 145.030 3	-5.09	Sucrose ester
25	Sipeimine-3β-D-glucoside¹⁾	C₃₃H₅₃NO₈	11.57	[M+H]⁺	592.387 6	574.367 8	-5.42	Alkaloid
26	1-O-Glycerol ferulate^[19]	C₁₃H₁₆O₆	12.07	[M-H]^-	267.087 0	252.065 5, 175.040 2, 149.060 7, 133.030 8	1.54	Phenylpropanoid
27	Ferulic acid¹⁾	C₁₀H₁₀O₄	12.18	[M-H]^-	193.051 8	178.028 3, 134.038 4, 133.030 2	-6.02	Organic acid
28	(2S)-3-Acetoxy-2-(hexopyranosyloxy) propyl 3-(4-hydroxyphenyl) acrylate^[19]	C₂₀H₂₆O₁₁	12.24	[M-H]^-	441.142 7	163.040 8, 145.030 8	-5.57	Phenylpropanoid
29	Sipeimine¹⁾	C₂₇H₄₃NO₃	12.46	[M+H]⁺	430.334 3	412.318 2, 138.125 0	-6.36	Alkaloid
30	Edpetiline or isomer^[20]	C₃₃H₅₃NO₈	12.86	[M+H]⁺	592.387 4	574.370 9, 287.056 1	-5.08	Alkaloid
31	Peiminine¹⁾	C₂₇H₄₃NO₃	13.99	[M+H]⁺	430.333 8	412.323 4	-5.19	Alkaloid
32	Peimine¹⁾	C₂₇H₄₅NO₃	14.28	[M+H]⁺	432.349 7	414.339 0, 398.305 3, 176.143 3, 138.111 7, 124.112 0	-5.75	Alkaloid
33	Hyperoside^[14]	C₂₁H₂₀O₁₂	14.57	[M-H]^-	463.089 8	300.028 9, 271.026 5, 243.029 8, 151.004 6	-3.45	Flavonoid
34	Rutin and isomer^[14]	C₂₇H₃₀O₁₆	14.71	[M-H]^-	609.147 4	463.146 5, 301.035 7, 300.028 9	-2.12	Vitamin
35	Rutin and isomer^[14]	C₂₇H₃₀O₁₆	14.93	[M-H]^-	609.147 6	463.146 9, 301.035 2, 300.029 5	-2.44	Vitamin
36	Edpetiline or isomer^[20]	C₃₃H₅₃NO₈	14.94	[M+H]⁺	592.388 1	574.375 7	-6.27	Alkaloid
37	Yibeinoside A or isomer^[21]	C₃₃H₅₃NO₇	15.13	[M+H]⁺	576.392 3	414.334 0, 396.328 9, 98.098 1	-4.90	Alkaloid
38	Peimisine¹⁾	C₂₇H₄₁NO₃	15.40	[M+H]⁺	428.318 2	410.300 5, 393.274 5, 337.213 4	-5.33	Alkaloid
39	Yibeinoside A or isomer^[21]	C₃₃H₅₃NO₇	15.58	[M+H]⁺	576.392 3	414.335 9, 396.325 4, 98.096 7	-4.90	Alkaloid
40	3'-O-Methylquercetin 3-galacto- side^[14]	C₂₂H₂₂O₁₂	15.75	[M-H]^-	477.104 8	449.108 2, 357.062 9, 314.044 4, 243.031 8	-1.99	Flavonoid
41	Astragalin^[15]	C₂₁H₂₀O₁₁	15.76	[M-H]^-	447.094 7	285.039 8, 284.035 5, 255.028 0, 227.037 6	-3.16	Flavonoid
42	Litseagermacrane^[15]	C₁₅H₂₄O₂	15.82	[M+H]⁺	237.186 4	219.175 2, 167.106 9, 151.112 5, 135.118 3, 107.086 5	-6.32	Terpenoid
43	Kaempferol^[14]	C₁₅H₁₀O₆	16.04	[M-H]^-	285.041 9	151.004 2, 135.043 8, 133.030 2, 83.014 7, 65.725 8	-5.03	Flavonoid
44	Isorhamnetin-3-glucoside^[14]	C₂₂H₂₂O₁₂	16.29	[M-H]^-	477.104 8	315.049 9, 314.042 3, 299.021 8, 243.028 6, 151.003 1	-1.99	Flavonoid
45	Narcissoside¹⁾	C₂₈H₃₂O₁₆	16.44	[M-H]^-	623.163 8	315.052 3, 271.026 5, 151.004 6	-5.04	Flavonoid
46	Ebeiedinone^[21]	C₂₇H₄₃NO₂	16.79	[M+H]⁺	414.338 3	396.327 9, 119.085 5, 98.096 4, 95.085 3	-3.98	Alkaloid
47	Puqienine E^[20]	C₂₈H₄₃NO₃	16.82	[M+H]⁺	442.334 0	424.319 3	-5.50	Alkaloid
48	Quercitrin^[15]	C₂₁H₂₀O₁₁	17.15	[M-H]^-	447.094 7	314.042 5, 300.024 4, 271.019 5, 243.030 6	-3.16	Flavonoid
49	Hupeheninoside^[21]	C₃₃H₅₅NO₇	17.18	[M+H]⁺	578.407 9	398.341 2, 98.097 5, 85.0291, 69.033 9	-4.80	Alkaloid
50	β-Solanine or isomer^[22]	C₃₉H₆₃NO₁₁	17.62	[M+H]⁺	722.451 3	560.394 4, 398.344 2, 380.332 0, 98.097 6	-5.42	Alkaloid
51	Spirosol-5-en-3-ol 4-O-α-L-rhamnopyranosyl-(1-6)-β-D-glucopyranoside or isomer^[19]	C₃₉H₆₃NO₁₁	17.73	[M+COOH]^-	766.440 0	720.434 9, 179.056 3, 161.046 1	-2.43	Alkaloid
52	Quercetin¹⁾	C₁₅H₁₀O₇	18.23	[M+H]⁺	303.051 8	257.042 2, 229.048 3, 201.050 8, 153.018 8	-6.19	Flavonoid
53	β-Solanine or isomer^[22]	C₃₉H₆₃NO₁₁	18.41	[M+H]⁺	722.451 3	560.397 1, 398.342 1, 380.333 4, 98.097 2	-5.42	Alkaloid
54	Formononetin-7-O-glucoside^[19]	C₂₂H₂₂O₉	19.01	[M-H]^-	429.121 6	253.073 7, 193.051 0, 161.024 9	-5.80	Flavonoid
55	Demissidine-3-O-β-D-glucopyeanosyl(1→4) glucopyranoside or isomer	C₃₉H₆₅NO₁₁	19.24	[M+COOH]^-	768.457 6	722.450 8, 161.046 8, 101.025 5	-5.02	Alkaloid
56	Luteolin¹⁾	C₁₅H₁₀O₆	19.29	[M-H]^-	285.041 3	133.029 9	-6.81	Flavonoid
57	α-Solamarine or isomer^[22]	C₄₅H₇₃NO₁₆	21.18	[M+H]⁺	884.504 5	738.443 7, 414.337 5	-4.85	Alkaloid
58	Puqiedinone^[21]	C₂₇H₄₃NO₂	21.26	[M+H]⁺	414.338 3	396.327 1, 119.084 5, 105.070 3, 95.084 4, 81.070 6	-3.98	Alkaloid
59	Podophyllotoxin^[19]	C₂₂H₂₂O₈	21.55	[M-H]^-	413.126 9	219.070 5, 193.053 5, 175.039 3, 134.030 1	-6.54	Lignan
60	Puqienine A^[21]	C₂₈H₄₇NO₃	21.74	[M+H]⁺	446.364 8	428.352 5, 253.196 0, 145.100 0, 107.087 2, 105.069 7, 98.095 6, 95.085 6, 81.071 0	-4.33	Alkaloid
61	Imperialine N-oxide^[20]	C₂₇H₄₃NO₄	21.77	[M+H]⁺	446.329 0	428.315 1	-5.65	Alkaloid
62	Ebeienine^[21]	C₂₇H₄₃NO₂	22.26	[M+H]⁺	414.338 3	396.327 3, 98.085 5, 81.071 1, 67.053 8	-3.98	Alkaloid
63	Spirosol-5-en-3-ol 4-O-α-L-rhamnopyranosyl-(1-6)-β-D-glucopyranoside or isomer^[19]	C₃₉H₆₃NO₁₁	23.13	[M+COOH]^-	766.440 0	720.435 9, 179.056 2, 161.047 4	-2.43	Alkaloid
64	α-Solamarine or isomer^[22]	C₄₅H₇₃NO₁₆	23.36	[M+H]⁺	884.504 5	738.444 3, 414.339 4	-4.85	Alkaloid
65	Demissidine-3-O-β-D-glucopyeanosyl (1→4) glucopyranoside or isomer^[19]	C₃₉H₆₅NO₁₁	24.95	[M+COOH]^-	768.457 6	722.451 9, 161.046 8, 101.025 2	-5.02	Alkaloid
66	Pinellic acid^[19]	C₁₈H₃₄O₅	28.07	[M-H]^-	329.235 4	229.145 9, 211.136 3, 171.103 9	-6.21	Organic acid
67	2β, 3β, 14-Trihydroxy-cholest-7-en-6-one 3-O-α-L-rhamanopyranosyl-(1-3)-[β-D-glucopyranosyl-(1-2)]-β-D-glucopyranoside^[19]	C₅₁H₈₄O₂₃	31.01	[M+COOH]^-	1109.543 9	917.475 5, 901.492 1, 755.419 6	-5.03	Saponin
68	(2α, 3β, 5α, 25R)-2-Hydroxyspirostan-3-O-α-L-rhamnopyranosyl-(1-2)-β-D-glucopyranosyl-(1-2)-β-D-glucopyranoside^[19]	C₄₅H₇₄O₁₈	31.89	[M+COOH]^-	947.489 6	901.484 5, 755.421 6	-4.30	Saponin
69	α-Linolenic acid or isomer^[13]	C₁₈H₃₀O₂	37.26	[M+H]⁺	279.234 0	149.024 3, 81.070 7, 67.054 9	-7.70	Organic acid
70	α-Linolenic acid or isomer^[13]	C₁₈H₃₀O₂	37.44	[M+H]⁺	279.234 0	149.025 0, 81.070 3, 67.054 4	-7.70	Organic acid
71	9-Hydroxy-10(E), 12(Z)-octadecadienoic acid^[19]	C₁₈H₃₂O₃	38.67	[M-H]^-	295.230 3	277.220 4, 195.141 0, 183.012 8	-8.21	Organic acid

No.	Name	Formula	t_R/min	ESI^+/-	m/z(MS)	m/z(MS/MS)	Error/×10^-6	Structure class
1	Arginine¹⁾	C₆H₁₄N₄O₂	1.21	[M+H]⁺	175.119 9	158.090 0, 116.064 8	-5.40	Amino acid
2	Anthranilic acid^[13]	C₇H₇NO₂	1.31	[M+H]⁺	138.055 5	94.066 2, 93.056 1, 92.050 4	-3.98	Organic acid
3	Proline¹⁾	C₅H₉NO₂	1.39	[M+H]⁺	116.069 9	70.065 8	6.13	Amino acid
4	L-Valine^[14]	C₅H₁₁NO₂	1.62	[M+H]⁺	118.085 3	72.081 8, 55.055 0	8.16	Amino acid
5	Adenine^[13]	C₅H₅N₅	1.69	[M+H]⁺	136.062 4	119.036 3, 92.025 3, 67.030 1	-4.56	Amino acid
6	Citric acid or isomer^[15]	C₆H₈O₇	1.69	[M-H]^-	191.021 2	387.009 8, 129.020 0, 111.010 2	-7.68	Organic acid
7	Nicotinic acid¹⁾	C₆H₅NO₂	1.74	[M+H]⁺	124.040 0	78.034 9, 53.039 2	-5.65	Vitamin
8	Citric acid or isomer^[15]	C₆H₈O₇	1.75	[M-H]^-	191.021 1	387.009 0, 129.020 5, 111.011 5	-7.47	Organic acid
9	Uracil¹⁾	C₄H₄N₂O₂	2.17	[M+H]⁺	113.034 7	96.008 2, 95.023 5	-1.3	Nucleoside
10	Uridine^[16]	C₉H₁₂N₂O₆	2.25	[M+H]⁺	245.078 1	113.035 4, 96.009 1, 70.029 2	-5.27	Nucleoside
11	L-Tyrosine^[14]	C₉H₁₁NO₃	2.4	[M+H]⁺	182.082 5	165.055 1, 147.044 7, 136.076 6, 123.045 1, 91.055 1, 77.039 2	-7.35	Amino acid
12	L-isoleucine^[14]	C₆H₁₃NO₂	2.62	[M+H]⁺	132.102 9	86.097 7, 69.070 9, 57.058 0	-7.59	Amino acid
13	L-leucine¹⁾	C₆H₁₃NO₂	2.80	[M+H]⁺	132.102 8	86.097 5, 69.071 4, 57.058 3	-6.83	Amino acid
14	Adenosine¹⁾	C₁₀H₁₃N₅O₄	2.87	[M+H]⁺	268.105 6	136.062 4, 57.034 3	-5.88	Nucleoside
15	Pyridoxine^[14]	C₈H₁₁NO₃	2.94	[M+H]⁺	170.081 8	152.071 6, 134.061 2, 124.077 0, 106.066 6, 77.039 7, 65.038 7	-3.73	Vitamin
16	Guanosine^[16]	C₁₀H₁₃N₅O₅	3.06	[M+H]⁺	284.100 3	152.057 2, 135.031 0, 98.060 8	-4.79	Nucleoside
17	5'-Deoxyadenosine^[13]	C₁₀H₁₃N₅O₃	3.08	[M+H]⁺	252.110 4	136.062 2, 117.054 7	-5.11	Nucleoside
18	Phenylalanine^[13]	C₉H₁₁NO₂	4.10	[M+H]⁺	166.087 0	120.081 9, 103.055 2, 93.070 7, 77.039 6	-4.51	Amino acid
19	Protocatechuic acid¹⁾	C₇H₆O₄	5.05	[M-H]^-	153.020 3	109.030 8, 108.022 9, 65.003 7, 53.030 9,	-6.28	Organic acid
20	6-O-caffeoyl-α-D-fructofuranosyl- (2→1)-α-D-glucopyranoside^[17]	C₂₁H₂₈O₁₄	5.76	[M-H]^-	503.143 5	485.134 2, 341.111 6, 323.079 9, 281.073 5, 221.047 6, 179.034 9, 161.024 6	-5.69	Phenylpropanoids
21	5'-Deoxy-5'-methylthio adeno- sine^[18]	C₁₁H₁₅N₅O₃S	6.58	[M+H]⁺	298.098 1	136.062 6, 127.021 1, 119.106 4, 97.029 5	-4.25	Nucleoside
22	Aesculetin¹⁾	C₉H₆O₄	8.35	[M+H]⁺	179.034 5	151.039 2, 123.044 9, 105.034 6, 77.039 5	-3.45	Coumarin
23	Caffeic acid¹⁾	C₉H₈O₄	8.87	[M-H]^-	179.034 8	135.046 3, 107.051 3	1.01	Organic acid
24	Acretoside^[17]	C₂₁H₂₈O₁₃	9.59	[M-H]^-	487.148 2	307.080 6, 163.040 5, 145.030 3	-5.09	Sucrose ester
25	Sipeimine-3β-D-glucoside¹⁾	C₃₃H₅₃NO₈	11.57	[M+H]⁺	592.387 6	574.367 8	-5.42	Alkaloid
26	1-O-Glycerol ferulate^[19]	C₁₃H₁₆O₆	12.07	[M-H]^-	267.087 0	252.065 5, 175.040 2, 149.060 7, 133.030 8	1.54	Phenylpropanoid
27	Ferulic acid¹⁾	C₁₀H₁₀O₄	12.18	[M-H]^-	193.051 8	178.028 3, 134.038 4, 133.030 2	-6.02	Organic acid
28	(2S)-3-Acetoxy-2-(hexopyranosyloxy) propyl 3-(4-hydroxyphenyl) acrylate^[19]	C₂₀H₂₆O₁₁	12.24	[M-H]^-	441.142 7	163.040 8, 145.030 8	-5.57	Phenylpropanoid
29	Sipeimine¹⁾	C₂₇H₄₃NO₃	12.46	[M+H]⁺	430.334 3	412.318 2, 138.125 0	-6.36	Alkaloid
30	Edpetiline or isomer^[20]	C₃₃H₅₃NO₈	12.86	[M+H]⁺	592.387 4	574.370 9, 287.056 1	-5.08	Alkaloid
31	Peiminine¹⁾	C₂₇H₄₃NO₃	13.99	[M+H]⁺	430.333 8	412.323 4	-5.19	Alkaloid
32	Peimine¹⁾	C₂₇H₄₅NO₃	14.28	[M+H]⁺	432.349 7	414.339 0, 398.305 3, 176.143 3, 138.111 7, 124.112 0	-5.75	Alkaloid
33	Hyperoside^[14]	C₂₁H₂₀O₁₂	14.57	[M-H]^-	463.089 8	300.028 9, 271.026 5, 243.029 8, 151.004 6	-3.45	Flavonoid
34	Rutin and isomer^[14]	C₂₇H₃₀O₁₆	14.71	[M-H]^-	609.147 4	463.146 5, 301.035 7, 300.028 9	-2.12	Vitamin
35	Rutin and isomer^[14]	C₂₇H₃₀O₁₆	14.93	[M-H]^-	609.147 6	463.146 9, 301.035 2, 300.029 5	-2.44	Vitamin
36	Edpetiline or isomer^[20]	C₃₃H₅₃NO₈	14.94	[M+H]⁺	592.388 1	574.375 7	-6.27	Alkaloid
37	Yibeinoside A or isomer^[21]	C₃₃H₅₃NO₇	15.13	[M+H]⁺	576.392 3	414.334 0, 396.328 9, 98.098 1	-4.90	Alkaloid
38	Peimisine¹⁾	C₂₇H₄₁NO₃	15.40	[M+H]⁺	428.318 2	410.300 5, 393.274 5, 337.213 4	-5.33	Alkaloid
39	Yibeinoside A or isomer^[21]	C₃₃H₅₃NO₇	15.58	[M+H]⁺	576.392 3	414.335 9, 396.325 4, 98.096 7	-4.90	Alkaloid
40	3'-O-Methylquercetin 3-galacto- side^[14]	C₂₂H₂₂O₁₂	15.75	[M-H]^-	477.104 8	449.108 2, 357.062 9, 314.044 4, 243.031 8	-1.99	Flavonoid
41	Astragalin^[15]	C₂₁H₂₀O₁₁	15.76	[M-H]^-	447.094 7	285.039 8, 284.035 5, 255.028 0, 227.037 6	-3.16	Flavonoid
42	Litseagermacrane^[15]	C₁₅H₂₄O₂	15.82	[M+H]⁺	237.186 4	219.175 2, 167.106 9, 151.112 5, 135.118 3, 107.086 5	-6.32	Terpenoid
43	Kaempferol^[14]	C₁₅H₁₀O₆	16.04	[M-H]^-	285.041 9	151.004 2, 135.043 8, 133.030 2, 83.014 7, 65.725 8	-5.03	Flavonoid
44	Isorhamnetin-3-glucoside^[14]	C₂₂H₂₂O₁₂	16.29	[M-H]^-	477.104 8	315.049 9, 314.042 3, 299.021 8, 243.028 6, 151.003 1	-1.99	Flavonoid
45	Narcissoside¹⁾	C₂₈H₃₂O₁₆	16.44	[M-H]^-	623.163 8	315.052 3, 271.026 5, 151.004 6	-5.04	Flavonoid
46	Ebeiedinone^[21]	C₂₇H₄₃NO₂	16.79	[M+H]⁺	414.338 3	396.327 9, 119.085 5, 98.096 4, 95.085 3	-3.98	Alkaloid
47	Puqienine E^[20]	C₂₈H₄₃NO₃	16.82	[M+H]⁺	442.334 0	424.319 3	-5.50	Alkaloid
48	Quercitrin^[15]	C₂₁H₂₀O₁₁	17.15	[M-H]^-	447.094 7	314.042 5, 300.024 4, 271.019 5, 243.030 6	-3.16	Flavonoid
49	Hupeheninoside^[21]	C₃₃H₅₅NO₇	17.18	[M+H]⁺	578.407 9	398.341 2, 98.097 5, 85.0291, 69.033 9	-4.80	Alkaloid
50	β-Solanine or isomer^[22]	C₃₉H₆₃NO₁₁	17.62	[M+H]⁺	722.451 3	560.394 4, 398.344 2, 380.332 0, 98.097 6	-5.42	Alkaloid
51	Spirosol-5-en-3-ol 4-O-α-L-rhamnopyranosyl-(1-6)-β-D-glucopyranoside or isomer^[19]	C₃₉H₆₃NO₁₁	17.73	[M+COOH]^-	766.440 0	720.434 9, 179.056 3, 161.046 1	-2.43	Alkaloid
52	Quercetin¹⁾	C₁₅H₁₀O₇	18.23	[M+H]⁺	303.051 8	257.042 2, 229.048 3, 201.050 8, 153.018 8	-6.19	Flavonoid
53	β-Solanine or isomer^[22]	C₃₉H₆₃NO₁₁	18.41	[M+H]⁺	722.451 3	560.397 1, 398.342 1, 380.333 4, 98.097 2	-5.42	Alkaloid
54	Formononetin-7-O-glucoside^[19]	C₂₂H₂₂O₉	19.01	[M-H]^-	429.121 6	253.073 7, 193.051 0, 161.024 9	-5.80	Flavonoid
55	Demissidine-3-O-β-D-glucopyeanosyl(1→4) glucopyranoside or isomer	C₃₉H₆₅NO₁₁	19.24	[M+COOH]^-	768.457 6	722.450 8, 161.046 8, 101.025 5	-5.02	Alkaloid
56	Luteolin¹⁾	C₁₅H₁₀O₆	19.29	[M-H]^-	285.041 3	133.029 9	-6.81	Flavonoid
57	α-Solamarine or isomer^[22]	C₄₅H₇₃NO₁₆	21.18	[M+H]⁺	884.504 5	738.443 7, 414.337 5	-4.85	Alkaloid
58	Puqiedinone^[21]	C₂₇H₄₃NO₂	21.26	[M+H]⁺	414.338 3	396.327 1, 119.084 5, 105.070 3, 95.084 4, 81.070 6	-3.98	Alkaloid
59	Podophyllotoxin^[19]	C₂₂H₂₂O₈	21.55	[M-H]^-	413.126 9	219.070 5, 193.053 5, 175.039 3, 134.030 1	-6.54	Lignan
60	Puqienine A^[21]	C₂₈H₄₇NO₃	21.74	[M+H]⁺	446.364 8	428.352 5, 253.196 0, 145.100 0, 107.087 2, 105.069 7, 98.095 6, 95.085 6, 81.071 0	-4.33	Alkaloid
61	Imperialine N-oxide^[20]	C₂₇H₄₃NO₄	21.77	[M+H]⁺	446.329 0	428.315 1	-5.65	Alkaloid
62	Ebeienine^[21]	C₂₇H₄₃NO₂	22.26	[M+H]⁺	414.338 3	396.327 3, 98.085 5, 81.071 1, 67.053 8	-3.98	Alkaloid
63	Spirosol-5-en-3-ol 4-O-α-L-rhamnopyranosyl-(1-6)-β-D-glucopyranoside or isomer^[19]	C₃₉H₆₃NO₁₁	23.13	[M+COOH]^-	766.440 0	720.435 9, 179.056 2, 161.047 4	-2.43	Alkaloid
64	α-Solamarine or isomer^[22]	C₄₅H₇₃NO₁₆	23.36	[M+H]⁺	884.504 5	738.444 3, 414.339 4	-4.85	Alkaloid
65	Demissidine-3-O-β-D-glucopyeanosyl (1→4) glucopyranoside or isomer^[19]	C₃₉H₆₅NO₁₁	24.95	[M+COOH]^-	768.457 6	722.451 9, 161.046 8, 101.025 2	-5.02	Alkaloid
66	Pinellic acid^[19]	C₁₈H₃₄O₅	28.07	[M-H]^-	329.235 4	229.145 9, 211.136 3, 171.103 9	-6.21	Organic acid
67	2β, 3β, 14-Trihydroxy-cholest-7-en-6-one 3-O-α-L-rhamanopyranosyl-(1-3)-[β-D-glucopyranosyl-(1-2)]-β-D-glucopyranoside^[19]	C₅₁H₈₄O₂₃	31.01	[M+COOH]^-	1109.543 9	917.475 5, 901.492 1, 755.419 6	-5.03	Saponin
68	(2α, 3β, 5α, 25R)-2-Hydroxyspirostan-3-O-α-L-rhamnopyranosyl-(1-2)-β-D-glucopyranosyl-(1-2)-β-D-glucopyranoside^[19]	C₄₅H₇₄O₁₈	31.89	[M+COOH]^-	947.489 6	901.484 5, 755.421 6	-4.30	Saponin
69	α-Linolenic acid or isomer^[13]	C₁₈H₃₀O₂	37.26	[M+H]⁺	279.234 0	149.024 3, 81.070 7, 67.054 9	-7.70	Organic acid
70	α-Linolenic acid or isomer^[13]	C₁₈H₃₀O₂	37.44	[M+H]⁺	279.234 0	149.025 0, 81.070 3, 67.054 4	-7.70	Organic acid
71	9-Hydroxy-10(E), 12(Z)-octadecadienoic acid^[19]	C₁₈H₃₂O₃	38.67	[M-H]^-	295.230 3	277.220 4, 195.141 0, 183.012 8	-8.21	Organic acid

基于UHPLC-Q-TOF-MS技术分析暗紫贝母花的化学成分

PDF下载

任奕洁 ¹^,² , 耿昭 ²^,^* , 何成军 ² , 钟恋 ² , 苟琰 ² , 高必兴 ² , 蒲婧哲 ³ , 张亚中 ³ , 张志淳 ¹^,² , 李小红 ¹^,^*

中国药学杂志 | 论著 2025,60(1): 32-38

收起

中国药学杂志 | 论著 2025, 60(1): 32-38

基于UHPLC-Q-TOF-MS技术分析暗紫贝母花的化学成分

全屏

任奕洁¹^,², 耿昭²^,^*, 何成军², 钟恋², 苟琰², 高必兴², 蒲婧哲³, 张亚中³, 张志淳¹^,², 李小红¹^,^*

作者信息

¹ 成都大学食品与生物工程学院, 成都 610106

² 四川省药品检验研究院(四川省医疗器械检测中心), 国家药品监督管理局中成药质量评价重点实验室, 工业和信息化部产业技术基础公共服务平台, 成都 611731

³ 安徽省食品药品检验研究院, 国家药品监督管理局中药质量研究与评价重点实验室, 合肥 230051

任奕洁,男,硕士研究生研究方向:中药天然产物研究

通讯作者:

*耿昭,男,副主任中药师,硕士生导师研究方向:中药民族药质量评价与资源开发 Tel:(028)87877195;

李小红,男,实验师研究方向:中药化学成分及质量分析 Tel:(028)84616370

Analysis of Chemical Constituents in Flower of Fritillaria unibracteata P. K. Hsiao et K. C. Hsia by UHPLC-Q-TOF-MS

Yijie REN¹^,², Zhao GENG²^,^*, Chengjun HE², Lian ZHONG², Yan GOU², Bixing GAO², Jingzhe PU³, Yazhong ZHANG³, Zhichun ZHANG¹^,², Xiaohong Li¹^,^*

Affiliations

¹ College of Food and Biological Engineering, Chengdu University, Chengdu 610106, China

² MIIT Public Service Platforms for Industrial Technological Base, NMPA Key Laboratory for Quality Evaluation of Traditional Chinese Medicine, Traditional Chinese Patent Medicine, Sichuan Institute for Drug Control(Sichuan Testing Center of Medical Devices), Chengdu 611731, China

³ NMPA Key Laboratory for Quality Research and Evaluation of Traditional Chinese Medicine, Anhui Institute for Food and Drug Control, Hefei 230051, China

出版时间: 2025-01-08 doi: 10.11669/cpj.2025.01.004

文章导航

摘要

收起

目的为充分利用川贝母资源,本研究通过超高效液相色谱-四极杆飞行时间质谱联用技术(UHPLC-Q-TOF-MS)鉴定暗紫贝母花中化学成分。方法采用Thermo Hypersil GOLD aQ(2.1 mm×150 mm,1.9 μm)色谱柱,0.1%甲酸水溶液-甲醇梯度洗脱,流速0.3 mL·min^-1,柱温35 ℃,采用电喷雾电离源(ESI),正、负离子模式分别扫描。结果通过对照品比对、一级质谱精确测定相对分子质量、二级质谱碎片信息,结合文献报道,从暗紫贝母花中鉴定了71个化学成分,包括生物碱24个,黄酮12个,氨基酸9个等,并鉴定出贝母素甲、贝母素乙等有效成分。结论本研究运用UHPLC-Q-TOF-MS技术对其化学组成进行了详尽解析,结果表明暗紫贝母花存在潜在的药用价值,研究结论为其资源的合理开发与可持续利用提供了科学依据。

关键词

暗紫贝母花 / 超高效液相色谱-四极杆飞行时间质谱联用 / 成分鉴定 / 裂解规律

Abstract

收起

OBJECTIVE To identify the chemical constituents in flower of Fritillaria unibracteata P. K. Hsiao et K. C. Hsia (F-F, Chinese: Anzibeimu Hua) by employing ultra high performance liquid chromatography coupled with quadrupole time-of-flight mass spectrometry(UHPLC-Q-TOF-MS) for the optimal utilization of Fritillaria cirrhosa D. Don (Chinese: Chuanbeimu) resources. METHODS The separation was conducted on Thermo Hypersil GOLD aQ column (2.1 mm×150 mm, 1.9 μm) eluted with methanol-0.1% formic acid in a gradient mode at a flow rate of 0.3 mL·min^-1, the column temperature was maintained at 35 ℃, and positive and negative electrospray ionization(ESI) was adopted for determine the chromatographic effluents. RESULTS Through comparison with reference standards, precise molecular weight determination from primary mass spectrometry, and analysis of fragmentation patterns from secondary mass spectrometry, combined with existing literature, 71 chemical constituents were identified in F-F. These identified compounds encompass 24 alkaloids, 12 flavonoids, 9 amino acids, and additional substances, including the notable detection of peimine and peiminine within F-F. CONCLUSION This study employs UHPLC-Q-TOF-MS technology to conduct an exhaustive analysis of the chemical composition of F-F. From the results, it can be seen that the F-F possess potential medicinal value. This study provides scientific basis for the rational development and sustainable utilization of its resources.

Key words

Fritillaria unibracteata flower / UHPLC-Q-TOF-MS / chemical constituent identification / cleavage pattern

引用本文

任奕洁, 耿昭, 何成军, 钟恋, 苟琰, 高必兴, 蒲婧哲, 张亚中, 张志淳, 李小红. 基于UHPLC-Q-TOF-MS技术分析暗紫贝母花的化学成分. 中国药学杂志, 2025 , 60 (1) : 32 -38 . DOI: 10.11669/cpj.2025.01.004

Yijie REN, Zhao GENG, Chengjun HE, Lian ZHONG, Yan GOU, Bixing GAO, Jingzhe PU, Yazhong ZHANG, Zhichun ZHANG, Xiaohong Li. Analysis of Chemical Constituents in Flower of Fritillaria unibracteata P. K. Hsiao et K. C. Hsia by UHPLC-Q-TOF-MS[J]. Chinese Pharmaceutical Journal, 2025 , 60 (1) : 32 -38 . DOI: 10.11669/cpj.2025.01.004

正文

收起

川贝母是四川道地药材,被收载于《中国药典》2020年版,共有6种基原植物:包括川贝母(Fritillaria cirrhosa D.Don)、暗紫贝母(Fritillaria unibracteata Hsiao et K.C.Hsia)、甘肃贝母(Fritillaria przewalskii Maxim.)、梭砂贝母(Fritillaria delavayi Franch.)、太白贝母(Fritillaria taipaiensis P.Y.Li)或瓦布贝母[Fritillaria unibracteata Hsiao et K.C.Hsia var.wabuensis(S.Y.Tang et S.C.Yue)Z.D.Liu,S.Wang et S.C.Chen]。川贝母以其鳞茎入药,具有清热润肺、化痰止咳的功效^[1],其疗效在医疗实践中获得了广泛认可^[2-3]。川贝母中含有氨基酸类、有机酸类、黄酮类、生物碱类、皂苷类、香豆素类化学成分等,其中生物碱类是川贝母中重要的化学成分,在《中国药典》2020年版中也以生物碱作为含量控制指标^[1]。

川贝母根据其不同的形态特征,常被分为“松贝” “青贝” “炉贝”与“栽培品”等商品规格^[1],其中“松贝”因其优良的品质而历来被认为是川贝母中最优品,而暗紫贝母即是“松贝”的主要来源^[4]。基于其良好的临床效果,近年来川贝母的需求量持续攀升^[5],野生川贝母自然繁殖率低且由于人为过度采挖^[6],导致川贝母资源长期供不应求,人工种植虽有所突破,但产量十分有限,因此市场价格持续高企。

清初名医刘潜江在《本经疏证》(中品)草十五味中就曾提到:“是皆误于以贝母为其根,而遗却其附根以生,连累相著,且有分解一层矣”,意为不要仅仅关注于贝母鳞茎部分,需要对其他部分也适当考虑,提示人们在药物功效与药用部位上应更加细致与全面,在药用部位细分上,不应该仅仅局限于鳞茎上。

贝母属植物的花部通常被直接丢弃,然而根据前期调研,部分川贝母种植基地中,有种植工人提到暗紫贝母花(Flower of Fritillaria unibracteata, F-F)采摘晒干后可泡水后饮用。此外,其他贝母属植物的花部,如浙贝母花^[7-8],平贝母花^[9]与湖北贝母花^[10],也被发现含有与鳞茎相似的生物碱等活性成分,表明其可能有一定的药用价值。然而,关于川贝母花的相关研究尚属空白。鉴于当前川贝母资源紧缺且价格昂贵,扩大川贝母药用部位可能为缓解资源压力问题供一种解决方案。

超高效液相色谱-四极杆飞行时间质谱联用(UHPLC-Q-TOF-MS)技术因其高分辨率、稳定性和准确性,已成为中医药物质基础研究中的重要分析工具^[11-12]。因此,本研究选择已基本实现人工种植的暗紫贝母的花部为研究对象,采用UHPLC-Q-TOF-MS技术,对其化学成分进行系统分析,为川贝母资源的进一步合理开发和综合利用提供科学的依据。

1 材料与方法

收起

1.1 药物与试剂

F-F为采集于四川阿坝藏族羌族自治州阿坝县的暗紫贝母的干燥花,由四川省药品检验研究院(四川省医疗器械检测中心)副主任中药师齐景梁鉴定。

对照品:贝母素甲(批号110750-200612)、贝母素乙(批号110751-201712)、腺苷(批号110879-202204)、原儿茶酸(批号110809-201906)、咖啡酸(批号110885-201703)、阿魏酸(批号110773-201614)、脯氨酸(批号140677-201808)、水仙苷(批号111977-201501)、秦皮乙素(批号110741-202109)、精氨酸(批号140685-201707)、尿嘧啶(批号100469-201302)、亮氨酸(批号110876-200204)、槲皮素(批号100081-201509)、烟酸(批号100434-201102)、木犀草素(批号111520-202006)、西贝母碱(批号110767-201710)、贝母辛(批号111892-201402)、西贝母碱苷(批号111917-201202)(中国食品药品检定研究院)。甲醇、甲酸铵与甲酸(质谱级,美国Fisher公司),其他试剂为分析纯。

1.2 仪器

Agilent 1290-6540 UHPLC-Q-TOF-MS(美国Agilent公司);Millipore Q超纯水系统(美国Millipore公司)。

1.3 样品与对照品制备

取F-F粉末(过三号筛)1 g,精密称定,置具塞锥形瓶中,精密加入体积分数80%甲醇25 mL,称定质量,超声处理30 min,再称定质量,用体积分数80%甲醇补足减失的质量,摇匀,滤过,取续滤液,即得F-F供试品溶液。

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

1.4 色谱条件

色谱柱Thermo Hypersil GOLD aQ(2.1 mm×150 mm,1.9 μm),以0.1%甲酸溶液为流动相A,以甲醇为流动相B,梯度洗脱:0~15.5 min,95%~50% A;15.5~25 min,50%~45% A;25~42 min,45%~5% A;42~47 min,5% A;47~47.1 min,5%~95%A;47.1~50.1 min,95%A。流速0.3 mL·min^-1;柱温35 ℃;进样量1 μL。

1.5 质谱条件

带鞘流气的电喷雾离子源(AJS-ESI+/-);气体温度:325 ℃;气体流速:8 L·min^-1;喷雾器压力:0.24 MPa;鞘气温度:350 ℃;鞘气流速:11 L·min^-1;碎裂电压:110 V; 喷雾电压:Pos 4 000 V/neg 3 500 V;喷嘴电压:Pos 0 V/neg 1 000 V。Agilent MassHunter 数据采集软件(Ver. B.08.00);MassHunter Workstation 定量分析软件(Ver. B.07.00)。

1.6 数据处理

为了便于对F-F中成分进行系统定性的分析,本研究收集贝母属已鉴定化学成分的对照品进行质谱分析,总结出其色谱保留行为、裂解规律以及特征碎片离子等。再通过PubChem、SciFinder、Chem‐spider及CNKI等数据库和相关文献的检索对有关贝母属植物的化学成分信息进行收集汇总,包括名称、分子式、结构式等。然后,采用MassHunter分析软件对一级质谱提供的精确准分子离子进行分析,计算未知化合物的元素组成和可能的分子式,再选择目标化合物的二级质谱碎片离子信息,与对照品、数据库及文献报道提供的保留时间、裂解规律等信息进行比对,以确认化学成分及结构。

2 结果

收起

2.1 化合物鉴定结果

按“1.6”项下方法对F-F化合物色谱峰进行提取匹配和分析鉴定,结果共鉴定了71个化合物,其中有18个化合物通过对照品确认。正、负离子模式下的总离子流图(TIC)见图1,所鉴定化学成分的具体信息见表1。

2.2 代表化合物结构解析过程

2.2.1 生物碱类化学成分

贝母中的贝母素甲与贝母素乙等生物碱类化学成分被认为是镇咳祛痰的有效成分^[23],具有毒性低、不良反应少、不易复发等优点^[24]。本节以贝母素甲阐述生物碱类化学成分的裂解过程。

化合物32在正离子模式下,其准分子离子峰为m/z 432.349 7[M+H]⁺,主要二级质谱离子碎片有m/z 414.339 0、398.305 3、176.143 3、138.111 7、124.112 0等。其中碎片m/z 414.339 0由母离子m/z 432.349 7脱去1分子H₂O形成,紧接着脱去1分子CH₄形成碎片m/z 398.305 3。根据加合物不同攻击位点,存在3个特征离子碎片:碎片m/z 176.143 3、m/z 138.111 7、m/z 124.112 0,分别由母离子脱去C₁₅H₂₈O₃、C₁₈H₃₀O₃与C₁₉H₃₂O₃形成。根据以上裂解规律,结合对照品,鉴定该化合物为贝母素甲(C₂₇H₄₅NO₃)(图2)。

2.2.2 黄酮类化学成分

黄酮类化学成分常与糖结合形成苷或以游离苷元的形式存在,其裂解过程容易发生逆-狄尔斯-阿尔德(Retro Diels-Alder,RDA)裂解,脱去糖基等。本节以水仙苷阐述黄酮类化学成分的裂解过程。

化合物45在负离子模式下,其准分子离子峰为m/z 623.163 8[M-H]^-,主要二级质谱离子碎片有m/z 315.052 3、271.026 5、151.004 6等。其中碎片m/z 315.052 3由母离子m/z 623.163 8连续脱去C₆H₁₀O₄与C₆H₁₀O₅基团形成,再脱去1分子CO₂形成m/z 271.026 5,离子碎片m/z 151.004 6是由水仙苷发生RDA裂解,脱去C₂₁H₂₈O₁₂而形成。结合对照品和文献^[25],鉴定该化合物为水仙苷(C₂₈H₃₂O₁₆)(图3)。

2.2.3 有机酸类化学成分

有机酸是一类具有羧基、磺酸基、亚磺酸基与硫羧酸基等酸性基团的有机化合物,具有抗菌、抗肿瘤等活性^[26]。本节以咖啡酸阐述有机酸类化学成分的裂解过程。

化合物23在负离子模式下,其准分子离子峰为m/z 179.034 8[M-H]^-,主要二级质谱离子碎片有m/z 135.046 3、107.051 3等。其中碎片m/z 135.046 3由母离子m/z 179.034 8脱去1个CO₂基团形成,接着脱去1个CO基团形成m/z 107.051 3,结合对照品和文献[26],鉴定该化合物为咖啡酸(C₉H₈O₄)(图4)。

2.2.4 氨基酸类化学成分

氨基酸,是含有碱性氨基和酸性羧基的有机化合物,本节以精氨酸阐述有氨基酸类化学成分的裂解过程。

化合物1在正离子模式下,其准分子离子峰为m/z 175.119 9[M+H]⁺,主要二级质谱离子碎片有m/z 158.090 0、116.068 4等。其中碎片m/z 158.090 0由母离子m/z 175.119 9脱去1个NH₃基团形成,接着脱1个CH₂N₂基团形成m/z 116.068 4,结合对照品和文献[26],鉴定该化合物为精氨酸(C₆N₁₄H₄O₂)(图5)。

2.2.5 香豆素类化学成分

香豆素类化学成分具有抗菌抗炎、止咳、化痰、平喘等功效^[27],与贝母中生物碱类化学成分药效重合,可能存在药物协同作用,本节以秦皮乙素阐述香豆素类化学成分的裂解过程。

化合物22在正离子模式下,其准分子离子峰为m/z 179.034 5[M+H]⁺,主要二级质谱离子碎片有m/z 151.039 2、123.044 9、105.034 6与77.039 5等。其中碎片m/z 151.039 2与123.044 9由母离子m/z 179.034 5逐步脱去1个CO基团形成,接着脱去1个H₂O基团形成m/z 105.034 6,随后再次脱去1个CO基团形成m/z 77.039 5,结合对照品,鉴定该化合物为秦皮乙素(C₉H₆O₄)(图6)。

3 讨论

收起

本研究对分析条件进行了多重优化,在考察流动相时,水相分别比较体积分数0.1%甲酸溶液、10 mmol·L^-1甲酸铵溶液、10 mmol·L^-1甲酸铵溶液(含体积分数0.1%甲酸),有机相分别比较了甲醇和乙腈,在考察供试品制备时分别考察了甲醇、80%甲醇和50%甲醇等溶剂,以质谱响应值较好且峰数量最多作为评判标准,最终分别确定了体积分数0.1%甲酸溶液-甲醇的流动相洗脱体系和体积分数80%甲醇供试品制备溶剂。

川贝母,作为四川的传统道地药材,承载着悠久的历史与丰富的文化内涵,在当前其市场供需矛盾不断加剧的背景下,也促使人们思考如何更加高效与创新地利用这一珍贵资源。川贝母的花部,尽管在某些地区已有零星的使用,其潜在的药用价值却尚未得到系统的科学研究和开发。在此前提下,本研究首次聚焦于暗紫贝母的花部,运用前沿的UHPLC-Q-TOF-MS技术对其化学组成进行了详尽解析,共鉴定出71个化学成分,特别是24个传统上被认为与川贝母鳞茎的化痰止咳等功效密切相关的生物碱成分,如贝母素甲、贝母素乙和西贝母碱等,还鉴定了12个黄酮类、10个有机酸类、9个氨基酸类、6个核苷类、4个维生素类、3个苯丙素类以及少量皂苷类、香豆素类、蔗糖酯类、木脂素类等成分。这一结果不仅揭示了F-F潜在的药用价值,更为其资源的合理开发与可持续利用开辟了新途径。

基金

收起

国家药品监督管理局中药质量研究与评价重点实验室开放课题资助(AHYJ-KFKT-202401)

参考文献

收起

文献

收起

参考文献引证文献

排序方式：

[1]

Ch.P(2020)VolⅠ(中国药典2020年版. 一部)[S]. 2020:38.

[2]

GUO

J X

, LEI

Y T

, HAN

H P

, et al. Supercritical CO₂, extraction of volatile oil from Fritillaria unibracteata Hsiao et K.C.Hsia and analysis of its chemica components[J]. J Qinghai Norm Univ(青海师范大学学报), 2022, 38(4):69-76.

[3]

M M

, XU

, ZHOU

, et al. Exploration on Medication Law of TCM Treatment for Chronic Bronchitis Based on Real World Data[J]. Chin J Inf Tradit Chin Med(中国中医药信息杂志), 2024, 31(2):50-58.

[4]

FANG

Q M

, WANG

H S

, WU

, et al. Dynamic Monitoring on the Ecological Factors of Fritillaria unibracteata in Sichuan[J]. World Chin Med(世界中医药), 2023, 18(17):2430-2434.

[5]

LONG

P Z

, XIE

H M

, XIE

H G

, et al. Study on establishment and comparative analysis of fingerprints of the cultivated Fritillaria unibracteata and the cultivated F. cirrhosa by HPLC-ELSD[J]. West China J Pharm Sci(华西药学杂志), 2019, 34(5):485-489.

[6]

ZHANG

S B

, ZHANG

D N

. Fritillaria unibracteata[J]. Biol Bull(生物学通报), 2023, 58(2):30.

[7]

MIN

, WU

, LOU

F F

, et al. Determination of peimine and peiminine in Fritillariaethunbergii Flos by HPLC[J]. West China J Pharm Sci(华西药学杂志), 2016, 31(3):307-309.

[8]

G Z

, CUI

M C

, YAO

, et al. Chemical constituents of flowers of Fritillariae Thunbergii Mig[J]. Shandong Sci(山东科学), 2020, 33(6):22-26.

[9]

M L

, XU

D M

, HUANG

E X

, et al. The research on alkaloids in Fritillaria pingbei flowers[J]. Bull Chin Mater Med(中药通报), 1988,(8):32-33.

[10]

H F

, ZHANG

J L

, WU

, et al. The 11th Members' Congress of Hubei Pharmaceutical Association and the 2007 Annual Academic Conference[C]. Wuhan, 2007:152-153.

[11]

CHENG

S H

, LEI

X Y

, KANG

, et al. Analysis of Chemical Constituents of Zhuang Medicine Longzuan Tongbi Granules by LC-MS/MS[J]. Chin Pharm J(中国药学杂志), 2024, 59(9):818-826.

[12]

ZHANG

, TAN

C M

, MA

L K

, et al. Rapid Analysis of Chemical Components in Tripterospermum chinense(Migo)H. Smith Based on HPLC-LTQ-Orbitrap-MS/MS Technology[J]. Chin Pharm J (中国药学杂志), 2024, 59(6):491-500.

[13]

LUO

Y Y

, CUI

M C

, WANG

H H

, et al. Analysis of chemical Composition in Diferent Parts of Fritilaria Thunbergii Using UHPLC-QTOF-MS/MS[J]. Chin J Mod Appl Pharm (中国现代应用药学), 2022, 39(15):1984-1991.

[14]

ZHAO

, ZHAO

, XU

, et al. Simultaneous determination of 49 amino acids, B vitamins, flavonoids, and phenolic acids in commonly consumed vegetables by ultra-performance liquid chromatography-tandem mass spectrometry[J]. Food Chem, 2021, 344:128712.

[15]

WOJTANOWSKI

K K

, MROCZEK

. Study of a complex secondary metabolites with potent anti-radical activity by two dimensional TLC/HPLC coupled to electrospray ionization time-of-flight mass spectrometry and bioautography[J]. Anal Chim Acta, 2018, 1029:104-115.

[16]

STRUCK-LEWICKA

, KALISZAN

, MARKUSZEWSKI

M J

. Analysis of urinary nucleosides as potential cancer markers determined using LC-MS technique[J]. J Pharm Biomed Anal, 2014, 101:50-57.

[17]

CHEN

Y H

, QI

, HUA

, et al. Structural characterization and identification of major constituents in radix scrophulariae by HPLC coupled with electrospray ionization quadrupole time-of-flight tandem mass spectrometry[J]. Chin J Nat Med(中国天然药物), 2014, 12(1):47-54.

[18]

, WANG

, et al. Using UHPLC Q-Trap/MS as a complementary technique to in-depth mine UPLC Q-TOF/MS data for identifying modified nucleosides in urine[J]. J Chromatogr B, 2017, 1051:108-117.

[19]

. Analysis of chemical constituents differencesbetween Fritillaria cirrhosa D, Don and Fritillariathunbergiiand its metabolomics based on UPLC-Q-TOF-MS/MS technology[D]. Qinghai: Qinghai Normal University, 2022.

[20]

BORA

P S

, AGRAWAL

, KAUSHIK

N K

, et al. Antiplasmodial activity of the bulbs of Fritillaria cirrhosa D.Don(Syn:Fritillaria roylei Hook.):UPLC-IM-Q-TOF-MS/MS-based biochemometric approach for the identification of marker compounds[J]. J Ethnopharmacol, 2023, 310:116389.

[21]

ZHOU

J L

, XIN

G Z

, SHI

Z Q

, et al. Characterization and identification of steroidal alkaloids in Fritillaria species using liquid chromatography coupled with electrospray ionization quadrupole time-of-flight tandem mass spectrometry[J]. J Chromatogr A, 2010, 1217(45):7109-7122.

[22]

JIANG

, LI

, ZHAO

W J

, et al. Integration of untargeted and pseudotargeted metabolomics reveals specific markers for authentication and adulteration detection of Fritillariae Bulbus using tandem mass spectrometry and chemometrics[J]. J Pharm Biomed Anal, 2024, 242:116013.

[23]

CUI

M C

, CHENG

H J

, et al. Study on TLC and Content Determination for Flowers of Fritillaria Thunbergii Mig[J]. Inf Tradit Chin Med(中医药信息), 2014, 31(4):20-22.

[24]

CHENG

Y T

, YE

L R

, CUI

, et al. Research Progress on Chemical Constituents and Pharmacological Effects of Fritilaria thunbergii Mig. and its Predictive Analysis of Quality Markers[J]. Inf Tradit Chin Med(中医药信息), 2024, 41(6):60-75.

[25]

Y Y

, PAN

T F

, YE

R M

, et al. Extraction and Characterization of Flavonoids of Narcissus Flower by Non-acid Hydrolyzation and HPLC-MSⁿ Methods[J]. Chin J Trop Crops (热带作物学报), 2016, 37(8):1622-1626.

[26]

WANG

, TIAN

, ZHEN

Y Q

, et al. Analysis of Chemical Constituents in Yi Medicine Micromeria biflora(Buch.-Ham.exD.Don) Benth.by UPLC-Q-TOF/MS[J]. Chin Pharm J(中国药学杂志), 2022, 57(20):1717-1725.

[27]

YAN

J L

, WANG

H C

, ZHANG

, et al. Component Analysis of Fraxini Cortex Based on UPLC-Q-Exactive Orbitrap MS[J]. Chin J Mod Appl Pharm (中国现代应用药学), 2023, 40(8):1009-1020.

2025年第60卷第1期

PDF下载

117

引用本文

BibTeX

文章信息

doi: 10.11669/cpj.2025.01.004

接收时间：2024-07-15
首发时间：2025-11-24
出版时间：2025-01-08

补充材料

相关文章

文章信息

作者

出版历史

收稿日期：2024-07-15

基金

国家药品监督管理局中药质量研究与评价重点实验室开放课题资助(AHYJ-KFKT-202401)

作者信息

¹ 成都大学食品与生物工程学院, 成都 610106

³ 安徽省食品药品检验研究院, 国家药品监督管理局中药质量研究与评价重点实验室, 合肥 230051

通讯作者:

*耿昭,男,副主任中药师,硕士生导师研究方向:中药民族药质量评价与资源开发 Tel:(028)87877195;

李小红,男,实验师研究方向:中药化学成分及质量分析 Tel:(028)84616370

参考文献

分享链接

https://castjournals.cast.org.cn/joweb/zgyxzz/CN/10.11669/cpj.2025.01.004

分享至

全文二维码

扫描看全文

引用本文

BibTeX

本文的引用情况

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

关闭全屏

BibTeX
EndNote
RefWorks
TxT

No.	Name	Formula	t_R/min	ESI^+/-	m/z(MS)	m/z(MS/MS)	Error/×10^-6	Structure class
1	Arginine¹⁾	C₆H₁₄N₄O₂	1.21	[M+H]⁺	175.119 9	158.090 0, 116.064 8	-5.40	Amino acid
2	Anthranilic acid^[13]	C₇H₇NO₂	1.31	[M+H]⁺	138.055 5	94.066 2, 93.056 1, 92.050 4	-3.98	Organic acid
3	Proline¹⁾	C₅H₉NO₂	1.39	[M+H]⁺	116.069 9	70.065 8	6.13	Amino acid
4	L-Valine^[14]	C₅H₁₁NO₂	1.62	[M+H]⁺	118.085 3	72.081 8, 55.055 0	8.16	Amino acid
5	Adenine^[13]	C₅H₅N₅	1.69	[M+H]⁺	136.062 4	119.036 3, 92.025 3, 67.030 1	-4.56	Amino acid
6	Citric acid or isomer^[15]	C₆H₈O₇	1.69	[M-H]^-	191.021 2	387.009 8, 129.020 0, 111.010 2	-7.68	Organic acid
7	Nicotinic acid¹⁾	C₆H₅NO₂	1.74	[M+H]⁺	124.040 0	78.034 9, 53.039 2	-5.65	Vitamin
8	Citric acid or isomer^[15]	C₆H₈O₇	1.75	[M-H]^-	191.021 1	387.009 0, 129.020 5, 111.011 5	-7.47	Organic acid
9	Uracil¹⁾	C₄H₄N₂O₂	2.17	[M+H]⁺	113.034 7	96.008 2, 95.023 5	-1.3	Nucleoside
10	Uridine^[16]	C₉H₁₂N₂O₆	2.25	[M+H]⁺	245.078 1	113.035 4, 96.009 1, 70.029 2	-5.27	Nucleoside
11	L-Tyrosine^[14]	C₉H₁₁NO₃	2.4	[M+H]⁺	182.082 5	165.055 1, 147.044 7, 136.076 6, 123.045 1, 91.055 1, 77.039 2	-7.35	Amino acid
12	L-isoleucine^[14]	C₆H₁₃NO₂	2.62	[M+H]⁺	132.102 9	86.097 7, 69.070 9, 57.058 0	-7.59	Amino acid
13	L-leucine¹⁾	C₆H₁₃NO₂	2.80	[M+H]⁺	132.102 8	86.097 5, 69.071 4, 57.058 3	-6.83	Amino acid
14	Adenosine¹⁾	C₁₀H₁₃N₅O₄	2.87	[M+H]⁺	268.105 6	136.062 4, 57.034 3	-5.88	Nucleoside
15	Pyridoxine^[14]	C₈H₁₁NO₃	2.94	[M+H]⁺	170.081 8	152.071 6, 134.061 2, 124.077 0, 106.066 6, 77.039 7, 65.038 7	-3.73	Vitamin
16	Guanosine^[16]	C₁₀H₁₃N₅O₅	3.06	[M+H]⁺	284.100 3	152.057 2, 135.031 0, 98.060 8	-4.79	Nucleoside
17	5'-Deoxyadenosine^[13]	C₁₀H₁₃N₅O₃	3.08	[M+H]⁺	252.110 4	136.062 2, 117.054 7	-5.11	Nucleoside
18	Phenylalanine^[13]	C₉H₁₁NO₂	4.10	[M+H]⁺	166.087 0	120.081 9, 103.055 2, 93.070 7, 77.039 6	-4.51	Amino acid
19	Protocatechuic acid¹⁾	C₇H₆O₄	5.05	[M-H]^-	153.020 3	109.030 8, 108.022 9, 65.003 7, 53.030 9,	-6.28	Organic acid
20	6-O-caffeoyl-α-D-fructofuranosyl- (2→1)-α-D-glucopyranoside^[17]	C₂₁H₂₈O₁₄	5.76	[M-H]^-	503.143 5	485.134 2, 341.111 6, 323.079 9, 281.073 5, 221.047 6, 179.034 9, 161.024 6	-5.69	Phenylpropanoids
21	5'-Deoxy-5'-methylthio adeno- sine^[18]	C₁₁H₁₅N₅O₃S	6.58	[M+H]⁺	298.098 1	136.062 6, 127.021 1, 119.106 4, 97.029 5	-4.25	Nucleoside
22	Aesculetin¹⁾	C₉H₆O₄	8.35	[M+H]⁺	179.034 5	151.039 2, 123.044 9, 105.034 6, 77.039 5	-3.45	Coumarin
23	Caffeic acid¹⁾	C₉H₈O₄	8.87	[M-H]^-	179.034 8	135.046 3, 107.051 3	1.01	Organic acid
24	Acretoside^[17]	C₂₁H₂₈O₁₃	9.59	[M-H]^-	487.148 2	307.080 6, 163.040 5, 145.030 3	-5.09	Sucrose ester
25	Sipeimine-3β-D-glucoside¹⁾	C₃₃H₅₃NO₈	11.57	[M+H]⁺	592.387 6	574.367 8	-5.42	Alkaloid
26	1-O-Glycerol ferulate^[19]	C₁₃H₁₆O₆	12.07	[M-H]^-	267.087 0	252.065 5, 175.040 2, 149.060 7, 133.030 8	1.54	Phenylpropanoid
27	Ferulic acid¹⁾	C₁₀H₁₀O₄	12.18	[M-H]^-	193.051 8	178.028 3, 134.038 4, 133.030 2	-6.02	Organic acid
28	(2S)-3-Acetoxy-2-(hexopyranosyloxy) propyl 3-(4-hydroxyphenyl) acrylate^[19]	C₂₀H₂₆O₁₁	12.24	[M-H]^-	441.142 7	163.040 8, 145.030 8	-5.57	Phenylpropanoid
29	Sipeimine¹⁾	C₂₇H₄₃NO₃	12.46	[M+H]⁺	430.334 3	412.318 2, 138.125 0	-6.36	Alkaloid
30	Edpetiline or isomer^[20]	C₃₃H₅₃NO₈	12.86	[M+H]⁺	592.387 4	574.370 9, 287.056 1	-5.08	Alkaloid
31	Peiminine¹⁾	C₂₇H₄₃NO₃	13.99	[M+H]⁺	430.333 8	412.323 4	-5.19	Alkaloid
32	Peimine¹⁾	C₂₇H₄₅NO₃	14.28	[M+H]⁺	432.349 7	414.339 0, 398.305 3, 176.143 3, 138.111 7, 124.112 0	-5.75	Alkaloid
33	Hyperoside^[14]	C₂₁H₂₀O₁₂	14.57	[M-H]^-	463.089 8	300.028 9, 271.026 5, 243.029 8, 151.004 6	-3.45	Flavonoid
34	Rutin and isomer^[14]	C₂₇H₃₀O₁₆	14.71	[M-H]^-	609.147 4	463.146 5, 301.035 7, 300.028 9	-2.12	Vitamin
35	Rutin and isomer^[14]	C₂₇H₃₀O₁₆	14.93	[M-H]^-	609.147 6	463.146 9, 301.035 2, 300.029 5	-2.44	Vitamin
36	Edpetiline or isomer^[20]	C₃₃H₅₃NO₈	14.94	[M+H]⁺	592.388 1	574.375 7	-6.27	Alkaloid
37	Yibeinoside A or isomer^[21]	C₃₃H₅₃NO₇	15.13	[M+H]⁺	576.392 3	414.334 0, 396.328 9, 98.098 1	-4.90	Alkaloid
38	Peimisine¹⁾	C₂₇H₄₁NO₃	15.40	[M+H]⁺	428.318 2	410.300 5, 393.274 5, 337.213 4	-5.33	Alkaloid
39	Yibeinoside A or isomer^[21]	C₃₃H₅₃NO₇	15.58	[M+H]⁺	576.392 3	414.335 9, 396.325 4, 98.096 7	-4.90	Alkaloid
40	3'-O-Methylquercetin 3-galacto- side^[14]	C₂₂H₂₂O₁₂	15.75	[M-H]^-	477.104 8	449.108 2, 357.062 9, 314.044 4, 243.031 8	-1.99	Flavonoid
41	Astragalin^[15]	C₂₁H₂₀O₁₁	15.76	[M-H]^-	447.094 7	285.039 8, 284.035 5, 255.028 0, 227.037 6	-3.16	Flavonoid
42	Litseagermacrane^[15]	C₁₅H₂₄O₂	15.82	[M+H]⁺	237.186 4	219.175 2, 167.106 9, 151.112 5, 135.118 3, 107.086 5	-6.32	Terpenoid
43	Kaempferol^[14]	C₁₅H₁₀O₆	16.04	[M-H]^-	285.041 9	151.004 2, 135.043 8, 133.030 2, 83.014 7, 65.725 8	-5.03	Flavonoid
44	Isorhamnetin-3-glucoside^[14]	C₂₂H₂₂O₁₂	16.29	[M-H]^-	477.104 8	315.049 9, 314.042 3, 299.021 8, 243.028 6, 151.003 1	-1.99	Flavonoid
45	Narcissoside¹⁾	C₂₈H₃₂O₁₆	16.44	[M-H]^-	623.163 8	315.052 3, 271.026 5, 151.004 6	-5.04	Flavonoid
46	Ebeiedinone^[21]	C₂₇H₄₃NO₂	16.79	[M+H]⁺	414.338 3	396.327 9, 119.085 5, 98.096 4, 95.085 3	-3.98	Alkaloid
47	Puqienine E^[20]	C₂₈H₄₃NO₃	16.82	[M+H]⁺	442.334 0	424.319 3	-5.50	Alkaloid
48	Quercitrin^[15]	C₂₁H₂₀O₁₁	17.15	[M-H]^-	447.094 7	314.042 5, 300.024 4, 271.019 5, 243.030 6	-3.16	Flavonoid
49	Hupeheninoside^[21]	C₃₃H₅₅NO₇	17.18	[M+H]⁺	578.407 9	398.341 2, 98.097 5, 85.0291, 69.033 9	-4.80	Alkaloid
50	β-Solanine or isomer^[22]	C₃₉H₆₃NO₁₁	17.62	[M+H]⁺	722.451 3	560.394 4, 398.344 2, 380.332 0, 98.097 6	-5.42	Alkaloid
51	Spirosol-5-en-3-ol 4-O-α-L-rhamnopyranosyl-(1-6)-β-D-glucopyranoside or isomer^[19]	C₃₉H₆₃NO₁₁	17.73	[M+COOH]^-	766.440 0	720.434 9, 179.056 3, 161.046 1	-2.43	Alkaloid
52	Quercetin¹⁾	C₁₅H₁₀O₇	18.23	[M+H]⁺	303.051 8	257.042 2, 229.048 3, 201.050 8, 153.018 8	-6.19	Flavonoid
53	β-Solanine or isomer^[22]	C₃₉H₆₃NO₁₁	18.41	[M+H]⁺	722.451 3	560.397 1, 398.342 1, 380.333 4, 98.097 2	-5.42	Alkaloid
54	Formononetin-7-O-glucoside^[19]	C₂₂H₂₂O₉	19.01	[M-H]^-	429.121 6	253.073 7, 193.051 0, 161.024 9	-5.80	Flavonoid
55	Demissidine-3-O-β-D-glucopyeanosyl(1→4) glucopyranoside or isomer	C₃₉H₆₅NO₁₁	19.24	[M+COOH]^-	768.457 6	722.450 8, 161.046 8, 101.025 5	-5.02	Alkaloid
56	Luteolin¹⁾	C₁₅H₁₀O₆	19.29	[M-H]^-	285.041 3	133.029 9	-6.81	Flavonoid
57	α-Solamarine or isomer^[22]	C₄₅H₇₃NO₁₆	21.18	[M+H]⁺	884.504 5	738.443 7, 414.337 5	-4.85	Alkaloid
58	Puqiedinone^[21]	C₂₇H₄₃NO₂	21.26	[M+H]⁺	414.338 3	396.327 1, 119.084 5, 105.070 3, 95.084 4, 81.070 6	-3.98	Alkaloid
59	Podophyllotoxin^[19]	C₂₂H₂₂O₈	21.55	[M-H]^-	413.126 9	219.070 5, 193.053 5, 175.039 3, 134.030 1	-6.54	Lignan
60	Puqienine A^[21]	C₂₈H₄₇NO₃	21.74	[M+H]⁺	446.364 8	428.352 5, 253.196 0, 145.100 0, 107.087 2, 105.069 7, 98.095 6, 95.085 6, 81.071 0	-4.33	Alkaloid
61	Imperialine N-oxide^[20]	C₂₇H₄₃NO₄	21.77	[M+H]⁺	446.329 0	428.315 1	-5.65	Alkaloid
62	Ebeienine^[21]	C₂₇H₄₃NO₂	22.26	[M+H]⁺	414.338 3	396.327 3, 98.085 5, 81.071 1, 67.053 8	-3.98	Alkaloid
63	Spirosol-5-en-3-ol 4-O-α-L-rhamnopyranosyl-(1-6)-β-D-glucopyranoside or isomer^[19]	C₃₉H₆₃NO₁₁	23.13	[M+COOH]^-	766.440 0	720.435 9, 179.056 2, 161.047 4	-2.43	Alkaloid
64	α-Solamarine or isomer^[22]	C₄₅H₇₃NO₁₆	23.36	[M+H]⁺	884.504 5	738.444 3, 414.339 4	-4.85	Alkaloid
65	Demissidine-3-O-β-D-glucopyeanosyl (1→4) glucopyranoside or isomer^[19]	C₃₉H₆₅NO₁₁	24.95	[M+COOH]^-	768.457 6	722.451 9, 161.046 8, 101.025 2	-5.02	Alkaloid
66	Pinellic acid^[19]	C₁₈H₃₄O₅	28.07	[M-H]^-	329.235 4	229.145 9, 211.136 3, 171.103 9	-6.21	Organic acid
67	2β, 3β, 14-Trihydroxy-cholest-7-en-6-one 3-O-α-L-rhamanopyranosyl-(1-3)-[β-D-glucopyranosyl-(1-2)]-β-D-glucopyranoside^[19]	C₅₁H₈₄O₂₃	31.01	[M+COOH]^-	1109.543 9	917.475 5, 901.492 1, 755.419 6	-5.03	Saponin
68	(2α, 3β, 5α, 25R)-2-Hydroxyspirostan-3-O-α-L-rhamnopyranosyl-(1-2)-β-D-glucopyranosyl-(1-2)-β-D-glucopyranoside^[19]	C₄₅H₇₄O₁₈	31.89	[M+COOH]^-	947.489 6	901.484 5, 755.421 6	-4.30	Saponin
69	α-Linolenic acid or isomer^[13]	C₁₈H₃₀O₂	37.26	[M+H]⁺	279.234 0	149.024 3, 81.070 7, 67.054 9	-7.70	Organic acid
70	α-Linolenic acid or isomer^[13]	C₁₈H₃₀O₂	37.44	[M+H]⁺	279.234 0	149.025 0, 81.070 3, 67.054 4	-7.70	Organic acid
71	9-Hydroxy-10(E), 12(Z)-octadecadienoic acid^[19]	C₁₈H₃₂O₃	38.67	[M-H]^-	295.230 3	277.220 4, 195.141 0, 183.012 8	-8.21	Organic acid

No.

Name

Formula

t_R/min

ESI^+/-

m/z(MS)

m/z(MS/MS)

Error/×10^-6

Structure class

Arginine¹⁾

C₆H₁₄N₄O₂

1.21

[M+H]⁺

175.119 9

158.090 0, 116.064 8

-5.40

Amino acid

Anthranilic acid^[13]

C₇H₇NO₂

1.31

[M+H]⁺

138.055 5

94.066 2, 93.056 1, 92.050 4

-3.98

Organic acid

Proline¹⁾

C₅H₉NO₂

1.39

[M+H]⁺

116.069 9

70.065 8

6.13

Amino acid

L-Valine^[14]

C₅H₁₁NO₂

1.62

[M+H]⁺

118.085 3

72.081 8, 55.055 0

8.16

Amino acid

Adenine^[13]

C₅H₅N₅

1.69

[M+H]⁺

136.062 4

119.036 3, 92.025 3, 67.030 1

-4.56

Amino acid

Citric acid or isomer^[15]

C₆H₈O₇

1.69

[M-H]^-

191.021 2

387.009 8, 129.020 0, 111.010 2

-7.68

Organic acid

Nicotinic acid¹⁾

C₆H₅NO₂

1.74

[M+H]⁺

124.040 0

78.034 9, 53.039 2

-5.65

Vitamin

Citric acid or isomer^[15]

C₆H₈O₇

1.75

[M-H]^-

191.021 1

387.009 0, 129.020 5, 111.011 5

-7.47

Organic acid

Uracil¹⁾

C₄H₄N₂O₂

2.17

[M+H]⁺

113.034 7

96.008 2, 95.023 5

-1.3

Nucleoside

Uridine^[16]

C₉H₁₂N₂O₆

2.25

[M+H]⁺

245.078 1

113.035 4, 96.009 1, 70.029 2

-5.27

Nucleoside

L-Tyrosine^[14]

C₉H₁₁NO₃

2.4

[M+H]⁺

182.082 5

165.055 1, 147.044 7, 136.076 6, 123.045 1, 91.055 1, 77.039 2

-7.35

Amino acid

L-isoleucine^[14]

C₆H₁₃NO₂

2.62

[M+H]⁺

132.102 9

86.097 7, 69.070 9, 57.058 0

-7.59

Amino acid

L-leucine¹⁾

C₆H₁₃NO₂

2.80

[M+H]⁺

132.102 8

86.097 5, 69.071 4, 57.058 3

-6.83

Amino acid

Adenosine¹⁾

C₁₀H₁₃N₅O₄

2.87

[M+H]⁺

268.105 6

136.062 4, 57.034 3

-5.88

Nucleoside

Pyridoxine^[14]

C₈H₁₁NO₃

2.94

[M+H]⁺

170.081 8

152.071 6, 134.061 2, 124.077 0, 106.066 6, 77.039 7, 65.038 7

-3.73

Vitamin

Guanosine^[16]

C₁₀H₁₃N₅O₅

3.06

[M+H]⁺

284.100 3

152.057 2, 135.031 0, 98.060 8

-4.79

Nucleoside

5'-Deoxyadenosine^[13]

C₁₀H₁₃N₅O₃

3.08

[M+H]⁺

252.110 4

136.062 2, 117.054 7

-5.11

Nucleoside

Phenylalanine^[13]

C₉H₁₁NO₂

4.10

[M+H]⁺

166.087 0

120.081 9, 103.055 2, 93.070 7, 77.039 6

-4.51

Amino acid

Protocatechuic acid¹⁾

C₇H₆O₄

5.05

[M-H]^-

153.020 3

109.030 8, 108.022 9, 65.003 7, 53.030 9,

-6.28

Organic acid

6-O-caffeoyl-α-D-fructofuranosyl-
(2→1)-α-D-glucopyranoside^[17]

C₂₁H₂₈O₁₄

5.76

[M-H]^-

503.143 5

485.134 2, 341.111 6, 323.079 9, 281.073 5, 221.047 6, 179.034 9, 161.024 6

-5.69

Phenylpropanoids

5'-Deoxy-5'-methylthio adeno-
sine^[18]

C₁₁H₁₅N₅O₃S

6.58

[M+H]⁺

298.098 1

136.062 6, 127.021 1, 119.106 4, 97.029 5

-4.25

Nucleoside

Aesculetin¹⁾

C₉H₆O₄

8.35

[M+H]⁺

179.034 5

151.039 2, 123.044 9, 105.034 6, 77.039 5

-3.45

Coumarin

Caffeic acid¹⁾

C₉H₈O₄

8.87

[M-H]^-

179.034 8

135.046 3, 107.051 3

1.01

Organic acid

Acretoside^[17]

C₂₁H₂₈O₁₃

9.59

[M-H]^-

487.148 2

307.080 6, 163.040 5, 145.030 3

-5.09

Sucrose ester

Sipeimine-3β-D-glucoside¹⁾

C₃₃H₅₃NO₈

11.57

[M+H]⁺

592.387 6

574.367 8

-5.42

Alkaloid

1-O-Glycerol ferulate^[19]

C₁₃H₁₆O₆

12.07

[M-H]^-

267.087 0

252.065 5, 175.040 2, 149.060 7, 133.030 8

1.54

Phenylpropanoid

Ferulic acid¹⁾

C₁₀H₁₀O₄

12.18

[M-H]^-

193.051 8

178.028 3, 134.038 4, 133.030 2

-6.02

Organic acid

(2S)-3-Acetoxy-2-(hexopyranosyloxy) propyl 3-(4-hydroxyphenyl) acrylate^[19]

C₂₀H₂₆O₁₁

12.24

[M-H]^-

441.142 7

163.040 8, 145.030 8

-5.57

Phenylpropanoid

Sipeimine¹⁾

C₂₇H₄₃NO₃

12.46

[M+H]⁺

430.334 3

412.318 2, 138.125 0

-6.36

Alkaloid

Edpetiline or isomer^[20]

C₃₃H₅₃NO₈

12.86

[M+H]⁺

592.387 4

574.370 9, 287.056 1

-5.08

Alkaloid

Peiminine¹⁾

C₂₇H₄₃NO₃

13.99

[M+H]⁺

430.333 8

412.323 4

-5.19

Alkaloid

Peimine¹⁾

C₂₇H₄₅NO₃

14.28

[M+H]⁺

432.349 7

414.339 0, 398.305 3, 176.143 3, 138.111 7, 124.112 0

-5.75

Alkaloid

Hyperoside^[14]

C₂₁H₂₀O₁₂

14.57

[M-H]^-

463.089 8

300.028 9, 271.026 5, 243.029 8, 151.004 6

-3.45

Flavonoid

Rutin and isomer^[14]

C₂₇H₃₀O₁₆

14.71

[M-H]^-

609.147 4

463.146 5, 301.035 7, 300.028 9

-2.12

Vitamin

Rutin and isomer^[14]

C₂₇H₃₀O₁₆

14.93

[M-H]^-

609.147 6

463.146 9, 301.035 2, 300.029 5

-2.44

Vitamin

Edpetiline or isomer^[20]

C₃₃H₅₃NO₈

14.94

[M+H]⁺

592.388 1

574.375 7

-6.27

Alkaloid

Yibeinoside A or isomer^[21]

C₃₃H₅₃NO₇

15.13

[M+H]⁺

576.392 3

414.334 0, 396.328 9, 98.098 1

-4.90

Alkaloid

Peimisine¹⁾

C₂₇H₄₁NO₃

15.40

[M+H]⁺

428.318 2

410.300 5, 393.274 5, 337.213 4

-5.33

Alkaloid

Yibeinoside A or isomer^[21]

C₃₃H₅₃NO₇

15.58

[M+H]⁺

576.392 3

414.335 9, 396.325 4, 98.096 7

-4.90

Alkaloid

3'-O-Methylquercetin 3-galacto-
side^[14]

C₂₂H₂₂O₁₂

15.75

[M-H]^-

477.104 8

449.108 2, 357.062 9, 314.044 4, 243.031 8

-1.99

Flavonoid

Astragalin^[15]

C₂₁H₂₀O₁₁

15.76

[M-H]^-

447.094 7

285.039 8, 284.035 5, 255.028 0, 227.037 6

-3.16

Flavonoid

Litseagermacrane^[15]

C₁₅H₂₄O₂

15.82

[M+H]⁺

237.186 4

219.175 2, 167.106 9, 151.112 5, 135.118 3, 107.086 5

-6.32

Terpenoid

Kaempferol^[14]

C₁₅H₁₀O₆

16.04

[M-H]^-

285.041 9

151.004 2, 135.043 8, 133.030 2, 83.014 7, 65.725 8

-5.03

Flavonoid

Isorhamnetin-3-glucoside^[14]

C₂₂H₂₂O₁₂

16.29

[M-H]^-

477.104 8

315.049 9, 314.042 3, 299.021 8, 243.028 6, 151.003 1

-1.99

Flavonoid

Narcissoside¹⁾

C₂₈H₃₂O₁₆

16.44

[M-H]^-

623.163 8

315.052 3, 271.026 5, 151.004 6

-5.04

Flavonoid

Ebeiedinone^[21]

C₂₇H₄₃NO₂

16.79

[M+H]⁺

414.338 3

396.327 9, 119.085 5, 98.096 4, 95.085 3

-3.98

Alkaloid

Puqienine E^[20]

C₂₈H₄₃NO₃

16.82

[M+H]⁺

442.334 0

424.319 3

-5.50

Alkaloid

Quercitrin^[15]

C₂₁H₂₀O₁₁

17.15

[M-H]^-

447.094 7

314.042 5, 300.024 4, 271.019 5, 243.030 6

-3.16

Flavonoid

Hupeheninoside^[21]

C₃₃H₅₅NO₇

17.18

[M+H]⁺

578.407 9

398.341 2, 98.097 5, 85.0291, 69.033 9

-4.80

Alkaloid

β-Solanine or isomer^[22]

C₃₉H₆₃NO₁₁

17.62

[M+H]⁺

722.451 3

560.394 4, 398.344 2, 380.332 0, 98.097 6

-5.42

Alkaloid

Spirosol-5-en-3-ol 4-O-α-L-rhamnopyranosyl-(1-6)-β-D-glucopyranoside or isomer^[19]

C₃₉H₆₃NO₁₁

17.73

[M+COOH]^-

766.440 0

720.434 9, 179.056 3, 161.046 1

-2.43

Alkaloid

Quercetin¹⁾

C₁₅H₁₀O₇

18.23

[M+H]⁺

303.051 8

257.042 2, 229.048 3, 201.050 8, 153.018 8

-6.19

Flavonoid

β-Solanine or isomer^[22]

C₃₉H₆₃NO₁₁

18.41

[M+H]⁺

722.451 3

560.397 1, 398.342 1, 380.333 4, 98.097 2

-5.42

Alkaloid

Formononetin-7-O-glucoside^[19]

C₂₂H₂₂O₉

19.01

[M-H]^-

429.121 6

253.073 7, 193.051 0, 161.024 9

-5.80

Flavonoid

Demissidine-3-O-β-D-glucopyeanosyl(1→4) glucopyranoside or isomer

C₃₉H₆₅NO₁₁

19.24

[M+COOH]^-

768.457 6

722.450 8, 161.046 8, 101.025 5

-5.02

Alkaloid

Luteolin¹⁾

C₁₅H₁₀O₆

19.29

[M-H]^-

285.041 3

133.029 9

-6.81

Flavonoid

α-Solamarine or isomer^[22]

C₄₅H₇₃NO₁₆

21.18

[M+H]⁺

884.504 5

738.443 7, 414.337 5

-4.85

Alkaloid

Puqiedinone^[21]

C₂₇H₄₃NO₂

21.26

[M+H]⁺

414.338 3

396.327 1, 119.084 5, 105.070 3, 95.084 4, 81.070 6

-3.98

Alkaloid

Podophyllotoxin^[19]

C₂₂H₂₂O₈

21.55

[M-H]^-

413.126 9

219.070 5, 193.053 5, 175.039 3, 134.030 1

-6.54

Lignan

Puqienine A^[21]

C₂₈H₄₇NO₃

21.74

[M+H]⁺

446.364 8

428.352 5, 253.196 0, 145.100 0, 107.087 2, 105.069 7, 98.095 6, 95.085 6, 81.071 0

-4.33

Alkaloid

Imperialine N-oxide^[20]

C₂₇H₄₃NO₄

21.77

[M+H]⁺

446.329 0

428.315 1

-5.65

Alkaloid

Ebeienine^[21]

C₂₇H₄₃NO₂

22.26

[M+H]⁺

414.338 3

396.327 3, 98.085 5, 81.071 1, 67.053 8

-3.98

Alkaloid

Spirosol-5-en-3-ol 4-O-α-L-rhamnopyranosyl-(1-6)-β-D-glucopyranoside or isomer^[19]

C₃₉H₆₃NO₁₁

23.13

[M+COOH]^-

766.440 0

720.435 9, 179.056 2, 161.047 4

-2.43

Alkaloid

α-Solamarine or isomer^[22]

C₄₅H₇₃NO₁₆

23.36

[M+H]⁺

884.504 5

738.444 3, 414.339 4

-4.85

Alkaloid

Demissidine-3-O-β-D-glucopyeanosyl
(1→4) glucopyranoside or isomer^[19]

C₃₉H₆₅NO₁₁

24.95

[M+COOH]^-

768.457 6

722.451 9, 161.046 8, 101.025 2

-5.02

Alkaloid

Pinellic acid^[19]

C₁₈H₃₄O₅

28.07

[M-H]^-

329.235 4

229.145 9, 211.136 3, 171.103 9

-6.21

Organic acid

2β, 3β, 14-Trihydroxy-cholest-7-en-6-one 3-O-α-L-rhamanopyranosyl-(1-3)-[β-D-glucopyranosyl-(1-2)]-β-D-glucopyranoside^[19]

C₅₁H₈₄O₂₃

31.01

[M+COOH]^-

1109.543 9

917.475 5, 901.492 1, 755.419 6

-5.03

Saponin

(2α, 3β, 5α, 25R)-2-Hydroxyspirostan-3-O-α-L-rhamnopyranosyl-(1-2)-β-D-glucopyranosyl-(1-2)-β-D-glucopyranoside^[19]

C₄₅H₇₄O₁₈

31.89

[M+COOH]^-

947.489 6

901.484 5, 755.421 6

-4.30

Saponin

α-Linolenic acid or isomer^[13]

C₁₈H₃₀O₂

37.26

[M+H]⁺

279.234 0

149.024 3, 81.070 7, 67.054 9

-7.70

Organic acid

α-Linolenic acid or isomer^[13]

C₁₈H₃₀O₂

37.44

[M+H]⁺

279.234 0

149.025 0, 81.070 3, 67.054 4

-7.70

Organic acid

9-Hydroxy-10(E), 12(Z)-octadecadienoic acid^[19]

C₁₈H₃₂O₃

38.67

[M-H]^-

295.230 3

277.220 4, 195.141 0, 183.012 8

-8.21

Organic acid