药学学报

No.	t_R/min	Identification	Molecular formula	[M+H]⁺/[M-H]^-	Mass	Error /ppm	Fragment ion	W	G	Source
1	21.86	β-Sitosterol-3-O-β-D-glucuronoside+2Rha+Glc	C₅₁H₈₀O₂₂	[M+H]⁺	1 045.521 0	0.2	883.466 6, 737.408 4, 591.352 6	+	+	c
2	21.92	Stigmasterol glucoside+2Rha	C₄₅H₇₀O₁₆	[M+H]⁺	867.472 0	-0.3	849.461 8, 721.410 5, 705.417 6, 575.356 5, 559.356 9, 413.304 0	+	-	c
3	22.10	Gracillin+Glc	C₅₁H₈₂O₂₂	[M+H]⁺	1 047.533 0	0.0	885.483 5, 723.354 9, 577.299 3, 415.251 9, 271.205 3, 253.195 0	+	+	c
4	22.24	β-Sitosterol-3-O-β-D-glucuronoside+Rha+Glc	C₄₅H₇₀O₁₈	[M+H]⁺	899.463 0	0.0	737.408 6, 593.294 3, 591.350 7	+	+	c
5	22.36	Dongnoside E	C₅₀H₈₂O₂₂	[M+H]⁺	1 035.533 0	-0.9	903.483 1, 873.484 3, 741.443 1, 579.387 9, 417.336 0, 273.221 1	+	+	c
6	22.37	Pamaqueside / agavoside B	C₃₉H₆₂O₁₄	[M+H]⁺	755.420 0	-1.4	737.405 6, 593.368 7, 431.243 2, 413.311 5, 395.294 0	+	+	c
7	22.43	Pseudoprotoneodioscin+Glc	C₅₇H₉₂O₂₆	[M+H]⁺	1 193.596 0	-0.5	1 031.538 3, 869.486 1, 723.427 7, 577.373 0, 415.320 1, 253.194 1	+	+	c
8	22.57	Aspidistrin	C₅₀H₈₀O₂₂	[M+H]⁺	1 033.521 0	-0.6	871.470 1, 739.430 7, 577.373 5, 415.320 9, 397.310 2, 271.205 6	+	+	c
9	22.71	Shatavarin Ⅸ	C₄₅H₇₄O₁₈	[M+H]⁺	903.495 0	-0.5	741.440 6, 597.325 8, 579.386 9, 417.335 6, 285.257 5, 273.221 6, 255.210 5	+	+	a^[20]
10	22.82	Protodioscin	C₅₁H₈₄O₂₂	[M+H]⁺	1 049.553 0	-0.3	887.498 1, 741.438 8, 725.371 0, 433.330 1, 415.322 2	+	+	a^[21]
11	22.96	(25S)-26-O-β-D-Glucopyranosyl-5β-furost-20(22)-ene-3β, 26-diol-3-O-β-D-glucopyranosyl-(1→2)-β-D-glucopyranoside	C₄₅H₇₂O₁₈	[M+H]⁺	901.478 0	-1.3	739.425 9, 577.372 0, 433.258 1, 415.320 0, 283.242 6, 271.205 9, 253.195 1	+	+	a^[22]
12	23.25	Compound 7 (isomer)	C₅₇H₉₂O₂₆	[M+H]⁺	1 193.596 0	-0.7	1 031.545 1, 869.489 4, 723.431 3, 577.371 2, 415.319 9, 253.192 6	+	+	c
13	23.27	Stigmasterol glucoside+Hex+2Rha	C₅₁H₈₀O₂₁	[M+H]⁺	1 029.526 0	-1.9	867.469 4, 721.413 5, 575.358 1, 413.303 1, 395.291 5	-	+	c
14	23.42	Pseudoprotoneodioscin	C₅₁H₈₂O₂₁	[M+H]⁺	1 031.542 0	-0.9	869.484 9, 577.371 6, 415.318 5, 271.204 6, 253.194 1	+	+	a^[23]
15	23.50	Polyphyllin D+Glc/parisyunnanoside B	C₅₀H₈₀O₂₁	[M+H]⁺	1 017.525 0	-0.6	855.471 7, 709.414 3, 577.372 6, 415.319 6, 271.205 1, 253.194 6	+	+	c
16	23.53	Asparanin B5	C₅₀H₈₂O₂₁	[M+H]⁺	1 019.542 0	-6.8	857.480 6, 713.365 0, 579.386 9, 417.333 5, 273.221 7, 255.209 3	-	+	c
17	23.71	Yamogenin glucoside+Glc+xyl	C₄₄H₇₀O₁₇	[M+H]⁺	871.468 0	-0.7	709.415 1, 577.372 6, 415.320 7, 271.206 0, 253.194 8	+	+	c
18	23.73	Gracillin	C₄₅H₇₂O₁₇	[M+H]⁺	885.484 0	-0.8	723.430 3, 577.374 3, 415.320 8, 271.205 6, 253.194 9	+	+	c
19	23.85	Polyphyllin VI	C₃₉H₆₂O₁₃	[M+H]⁺	739.426 0	-0.9	577.373 2, 433.258 7, 415.318 2, 397.311 2, 271.205 6, 253.195 2	+	+	c
20	23.99	Aspacochioside D/asparinin B	C₄₅H₇₄O₁₇	[M+H]⁺	887.498 0	-2.3	741.441 7, 579.387 9, 417.336 7, 273.222 0, 255.211 1	+	+	a^{[23, 24]}
21	24.01	(25S)-5β-Spirostan-3β-yl-O-[O-α-L-rhamnopyranosyl-(1-4)]-β-D-glucopyranoside	C₃₉H₆₄O₁₂	[M+H]⁺	725.447 0	0.0	581.330 2, 563.392 4, 417.333 4, 273.220 6, 255.210 1	+	+	a^[23]
22	24.02	(25S)-5β-Spirostan-3β-ol-3-O-β-D-glucopyranosyl-(1→2)-[β-D-xylopyranosyl-(1→4)]-β-D-glucopyranoside	C₄₄H₇₂O₁₇	[M+H]⁺	873.484 0	-1.4	711.426 9, 579.389 1, 435.273 6, 417.335 8, 285.258 6, 273.219 9, 255.210 0	+	-	a^[22]
23	24.06	Dioscin+2Rha	C₅₆H₈₈O₂₅	[M+H]⁺	1 161.565 0	0.3	1 015.503 7, 723.430 4, 577.371 8, 415.319 3, 397.308 4, 253.195 2	+	+	c
24	24.34	Dioscin+Rha	C₅₀H₇₈O₂₁	[M+H]⁺	1 015.543 0	-0.1	869.485 8, 577.373 4, 415.319 7, 379.312 6, 253.195 9	+	+	c
25	24.58	Asparagoside A	C₃₃H₅₄O₈	[M+H]⁺	579.389 0	-1.5	417.335 2, 285.257 0, 273.221 3, 255.211 5	+	+	a^[22]
26	24.60	β-Sitosterol-3-O-β-D-glucuronoside+Glc	C₄₀H₆₄O₁₃	[M+H]⁺	753.442 0	-3.1	591.384 1, 271.206 8, 253.195 2	-	+	c
27	25.10	Stigmasterol glucoside	C₃₃H₅₀O₈	[M+H]⁺	575.358 0	-0.7	557.344 8, 413.301 5, 377.279 9	+	+	c
28	25.44	Compound 9 (isomer)	C₄₅H₇₄O₁₈	[M+H]⁺	903.495 0	0.5	741.442 2, 597.321 0, 579.388 7, 417.336 9, 285.260 6, 273.221 2, 255.211 9	+	-	a^[20]
29	25.88	Stigmasterol glucoside+Rha	C₃₉H₆₀O₁₂	[M+H]⁺	721.415 0	0.7	575.360 4, 541.348 6, 413.306 0	+	+	c
30	25.89	Compound 14 (isomer)	C₅₁H₈₂O₂₁	[M+H]⁺	1 031.542 0	0.2	869.489 0, 723.432 5, 577.373 0, 415.321 0, 271.205 3, 253.195 8	+	+	a^[23]
31	26.09	Compound 22 (isomer)	C₄₄H₇₂O₁₇	[M+H]⁺	873.484 0	-1.4	711.426 9, 579.389 1, 435.273 6, 417.335 8, 285.258 6, 273.219 9, 255.210 0	+	-	a^[22]
32	26.09	Sarsasapogenin+H₂O	C₂₇H₄₆O₄	[M+H]⁺	435.347 0	-0.7	417.337 9, 399.320 9, 303.228 7, 277.218 9	+	+	c
33	26.32	Compound 20 (isomer)	C₄₅H₇₄O₁₇	[M+H]⁺	887.500 0	-1.6	725.443 2, 579.387 9, 417.333 9, 273.220 9, 255.210 7	+	-	a^{[23, 24]}
34	26.66	Sarsasapogenin	C₂₇H₄₄O₃	[M+H]⁺	417.336 0	-1.0	399.328 2, 273.221 7, 255.210 9, 199.148 7	+	+	a^[22]
35	28.04	Sarsasapogenin M	C₃₉H₆₄O₁₄	[M+H]⁺	757.437 0	-0.8	595.306 0, 577.297 7, 415.247 8, 397.242 0	+	+	a^[22]
36	28.39	Yamogenin+H₂O	C₂₇H₄₄O₄	[M+H]⁺	433.331 0	-2.2	415.268 7, 397.314 2, 279.231 0, 253.191 0, 147.117 4	+	-	c
37	28.82	Filiasparoside D	C₃₈H₆₂O₁₂	[M+H]⁺	711.431 0	0.3	579.385 3, 567.317 4, 417.335 1, 399.325 0, 285.255 4, 273.220 9, 255.210 9	+	+	a^[25]
38	28.95	Dioscin	C₄₅H₇₂O₁₆	[M+H]⁺	869.489 0	0.0	723.430 8, 577.371 1, 415.320 4, 397.309 6, 271.206 4, 253.196 0	+	+	a^[26]
39	29.22	Asparanin A/ (25S)-5β-spirostan-3β-ol-3-O-β-D-glucopyranosyl-(1→2)-β-D-glucopyranoside	C₃₉H₆₄O₁₃	[M+H]⁺	741.442 0	-0.1	579.387 5, 435.273 5, 417.335 8, 285.258 3, 273.221 2, 255.210 1	+	+	a^{[22, 27]}
40	29.42	Prosapogenin A/ polyphyllin C	C₃₉H₆₂O₁₂	[M+H]⁺	723.431 0	-0.4	577.370 0, 415.319 4, 271.205 5, 253.195 1, 157.100 5, 85.027 8	+	+	b
41	29.46	Polyphyllin D	C₄₄H₇₀O₁₆	[M+H]⁺	855.473 0	0.2	711.360 1, 709.408 7, 577.369 0, 415.318 8, 271.205 4, 253.194 4	+	+	c
42	29.71	(25S)-5β-Spirostan-3β-ol-3-O-α-L-rhamnopyranosyl-(1, 2)-[α-L-rhamnopyranosyl-(1, 4)]-β-D-glucopyranoside	C₄₅H₇₄O₁₆	[M+H]⁺	871.505 0	-1.1	579.391 0, 417.337 2, 293.123 6, 273.221 9, 255.210 6	+	-	a^[22]
43	29.75	Filiasparoside C	C₄₄H₇₂O₁₆	[M+H]⁺	857.489 0	-0.5	725.448 0, 579.387 7, 417.335 1, 273.220 9, 255.210 7	+	-	a^[25]
44	30.37	Yamogenin	C₂₇H₄₂O₃	[M+H]⁺	415.321 0	-0.8	397.313 1, 271.205 3, 253.195 1, 147.116 4	+	+	b
45	32.83	Stigmasterol	C₂₉H₄₈O	[M+H]⁺	413.378 0	-2.0	395.366 3, 315.225 4, 271.203 8, 173.130 8	+	-	a^[22]
46	35.40	25S-Spirosta-1, 4-dien-3-one	C₂₇H₃₈O₃	[M+H]⁺	411.289 0	0.0	393.277 1, 267.174 4, 239.179 3	+	-	a^[22]
47	9.52	Kaempferol-3-O-rutinoside-7-O-glucoside	C₃₃H₄₀O₂₀	[M+H]⁺	757.219 0	-0.2	595.160 0, 449.106 3, 287.055 0	-	+	a^[28]
48	9.61	Quercetin diglucoside	C₂₇H₃₀O₁₇	[M+H]⁺	627.155 0	-0.4	609.253 7, 465.103 6, 303.050 1, 257.044 0, 165.014 8, 85.028 6	-	+	a^[29]
49	10.84	Isorhamnetin-3-rhamnosyl-rutinoside	C₃₄H₄₂O₂₀	[M+H]⁺	771.234 0	-1.3	609.172 0, 463.120 8, 317.065 0	-	+	a^[7]
50	11.21	Isorhamnetion-3-O-rutinoside-7-O-glucoside	C₃₄H₄₂O₂₁	[M+H]⁺	787.229 0	-1.7	641.170 2, 625.176 3, 479.118 2, 317.065 0	-	+	a^[28]
51	13.43	Quercitin-3-O-glucosylrutinoside	C₃₃H₄₀O₂₁	[M+H]⁺	773.213 0	-0.7	611.153 2, 465.102 1, 303.049 3, 129.052 1, 85.027 3	+	+	b
52	14.31	Rutin	C₂₇H₃₀O₁₆	[M+H]⁺	611.161 0	-0.5	465.101 9, 303.050 2, 285.040 6, 257.044 0, 229.049 7	+	+	d, a^[28]
53	14.33	Isoquercetin	C₂₁H₂₀O₁₂	[M+H]⁺	465.103 0	0.3	303.049 6, 285.038 3, 257.047 9, 165.018 2, 153.018 4	+	+	a^[28]
54	15.09	Astragalin	C₂₁H₂₀O₁₁	[M+H]⁺	449.108 0	-1.0	287.054 9, 213.056 0, 165.018 5, 153.018 8	-	+	a^[28]
55	15.62	Narcissoside	C₂₈H₃₂O₁₆	[M+H]⁺	625.176 0	0.1	479.116 1, 317.065 4, 285.033 5, 147.069 0, 129.054 3, 85.028 8	+	+	b
56	16.22	Kaempferol-3-O-rutinoside	C₂₇H₃₀O₁₅	[M+H]⁺	595.166 0	-0.2	449.107 0, 287.055 0, 269.047 5, 213.054 4, 165.017 1	-	+	a^[28]
57	16.76	Isorhamnetin	C₁₆H₁₂O₇	[M+H]⁺	317.066 0	0.1	302.048 0, 274.047 9, 165.018 8, 153.018 0	-	+	d, a^[7]
58	18.07	Chrysoeriol-7-O-β-D-glucoside	C₂₂H₂₂O₁₁	[M+H]⁺	463.123 0	-1.0	301.071 1, 286.047 3, 153.016 2	-	+	b
59	24.97	Diosmetin	C₁₆H₁₂O₆	[M+H]⁺	301.071 0	-0.4	286.046 2, 258.050 8	-	+	a^[7]
60	0.86	Aspartic acid	C₄H₇NO₄	[M-H]^-	132.031 0	-0.2	115.008 9, 71.014 9	+	+	b
61	0.88	L-Arginine	C₆H₁₄N₄O₂	[M+H]⁺	175.119 0	1.7	158.091 7, 116.070 4, 112.085 9, 70.064 9	+	-	b
62	0.91	L-Glutamic acid	C₅H₉NO₄	[M+H]⁺	148.060 0	0.1	130.049 6, 102.054 2, 85.028 6, 84.043 9, 56.049 3	+	-	b
63	0.99	Proline	C₅H₉NO₂	[M+H]⁺	116.070 0	-4.5	70.065 1, 53.039 0	+	+	b
64	1.07	L-Valine	C₅H₁₁NO₂	[M+H]⁺	118.086 0	-1.1	73.085 0, 72.080 9, 59.049 0, 57.057 1, 56.049 5, 55.054 1, 53.038 5	-	+	b
65	1.81	Nicotinic acid	C₆H₅NO₂	[M+H]⁺	124.039 0	-3.8	106.028 4, 80.048 8, 78.033 5, 53.038 2, 52.018 2	+	+	b
66	2.48	Isoleucine	C₆H₁₃NO₂	[M+H]⁺	132.102 0	-1.7	87.099 1, 86.096 1, 74.057 5, 70.067 4, 69.069 7, 58.064 7	+	+	a^[30]
67	2.84	Leucine	C₆H₁₃NO₂	[M-H]^-	130.087 0	0.5	113.063 0, 86.062 7, 84.083 5	+	+	a^[30]
68	3.97	Phenylalanine	C₉H₁₁NO₂	[M+H]⁺	166.086 0	-2.7	120.080 2, 104.057 2, 103.053 6, 91.053 9, 77.038 3	+	+	b
69	6.17	L-Tryptophan	C₁₁H₁₂N₂O₂	[M-H]^-	203.083 0	4.5	186.060 4, 159.095 4, 142.069 0, 130.068 7	+	+	b
70	0.97	Quinic acid	C₇H₁₂O₆	[M-H]^-	191.056 0	1.8	173.012 4, 127.044 0, 111.010 1, 85.030 3, 73.030 3	-	+	b
71	0.99	Malic acid	C₄H₆O₅	[M-H]^-	133.014 0	-0.1	114.036 1, 73.014 7, 70.031 2	+	+	b
72	1.01	Fumaric acid/maleic acid	C₄H₄O₄	[M-H]^-	115.004 0	-0.7	97.930 6, 71.016 3	-	+	b
73	1.23	Citric acid	C₆H₈O₇	[M-H]^-	191.020 0	2.8	173.013 0, 155.001 4, 147.033 1, 111.010 7, 87.010 1	+	+	b
74	1.64	Pipecolic acid	C₆H₁₁NO₂	[M+H]⁺	130.086 0	-3.7	84.080 1, 67.053 7, 62.024 6, 56.048 9	+	+	b
75	2.35	Amber acid	C₄H₆O₄	[M-H]^-	117.019 0	-0.9	99.011 8, 73.030 3, 55.019 3	+	+	b
76	3.97	Cinnamic acid	C₉H₈O₂	[M+H]⁺	149.060 0	-3.7	131.048 1, 103.053 5, 77.038 5, 65.038 1	+	+	b
77	5.15	Protocatechuic acid	C₇H₆O₄	[M-H]^-	153.019 0	0.7	109.033 8, 91.021 7	+	+	b
78	6.33	Chlorogenic acid	C₁₆H₁₈O₉	[M+H]⁺	355.102 0	-0.5	181.050 1, 163.038 7, 145.027 9, 135.043 5, 117.032 9, 89.038 0	-	+	b
79	7.25	p-Hydroxybenzoic acid	C₇H₆O₃	[M-H]^-	138.024 0	-0.5	93.037 2, 65.050 2	+	+	b
80	7.89	p-Coumaroylquinic acid	C₁₆H₁₈O₈	[M+H]⁺	339.107 0	0.2	119.048 6, 91.053 0	-	+	a^[29]
81	8.99	Feruloylquinic acid	C₁₇H₂₀O₉	[M+H]⁺	369.118 0	-0.3	178.058 1, 177.054 1, 149.059 1, 146.031 3, 134.035 3, 117.033 2	-	+	a^[29]
82	9.16	Caffeic acid	C₉H₈O₄	[M-H]^-	179.035 0	3.2	135.048 8, 133.031 6, 89.041 4	-	+	a^[31]
83	9.80	Ferulic acid	C₁₀H₁₀O₄	[M+H]⁺	195.065 0	0.4	177.054 6, 149.059 2, 145.028 2	+	+	a^[32]
84	11.8	p-Coumaric acid	C₉H₈O₃	[M-H]^-	163.044 0	3.5	119.052 3, 91.035 9, 65.040 6	+	+	b
85	13.33	Isoferulic acid	C₁₀H₁₀O₄	[M+H]⁺	195.065 0	-1.0	177.054 6, 149.059 2, 145.028 2	+	+	a^[32]
86	0.95	D-(+)Glucose/fructose	C₆H₁₂O₆	[M-H]^-	179.056 0	2.3	119.033 4, 115.043 2, 101.028 1	+	+	b
87	1.00	Sucrose	C₁₂H₂₂O₁₁	[M-H]^-	341.109 0	1.9	179.059 3, 119.036 6, 101.026 5	-	+	b
88	1.67	1-Kestose/Neokestose	C₁₈H₃₂O₁₆	[M-H]^-	503.162 0	2.1	341.117 6, 179.059 2, 161.046 9, 119.036 5	-	+	b
89	12.85	Nystose	C₂₄H₄₂O₂₁	[M-H]^-	665.215 0	2.5	503.177 1, 341.112 4, 179.059 2	-	+	b
90	1.69	Adenine	C₅H₅N₅	[M+H]⁺	136.062 0	-1.9	119.035 4, 94.040 2, 92.024 4, 65.013 2	+	+	b
91	1.77	Cytidine	C₉H₁₃N₃O₅	[M+H]⁺	244.093 0	1.8	112.049 6, 95.023 3, 69.043 9, 67.028 4	+	+	b
92	1.91	Nicotinamide	C₆H₆N₂O	[M+H]⁺	123.055 0	-2.9	106.030 4, 78.034 1, 53.038 8, 51.022 9	+	+	b
93	2.46	Uridine	C₉H₁₂N₂O₆	[M-H]^-	243.062 0	4.3	200.060 7, 152.038 6, 111.021 8, 83.014 0, 55.019 9	-	+	b
94	3.00	Adenosine	C₁₀H₁₃N₅O₄	[M-H]^-	266.089 0	3.0	134.049 8, 107.037 9, 92.027 6	-	+	b
95	3.17	Guanosine	C₁₀H₁₃N₅O₅	[M+H]⁺	284.099 0	0.5	152.056 0, 135.029 3, 110.034 3	-	+	b
96	3.18	2-Hydroxyadenosine	C₁₀H₁₃N₅O₅	[M-H]^-	282.084 0	3.8	150.045 8, 133.018 5, 107.038 3	+	+	b
97	9.22	p-Hydroxybenzaldehyde	C₇H₆O₂	[M-H]^-	121.030 0	-0.7	92.027 5, 65.042 3	+	+	b
98	10.85	Vitamin B₂	C₁₆H₂₄O₁₀	[M+H]⁺	377.145 0	2.6	243.087 8, 172.086 4, 69.033 0	+	+	b
99	25.41	Coumarin	C₉H₆O₂	[M+H]⁺	147.044 0	-1.4	119.049 9, 91.054 0, 75.022 0, 65.038 5	+	+	b
100	25.42	Dicoumaroyl glycerol	C₂₁H₂₀O₇	[M+H]⁺	385.128 0	-1.3	367.116 8, 221.080 9, 147.044 1, 119.049 3, 91.054 3	-	+	a^[29]
101	25.75	Coumaroyl feruloyl glycerol	C₂₂H₂₂O₈	[M+H]⁺	415.139 0	-0.8	397.126 6, 271.204 0, 221.080 3, 177.054 1, 147.043 5	-	+	a^[29]
102	26.04	Diferuoloyl glycerol	C₂₃H₂₄O₉	[M+H]⁺	445.149 0	-0.9	427.137 0, 251.091 2, 177.054 2, 149.058 9, 145.028 1	-	+	a^[29]
103	27.11	Sedanolide	C₁₂H₁₈O₂	[M+H]⁺	195.138 0	0.0	167.091 4, 149.133 1, 135.115 2, 111.078 8, 93.069 6, 91.053 8, 69.070 2	+	+	b
104	30.58	Linolenic acid	C₁₈H₃₀O₂	[M+H]⁺	279.232 0	0.1	261.221 3, 149.022 9, 123.116 1	+	+	b
105	33.09	Oleamide	C₁₈H₃₅NO	[M+H]⁺	282.279 0	-0.2	265.251 1, 247.240 6, 135.115 9, 121.099 6, 114.091 1, 95.084 7	+	+	b
106	33.17	Muscone	C₁₆H₃₀O	[M+H]⁺	239.237 0	0.0	183.083 3, 157.073 5, 143.090 0, 109.101 1, 95.085 6, 81.068 6, 67.054 3	+	+	b
107	36.08	Erucamide	C₂₂H₄₃NO	[M+H]⁺	338.342 0	-0.5	321.314 3, 303.030 5, 177.163 0, 153.127 5, 149.131 4	+	+	b

No.	t_R/min	Identification	Molecular formula	[M+H]⁺/[M-H]^-	Mass	Error /ppm	Fragment ion	W	G	Source
1	21.86	β-Sitosterol-3-O-β-D-glucuronoside+2Rha+Glc	C₅₁H₈₀O₂₂	[M+H]⁺	1 045.521 0	0.2	883.466 6, 737.408 4, 591.352 6	+	+	c
2	21.92	Stigmasterol glucoside+2Rha	C₄₅H₇₀O₁₆	[M+H]⁺	867.472 0	-0.3	849.461 8, 721.410 5, 705.417 6, 575.356 5, 559.356 9, 413.304 0	+	-	c
3	22.10	Gracillin+Glc	C₅₁H₈₂O₂₂	[M+H]⁺	1 047.533 0	0.0	885.483 5, 723.354 9, 577.299 3, 415.251 9, 271.205 3, 253.195 0	+	+	c
4	22.24	β-Sitosterol-3-O-β-D-glucuronoside+Rha+Glc	C₄₅H₇₀O₁₈	[M+H]⁺	899.463 0	0.0	737.408 6, 593.294 3, 591.350 7	+	+	c
5	22.36	Dongnoside E	C₅₀H₈₂O₂₂	[M+H]⁺	1 035.533 0	-0.9	903.483 1, 873.484 3, 741.443 1, 579.387 9, 417.336 0, 273.221 1	+	+	c
6	22.37	Pamaqueside / agavoside B	C₃₉H₆₂O₁₄	[M+H]⁺	755.420 0	-1.4	737.405 6, 593.368 7, 431.243 2, 413.311 5, 395.294 0	+	+	c
7	22.43	Pseudoprotoneodioscin+Glc	C₅₇H₉₂O₂₆	[M+H]⁺	1 193.596 0	-0.5	1 031.538 3, 869.486 1, 723.427 7, 577.373 0, 415.320 1, 253.194 1	+	+	c
8	22.57	Aspidistrin	C₅₀H₈₀O₂₂	[M+H]⁺	1 033.521 0	-0.6	871.470 1, 739.430 7, 577.373 5, 415.320 9, 397.310 2, 271.205 6	+	+	c
9	22.71	Shatavarin Ⅸ	C₄₅H₇₄O₁₈	[M+H]⁺	903.495 0	-0.5	741.440 6, 597.325 8, 579.386 9, 417.335 6, 285.257 5, 273.221 6, 255.210 5	+	+	a^[20]
10	22.82	Protodioscin	C₅₁H₈₄O₂₂	[M+H]⁺	1 049.553 0	-0.3	887.498 1, 741.438 8, 725.371 0, 433.330 1, 415.322 2	+	+	a^[21]
11	22.96	(25S)-26-O-β-D-Glucopyranosyl-5β-furost-20(22)-ene-3β, 26-diol-3-O-β-D-glucopyranosyl-(1→2)-β-D-glucopyranoside	C₄₅H₇₂O₁₈	[M+H]⁺	901.478 0	-1.3	739.425 9, 577.372 0, 433.258 1, 415.320 0, 283.242 6, 271.205 9, 253.195 1	+	+	a^[22]
12	23.25	Compound 7 (isomer)	C₅₇H₉₂O₂₆	[M+H]⁺	1 193.596 0	-0.7	1 031.545 1, 869.489 4, 723.431 3, 577.371 2, 415.319 9, 253.192 6	+	+	c
13	23.27	Stigmasterol glucoside+Hex+2Rha	C₅₁H₈₀O₂₁	[M+H]⁺	1 029.526 0	-1.9	867.469 4, 721.413 5, 575.358 1, 413.303 1, 395.291 5	-	+	c
14	23.42	Pseudoprotoneodioscin	C₅₁H₈₂O₂₁	[M+H]⁺	1 031.542 0	-0.9	869.484 9, 577.371 6, 415.318 5, 271.204 6, 253.194 1	+	+	a^[23]
15	23.50	Polyphyllin D+Glc/parisyunnanoside B	C₅₀H₈₀O₂₁	[M+H]⁺	1 017.525 0	-0.6	855.471 7, 709.414 3, 577.372 6, 415.319 6, 271.205 1, 253.194 6	+	+	c
16	23.53	Asparanin B5	C₅₀H₈₂O₂₁	[M+H]⁺	1 019.542 0	-6.8	857.480 6, 713.365 0, 579.386 9, 417.333 5, 273.221 7, 255.209 3	-	+	c
17	23.71	Yamogenin glucoside+Glc+xyl	C₄₄H₇₀O₁₇	[M+H]⁺	871.468 0	-0.7	709.415 1, 577.372 6, 415.320 7, 271.206 0, 253.194 8	+	+	c
18	23.73	Gracillin	C₄₅H₇₂O₁₇	[M+H]⁺	885.484 0	-0.8	723.430 3, 577.374 3, 415.320 8, 271.205 6, 253.194 9	+	+	c
19	23.85	Polyphyllin VI	C₃₉H₆₂O₁₃	[M+H]⁺	739.426 0	-0.9	577.373 2, 433.258 7, 415.318 2, 397.311 2, 271.205 6, 253.195 2	+	+	c
20	23.99	Aspacochioside D/asparinin B	C₄₅H₇₄O₁₇	[M+H]⁺	887.498 0	-2.3	741.441 7, 579.387 9, 417.336 7, 273.222 0, 255.211 1	+	+	a^{[23, 24]}
21	24.01	(25S)-5β-Spirostan-3β-yl-O-[O-α-L-rhamnopyranosyl-(1-4)]-β-D-glucopyranoside	C₃₉H₆₄O₁₂	[M+H]⁺	725.447 0	0.0	581.330 2, 563.392 4, 417.333 4, 273.220 6, 255.210 1	+	+	a^[23]
22	24.02	(25S)-5β-Spirostan-3β-ol-3-O-β-D-glucopyranosyl-(1→2)-[β-D-xylopyranosyl-(1→4)]-β-D-glucopyranoside	C₄₄H₇₂O₁₇	[M+H]⁺	873.484 0	-1.4	711.426 9, 579.389 1, 435.273 6, 417.335 8, 285.258 6, 273.219 9, 255.210 0	+	-	a^[22]
23	24.06	Dioscin+2Rha	C₅₆H₈₈O₂₅	[M+H]⁺	1 161.565 0	0.3	1 015.503 7, 723.430 4, 577.371 8, 415.319 3, 397.308 4, 253.195 2	+	+	c
24	24.34	Dioscin+Rha	C₅₀H₇₈O₂₁	[M+H]⁺	1 015.543 0	-0.1	869.485 8, 577.373 4, 415.319 7, 379.312 6, 253.195 9	+	+	c
25	24.58	Asparagoside A	C₃₃H₅₄O₈	[M+H]⁺	579.389 0	-1.5	417.335 2, 285.257 0, 273.221 3, 255.211 5	+	+	a^[22]
26	24.60	β-Sitosterol-3-O-β-D-glucuronoside+Glc	C₄₀H₆₄O₁₃	[M+H]⁺	753.442 0	-3.1	591.384 1, 271.206 8, 253.195 2	-	+	c
27	25.10	Stigmasterol glucoside	C₃₃H₅₀O₈	[M+H]⁺	575.358 0	-0.7	557.344 8, 413.301 5, 377.279 9	+	+	c
28	25.44	Compound 9 (isomer)	C₄₅H₇₄O₁₈	[M+H]⁺	903.495 0	0.5	741.442 2, 597.321 0, 579.388 7, 417.336 9, 285.260 6, 273.221 2, 255.211 9	+	-	a^[20]
29	25.88	Stigmasterol glucoside+Rha	C₃₉H₆₀O₁₂	[M+H]⁺	721.415 0	0.7	575.360 4, 541.348 6, 413.306 0	+	+	c
30	25.89	Compound 14 (isomer)	C₅₁H₈₂O₂₁	[M+H]⁺	1 031.542 0	0.2	869.489 0, 723.432 5, 577.373 0, 415.321 0, 271.205 3, 253.195 8	+	+	a^[23]
31	26.09	Compound 22 (isomer)	C₄₄H₇₂O₁₇	[M+H]⁺	873.484 0	-1.4	711.426 9, 579.389 1, 435.273 6, 417.335 8, 285.258 6, 273.219 9, 255.210 0	+	-	a^[22]
32	26.09	Sarsasapogenin+H₂O	C₂₇H₄₆O₄	[M+H]⁺	435.347 0	-0.7	417.337 9, 399.320 9, 303.228 7, 277.218 9	+	+	c
33	26.32	Compound 20 (isomer)	C₄₅H₇₄O₁₇	[M+H]⁺	887.500 0	-1.6	725.443 2, 579.387 9, 417.333 9, 273.220 9, 255.210 7	+	-	a^{[23, 24]}
34	26.66	Sarsasapogenin	C₂₇H₄₄O₃	[M+H]⁺	417.336 0	-1.0	399.328 2, 273.221 7, 255.210 9, 199.148 7	+	+	a^[22]
35	28.04	Sarsasapogenin M	C₃₉H₆₄O₁₄	[M+H]⁺	757.437 0	-0.8	595.306 0, 577.297 7, 415.247 8, 397.242 0	+	+	a^[22]
36	28.39	Yamogenin+H₂O	C₂₇H₄₄O₄	[M+H]⁺	433.331 0	-2.2	415.268 7, 397.314 2, 279.231 0, 253.191 0, 147.117 4	+	-	c
37	28.82	Filiasparoside D	C₃₈H₆₂O₁₂	[M+H]⁺	711.431 0	0.3	579.385 3, 567.317 4, 417.335 1, 399.325 0, 285.255 4, 273.220 9, 255.210 9	+	+	a^[25]
38	28.95	Dioscin	C₄₅H₇₂O₁₆	[M+H]⁺	869.489 0	0.0	723.430 8, 577.371 1, 415.320 4, 397.309 6, 271.206 4, 253.196 0	+	+	a^[26]
39	29.22	Asparanin A/ (25S)-5β-spirostan-3β-ol-3-O-β-D-glucopyranosyl-(1→2)-β-D-glucopyranoside	C₃₉H₆₄O₁₃	[M+H]⁺	741.442 0	-0.1	579.387 5, 435.273 5, 417.335 8, 285.258 3, 273.221 2, 255.210 1	+	+	a^{[22, 27]}
40	29.42	Prosapogenin A/ polyphyllin C	C₃₉H₆₂O₁₂	[M+H]⁺	723.431 0	-0.4	577.370 0, 415.319 4, 271.205 5, 253.195 1, 157.100 5, 85.027 8	+	+	b
41	29.46	Polyphyllin D	C₄₄H₇₀O₁₆	[M+H]⁺	855.473 0	0.2	711.360 1, 709.408 7, 577.369 0, 415.318 8, 271.205 4, 253.194 4	+	+	c
42	29.71	(25S)-5β-Spirostan-3β-ol-3-O-α-L-rhamnopyranosyl-(1, 2)-[α-L-rhamnopyranosyl-(1, 4)]-β-D-glucopyranoside	C₄₅H₇₄O₁₆	[M+H]⁺	871.505 0	-1.1	579.391 0, 417.337 2, 293.123 6, 273.221 9, 255.210 6	+	-	a^[22]
43	29.75	Filiasparoside C	C₄₄H₇₂O₁₆	[M+H]⁺	857.489 0	-0.5	725.448 0, 579.387 7, 417.335 1, 273.220 9, 255.210 7	+	-	a^[25]
44	30.37	Yamogenin	C₂₇H₄₂O₃	[M+H]⁺	415.321 0	-0.8	397.313 1, 271.205 3, 253.195 1, 147.116 4	+	+	b
45	32.83	Stigmasterol	C₂₉H₄₈O	[M+H]⁺	413.378 0	-2.0	395.366 3, 315.225 4, 271.203 8, 173.130 8	+	-	a^[22]
46	35.40	25S-Spirosta-1, 4-dien-3-one	C₂₇H₃₈O₃	[M+H]⁺	411.289 0	0.0	393.277 1, 267.174 4, 239.179 3	+	-	a^[22]
47	9.52	Kaempferol-3-O-rutinoside-7-O-glucoside	C₃₃H₄₀O₂₀	[M+H]⁺	757.219 0	-0.2	595.160 0, 449.106 3, 287.055 0	-	+	a^[28]
48	9.61	Quercetin diglucoside	C₂₇H₃₀O₁₇	[M+H]⁺	627.155 0	-0.4	609.253 7, 465.103 6, 303.050 1, 257.044 0, 165.014 8, 85.028 6	-	+	a^[29]
49	10.84	Isorhamnetin-3-rhamnosyl-rutinoside	C₃₄H₄₂O₂₀	[M+H]⁺	771.234 0	-1.3	609.172 0, 463.120 8, 317.065 0	-	+	a^[7]
50	11.21	Isorhamnetion-3-O-rutinoside-7-O-glucoside	C₃₄H₄₂O₂₁	[M+H]⁺	787.229 0	-1.7	641.170 2, 625.176 3, 479.118 2, 317.065 0	-	+	a^[28]
51	13.43	Quercitin-3-O-glucosylrutinoside	C₃₃H₄₀O₂₁	[M+H]⁺	773.213 0	-0.7	611.153 2, 465.102 1, 303.049 3, 129.052 1, 85.027 3	+	+	b
52	14.31	Rutin	C₂₇H₃₀O₁₆	[M+H]⁺	611.161 0	-0.5	465.101 9, 303.050 2, 285.040 6, 257.044 0, 229.049 7	+	+	d, a^[28]
53	14.33	Isoquercetin	C₂₁H₂₀O₁₂	[M+H]⁺	465.103 0	0.3	303.049 6, 285.038 3, 257.047 9, 165.018 2, 153.018 4	+	+	a^[28]
54	15.09	Astragalin	C₂₁H₂₀O₁₁	[M+H]⁺	449.108 0	-1.0	287.054 9, 213.056 0, 165.018 5, 153.018 8	-	+	a^[28]
55	15.62	Narcissoside	C₂₈H₃₂O₁₆	[M+H]⁺	625.176 0	0.1	479.116 1, 317.065 4, 285.033 5, 147.069 0, 129.054 3, 85.028 8	+	+	b
56	16.22	Kaempferol-3-O-rutinoside	C₂₇H₃₀O₁₅	[M+H]⁺	595.166 0	-0.2	449.107 0, 287.055 0, 269.047 5, 213.054 4, 165.017 1	-	+	a^[28]
57	16.76	Isorhamnetin	C₁₆H₁₂O₇	[M+H]⁺	317.066 0	0.1	302.048 0, 274.047 9, 165.018 8, 153.018 0	-	+	d, a^[7]
58	18.07	Chrysoeriol-7-O-β-D-glucoside	C₂₂H₂₂O₁₁	[M+H]⁺	463.123 0	-1.0	301.071 1, 286.047 3, 153.016 2	-	+	b
59	24.97	Diosmetin	C₁₆H₁₂O₆	[M+H]⁺	301.071 0	-0.4	286.046 2, 258.050 8	-	+	a^[7]
60	0.86	Aspartic acid	C₄H₇NO₄	[M-H]^-	132.031 0	-0.2	115.008 9, 71.014 9	+	+	b
61	0.88	L-Arginine	C₆H₁₄N₄O₂	[M+H]⁺	175.119 0	1.7	158.091 7, 116.070 4, 112.085 9, 70.064 9	+	-	b
62	0.91	L-Glutamic acid	C₅H₉NO₄	[M+H]⁺	148.060 0	0.1	130.049 6, 102.054 2, 85.028 6, 84.043 9, 56.049 3	+	-	b
63	0.99	Proline	C₅H₉NO₂	[M+H]⁺	116.070 0	-4.5	70.065 1, 53.039 0	+	+	b
64	1.07	L-Valine	C₅H₁₁NO₂	[M+H]⁺	118.086 0	-1.1	73.085 0, 72.080 9, 59.049 0, 57.057 1, 56.049 5, 55.054 1, 53.038 5	-	+	b
65	1.81	Nicotinic acid	C₆H₅NO₂	[M+H]⁺	124.039 0	-3.8	106.028 4, 80.048 8, 78.033 5, 53.038 2, 52.018 2	+	+	b
66	2.48	Isoleucine	C₆H₁₃NO₂	[M+H]⁺	132.102 0	-1.7	87.099 1, 86.096 1, 74.057 5, 70.067 4, 69.069 7, 58.064 7	+	+	a^[30]
67	2.84	Leucine	C₆H₁₃NO₂	[M-H]^-	130.087 0	0.5	113.063 0, 86.062 7, 84.083 5	+	+	a^[30]
68	3.97	Phenylalanine	C₉H₁₁NO₂	[M+H]⁺	166.086 0	-2.7	120.080 2, 104.057 2, 103.053 6, 91.053 9, 77.038 3	+	+	b
69	6.17	L-Tryptophan	C₁₁H₁₂N₂O₂	[M-H]^-	203.083 0	4.5	186.060 4, 159.095 4, 142.069 0, 130.068 7	+	+	b
70	0.97	Quinic acid	C₇H₁₂O₆	[M-H]^-	191.056 0	1.8	173.012 4, 127.044 0, 111.010 1, 85.030 3, 73.030 3	-	+	b
71	0.99	Malic acid	C₄H₆O₅	[M-H]^-	133.014 0	-0.1	114.036 1, 73.014 7, 70.031 2	+	+	b
72	1.01	Fumaric acid/maleic acid	C₄H₄O₄	[M-H]^-	115.004 0	-0.7	97.930 6, 71.016 3	-	+	b
73	1.23	Citric acid	C₆H₈O₇	[M-H]^-	191.020 0	2.8	173.013 0, 155.001 4, 147.033 1, 111.010 7, 87.010 1	+	+	b
74	1.64	Pipecolic acid	C₆H₁₁NO₂	[M+H]⁺	130.086 0	-3.7	84.080 1, 67.053 7, 62.024 6, 56.048 9	+	+	b
75	2.35	Amber acid	C₄H₆O₄	[M-H]^-	117.019 0	-0.9	99.011 8, 73.030 3, 55.019 3	+	+	b
76	3.97	Cinnamic acid	C₉H₈O₂	[M+H]⁺	149.060 0	-3.7	131.048 1, 103.053 5, 77.038 5, 65.038 1	+	+	b
77	5.15	Protocatechuic acid	C₇H₆O₄	[M-H]^-	153.019 0	0.7	109.033 8, 91.021 7	+	+	b
78	6.33	Chlorogenic acid	C₁₆H₁₈O₉	[M+H]⁺	355.102 0	-0.5	181.050 1, 163.038 7, 145.027 9, 135.043 5, 117.032 9, 89.038 0	-	+	b
79	7.25	p-Hydroxybenzoic acid	C₇H₆O₃	[M-H]^-	138.024 0	-0.5	93.037 2, 65.050 2	+	+	b
80	7.89	p-Coumaroylquinic acid	C₁₆H₁₈O₈	[M+H]⁺	339.107 0	0.2	119.048 6, 91.053 0	-	+	a^[29]
81	8.99	Feruloylquinic acid	C₁₇H₂₀O₉	[M+H]⁺	369.118 0	-0.3	178.058 1, 177.054 1, 149.059 1, 146.031 3, 134.035 3, 117.033 2	-	+	a^[29]
82	9.16	Caffeic acid	C₉H₈O₄	[M-H]^-	179.035 0	3.2	135.048 8, 133.031 6, 89.041 4	-	+	a^[31]
83	9.80	Ferulic acid	C₁₀H₁₀O₄	[M+H]⁺	195.065 0	0.4	177.054 6, 149.059 2, 145.028 2	+	+	a^[32]
84	11.8	p-Coumaric acid	C₉H₈O₃	[M-H]^-	163.044 0	3.5	119.052 3, 91.035 9, 65.040 6	+	+	b
85	13.33	Isoferulic acid	C₁₀H₁₀O₄	[M+H]⁺	195.065 0	-1.0	177.054 6, 149.059 2, 145.028 2	+	+	a^[32]
86	0.95	D-(+)Glucose/fructose	C₆H₁₂O₆	[M-H]^-	179.056 0	2.3	119.033 4, 115.043 2, 101.028 1	+	+	b
87	1.00	Sucrose	C₁₂H₂₂O₁₁	[M-H]^-	341.109 0	1.9	179.059 3, 119.036 6, 101.026 5	-	+	b
88	1.67	1-Kestose/Neokestose	C₁₈H₃₂O₁₆	[M-H]^-	503.162 0	2.1	341.117 6, 179.059 2, 161.046 9, 119.036 5	-	+	b
89	12.85	Nystose	C₂₄H₄₂O₂₁	[M-H]^-	665.215 0	2.5	503.177 1, 341.112 4, 179.059 2	-	+	b
90	1.69	Adenine	C₅H₅N₅	[M+H]⁺	136.062 0	-1.9	119.035 4, 94.040 2, 92.024 4, 65.013 2	+	+	b
91	1.77	Cytidine	C₉H₁₃N₃O₅	[M+H]⁺	244.093 0	1.8	112.049 6, 95.023 3, 69.043 9, 67.028 4	+	+	b
92	1.91	Nicotinamide	C₆H₆N₂O	[M+H]⁺	123.055 0	-2.9	106.030 4, 78.034 1, 53.038 8, 51.022 9	+	+	b
93	2.46	Uridine	C₉H₁₂N₂O₆	[M-H]^-	243.062 0	4.3	200.060 7, 152.038 6, 111.021 8, 83.014 0, 55.019 9	-	+	b
94	3.00	Adenosine	C₁₀H₁₃N₅O₄	[M-H]^-	266.089 0	3.0	134.049 8, 107.037 9, 92.027 6	-	+	b
95	3.17	Guanosine	C₁₀H₁₃N₅O₅	[M+H]⁺	284.099 0	0.5	152.056 0, 135.029 3, 110.034 3	-	+	b
96	3.18	2-Hydroxyadenosine	C₁₀H₁₃N₅O₅	[M-H]^-	282.084 0	3.8	150.045 8, 133.018 5, 107.038 3	+	+	b
97	9.22	p-Hydroxybenzaldehyde	C₇H₆O₂	[M-H]^-	121.030 0	-0.7	92.027 5, 65.042 3	+	+	b
98	10.85	Vitamin B₂	C₁₆H₂₄O₁₀	[M+H]⁺	377.145 0	2.6	243.087 8, 172.086 4, 69.033 0	+	+	b
99	25.41	Coumarin	C₉H₆O₂	[M+H]⁺	147.044 0	-1.4	119.049 9, 91.054 0, 75.022 0, 65.038 5	+	+	b
100	25.42	Dicoumaroyl glycerol	C₂₁H₂₀O₇	[M+H]⁺	385.128 0	-1.3	367.116 8, 221.080 9, 147.044 1, 119.049 3, 91.054 3	-	+	a^[29]
101	25.75	Coumaroyl feruloyl glycerol	C₂₂H₂₂O₈	[M+H]⁺	415.139 0	-0.8	397.126 6, 271.204 0, 221.080 3, 177.054 1, 147.043 5	-	+	a^[29]
102	26.04	Diferuoloyl glycerol	C₂₃H₂₄O₉	[M+H]⁺	445.149 0	-0.9	427.137 0, 251.091 2, 177.054 2, 149.058 9, 145.028 1	-	+	a^[29]
103	27.11	Sedanolide	C₁₂H₁₈O₂	[M+H]⁺	195.138 0	0.0	167.091 4, 149.133 1, 135.115 2, 111.078 8, 93.069 6, 91.053 8, 69.070 2	+	+	b
104	30.58	Linolenic acid	C₁₈H₃₀O₂	[M+H]⁺	279.232 0	0.1	261.221 3, 149.022 9, 123.116 1	+	+	b
105	33.09	Oleamide	C₁₈H₃₅NO	[M+H]⁺	282.279 0	-0.2	265.251 1, 247.240 6, 135.115 9, 121.099 6, 114.091 1, 95.084 7	+	+	b
106	33.17	Muscone	C₁₆H₃₀O	[M+H]⁺	239.237 0	0.0	183.083 3, 157.073 5, 143.090 0, 109.101 1, 95.085 6, 81.068 6, 67.054 3	+	+	b
107	36.08	Erucamide	C₂₂H₄₃NO	[M+H]⁺	338.342 0	-0.5	321.314 3, 303.030 5, 177.163 0, 153.127 5, 149.131 4	+	+	b

Compounds type	Aglycone	Characteristic ion
Saponin	Sarsasapogenin	417.335 8, 399.325 1, 273.221 7, 255.210 9
Yamogenin	415.320 1, 397.313 1, 271.205 3, 253.195 1
Flavonol	Kaempferol	287.055 0, 269.043 7, 213.054 2, 165.017 8
Quercetin	303.049 6, 285.038 3, 257.047 9, 165.018 2
Isorhamnetin	317.066 6, 302.048 0, 274.047 9, 165.018 8

Compounds type	Aglycone	Characteristic ion
Saponin	Sarsasapogenin	417.335 8, 399.325 1, 273.221 7, 255.210 9
Yamogenin	415.320 1, 397.313 1, 271.205 3, 253.195 1
Flavonol	Kaempferol	287.055 0, 269.043 7, 213.054 2, 165.017 8
Quercetin	303.049 6, 285.038 3, 257.047 9, 165.018 2
Isorhamnetin	317.066 6, 302.048 0, 274.047 9, 165.018 8

基于UPLC-Q-TOF-MS/MS和分子网络技术快速鉴定芦笋茎皮中的化学成分

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卫瑞 , 杨琳娇 , 秦雪梅 , 李震宇 ^*

药学学报 | 研究论文 2022,57(9): 2839-2850

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药学学报 | 研究论文 2022, 57(9): 2839-2850

基于UPLC-Q-TOF-MS/MS和分子网络技术快速鉴定芦笋茎皮中的化学成分

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卫瑞, 杨琳娇, 秦雪梅, 李震宇^*

作者信息

山西大学化学生物学与分子工程教育部重点实验室, 中医药现代研究中心, 山西太原 030006

通讯作者:

*李震宇, Tel: 86-351-7011202, E-mail: lizhenyu@sxu.edu.cn

Rapid identification of chemical constituents in the dried stem bark of Asparagus officinalis L. based on UPLC-Q-TOF-MS/MS

Rui WEI, Lin-jiao YANG, Xue-mei QIN, Zhen-yu LI^*

Affiliations

Modern Research Center for Traditional Chinese Medicine, the Key Laboratory of Chemical Biology and Molecular Engineering of Ministry of Education, Shanxi University, Taiyuan 030006, China

出版时间: 2022-09-12 doi: 10.16438/j.0513-4870.2022-0652

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摘要

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本研究采用超高效液相-四级杆-飞行时间高分辨质谱联用(UPLC-Q-TOF-MS/MS) 结合分子网络技术快速分析鉴定两种芦笋茎皮中的化学成分。通过化合物精确分子量、MS/MS裂解规律和文献报道数据等信息对两种芦笋茎皮中的化学成分进行鉴定, 并根据MS/MS碎片的相似性创建分子网络。两种芦笋茎皮共鉴定107个化合物, 包括皂苷类化合物46个、黄酮类化合物13个, 有机酸类、氨基酸类和糖类等其他类成分48个。两种芦笋茎皮成分种类差异明显, 白笋茎皮中富含皂苷类成分, 而绿笋茎皮中富含黄酮类成分。本研究运用液质联用结合分子网络技术对芦笋茎皮中的化学成分进行快速分析, 利用HIT 2.0中草药成分靶点数据库结合文献报道确定了芦笋茎皮中10个皂苷和黄酮类成分对乳腺癌的45个作用靶点, 为芦笋资源的开发利用奠定了理论基础。

关键词

芦笋茎皮 / 化学成分 / 定性分析 / UPLC-Q-TOF-MS/MS / 分子网络

Abstract

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Ultra-performance liquid chromatography-quadrupole-time of flight mass spectrometry (UPLC-Q-TOF-MS/MS) coupled with a molecular network analysis strategy was used to identify the chemical constituents of the stem bark of two kinds of asparagus. The chemical constituents were identified by determining an accurate molecular weight, the fragmentation pathway, and comparison with the mass spectrometry data from the references. A molecular network was established based on the similarity of MS/MS fragmentation patterns. A total of 107 compounds were identified or tentatively deduced, which included 46 saponins, 13 flavonoids, and 48 other compounds. The chemical compounds identified in the stem bark of white and green asparagus differed greatly: the white asparagus was rich in saponins, while the green asparagus was rich in flavonoids. In conclusion, the chemical constituents of asparagus stem bark were characterized rapidly using UPLC-Q-TOF-MS/MS and molecular network analysis, with 10 compounds and 45 targets determined from the HIT 2.0 herbal ingredients' targets platform. This work will provide a theoretical basis for the resource utilization of asparagus.

Key words

asparagus stem bark / chemical constituent / qualitative analysis / UPLC-Q-TOF-MS/MS / molecular network

引用本文

卫瑞, 杨琳娇, 秦雪梅, 李震宇. 基于UPLC-Q-TOF-MS/MS和分子网络技术快速鉴定芦笋茎皮中的化学成分. 药学学报, 2022 , 57 (9) : 2839 -2850 . DOI: 10.16438/j.0513-4870.2022-0652

Rui WEI, Lin-jiao YANG, Xue-mei QIN, Zhen-yu LI. Rapid identification of chemical constituents in the dried stem bark of Asparagus officinalis L. based on UPLC-Q-TOF-MS/MS[J]. Acta Pharmaceutica Sinica, 2022 , 57 (9) : 2839 -2850 . DOI: 10.16438/j.0513-4870.2022-0652

正文

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芦笋(Asparagus officinalis L.), 天门冬科天门冬属植物, 又名石刁柏, 有益气、化热、清痰、润肺、利尿等功效^[1]。芦笋以嫩茎作为蔬菜食用, 最为常见的有白笋和绿笋, 未出土的呈白色称为白笋, 出土后照到阳光芦笋就会呈现出绿色, 称之为绿笋^[2]。研究表明, 芦笋中富含多种生物活性成分, 主要包括皂苷类化合物、黄酮类化合物和多糖类化合物。此外, 芦笋中还含有氨基酸、脂肪酸、维生素和微量元素等^[2]。芦笋中这些化学成分具有抗肿瘤、免疫调节、调节血脂、抗衰老、抗疲劳等方面的生物功能^{[2, 3]}, 已有文献^{[4, 5]}报道芦笋老茎中的提取物对乳腺癌细胞具有明显的抑制作用, 芦笋有抑制小鼠原发性乳腺癌肿瘤生长的作用^[6]。芦笋除了供新鲜食用外, 主要用于加工罐头和速冻食品, 而在加工过程中, 会产生大量的老茎和芦笋皮等废弃物, 收获芦笋后也有大量的老茎无法利用^[7]。研究表明, 芦笋茎皮废弃物中含有丰富的皂苷类、黄酮类成分等^{[7, 8]}, 已有研究从芦笋茎皮中制备得到总黄酮或总皂苷^[8-10]。对白笋和绿笋茎皮所含的化学成分进行系统的化学分析, 可以更精准地对其进行资源开发和合理利用。

UPLC-Q-TOF-MS/MS高分辨质谱具有高分辨、高分离度、高灵敏度的特点, 通过分析化合物的相对分子质量、裂解碎片等信息, 可快速识别中药复杂体系中各类化学成分, 如铁皮石斛^[11]、山楂叶^[12]、五味子藤茎^[13]、龙葵^[14]等。Global Natural Products Social Molecular Networking (GNPS) 是由Watrous等创建的分子网络数据库(http://gnps.ucsd.edu), 根据相关化合物的MS/MS二级质谱碎片的相似性, 同一类化合物分子会在一个分子网络中聚集成簇并进行可视化定性分析^{[15, 16]}。近年来研究表明, 该技术的应用能够加速对天然药物中未知化合物的指认。如Huang等^[17]基于GNPS分子网络方法鉴定了夏天无的异喹啉类生物碱成分52个, 其中包括21个潜在的新化合物; Zhao等^[18]基于GNPS质谱分子网络策略, 从岷江瑞香中靶向分离获得3个结构新颖的愈创木烷衍生物。

HIT 2.0中草药成分靶点数据库(http://hit2.badd-cao.net) 涵盖了2000~2020年之间PubMed数据库(https://pubmed.ncbi.nlm.nih.gov/) 中已发表文献中所有通过实验验证的中药成分-靶点关系, 以及化合物对靶点的调节趋势。目前该数据库收录1 250种草药的1 237个化合物, 2 208个靶点, 以及10 031个化合物-靶点作用关系^[19]。此外, HIT 2.0还支持从PubMed数据库中最新发布的文献中进行手动靶点检索, 为中药活性成分作用靶点的确定提供了有力的支持。

本研究拟采用UPLC-Q-TOF-MS/MS和GNPS分子网路技术对白笋、绿笋茎皮中的化学成分进行快速分析和鉴定, 并利用HIT 2.0中草药成分靶点数据库分析芦笋茎皮中的化学成分对乳腺癌的作用靶点, 为芦笋茎皮的资源合理利用奠定基础。

材料与方法

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仪器 Agilent 1290超高效液相色谱仪(美国Agilent Technologies公司); QTOF 5600+四极杆飞行时间质谱仪(美国AB SCIEX公司); KQ5200E超声波清洗器(昆山市超声仪器有限公司)。

试剂与样品 白笋、绿笋茎皮购买于山西省永济市耀辉绿色芦笋种植专业合作社, 样品经山西大学中医药现代研究中心秦雪梅教授鉴定为天门冬科天门冬属植物芦笋(Asparagus officinalis L.) 的茎皮, 留样保存于山西大学中医药现代研究中心; 甲醇(分析级, 天津市大茂化学试剂厂), 甲酸、乙腈(质谱级, 美国Thermo公司), 超纯水由Milli-Q纯净水系统(美国Millipore公司) 制备。

供试品溶液的制备 取干燥的白笋、绿笋茎皮粉末各5 g, 分别置于具塞锥形瓶中, 加入50%甲醇溶液50 mL, 超声提取30 min, 放冷, 过0.22 μm微孔滤膜, 取续滤液, 待用。

对照品溶液的制备 取对照品山柰酚、槲皮素、异鼠李素、芦丁各2 mg, 用2 mL甲醇溶解, 得到各对照品储备液。各取200 µL混匀, 用50%甲醇溶液定容至5 mL, 即得混合对照品溶液。

色谱条件 色谱柱: Waters Acquity UPLC HSS T3 column (100 mm × 2.1 mm, 1.8 µm); 流动相: 0.1%甲酸水(A)-乙腈(B), 梯度洗脱: 0~10 min, 2%~15% B; 10~20 min, 15%~25% B; 20~25 min, 25%~40% B; 25~30 min, 40%~80% B; 30~32 min, 80%~95% B; 32~35 min, 95%~95% B; 35~39 min, 95%~2% B; 柱温40 ℃; 流速0.3 mL·min^-1; 进样体积5 μL。

质谱条件 电喷雾离子源(ESI), 采用正负离子模式分别扫描, 离子源参数如下: 喷雾电压-4 500 V (负离子), 5 500 V (正离子), 离子源温度450 ℃, 喷雾气(Gas 1) 55 psi, 加热气(Gas 2) 55 psi, 气帘气(CUR) 30 psi, 去簇电压(DP) 60 V, 二级碰撞能量(CE) 为40 eV, CEs为20 eV。TOF MS一级扫描范围为m/z 100~1 500, Production scan二级扫描范围为m/z 50~1 250。

自建数据库的建立与SCIEX中药数据库的使用 查阅芦笋的相关文献, 整理并建立芦笋中皂苷类和黄酮类化合物信息数据库, 包括化合物名称、分子式、精确相对分子质量等信息。采用SCIEX OS 2.0软件进行峰提取、峰匹配分析处理, 在满足质量偏差≤ 5, 同位素丰度比≤ 5的基础上, 与文献中化合物的准分子离子峰、碎片裂解规律进行比对分析, 最终鉴定化合物的结构。此外, 采用SCIEX中药数据库进一步鉴定, 通过SCIEX OS 2.0软件进行峰提取、峰匹配, 在满足质量误差≤ 5, 同位素丰度比≤ 5, 数据库匹配得分≥ 85的基础上, 比对化合物的二级碎片, 对白笋、绿笋茎皮中的其他类成分进行快速鉴定。

GNPS分子网络的建立 正离子模式下白笋、绿笋茎皮样品的UPLC-Q-TOF MS/MS质谱数据文件, 先通过MS Convert软件转换为mzML文件格式, 登录WinSCP软件将mzML格式的文件上传至GNPS, 建立GNPS网络; Precursor Ion Mass Tolerance和Fragment Ion Mass Tolerance的质量误差设置为0.02 Da, 余弦分数阈值设置为0.7, 最小匹配碎片离子为6, 其余参数均选择默认值; 运用Cytoscape软件使分析结果可视化。在生成的GNPS分子网络中, 皂苷类成分能够很好地被聚集, 且皂苷类成分的质谱裂解存在一定的规律, 为了进一步发现芦笋中的微量皂苷类成分, 本研究继续采用基于MS/MS关联的分子网络分析芦笋茎皮中的皂苷成分。

芦笋茎皮成分作用靶点和相关疾病靶点的收集 在HIT 2.0数据库检索化合物Name、PubChem CID或CAS号并收集化合物靶点, 对于HIT 2.0数据库未收录的成分, 在PubMed数据库进行手动靶点检索, 整理化合物调节趋势, 将得到的化合物靶点去重复后构建芦笋茎皮作用靶点库。为了更加全面地找到与乳腺癌相关(基因) 靶点, 在DisGeNET数据库(http://www.disgenet.org/) 和GeneCards数据库(http://www.genecards.org/) 中分别以“Breast cancer”和“Inflammation”作为关键词进行检索, 得到与乳腺癌相关的靶点, 两个数据库筛选得到的靶点去重复后, 构建疾病靶点库。

结果

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1 芦笋茎皮中化学成分的定性分析

通过UPLC-Q-TOF-MS/MS高分辨质谱在正、负离子模式下分别采集芦笋茎皮样品的质谱数据, 代表性色谱图见图 1。采用SCIEX OS 2.0软件和分子网络进行分析, 共鉴定出107个化合物(表 1^[20-32]), 包括皂苷类46个、黄酮类13个、有机酸类16个、氨基酸类10个、

糖类4个和其他类化合物18个。其中通过GNPS网络解析得到首次在芦笋中发现的皂苷类成分23个。

1.1 采用UPLC-Q-TOF-MS/MS表征芦笋茎皮中的皂苷类成分

皂苷是芦笋中的活性成分之一, 芦笋皂苷多为螺甾皂苷。化合物9准分子离子峰为m/z 903.493 9 [M+H]⁺, 依次失去Hex后可产生碎片离子m/z 741.440 6 [M+H-Hex]⁺、m/z 579.386 9 [M+H-2Hex]⁺和m/z 417.335 6 [M+H-3Hex]⁺, 与文献^[20]报道的质谱数据一致, 因此推断化合物9为shatavarin Ⅸ。化合物14准分子离子峰为m/z 1 031.538 3 [M+H]⁺, 相继失去Hex、两分子Rha和一分子Hex, 产生二级碎片m/z 869.484 9 [M+H-Hex]⁺、m/z 577.371 6 [M+H-Hex-2Rha]⁺、m/z 415.318 5 [M+H-2Hex-2Rha]⁺, 与文献^[23]报道的质谱数据一致, 推断该化合物为Pseudoprotoneodioscin。

通过文献比对和质谱裂解规律的分析, 鉴定出皂苷类化合物23个, 其中包括以菝葜皂苷元为苷元的甾体皂苷13个, 以雅姆皂苷元为苷元的甾体皂苷3个, 以及其他类型皂苷化合物7个, 包括原薯蓣皂苷^[21]、伪原薯蓣皂苷^[23]、豆甾醇^[22]和25S-spirosta-1, 4-dien-3-one^[22]等。

芦笋皂苷类化合物具有如下质谱裂解规律(表 2): 通常先失去糖基等中性分子, 如Hex (m/z 162.05)、Rha (m/z 146.05)、Xyl (m/z 132.05) 生成母核离子, 即相应的皂苷元。在正离子模式下, 以菝葜皂苷元为苷元的芦笋皂苷脱去糖基后会产生m/z 417.335 8 [M+H]⁺, 进一步失去H₂O分子产生碎片m/z 399.325 1 [M+H-H₂O]⁺, 随后失去侧链C₈H₁₆O₂得到特征碎片m/z 255.210 9 [M+H-H₂O-C₈H₁₆O₂]⁺, 或直接失去侧链C₈H₁₆O₂得到特征碎片m/z 273.221 7 [M+H-C₈H₁₆O₂]⁺。雅姆皂苷元仅比菝葜皂苷元多了C-5, C-6位的不饱和双键, 因此雅姆皂苷元与菝葜皂苷元有相似的裂解规律。正离子模式下, 以雅姆皂苷元为苷元的皂苷在脱去糖基后产生m/z 415.320 1 [M+H]⁺, 然后依次失去H₂O、C₈H₁₆O₂得到碎片m/z 397.313 1 [M+H-H₂O]⁺、m/z 253.195 1 [M+H-H₂O-C₈H₁₆O₂]⁺, 或直接失去C₈H₁₆O₂得到特征碎片m/z 271.205 3 [M+H-C₈H₁₆O₂]⁺。

1.2 GNPS分子网络对皂苷类成分进行分析

正离子模式下的分子网络中共包括分子式92个, 其中通过文献数据鉴定的皂苷类化合物21个, 以及根据已知化合物和未知化合物在网络中的相关性和准分子离子质荷比差值, 进一步共推测皂苷类化合物23个。如化合物5在分子网络中的准分子离子为m/z 1 035.533 3 (图 2a), 与已鉴定的化合物9 (m/z 903.493 9) 分子质量相差132.045 0, 对应于一分子木糖(C₅H₈O₄), 故推测化合物5的分子式为C₅₀H₈₂O₂₂, 通过其精确分子质量m/z 1 035.533 3 (质量误差为-0.9 ppm), 以及两者共有的质谱碎片m/z 741.440 6、m/z 579.386 9和m/z 417.335 6, 推断化合物5比shatavarin Ⅸ多一分子木糖, 进一步通过Scifinder数据库(https://scifinder-n.cas.org/) 检索, 推测化合物5可能为Dongnoside E。化合物18在分子网络中的准分子离子为m/z 885.483 2 (图 2b), 与化合物14 (m/z 1 031.538 3) 的分子质量差146.059 0, 差值对应于一分子鼠李糖(C₆H₁₀O₄), 因此推测化合物18的分子式为C₄₅H₇₂O₁₇, 与其精确分子质量m/z 885.483 2 (质量误差为-0.8 ppm) 对应。此外, 其质谱碎片m/z 577.374 3、m/z 415.320 8、m/z 271.205 6和m/z 253.194 9与化合物14一致, 推测化合物18在化合物14的基础上失去一分子鼠李糖, 进一步通过Scifinder数据库检索, 推测化合物18为纤细薯蓣皂苷。

通过分子网络结合精确分子质量和质谱裂解规律, 推测出以菝葜皂苷元为苷元的甾体皂苷类化合物3个, 以雅姆皂苷元为苷元的甾体皂苷类化合物10个, 以豆甾醇为皂苷元的皂苷类化合物4个, 以β-谷甾醇为皂苷元的皂苷类化合物3个, 其他类型的甾体皂苷化合物3个。如图 2所示, 粉色表示白笋茎皮, 蓝色表示绿笋茎皮, 红色外圈的节点表示已鉴定的21个皂苷类化合物, 灰色外圈节点表示由GNPS推测得到的23个皂苷类化合物, 靓蓝色外圈节点的39个化合物可能是皂苷类化合物, 但未推测出可能的结构式。

1.3 黄酮类

除了皂苷, 芦笋中还富含黄酮类成分。在正离子模式下, 化合物47的准分子离子峰为m/z 757.216 8 [M+H]⁺, 失去一分子葡萄糖得到m/z 595.160 0 [M+H-Glc]⁺, 随后失去一分子芸香糖苷得到m/z 287.055 0 [M+H-Glc-rutinoside]⁺, 参照文献^[22]报道的质谱数据, 鉴定该化合物为山柰酚-3-O-芸香糖苷-7-O-葡萄糖苷。通过质谱分析和文献比对, 两种芦笋中共鉴定出13个黄酮类化合物, 包括以异鼠李素为苷元的黄酮醇苷4个、以槲皮素为苷元的黄酮醇苷4个、以山柰酚为苷元的黄酮醇苷3个, 以及黄酮类化合物2个(金圣草黄素-7-O-β-D-葡萄糖基和香叶木素^[7])。异鼠李素、槲皮素和山柰酚为苷元的黄酮醇类化合物在裂解时存在一定的规律, 一般会在C环上发生RDA裂解, 产生特征碎片m/z 165.02。除了共性的特征碎片, 3种黄酮醇苷元还有不同的碎片离子(表 2), 有助于苷元类型的判断。

1.4 其他类

除了皂苷类和黄酮类, 芦笋茎皮中鉴定的化合物还有有机酸类、糖类和氨基酸类等。16个有机酸类化合物包括绿原酸、阿魏酸、原儿茶酸和丁二酸等, 4个糖类化合物包括蔗糖、蔗果三糖和耐斯糖等, 10个氨基酸类化合物包括L-缬氨酸、亮氨酸、苯丙氨酸、L-天门冬氨酸和色氨酸等, 还包括维生素B2、腺嘌呤等18个其他类化合物。

1.5 绿笋茎皮和白笋茎皮定性化合物的比较

本研究共鉴定皂苷类成分46个, 其中白笋中检测到43个, 绿笋中检测到36个, 两者共有的皂苷33个(图 3)。此外, 从皂苷类成分分子网络(图 2) 中也能看出, 白笋茎皮的节点(粉色) 比绿笋茎皮的节点(蓝色) 多20个。对于13个黄酮类成分, 白笋中检测到4个, 绿笋中检测到13个, 两者共有的黄酮类成分4个(图 3)。对于糖类、有机酸类和氨基酸类等其他类型的成分, 在白笋和绿笋茎皮中均能检测到, 说明两者的这些成分种类差异较小。上述比较结果说明, 白笋茎皮中富含皂苷类成分, 而绿笋茎皮中富含黄酮类成分。

2 成分-调节趋势-靶点网络图分析

基于表 1中鉴定的化合物, 在HIT 2.0数据库中检索化合物靶点, 得到6个化合物的58个靶点; 对于HIT 2.0数据库未收录的化合物, 在PubMed数据库进行手动靶点检索, 得到4个化合物共41个靶点。文献^[6]报道芦笋提取物对小鼠原发性乳腺癌模型具有抑制作用, 因此以“Breast cancer”、“Inflammation”为关键词在DisGeNET及GeneCards数据库进行检索, 收集疾病靶点并进行去重复处理, 并以“score ≥ 0.3”或“Relevance score ≥ 30”为标准对疾病靶点进一步筛选, 共得到1 408个与乳腺癌相关的靶点, 将其与上述99个成分靶点进行比对, 共得到45个作用靶点。通过Cytoscape软件构建成分-靶点网络图, 如图 4所示, 橙黄色六边形代表化合物, 绿色椭圆形代表靶点。由图 4可知, 皂苷类化合物如菝葜皂苷元可直接抑制NLRP3蛋白的活性, 间接上调IL-10的靶点, 间接抑制TNF-α、IL-6和IL-1α三种靶点的活性^{[33, 34]}; 薯蓣皂苷可直接上调AHR、NR1H4蛋白的活性, 直接抑制NLRP3蛋白的活性, 间接上调GJA1、TNFRSF11B靶点的活性, 间接抑制AKT1蛋白的活性, 下调CTNNB1、ESR2、HOTAIR、MITF和STAT3五种基因发挥药效^[35-41]; 黄酮类化合物如异鼠李素可直接抑制PPARG、PTGS2蛋白的活性, 间接抑制NOS2、XDH和MAP2K1三种蛋白的活性^[42-44]; 芦丁可直接上调SIRT1、NR1H4蛋白的活性, 直接抑制PROCP、MPO、MTOR蛋白的活性, 间接上调CASP3蛋白的活性, 间接抑制Cat、TNF-α、IL-6和IL-1β四种靶点的活性, 下调TGFB1、ACTA2、FN1、BCL2基因发挥药效^[45-48]。

讨论

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本研究采用了高分辨液质联用和分子网络技术对白笋、绿笋茎皮中的化学成分进行分析, 共鉴定出或推断107个化合物, 包括皂苷类46个、黄酮类13个、有机酸类16个、氨基酸类10个、糖类4个和其他类成分18个。已有的芦笋化学成分研究主要采用植物化学方法, 在基于高分辨质谱的化学成分快速鉴定方面, Jiménez-Sánchez等^[29]从西班牙的芦笋中鉴定33个成分, 主要是酚酸类和黄酮类。本研究基于甾体皂苷的质谱和特征和GNPS分子网络, 除了鉴定到文献中已报道的23个甾体类成分, 而且推测出微量甾体皂苷类成分23个。GNPS分子网络已收录了22 644个化合物和235 850个谱图, 具有鉴定已知化合物的功能, 除此之外, 分子网络技术对于不同平台的质谱仪器产生的质谱数据具有兼容性, 可直观地观测到样品中的化合物分子离子, 利用二级质谱碎片的相似性, 可将同类别的化合物整合为一个可视化的网络图谱^[16], 能够加速促进未知化合物的指认。

此外, 本研究利用HIT 2.0中草药成分靶点数据库结合文献^[33-48]报道确定了芦笋茎皮中的10个皂苷和黄酮类成分对乳腺癌的45个作用靶点。HIT 2.0数据库不仅能给出化合物的作用靶点, 而且还能给出化合物对靶点的调节趋势, 包括直接上调蛋白、直接抑制蛋白、间接上调蛋白、间接抑制蛋白、上调或下调基因等, 与Swiss Target Prediction、BATMAN-TCM等网络药理数据库相比, HIT 2.0数据库中的靶点全部经过实验验证, 为芦笋茎皮活性成分真实靶点的获取提供了强有力的支持。

芦笋是一种兼药用和食用于一体的蔬菜, 除食用部位外, 芦笋皮和老茎等占芦笋原料的30%左右, 已有研究虽然考察了废弃的茎皮部位中总皂苷和总黄酮的提取工艺, 但所含的具体化学成分和结构并不完全清楚^{[9, 49]}。本研究基于高分辨质谱解析技术表明芦笋茎皮含有丰富的皂苷类成分和黄酮类成分, 具有较大的资源利用价值, 白笋茎皮和绿笋茎皮在黄酮类和皂苷类成分上的化学差异也为芦笋茎皮的精准开发利用奠定了理论基础。

作者贡献: 卫瑞、杨琳娇负责实验研究工作及数据分析处理, 并撰写稿件; 秦雪梅参与芦笋茎皮样品品种的鉴定; 李震宇对整个研究工作进行设计、监督和指导, 以及对稿件的修改。

利益冲突: 本文的研究无任何利益冲突。

基金

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山西省科技成果转化引导专项项目(201904D131027)

参考文献

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文献

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2022年第57卷第9期

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doi: 10.16438/j.0513-4870.2022-0652

接收时间：2022-05-26
首发时间：2025-12-24
出版时间：2022-09-12

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收稿日期：2022-05-26
修回日期：2022-07-19

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山西省科技成果转化引导专项项目(201904D131027)

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山西大学化学生物学与分子工程教育部重点实验室, 中医药现代研究中心, 山西太原 030006

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*李震宇, Tel: 86-351-7011202, 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	Molecular formula	[M+H]⁺/[M-H]^-	Mass	Error /ppm	Fragment ion	W	G	Source
1	21.86	β-Sitosterol-3-O-β-D-glucuronoside+2Rha+Glc	C₅₁H₈₀O₂₂	[M+H]⁺	1 045.521 0	0.2	883.466 6, 737.408 4, 591.352 6	+	+	c
2	21.92	Stigmasterol glucoside+2Rha	C₄₅H₇₀O₁₆	[M+H]⁺	867.472 0	-0.3	849.461 8, 721.410 5, 705.417 6, 575.356 5, 559.356 9, 413.304 0	+	-	c
3	22.10	Gracillin+Glc	C₅₁H₈₂O₂₂	[M+H]⁺	1 047.533 0	0.0	885.483 5, 723.354 9, 577.299 3, 415.251 9, 271.205 3, 253.195 0	+	+	c
4	22.24	β-Sitosterol-3-O-β-D-glucuronoside+Rha+Glc	C₄₅H₇₀O₁₈	[M+H]⁺	899.463 0	0.0	737.408 6, 593.294 3, 591.350 7	+	+	c
5	22.36	Dongnoside E	C₅₀H₈₂O₂₂	[M+H]⁺	1 035.533 0	-0.9	903.483 1, 873.484 3, 741.443 1, 579.387 9, 417.336 0, 273.221 1	+	+	c
6	22.37	Pamaqueside / agavoside B	C₃₉H₆₂O₁₄	[M+H]⁺	755.420 0	-1.4	737.405 6, 593.368 7, 431.243 2, 413.311 5, 395.294 0	+	+	c
7	22.43	Pseudoprotoneodioscin+Glc	C₅₇H₉₂O₂₆	[M+H]⁺	1 193.596 0	-0.5	1 031.538 3, 869.486 1, 723.427 7, 577.373 0, 415.320 1, 253.194 1	+	+	c
8	22.57	Aspidistrin	C₅₀H₈₀O₂₂	[M+H]⁺	1 033.521 0	-0.6	871.470 1, 739.430 7, 577.373 5, 415.320 9, 397.310 2, 271.205 6	+	+	c
9	22.71	Shatavarin Ⅸ	C₄₅H₇₄O₁₈	[M+H]⁺	903.495 0	-0.5	741.440 6, 597.325 8, 579.386 9, 417.335 6, 285.257 5, 273.221 6, 255.210 5	+	+	a^[20]
10	22.82	Protodioscin	C₅₁H₈₄O₂₂	[M+H]⁺	1 049.553 0	-0.3	887.498 1, 741.438 8, 725.371 0, 433.330 1, 415.322 2	+	+	a^[21]
11	22.96	(25S)-26-O-β-D-Glucopyranosyl-5β-furost-20(22)-ene-3β, 26-diol-3-O-β-D-glucopyranosyl-(1→2)-β-D-glucopyranoside	C₄₅H₇₂O₁₈	[M+H]⁺	901.478 0	-1.3	739.425 9, 577.372 0, 433.258 1, 415.320 0, 283.242 6, 271.205 9, 253.195 1	+	+	a^[22]
12	23.25	Compound 7 (isomer)	C₅₇H₉₂O₂₆	[M+H]⁺	1 193.596 0	-0.7	1 031.545 1, 869.489 4, 723.431 3, 577.371 2, 415.319 9, 253.192 6	+	+	c
13	23.27	Stigmasterol glucoside+Hex+2Rha	C₅₁H₈₀O₂₁	[M+H]⁺	1 029.526 0	-1.9	867.469 4, 721.413 5, 575.358 1, 413.303 1, 395.291 5	-	+	c
14	23.42	Pseudoprotoneodioscin	C₅₁H₈₂O₂₁	[M+H]⁺	1 031.542 0	-0.9	869.484 9, 577.371 6, 415.318 5, 271.204 6, 253.194 1	+	+	a^[23]
15	23.50	Polyphyllin D+Glc/parisyunnanoside B	C₅₀H₈₀O₂₁	[M+H]⁺	1 017.525 0	-0.6	855.471 7, 709.414 3, 577.372 6, 415.319 6, 271.205 1, 253.194 6	+	+	c
16	23.53	Asparanin B5	C₅₀H₈₂O₂₁	[M+H]⁺	1 019.542 0	-6.8	857.480 6, 713.365 0, 579.386 9, 417.333 5, 273.221 7, 255.209 3	-	+	c
17	23.71	Yamogenin glucoside+Glc+xyl	C₄₄H₇₀O₁₇	[M+H]⁺	871.468 0	-0.7	709.415 1, 577.372 6, 415.320 7, 271.206 0, 253.194 8	+	+	c
18	23.73	Gracillin	C₄₅H₇₂O₁₇	[M+H]⁺	885.484 0	-0.8	723.430 3, 577.374 3, 415.320 8, 271.205 6, 253.194 9	+	+	c
19	23.85	Polyphyllin VI	C₃₉H₆₂O₁₃	[M+H]⁺	739.426 0	-0.9	577.373 2, 433.258 7, 415.318 2, 397.311 2, 271.205 6, 253.195 2	+	+	c
20	23.99	Aspacochioside D/asparinin B	C₄₅H₇₄O₁₇	[M+H]⁺	887.498 0	-2.3	741.441 7, 579.387 9, 417.336 7, 273.222 0, 255.211 1	+	+	a^{[23, 24]}
21	24.01	(25S)-5β-Spirostan-3β-yl-O-[O-α-L-rhamnopyranosyl-(1-4)]-β-D-glucopyranoside	C₃₉H₆₄O₁₂	[M+H]⁺	725.447 0	0.0	581.330 2, 563.392 4, 417.333 4, 273.220 6, 255.210 1	+	+	a^[23]
22	24.02	(25S)-5β-Spirostan-3β-ol-3-O-β-D-glucopyranosyl-(1→2)-[β-D-xylopyranosyl-(1→4)]-β-D-glucopyranoside	C₄₄H₇₂O₁₇	[M+H]⁺	873.484 0	-1.4	711.426 9, 579.389 1, 435.273 6, 417.335 8, 285.258 6, 273.219 9, 255.210 0	+	-	a^[22]
23	24.06	Dioscin+2Rha	C₅₆H₈₈O₂₅	[M+H]⁺	1 161.565 0	0.3	1 015.503 7, 723.430 4, 577.371 8, 415.319 3, 397.308 4, 253.195 2	+	+	c
24	24.34	Dioscin+Rha	C₅₀H₇₈O₂₁	[M+H]⁺	1 015.543 0	-0.1	869.485 8, 577.373 4, 415.319 7, 379.312 6, 253.195 9	+	+	c
25	24.58	Asparagoside A	C₃₃H₅₄O₈	[M+H]⁺	579.389 0	-1.5	417.335 2, 285.257 0, 273.221 3, 255.211 5	+	+	a^[22]
26	24.60	β-Sitosterol-3-O-β-D-glucuronoside+Glc	C₄₀H₆₄O₁₃	[M+H]⁺	753.442 0	-3.1	591.384 1, 271.206 8, 253.195 2	-	+	c
27	25.10	Stigmasterol glucoside	C₃₃H₅₀O₈	[M+H]⁺	575.358 0	-0.7	557.344 8, 413.301 5, 377.279 9	+	+	c
28	25.44	Compound 9 (isomer)	C₄₅H₇₄O₁₈	[M+H]⁺	903.495 0	0.5	741.442 2, 597.321 0, 579.388 7, 417.336 9, 285.260 6, 273.221 2, 255.211 9	+	-	a^[20]
29	25.88	Stigmasterol glucoside+Rha	C₃₉H₆₀O₁₂	[M+H]⁺	721.415 0	0.7	575.360 4, 541.348 6, 413.306 0	+	+	c
30	25.89	Compound 14 (isomer)	C₅₁H₈₂O₂₁	[M+H]⁺	1 031.542 0	0.2	869.489 0, 723.432 5, 577.373 0, 415.321 0, 271.205 3, 253.195 8	+	+	a^[23]
31	26.09	Compound 22 (isomer)	C₄₄H₇₂O₁₇	[M+H]⁺	873.484 0	-1.4	711.426 9, 579.389 1, 435.273 6, 417.335 8, 285.258 6, 273.219 9, 255.210 0	+	-	a^[22]
32	26.09	Sarsasapogenin+H₂O	C₂₇H₄₆O₄	[M+H]⁺	435.347 0	-0.7	417.337 9, 399.320 9, 303.228 7, 277.218 9	+	+	c
33	26.32	Compound 20 (isomer)	C₄₅H₇₄O₁₇	[M+H]⁺	887.500 0	-1.6	725.443 2, 579.387 9, 417.333 9, 273.220 9, 255.210 7	+	-	a^{[23, 24]}
34	26.66	Sarsasapogenin	C₂₇H₄₄O₃	[M+H]⁺	417.336 0	-1.0	399.328 2, 273.221 7, 255.210 9, 199.148 7	+	+	a^[22]
35	28.04	Sarsasapogenin M	C₃₉H₆₄O₁₄	[M+H]⁺	757.437 0	-0.8	595.306 0, 577.297 7, 415.247 8, 397.242 0	+	+	a^[22]
36	28.39	Yamogenin+H₂O	C₂₇H₄₄O₄	[M+H]⁺	433.331 0	-2.2	415.268 7, 397.314 2, 279.231 0, 253.191 0, 147.117 4	+	-	c
37	28.82	Filiasparoside D	C₃₈H₆₂O₁₂	[M+H]⁺	711.431 0	0.3	579.385 3, 567.317 4, 417.335 1, 399.325 0, 285.255 4, 273.220 9, 255.210 9	+	+	a^[25]
38	28.95	Dioscin	C₄₅H₇₂O₁₆	[M+H]⁺	869.489 0	0.0	723.430 8, 577.371 1, 415.320 4, 397.309 6, 271.206 4, 253.196 0	+	+	a^[26]
39	29.22	Asparanin A/ (25S)-5β-spirostan-3β-ol-3-O-β-D-glucopyranosyl-(1→2)-β-D-glucopyranoside	C₃₉H₆₄O₁₃	[M+H]⁺	741.442 0	-0.1	579.387 5, 435.273 5, 417.335 8, 285.258 3, 273.221 2, 255.210 1	+	+	a^{[22, 27]}
40	29.42	Prosapogenin A/ polyphyllin C	C₃₉H₆₂O₁₂	[M+H]⁺	723.431 0	-0.4	577.370 0, 415.319 4, 271.205 5, 253.195 1, 157.100 5, 85.027 8	+	+	b
41	29.46	Polyphyllin D	C₄₄H₇₀O₁₆	[M+H]⁺	855.473 0	0.2	711.360 1, 709.408 7, 577.369 0, 415.318 8, 271.205 4, 253.194 4	+	+	c
42	29.71	(25S)-5β-Spirostan-3β-ol-3-O-α-L-rhamnopyranosyl-(1, 2)-[α-L-rhamnopyranosyl-(1, 4)]-β-D-glucopyranoside	C₄₅H₇₄O₁₆	[M+H]⁺	871.505 0	-1.1	579.391 0, 417.337 2, 293.123 6, 273.221 9, 255.210 6	+	-	a^[22]
43	29.75	Filiasparoside C	C₄₄H₇₂O₁₆	[M+H]⁺	857.489 0	-0.5	725.448 0, 579.387 7, 417.335 1, 273.220 9, 255.210 7	+	-	a^[25]
44	30.37	Yamogenin	C₂₇H₄₂O₃	[M+H]⁺	415.321 0	-0.8	397.313 1, 271.205 3, 253.195 1, 147.116 4	+	+	b
45	32.83	Stigmasterol	C₂₉H₄₈O	[M+H]⁺	413.378 0	-2.0	395.366 3, 315.225 4, 271.203 8, 173.130 8	+	-	a^[22]
46	35.40	25S-Spirosta-1, 4-dien-3-one	C₂₇H₃₈O₃	[M+H]⁺	411.289 0	0.0	393.277 1, 267.174 4, 239.179 3	+	-	a^[22]
47	9.52	Kaempferol-3-O-rutinoside-7-O-glucoside	C₃₃H₄₀O₂₀	[M+H]⁺	757.219 0	-0.2	595.160 0, 449.106 3, 287.055 0	-	+	a^[28]
48	9.61	Quercetin diglucoside	C₂₇H₃₀O₁₇	[M+H]⁺	627.155 0	-0.4	609.253 7, 465.103 6, 303.050 1, 257.044 0, 165.014 8, 85.028 6	-	+	a^[29]
49	10.84	Isorhamnetin-3-rhamnosyl-rutinoside	C₃₄H₄₂O₂₀	[M+H]⁺	771.234 0	-1.3	609.172 0, 463.120 8, 317.065 0	-	+	a^[7]
50	11.21	Isorhamnetion-3-O-rutinoside-7-O-glucoside	C₃₄H₄₂O₂₁	[M+H]⁺	787.229 0	-1.7	641.170 2, 625.176 3, 479.118 2, 317.065 0	-	+	a^[28]
51	13.43	Quercitin-3-O-glucosylrutinoside	C₃₃H₄₀O₂₁	[M+H]⁺	773.213 0	-0.7	611.153 2, 465.102 1, 303.049 3, 129.052 1, 85.027 3	+	+	b
52	14.31	Rutin	C₂₇H₃₀O₁₆	[M+H]⁺	611.161 0	-0.5	465.101 9, 303.050 2, 285.040 6, 257.044 0, 229.049 7	+	+	d, a^[28]
53	14.33	Isoquercetin	C₂₁H₂₀O₁₂	[M+H]⁺	465.103 0	0.3	303.049 6, 285.038 3, 257.047 9, 165.018 2, 153.018 4	+	+	a^[28]
54	15.09	Astragalin	C₂₁H₂₀O₁₁	[M+H]⁺	449.108 0	-1.0	287.054 9, 213.056 0, 165.018 5, 153.018 8	-	+	a^[28]
55	15.62	Narcissoside	C₂₈H₃₂O₁₆	[M+H]⁺	625.176 0	0.1	479.116 1, 317.065 4, 285.033 5, 147.069 0, 129.054 3, 85.028 8	+	+	b
56	16.22	Kaempferol-3-O-rutinoside	C₂₇H₃₀O₁₅	[M+H]⁺	595.166 0	-0.2	449.107 0, 287.055 0, 269.047 5, 213.054 4, 165.017 1	-	+	a^[28]
57	16.76	Isorhamnetin	C₁₆H₁₂O₇	[M+H]⁺	317.066 0	0.1	302.048 0, 274.047 9, 165.018 8, 153.018 0	-	+	d, a^[7]
58	18.07	Chrysoeriol-7-O-β-D-glucoside	C₂₂H₂₂O₁₁	[M+H]⁺	463.123 0	-1.0	301.071 1, 286.047 3, 153.016 2	-	+	b
59	24.97	Diosmetin	C₁₆H₁₂O₆	[M+H]⁺	301.071 0	-0.4	286.046 2, 258.050 8	-	+	a^[7]
60	0.86	Aspartic acid	C₄H₇NO₄	[M-H]^-	132.031 0	-0.2	115.008 9, 71.014 9	+	+	b
61	0.88	L-Arginine	C₆H₁₄N₄O₂	[M+H]⁺	175.119 0	1.7	158.091 7, 116.070 4, 112.085 9, 70.064 9	+	-	b
62	0.91	L-Glutamic acid	C₅H₉NO₄	[M+H]⁺	148.060 0	0.1	130.049 6, 102.054 2, 85.028 6, 84.043 9, 56.049 3	+	-	b
63	0.99	Proline	C₅H₉NO₂	[M+H]⁺	116.070 0	-4.5	70.065 1, 53.039 0	+	+	b
64	1.07	L-Valine	C₅H₁₁NO₂	[M+H]⁺	118.086 0	-1.1	73.085 0, 72.080 9, 59.049 0, 57.057 1, 56.049 5, 55.054 1, 53.038 5	-	+	b
65	1.81	Nicotinic acid	C₆H₅NO₂	[M+H]⁺	124.039 0	-3.8	106.028 4, 80.048 8, 78.033 5, 53.038 2, 52.018 2	+	+	b
66	2.48	Isoleucine	C₆H₁₃NO₂	[M+H]⁺	132.102 0	-1.7	87.099 1, 86.096 1, 74.057 5, 70.067 4, 69.069 7, 58.064 7	+	+	a^[30]
67	2.84	Leucine	C₆H₁₃NO₂	[M-H]^-	130.087 0	0.5	113.063 0, 86.062 7, 84.083 5	+	+	a^[30]
68	3.97	Phenylalanine	C₉H₁₁NO₂	[M+H]⁺	166.086 0	-2.7	120.080 2, 104.057 2, 103.053 6, 91.053 9, 77.038 3	+	+	b
69	6.17	L-Tryptophan	C₁₁H₁₂N₂O₂	[M-H]^-	203.083 0	4.5	186.060 4, 159.095 4, 142.069 0, 130.068 7	+	+	b
70	0.97	Quinic acid	C₇H₁₂O₆	[M-H]^-	191.056 0	1.8	173.012 4, 127.044 0, 111.010 1, 85.030 3, 73.030 3	-	+	b
71	0.99	Malic acid	C₄H₆O₅	[M-H]^-	133.014 0	-0.1	114.036 1, 73.014 7, 70.031 2	+	+	b
72	1.01	Fumaric acid/maleic acid	C₄H₄O₄	[M-H]^-	115.004 0	-0.7	97.930 6, 71.016 3	-	+	b
73	1.23	Citric acid	C₆H₈O₇	[M-H]^-	191.020 0	2.8	173.013 0, 155.001 4, 147.033 1, 111.010 7, 87.010 1	+	+	b
74	1.64	Pipecolic acid	C₆H₁₁NO₂	[M+H]⁺	130.086 0	-3.7	84.080 1, 67.053 7, 62.024 6, 56.048 9	+	+	b
75	2.35	Amber acid	C₄H₆O₄	[M-H]^-	117.019 0	-0.9	99.011 8, 73.030 3, 55.019 3	+	+	b
76	3.97	Cinnamic acid	C₉H₈O₂	[M+H]⁺	149.060 0	-3.7	131.048 1, 103.053 5, 77.038 5, 65.038 1	+	+	b
77	5.15	Protocatechuic acid	C₇H₆O₄	[M-H]^-	153.019 0	0.7	109.033 8, 91.021 7	+	+	b
78	6.33	Chlorogenic acid	C₁₆H₁₈O₉	[M+H]⁺	355.102 0	-0.5	181.050 1, 163.038 7, 145.027 9, 135.043 5, 117.032 9, 89.038 0	-	+	b
79	7.25	p-Hydroxybenzoic acid	C₇H₆O₃	[M-H]^-	138.024 0	-0.5	93.037 2, 65.050 2	+	+	b
80	7.89	p-Coumaroylquinic acid	C₁₆H₁₈O₈	[M+H]⁺	339.107 0	0.2	119.048 6, 91.053 0	-	+	a^[29]
81	8.99	Feruloylquinic acid	C₁₇H₂₀O₉	[M+H]⁺	369.118 0	-0.3	178.058 1, 177.054 1, 149.059 1, 146.031 3, 134.035 3, 117.033 2	-	+	a^[29]
82	9.16	Caffeic acid	C₉H₈O₄	[M-H]^-	179.035 0	3.2	135.048 8, 133.031 6, 89.041 4	-	+	a^[31]
83	9.80	Ferulic acid	C₁₀H₁₀O₄	[M+H]⁺	195.065 0	0.4	177.054 6, 149.059 2, 145.028 2	+	+	a^[32]
84	11.8	p-Coumaric acid	C₉H₈O₃	[M-H]^-	163.044 0	3.5	119.052 3, 91.035 9, 65.040 6	+	+	b
85	13.33	Isoferulic acid	C₁₀H₁₀O₄	[M+H]⁺	195.065 0	-1.0	177.054 6, 149.059 2, 145.028 2	+	+	a^[32]
86	0.95	D-(+)Glucose/fructose	C₆H₁₂O₆	[M-H]^-	179.056 0	2.3	119.033 4, 115.043 2, 101.028 1	+	+	b
87	1.00	Sucrose	C₁₂H₂₂O₁₁	[M-H]^-	341.109 0	1.9	179.059 3, 119.036 6, 101.026 5	-	+	b
88	1.67	1-Kestose/Neokestose	C₁₈H₃₂O₁₆	[M-H]^-	503.162 0	2.1	341.117 6, 179.059 2, 161.046 9, 119.036 5	-	+	b
89	12.85	Nystose	C₂₄H₄₂O₂₁	[M-H]^-	665.215 0	2.5	503.177 1, 341.112 4, 179.059 2	-	+	b
90	1.69	Adenine	C₅H₅N₅	[M+H]⁺	136.062 0	-1.9	119.035 4, 94.040 2, 92.024 4, 65.013 2	+	+	b
91	1.77	Cytidine	C₉H₁₃N₃O₅	[M+H]⁺	244.093 0	1.8	112.049 6, 95.023 3, 69.043 9, 67.028 4	+	+	b
92	1.91	Nicotinamide	C₆H₆N₂O	[M+H]⁺	123.055 0	-2.9	106.030 4, 78.034 1, 53.038 8, 51.022 9	+	+	b
93	2.46	Uridine	C₉H₁₂N₂O₆	[M-H]^-	243.062 0	4.3	200.060 7, 152.038 6, 111.021 8, 83.014 0, 55.019 9	-	+	b
94	3.00	Adenosine	C₁₀H₁₃N₅O₄	[M-H]^-	266.089 0	3.0	134.049 8, 107.037 9, 92.027 6	-	+	b
95	3.17	Guanosine	C₁₀H₁₃N₅O₅	[M+H]⁺	284.099 0	0.5	152.056 0, 135.029 3, 110.034 3	-	+	b
96	3.18	2-Hydroxyadenosine	C₁₀H₁₃N₅O₅	[M-H]^-	282.084 0	3.8	150.045 8, 133.018 5, 107.038 3	+	+	b
97	9.22	p-Hydroxybenzaldehyde	C₇H₆O₂	[M-H]^-	121.030 0	-0.7	92.027 5, 65.042 3	+	+	b
98	10.85	Vitamin B₂	C₁₆H₂₄O₁₀	[M+H]⁺	377.145 0	2.6	243.087 8, 172.086 4, 69.033 0	+	+	b
99	25.41	Coumarin	C₉H₆O₂	[M+H]⁺	147.044 0	-1.4	119.049 9, 91.054 0, 75.022 0, 65.038 5	+	+	b
100	25.42	Dicoumaroyl glycerol	C₂₁H₂₀O₇	[M+H]⁺	385.128 0	-1.3	367.116 8, 221.080 9, 147.044 1, 119.049 3, 91.054 3	-	+	a^[29]
101	25.75	Coumaroyl feruloyl glycerol	C₂₂H₂₂O₈	[M+H]⁺	415.139 0	-0.8	397.126 6, 271.204 0, 221.080 3, 177.054 1, 147.043 5	-	+	a^[29]
102	26.04	Diferuoloyl glycerol	C₂₃H₂₄O₉	[M+H]⁺	445.149 0	-0.9	427.137 0, 251.091 2, 177.054 2, 149.058 9, 145.028 1	-	+	a^[29]
103	27.11	Sedanolide	C₁₂H₁₈O₂	[M+H]⁺	195.138 0	0.0	167.091 4, 149.133 1, 135.115 2, 111.078 8, 93.069 6, 91.053 8, 69.070 2	+	+	b
104	30.58	Linolenic acid	C₁₈H₃₀O₂	[M+H]⁺	279.232 0	0.1	261.221 3, 149.022 9, 123.116 1	+	+	b
105	33.09	Oleamide	C₁₈H₃₅NO	[M+H]⁺	282.279 0	-0.2	265.251 1, 247.240 6, 135.115 9, 121.099 6, 114.091 1, 95.084 7	+	+	b
106	33.17	Muscone	C₁₆H₃₀O	[M+H]⁺	239.237 0	0.0	183.083 3, 157.073 5, 143.090 0, 109.101 1, 95.085 6, 81.068 6, 67.054 3	+	+	b
107	36.08	Erucamide	C₂₂H₄₃NO	[M+H]⁺	338.342 0	-0.5	321.314 3, 303.030 5, 177.163 0, 153.127 5, 149.131 4	+	+	b

No.

t_R/min

Identification

Molecular
formula

[M+H]⁺/[M-H]^-

Mass

Error /ppm

Fragment ion

Source

21.86

β-Sitosterol-3-O-β-D-glucuronoside+2Rha+Glc

C₅₁H₈₀O₂₂

[M+H]⁺

1 045.521 0

0.2

883.466 6, 737.408 4, 591.352 6

21.92

Stigmasterol glucoside+2Rha

C₄₅H₇₀O₁₆

[M+H]⁺

867.472 0

-0.3

849.461 8, 721.410 5, 705.417 6, 575.356 5, 559.356 9, 413.304 0

22.10

Gracillin+Glc

C₅₁H₈₂O₂₂

[M+H]⁺

1 047.533 0

0.0

885.483 5, 723.354 9, 577.299 3, 415.251 9, 271.205 3, 253.195 0

22.24

β-Sitosterol-3-O-β-D-glucuronoside+Rha+Glc

C₄₅H₇₀O₁₈

[M+H]⁺

899.463 0

0.0

737.408 6, 593.294 3, 591.350 7

22.36

Dongnoside E

C₅₀H₈₂O₂₂

[M+H]⁺

1 035.533 0

-0.9

903.483 1, 873.484 3, 741.443 1, 579.387 9, 417.336 0, 273.221 1

22.37

Pamaqueside / agavoside B

C₃₉H₆₂O₁₄

[M+H]⁺

755.420 0

-1.4

737.405 6, 593.368 7, 431.243 2, 413.311 5, 395.294 0

22.43

Pseudoprotoneodioscin+Glc

C₅₇H₉₂O₂₆

[M+H]⁺

1 193.596 0

-0.5

1 031.538 3, 869.486 1, 723.427 7, 577.373 0, 415.320 1, 253.194 1

22.57

Aspidistrin

C₅₀H₈₀O₂₂

[M+H]⁺

1 033.521 0

-0.6

871.470 1, 739.430 7, 577.373 5, 415.320 9, 397.310 2, 271.205 6

22.71

Shatavarin Ⅸ

C₄₅H₇₄O₁₈

[M+H]⁺

903.495 0

-0.5

741.440 6, 597.325 8, 579.386 9, 417.335 6, 285.257 5, 273.221 6, 255.210 5

a^[20]

22.82

Protodioscin

C₅₁H₈₄O₂₂

[M+H]⁺

1 049.553 0

-0.3

887.498 1, 741.438 8, 725.371 0, 433.330 1, 415.322 2

a^[21]

22.96

(25S)-26-O-β-D-Glucopyranosyl-5β-furost-20(22)-ene-3β, 26-diol-3-O-β-D-glucopyranosyl-(1→2)-β-D-glucopyranoside

C₄₅H₇₂O₁₈

[M+H]⁺

901.478 0

-1.3

739.425 9, 577.372 0, 433.258 1, 415.320 0, 283.242 6, 271.205 9, 253.195 1

a^[22]

23.25

Compound 7 (isomer)

C₅₇H₉₂O₂₆

[M+H]⁺

1 193.596 0

-0.7

1 031.545 1, 869.489 4, 723.431 3, 577.371 2, 415.319 9, 253.192 6

23.27

Stigmasterol glucoside+Hex+2Rha

C₅₁H₈₀O₂₁

[M+H]⁺

1 029.526 0

-1.9

867.469 4, 721.413 5, 575.358 1, 413.303 1, 395.291 5

23.42

Pseudoprotoneodioscin

C₅₁H₈₂O₂₁

[M+H]⁺

1 031.542 0

-0.9

869.484 9, 577.371 6, 415.318 5, 271.204 6, 253.194 1

a^[23]

23.50

Polyphyllin D+Glc/parisyunnanoside B

C₅₀H₈₀O₂₁

[M+H]⁺

1 017.525 0

-0.6

855.471 7, 709.414 3, 577.372 6, 415.319 6, 271.205 1, 253.194 6

23.53

Asparanin B5

C₅₀H₈₂O₂₁

[M+H]⁺

1 019.542 0

-6.8

857.480 6, 713.365 0, 579.386 9, 417.333 5, 273.221 7, 255.209 3

23.71

Yamogenin glucoside+Glc+xyl

C₄₄H₇₀O₁₇

[M+H]⁺

871.468 0

-0.7

709.415 1, 577.372 6, 415.320 7, 271.206 0, 253.194 8

23.73

Gracillin

C₄₅H₇₂O₁₇

[M+H]⁺

885.484 0

-0.8

723.430 3, 577.374 3, 415.320 8, 271.205 6, 253.194 9

23.85

Polyphyllin VI

C₃₉H₆₂O₁₃

[M+H]⁺

739.426 0

-0.9

577.373 2, 433.258 7, 415.318 2, 397.311 2, 271.205 6, 253.195 2

23.99

Aspacochioside D/asparinin B

C₄₅H₇₄O₁₇

[M+H]⁺

887.498 0

-2.3

741.441 7, 579.387 9, 417.336 7, 273.222 0, 255.211 1

a^{[23, 24]}

24.01

(25S)-5β-Spirostan-3β-yl-O-[O-α-L-rhamnopyranosyl-(1-4)]-β-D-glucopyranoside

C₃₉H₆₄O₁₂

[M+H]⁺

725.447 0

0.0

581.330 2, 563.392 4, 417.333 4, 273.220 6, 255.210 1

a^[23]

24.02

(25S)-5β-Spirostan-3β-ol-3-O-β-D-glucopyranosyl-(1→2)-[β-D-xylopyranosyl-(1→4)]-β-D-glucopyranoside

C₄₄H₇₂O₁₇

[M+H]⁺

873.484 0

-1.4

711.426 9, 579.389 1, 435.273 6, 417.335 8, 285.258 6, 273.219 9, 255.210 0

a^[22]

24.06

Dioscin+2Rha

C₅₆H₈₈O₂₅

[M+H]⁺

1 161.565 0

0.3

1 015.503 7, 723.430 4, 577.371 8, 415.319 3, 397.308 4, 253.195 2

24.34

Dioscin+Rha

C₅₀H₇₈O₂₁

[M+H]⁺

1 015.543 0

-0.1

869.485 8, 577.373 4, 415.319 7, 379.312 6, 253.195 9

24.58

Asparagoside A

C₃₃H₅₄O₈

[M+H]⁺

579.389 0

-1.5

417.335 2, 285.257 0, 273.221 3, 255.211 5

a^[22]

24.60

β-Sitosterol-3-O-β-D-glucuronoside+Glc

C₄₀H₆₄O₁₃

[M+H]⁺

753.442 0

-3.1

591.384 1, 271.206 8, 253.195 2

25.10

Stigmasterol glucoside

C₃₃H₅₀O₈

[M+H]⁺

575.358 0

-0.7

557.344 8, 413.301 5, 377.279 9

25.44

Compound 9 (isomer)

C₄₅H₇₄O₁₈

[M+H]⁺

903.495 0

0.5

741.442 2, 597.321 0, 579.388 7, 417.336 9, 285.260 6, 273.221 2, 255.211 9

a^[20]

25.88

Stigmasterol glucoside+Rha

C₃₉H₆₀O₁₂

[M+H]⁺

721.415 0

0.7

575.360 4, 541.348 6, 413.306 0

25.89

Compound 14 (isomer)

C₅₁H₈₂O₂₁

[M+H]⁺

1 031.542 0

0.2

869.489 0, 723.432 5, 577.373 0, 415.321 0, 271.205 3, 253.195 8

a^[23]

26.09

Compound 22 (isomer)

C₄₄H₇₂O₁₇

[M+H]⁺

873.484 0

-1.4

711.426 9, 579.389 1, 435.273 6, 417.335 8, 285.258 6, 273.219 9, 255.210 0

a^[22]

26.09

Sarsasapogenin+H₂O

C₂₇H₄₆O₄

[M+H]⁺

435.347 0

-0.7

417.337 9, 399.320 9, 303.228 7, 277.218 9

26.32

Compound 20 (isomer)

C₄₅H₇₄O₁₇

[M+H]⁺

887.500 0

-1.6

725.443 2, 579.387 9, 417.333 9, 273.220 9, 255.210 7

a^{[23, 24]}

26.66

Sarsasapogenin

C₂₇H₄₄O₃

[M+H]⁺

417.336 0

-1.0

399.328 2, 273.221 7, 255.210 9, 199.148 7

a^[22]

28.04

Sarsasapogenin M

C₃₉H₆₄O₁₄

[M+H]⁺

757.437 0

-0.8

595.306 0, 577.297 7, 415.247 8, 397.242 0

a^[22]

28.39

Yamogenin+H₂O

C₂₇H₄₄O₄

[M+H]⁺

433.331 0

-2.2

415.268 7, 397.314 2, 279.231 0, 253.191 0, 147.117 4

28.82

Filiasparoside D

C₃₈H₆₂O₁₂

[M+H]⁺

711.431 0

0.3

579.385 3, 567.317 4, 417.335 1, 399.325 0, 285.255 4, 273.220 9, 255.210 9

a^[25]

28.95

Dioscin

C₄₅H₇₂O₁₆

[M+H]⁺

869.489 0

0.0

723.430 8, 577.371 1, 415.320 4, 397.309 6, 271.206 4, 253.196 0

a^[26]

29.22

Asparanin A/ (25S)-5β-spirostan-3β-ol-3-O-β-D-glucopyranosyl-(1→2)-β-D-glucopyranoside

C₃₉H₆₄O₁₃

[M+H]⁺

741.442 0

-0.1

579.387 5, 435.273 5, 417.335 8, 285.258 3, 273.221 2, 255.210 1

a^{[22, 27]}

29.42

Prosapogenin A/ polyphyllin C

C₃₉H₆₂O₁₂

[M+H]⁺

723.431 0

-0.4

577.370 0, 415.319 4, 271.205 5, 253.195 1, 157.100 5, 85.027 8

29.46

Polyphyllin D

C₄₄H₇₀O₁₆

[M+H]⁺

855.473 0

0.2

711.360 1, 709.408 7, 577.369 0, 415.318 8, 271.205 4, 253.194 4

29.71

(25S)-5β-Spirostan-3β-ol-3-O-α-L-rhamnopyranosyl-(1, 2)-[α-L-rhamnopyranosyl-(1, 4)]-β-D-glucopyranoside

C₄₅H₇₄O₁₆

[M+H]⁺

871.505 0

-1.1

579.391 0, 417.337 2, 293.123 6, 273.221 9, 255.210 6

a^[22]

29.75

Filiasparoside C

C₄₄H₇₂O₁₆

[M+H]⁺

857.489 0

-0.5

725.448 0, 579.387 7, 417.335 1, 273.220 9, 255.210 7

a^[25]

30.37

Yamogenin

C₂₇H₄₂O₃

[M+H]⁺

415.321 0

-0.8

397.313 1, 271.205 3, 253.195 1, 147.116 4

32.83

Stigmasterol

C₂₉H₄₈O

[M+H]⁺

413.378 0

-2.0

395.366 3, 315.225 4, 271.203 8, 173.130 8

a^[22]

35.40

25S-Spirosta-1, 4-dien-3-one

C₂₇H₃₈O₃

[M+H]⁺

411.289 0

0.0

393.277 1, 267.174 4, 239.179 3

a^[22]

9.52

Kaempferol-3-O-rutinoside-7-O-glucoside

C₃₃H₄₀O₂₀

[M+H]⁺

757.219 0

-0.2

595.160 0, 449.106 3, 287.055 0

a^[28]

9.61

Quercetin diglucoside

C₂₇H₃₀O₁₇

[M+H]⁺

627.155 0

-0.4

609.253 7, 465.103 6, 303.050 1, 257.044 0, 165.014 8, 85.028 6

a^[29]

10.84

Isorhamnetin-3-rhamnosyl-rutinoside

C₃₄H₄₂O₂₀

[M+H]⁺

771.234 0

-1.3

609.172 0, 463.120 8, 317.065 0

a^[7]

11.21

Isorhamnetion-3-O-rutinoside-7-O-glucoside

C₃₄H₄₂O₂₁

[M+H]⁺

787.229 0

-1.7

641.170 2, 625.176 3, 479.118 2, 317.065 0

a^[28]

13.43

Quercitin-3-O-glucosylrutinoside

C₃₃H₄₀O₂₁

[M+H]⁺

773.213 0

-0.7

611.153 2, 465.102 1, 303.049 3, 129.052 1, 85.027 3

14.31

Rutin

C₂₇H₃₀O₁₆

[M+H]⁺

611.161 0

-0.5

465.101 9, 303.050 2, 285.040 6, 257.044 0, 229.049 7

d, a^[28]

14.33

Isoquercetin

C₂₁H₂₀O₁₂

[M+H]⁺

465.103 0

0.3

303.049 6, 285.038 3, 257.047 9, 165.018 2, 153.018 4

a^[28]

15.09

Astragalin

C₂₁H₂₀O₁₁

[M+H]⁺

449.108 0

-1.0

287.054 9, 213.056 0, 165.018 5, 153.018 8

a^[28]

15.62

Narcissoside

C₂₈H₃₂O₁₆

[M+H]⁺

625.176 0

0.1

479.116 1, 317.065 4, 285.033 5, 147.069 0, 129.054 3, 85.028 8

16.22

Kaempferol-3-O-rutinoside

C₂₇H₃₀O₁₅

[M+H]⁺

595.166 0

-0.2

449.107 0, 287.055 0, 269.047 5, 213.054 4, 165.017 1

a^[28]

16.76

Isorhamnetin

C₁₆H₁₂O₇

[M+H]⁺

317.066 0

0.1

302.048 0, 274.047 9, 165.018 8, 153.018 0

d, a^[7]

18.07

Chrysoeriol-7-O-β-D-glucoside

C₂₂H₂₂O₁₁

[M+H]⁺

463.123 0

-1.0

301.071 1, 286.047 3, 153.016 2

24.97

Diosmetin

C₁₆H₁₂O₆

[M+H]⁺

301.071 0

-0.4

286.046 2, 258.050 8

a^[7]

0.86

Aspartic acid

C₄H₇NO₄

[M-H]^-

132.031 0

-0.2

115.008 9, 71.014 9

0.88

L-Arginine

C₆H₁₄N₄O₂

[M+H]⁺

175.119 0

1.7

158.091 7, 116.070 4, 112.085 9, 70.064 9

0.91

L-Glutamic acid

C₅H₉NO₄

[M+H]⁺

148.060 0

0.1

130.049 6, 102.054 2, 85.028 6, 84.043 9, 56.049 3

0.99

Proline

C₅H₉NO₂

[M+H]⁺

116.070 0

-4.5

70.065 1, 53.039 0

1.07

L-Valine

C₅H₁₁NO₂

[M+H]⁺

118.086 0

-1.1

73.085 0, 72.080 9, 59.049 0, 57.057 1, 56.049 5, 55.054 1, 53.038 5

1.81

Nicotinic acid

C₆H₅NO₂

[M+H]⁺

124.039 0

-3.8

106.028 4, 80.048 8, 78.033 5, 53.038 2, 52.018 2

2.48

Isoleucine

C₆H₁₃NO₂

[M+H]⁺

132.102 0

-1.7

87.099 1, 86.096 1, 74.057 5, 70.067 4, 69.069 7, 58.064 7

a^[30]

2.84

Leucine

C₆H₁₃NO₂

[M-H]^-

130.087 0

0.5

113.063 0, 86.062 7, 84.083 5

a^[30]

3.97

Phenylalanine

C₉H₁₁NO₂

[M+H]⁺

166.086 0

-2.7

120.080 2, 104.057 2, 103.053 6, 91.053 9, 77.038 3

6.17

L-Tryptophan

C₁₁H₁₂N₂O₂

[M-H]^-

203.083 0

4.5

186.060 4, 159.095 4, 142.069 0, 130.068 7

0.97

Quinic acid

C₇H₁₂O₆

[M-H]^-

191.056 0

1.8

173.012 4, 127.044 0, 111.010 1, 85.030 3, 73.030 3

0.99

Malic acid

C₄H₆O₅

[M-H]^-

133.014 0

-0.1

114.036 1, 73.014 7, 70.031 2

1.01

Fumaric acid/maleic acid

C₄H₄O₄

[M-H]^-

115.004 0

-0.7

97.930 6, 71.016 3

1.23

Citric acid

C₆H₈O₇

[M-H]^-

191.020 0

2.8

173.013 0, 155.001 4, 147.033 1, 111.010 7, 87.010 1

1.64

Pipecolic acid

C₆H₁₁NO₂

[M+H]⁺

130.086 0

-3.7

84.080 1, 67.053 7, 62.024 6, 56.048 9

2.35

Amber acid

C₄H₆O₄

[M-H]^-

117.019 0

-0.9

99.011 8, 73.030 3, 55.019 3

3.97

Cinnamic acid

C₉H₈O₂

[M+H]⁺

149.060 0

-3.7

131.048 1, 103.053 5, 77.038 5, 65.038 1

5.15

Protocatechuic acid

C₇H₆O₄

[M-H]^-

153.019 0

0.7

109.033 8, 91.021 7

6.33

Chlorogenic acid

C₁₆H₁₈O₉

[M+H]⁺

355.102 0

-0.5

181.050 1, 163.038 7, 145.027 9, 135.043 5, 117.032 9, 89.038 0

7.25

p-Hydroxybenzoic acid

C₇H₆O₃

[M-H]^-

138.024 0

-0.5

93.037 2, 65.050 2

7.89

p-Coumaroylquinic acid

C₁₆H₁₈O₈

[M+H]⁺

339.107 0

0.2

119.048 6, 91.053 0

a^[29]

8.99

Feruloylquinic acid

C₁₇H₂₀O₉

[M+H]⁺

369.118 0

-0.3

178.058 1, 177.054 1, 149.059 1, 146.031 3, 134.035 3, 117.033 2

a^[29]

9.16

Caffeic acid

C₉H₈O₄

[M-H]^-

179.035 0

3.2

135.048 8, 133.031 6, 89.041 4

a^[31]

9.80

Ferulic acid

C₁₀H₁₀O₄

[M+H]⁺

195.065 0

0.4

177.054 6, 149.059 2, 145.028 2

a^[32]

11.8

p-Coumaric acid

C₉H₈O₃

[M-H]^-

163.044 0

3.5

119.052 3, 91.035 9, 65.040 6

13.33

Isoferulic acid

C₁₀H₁₀O₄

[M+H]⁺

195.065 0

-1.0

177.054 6, 149.059 2, 145.028 2

a^[32]

0.95

D-(+)Glucose/fructose

C₆H₁₂O₆

[M-H]^-

179.056 0

2.3

119.033 4, 115.043 2, 101.028 1

1.00

Sucrose

C₁₂H₂₂O₁₁

[M-H]^-

341.109 0

1.9

179.059 3, 119.036 6, 101.026 5

1.67

1-Kestose/Neokestose

C₁₈H₃₂O₁₆

[M-H]^-

503.162 0

2.1

341.117 6, 179.059 2, 161.046 9, 119.036 5

12.85

Nystose

C₂₄H₄₂O₂₁

[M-H]^-

665.215 0

2.5

503.177 1, 341.112 4, 179.059 2

1.69

Adenine

C₅H₅N₅

[M+H]⁺

136.062 0

-1.9

119.035 4, 94.040 2, 92.024 4, 65.013 2

1.77

Cytidine

C₉H₁₃N₃O₅

[M+H]⁺

244.093 0

1.8

112.049 6, 95.023 3, 69.043 9, 67.028 4

1.91

Nicotinamide

C₆H₆N₂O

[M+H]⁺

123.055 0

-2.9

106.030 4, 78.034 1, 53.038 8, 51.022 9

2.46

Uridine

C₉H₁₂N₂O₆

[M-H]^-

243.062 0

4.3

200.060 7, 152.038 6, 111.021 8, 83.014 0, 55.019 9

3.00

Adenosine

C₁₀H₁₃N₅O₄

[M-H]^-

266.089 0

3.0

134.049 8, 107.037 9, 92.027 6

3.17

Guanosine

C₁₀H₁₃N₅O₅

[M+H]⁺

284.099 0

0.5

152.056 0, 135.029 3, 110.034 3

3.18

2-Hydroxyadenosine

C₁₀H₁₃N₅O₅

[M-H]^-

282.084 0

3.8

150.045 8, 133.018 5, 107.038 3

9.22

p-Hydroxybenzaldehyde

C₇H₆O₂

[M-H]^-

121.030 0

-0.7

92.027 5, 65.042 3

10.85

Vitamin B₂

C₁₆H₂₄O₁₀

[M+H]⁺

377.145 0

2.6

243.087 8, 172.086 4, 69.033 0

25.41

Coumarin

C₉H₆O₂

[M+H]⁺

147.044 0

-1.4

119.049 9, 91.054 0, 75.022 0, 65.038 5

100

25.42

Dicoumaroyl glycerol

C₂₁H₂₀O₇

[M+H]⁺

385.128 0

-1.3

367.116 8, 221.080 9, 147.044 1, 119.049 3, 91.054 3

a^[29]

101

25.75

Coumaroyl feruloyl glycerol

C₂₂H₂₂O₈

[M+H]⁺

415.139 0

-0.8

397.126 6, 271.204 0, 221.080 3, 177.054 1, 147.043 5

a^[29]

102

26.04

Diferuoloyl glycerol

C₂₃H₂₄O₉

[M+H]⁺

445.149 0

-0.9

427.137 0, 251.091 2, 177.054 2, 149.058 9, 145.028 1

a^[29]

103

27.11

Sedanolide

C₁₂H₁₈O₂

[M+H]⁺

195.138 0

0.0

167.091 4, 149.133 1, 135.115 2, 111.078 8, 93.069 6, 91.053 8, 69.070 2

104

30.58

Linolenic acid

C₁₈H₃₀O₂

[M+H]⁺

279.232 0

0.1

261.221 3, 149.022 9, 123.116 1

105

33.09

Oleamide

C₁₈H₃₅NO

[M+H]⁺

282.279 0

-0.2

265.251 1, 247.240 6, 135.115 9, 121.099 6, 114.091 1, 95.084 7

106

33.17

Muscone

C₁₆H₃₀O

[M+H]⁺

239.237 0

0.0

183.083 3, 157.073 5, 143.090 0, 109.101 1, 95.085 6, 81.068 6, 67.054 3

107

36.08

Erucamide

C₂₂H₄₃NO

[M+H]⁺

338.342 0

-0.5

321.314 3, 303.030 5, 177.163 0, 153.127 5, 149.131 4

Compounds type	Aglycone	Characteristic ion
Saponin	Sarsasapogenin	417.335 8, 399.325 1, 273.221 7, 255.210 9
Yamogenin	415.320 1, 397.313 1, 271.205 3, 253.195 1
Flavonol	Kaempferol	287.055 0, 269.043 7, 213.054 2, 165.017 8
Quercetin	303.049 6, 285.038 3, 257.047 9, 165.018 2
Isorhamnetin	317.066 6, 302.048 0, 274.047 9, 165.018 8

Compounds type

Aglycone

Characteristic ion

Saponin

Sarsasapogenin

417.335 8, 399.325 1, 273.221 7, 255.210 9

Yamogenin

415.320 1, 397.313 1, 271.205 3, 253.195 1

Flavonol

Kaempferol

287.055 0, 269.043 7, 213.054 2, 165.017 8

Quercetin

303.049 6, 285.038 3, 257.047 9, 165.018 2

Isorhamnetin

317.066 6, 302.048 0, 274.047 9, 165.018 8