药学学报

No.	t_R /min	Molecular formula	Identification	Mass	Error (×10^-6)	Ion	Fragment ion
Saponins
1^a	2.96	C₂₇H₄₄O₄	Gitogenin^[28]	433.332 3	2.54	[M+H]⁺	415.320 8, 397.309 8, 271.205 3
2^a	3.94	C₂₇H₄₂O₅	Manogenin^[20]	447.306 9	-8.05	[M+H]⁺	429.119 1, 273.220 9, 255.210 2, 161.132 2
3^a	14.72	C₅₁H₈₂O₂₆	Solanigroside C^[31]	1 133.498 0	-0.53	[M+Na]⁺	971.444 8, 809.3927, 647.342 5, 467.137 5
4^a	15.70	C₅₇H₉₄O₂₈	Solanigroside Y5^[19]	1 271.591 8	2.16	[M+FA-H]^-	1 225.585 7, 1 063.538 0, 757.365 7, 431.310 6
5^a	16.65	C₂₇H₄₆O₄	25S-Furosta-5β, 3β, 20α, 26-triol^[23]	435.270 4	3.79	[M+H]⁺	417.266 5, 291.215 5, 273.221 5
6^b	16.89	C₅₆H₉₂O₂₈	Timosaponin H1^[33]	1 257.574 8	2.32	[M+FA-H]^-	1 211.570 9, 1 079.526 6, 1 049.519 7, 755.422 9, 593.369 9
7^a	16.91	C₃₃H₅₂O₈	Trillin^[17]	577.374 9	2.42	[M+H]⁺	415.320 5, 271.205 1, 253.194 8
8^a	16.93	C₅₁H₈₀O₂₆	Solanigroside Y3^[13]	1 131.482 2	-0.71	[M+Na]⁺	969.429 0, 807.377 8, 645.324 5
9^a	18.10	C₃₃H₅₄O₈	Tigogenin-hex^[10]	579.391 4	3.97	[M+H]⁺	579.391 4, 417.335 2, 399.335 2, 273.220 8
10^a	18.14	C₅₇H₉₄O₂₈	Trigoneoside XIIIa^[27]	1 227.589 4	-8.96	[M+H]⁺	904.140 3, 741.440 7, 579.388 1, 417.335 8
11^a	18.17	C₃₉H₆₄O₁₃	Timosaponin AⅢ^[28]	741.444 5	3.51	[M+H]⁺	579.388 2, 417.334 4, 273.220 8
12^a	18.23	C₅₇H₉₄O₂₇	Yuccaloiside B^[28]	1 193.604 7	8.21	[M-H₂O+H]⁺	1 031.536 3, 723.429 8, 577.372 4, 415.320 3
13^a	18.23	C₄₅H₇₄O₁₈	Shatavarin Ⅸ^[8]	903.494 1	-0.66	[M+H]⁺	741.439 1, 579.621 9, 417.335 6
14^a	18.23	C₅₇H₉₄O₂₇	Solanigroside Y6^[13]	1 255.595 2	2.69	[M+FA-H]^-	1 209.590 9, 1 047.538 0, 901.483 5, 755.423 2, 593.366 6, 431.316 0, 413.308 4
15^a	18.25	C₃₉H₆₂O₁₃	Diosgenin 3-O-cellobioside^[13]	739.427 4	1.49	[M+H]⁺	577.372 6, 415.320 1, 271.205 4, 253.194 7
16^b	18.41	C₅₁H₈₆O₂₄	Tomatoside A^[30]	1 117.520 4	5.61	[M+FA-H]^-	1 081.543 1, 919.492 0, 757.437 3, 595.384 9, 433.337 0
17^a	18.59	C₅₀H₈₂O₂₂	Degalactotigonin^[28]	1 035.544 9	7.63	[M+H]⁺	873.481 0, 741.441 0, 579.388 5, 417.335 8
18^a	18.70	C₅₆H₉₂O₂₇	Diurnoside^[25]	1 197.589 1	-0.58	[M+H]⁺	1035.534 3, 741.440 4, 579.388 2, 417.335 5
19^a	18.82	C₃₃H₅₂O₁₀	Chonglouoside SL-10^[12]	609.364 1	1.31	[M+H]⁺	609.364 1, 447.310 1, 429.299 6, 411, 288 5
20^a	18.89	C₅₁H₈₂O₂₂	Zingiberensis saponin^[35]	1 047.532 8	-4.01	[M+H]⁺	885.483 9, 723.433 2, 577.376 0, 415.320 5
21^b	18.91	C₅₁H₈₄O₂₃	25(27)-ene-Gurilioside H^[33]	1 109.501 8	8.65	[M+FA-H]^-	1 063.532 5, 917.474 9, 755.424 0, 575.373 3
22^a	19.14	C₅₁H₈₄O₂₂	Asparasaponin Ⅰ^[19]	1 031.544 2	2.04	[M-H₂O+H]⁺	869.487 4, 723.428 1, 577.372 7, 415.320 2
23^b	19.15	C₄₅H₇₆O₁₉	Timosaponin B Ⅱ^[14]	965.495 9	6.91	[M+FA-H]^-	919.490 9, 757.437 8, 595.385 5, 433.333 0, 330.488 9
24^a	19.21	C₄₅H₇₂O₁₇	Gracillin^[18]	885.481 9	-2.60	[M+H]⁺	723.429 6, 579.315 1, 415.320 1, 271.205 2
25^a	19.36	C₅₁H₈₄O₂₂	Zingiberensis saponin^[19]	1 049.549 6	-2.95	[M+H]⁺	869.488 0, 723.429 0, 577.372 4, 415.320 2
26^a	19.39	C₃₃H₅₀O₁₀	Kammogenin-glu^[20]	607.346 2	-2.31	[M+H]⁺	445.296 1, 427.273 0, 409.273 0
27^b	19.75	C₅₁H₈₄O₂₂	Compound 36 isomer^[35]	1 093.536 6	5.69	[M+FA-H]^-	1 047.538 2, 901.477 5, 575.372 6, 431.319 3
28^a	19.81	C₃₉H₆₂O₁₄	Pennogenin-rha^[12]	755.421 8	0.79	[M+H]⁺	579.389 3, 435.273 5, 399.324 5, 285.256 5
29^a	19.84	C₃₃H₅₂O₉	D-Glucuronic acid, (3β, 5β, 25R)-spirostan-3-yl ester^[20]	593.361 7	-9.10	[M+H]⁺	417.317 6, 399.325 3, 273.220 7
30^b	19.93	C₄₅H₇₆O₁₈	Aspacochioside A^[30]	949.485 7	6.18	[M+FA-H]^-	903.495 7, 757.444 2, 595.393 7, 433.330 5, 352.469 5
31^a	20.26	C₅₀H₈₂O₂₂	Melongoside F^[19]	1 033.522 1	-0.29	[M-H]^-	901.480 7, 739.4258, 577.374 6, 415.320 3
32^a	20.34	C₄₅H₇₄O₁₇	Shatavarin Ⅵ^[9]	887.491 1	-9.80	[M+H]⁺	725.443 7, 579.389 8, 417.336 2, 399.325 9
33^a	20.50	C₃₃H₅₀O₉	Spirost-9(11)-en-12-one^[20]	591.354 6	3.21	[M+H]⁺	429.300 1, 273.220 8, 255.210 3
34^a	20.51	C₃₉H₆₀O₁₄	β-Sitosterol-3-O-β-D-glucuronoside+glc^[8]	753.403 2	-3.05	[M+H]⁺	591.351 1, 273.221 0, 255.210 2
35^a	20.52	C₅₇H₉₆O₂₈	Trigoneoside XIIIb^[27]	1 227.606 1	3.75	[M+H]⁺	1065.540 9, 903.501 7, 741.443 1
36^b	20.82	C₅₁H₈₄O₂₂	Protodioscin^[35]	1 093.536 6	1.26	[M+FA-H]^-	1 047.536 5, 915.458 5, 885.449 5, 591.354 4, 429.303 5
37^a	20.84	C₂₇H₄₄O₃	Tigogenin^[15]	417.335 7	-1.44	[M+H]⁺	399.326 4, 273.220 8, 255.210 4, 161, 132 2
38^a	20.88	C₅₁H₈₂O₂₃	Deltoside^[19]	1 063.528 1	-3.76	[M+H]⁺	901.471 9, 739.429 5, 577.372 5, 415.320 0
39^a	21.14	C₂₇H₄₀O₅	Kammogenin^[20]	445.295 5	1.57	[M+H]⁺	445.295 5, 427.283 6, 409.273 8, 273.220 8, 255.213 0
40^b	21.26	C₅₀H₈₂O₂	Anemarrhenasaponin F^[33]	1 095.516 8	2.99	[M+FA-H]^-	1 049.517 5, 917.475 3, 887.464 7, 755.424 6, 593.369 6
41^a	21.77	C₂₇H₄₂O₃	Diosgenin^[19]	415.320 3	-0.72	[M+H]⁺	397.308 4, 271.205 3, 253.194 7
42^b	21.89	C₄₅H₇₄O₁₇	Deltonin^[35]	931.491 0	1.81	[M+FA-H]^-	885.485 3, 739.426 4, 575.357 2, 413.307 7
43^a	21.98	C₃₃H₅₀O₈	Ruscogenin-rha^[11]	575.357 7	-0.17	[M+H]⁺	415.320 3, 273.220 8, 255.210 1
44^a	22.28	C₂₇H₄₀O₄	9(11)-Dehydrohecogenin^[18]	429.301	2.56	[M+H]⁺	411.288 9, 384.297 0, 273.220 8
45^a	22.30	C₅₁H₈₈O₃₁	Solanigroside E^[19]	1 195.549 6	8.93	[M-H]^-	1 063.496 6, 931.450 1, 417.303 8
46^b	22.75	C₄₅H₇₂O₁₉	Chinenoside Ⅴ^[30]	961.463 9	-5.16	[M+FA-H]^-	915.459 2, 753.409 5, 607.349 2, 445.296 4, 417.292 5
47^b	22.83	C₅₀H₈₂O₂₂	Hamoside A^[33]	1 079.528 6	2.81	[M+FA-H]^-	1 033.521 0, 901.479 0, 871.470 6, 739.435 5, 577.374 9
48^b	23.01	C₄₅H₇₂O₁₈	Vaviloside B₁/B₂^[30]	945.469 8	-6.78	[M+FA-H]^-	899.464 7, 753.407 4, 607.349 1, 445.296 1
49^a	23.55	C₂₇H₄₂O₄	Yuccagenin^[35]	431.314 1	-3.25	[M+H]⁺	395.293 0, 273.220 9, 255.075 2
50^b	26.20	C₄₅H₇₀O₁₆	Sansevistatin 1^[30]	867.474 1	5.99	[M+H]⁺	721.414 6, 575.358 3, 413.307 9
51^b	26.27	C₂₇H₄₀O₃	Episceptrumgenin^[35]	413.326 8	-4.84	[M+H]⁺	395.292 9, 271.205 1, 253.194 8
52^a	26.29	C₅₆H₉₂O₂₈	Capsicosin E1^[28]	1 211.570 7	0.42	[M-H]^-	1 079.527 1, 593.369 7, 431.317 4
53^a	26.31	C₃₉H₆₂O₁₂	Prosapogenin A of dioscin^[35]	723.428 2	-4.42	[M+H]⁺	577.392 5, 415.320 0, 271.205 3
54^a	26.40	C₅₁H₈₆O₂₃	Shatavarin Ⅰ^[9]	1 065.550 2	2.44	[M-H]^-	903.491 8, 579.388 7, 417.335 4
55^b	27.35	C₄₅H₇₂O₁₇	Pennogenin 3-O-β-chacotrioside^[30]	929.475 1	5.27	[M+FA-H]^-	883.469 3, 737.412 4, 496.438 7, 417.401 9
56^b	28.66	C₄₄H₇₂O₁₆	Smilaxchinoside C^[30]	901.480 3	-2.88	[M+FA-H]^-	855.475 2, 723.433 2, 577.374 1, 415.325 6
57^b	28.98	C₅₁H₈₄O₂₃	Timosaponin B Ⅳ^[33]	1 109.501 8	7.33	[M+FA-H]^-	1 063.532 7, 901.480 0, 739.427 8, 577.374 6
58^b	29.22	C₅₀H₈₂O₂₂	Dongnoside E^[33]	1 079.528 6	0.86	[M+FA-H]^-	1 033.522 1, 871.469 5, 739.426 6, 577.374 6
59^a	29.42	C₃₉H₆₄O₁₂	Prosapogenin B^[15]	725.445 5	-2.07	[M+H]⁺	579.388 4, 417.335 7, 255.210 3
60^b	29.47	C₄₅H₇₄O₁₈	Protobioside^[35]	947.485 0	5.98	[M+FA-H]^-	901.479 7, 739.427 2, 577.374 5, 252.392 5
61^b	29.66	C₄₅H₇₄O₁₆	Indioside Ⅰ^[30]	915.496 0	-1.89	[M+FA-H]^-	869.490 1, 723.431 9, 577.375 2, 415.330 9
Alkaloids
62^c	5.02	C₄₅H₇₁NO₁₉	Alkaloid 1^[10]	930.467 8	-0.32	[M+H]⁺	930.467 8, 912.458 2, 894.446 2, 739.974 9
63^a	5.41	C₄₅H₇₃NO₁₈	Compound 74 isomer^[10]	916.489 1	0.00	[M+H]⁺	898.476 8, 829.415 6, 670.498 4, 410.306 1
64^a	6.41	C₄₅H₇₁NO₁₈	22α, 23α-Epoxysolasodine-hex-hex-hex^[10]	914.473 3	-0.55	[M+H]⁺	878.452 9, 732.396 7, 424.285 1, 287.201 3
65^a	9.18	C₃₃H₅₃NO₈	Solasodine-OH-hex^[10]	592.385 2	2.53	[M+H]⁺	574.373 0, 433.258 1, 271.205 1
66^a	9.24	C₃₉H₆₃NO₁₃	Solasodine-OH-hex-hex^[10]	754.435 9	-0.27	[M+H]⁺	718.416 3, 572.359 8, 410.304 8
67^a	11.59	C₄₅H₇₅NO₁₈	Dihydrosolasodine-2OH-hex-hex-rha^[10]	918.504 7	-0.22	[M+H]⁺	696.667 0, 396.679 9, 269.189 5
68^b	12.35	C₄₅H₇₅NO₁₇	Compound 70 isomer^[21]	902.509 0	-1.99	[M+H]⁺	884.453 4, 756.415 5, 448.305 3, 430.290 9
69^a	12.47	C₃₉H₆₅NO₁₃	Dihydrosolasodine-2OH-hex-rha^[10]	756.451 7	0.00	[M+H]⁺	738.442 1, 269.189 7, 251.178 9
70^b	12.90	C₄₅H₇₅NO₁₇	Dihydrosolasodine-2OH-rha-rha-hex^[21]	902.509 0	-1.99	[M+H]⁺	884.506 7, 725.094 5, 430.328 7
71^b	13.45	C₄₅H₇₃NO₁₇	Compound 76 isomer^[35]	900.493 7	-1.55	[M+H]⁺	864.472 3, 834.430 8, 702.418 1, 430.334 3
72^c	14.99	C₄₅H₆₉NO₁₅	Unknown alkaloid 1	864.474 0	2.31	[M+H]⁺	583.515 0, 455.002 0, 392.297 3
73^a	15.06	C₂₇H₄₃NO₄	(3β, 22α, 25R)-3, 12-Dihydroxy-spirosol-27-oic-acid^[31]	446.326 0	0.22	[M+H]⁺	428.315 9, 410.304 8, 395.279 3, 287.200 3
74^c	15.21	C₄₅H₇₃NO₁₈	Alkaloid 2^[10]	916.490 2	0.00	[M+H]⁺	832.430 1, 592.374 2, 446.326 0, 410.308 5
75^c	15.54	C₄₅H₇₁NO₁₆	Alkaloid 3^[10]	882.483	-0.68	[M+H]⁺	864.475 3, 795.405 1, 736.425 0, 410.305 0
76^b	15.64	C₄₅H₇₃NO₁₇	Peimisine+rha+hex+rha+OH^[35]	900.493 4	-1.89	[M+H]⁺	882.481 0, 558.377 9, 412.320 4
77^a	17.31	C₃₃H₅₅NO₇	δ-Tomatine^[29]	578.403 9	-2.07	[M+H]⁺	416.336 6, 273.205 5, 255.194 3
78^a	17.31	C₂₇H₄₅NO₂	Tomatidine^[29]	416.351 8	-1.20	[M+H]⁺	398.342 0, 273.221 3, 255.210 4
79^d	17.45	C₄₅H₇₃NO₁₆	Solasonine	884.498 7	-1.70	[M+H]⁺	738.430 8, 576.392 5, 414.338 3, 396.328 5
80^a	17.49	C₃₃H₅₃NO₇	γ-Solamargine^[29]	576.388 7	-1.21	[M+H]⁺	576.388 7, 414.336 6, 396.324 1, 271.205 0
81^a	17.52	C₃₉H₆₃NO₁₂	Solanigroside P^[35]	738.440 7	-2.17	[M+H]⁺	414.334 7, 253.194 6, 157.101 0
82^b	17.86	C₅₀H₈₁NO₁₉	Sycophantine^[35]	1 000.545 5	-2.10	[M+H]⁺	868.495 5, 722.420 9, 414.329 7, 396.326 3
83^a	18.10	C₄₅H₇₃NO₁₅	δ-Solanigrine^[35]	868.504 6	-0.69	[M+H]⁺	722.445 6, 576.388 3, 414.335 6
84^a	18.32	C₄₅H₇₅NO₁₆	Solaverbascine Solatrioside^[10]	886.514 6	-1.47	[M+H]⁺	868.469 8, 740.419 5, 594.357 8, 414.299 1
85^b	18.16	C₄₅H₇₃NO₁₅	α-Solanine^[31]	912.496 0	2.99	[M+FA-H]^-	866.490 6, 720.432 7, 412.331 2
86^a	20.02	C₃₉H₆₃NO₁₁	β2-Solanine^[35]	722.446 2	-1.52	[M+H]⁺	416.351 8, 253.193 7, 157.100 9
87^c	20.69	C₃₉H₆₅NO₁₁	Unknown alkaloid 2	724.461 2	-1.10	[M+H]⁺	704.451 2, 445.495 2, 398.344 4
88^a	21.98	C₃₃H₅₃NO₉	Solasodine-2OH-hex^[10]	608.275 1	3.62	[M+H]⁺	599.177 9, 529.257 8, 479.137 6, 447.312 6
89^d	25.01	C₂₇H₄₃NO₂	Solasodine	414.336 2	-0.97	[M+H]⁺	396.325 9, 271.204 7, 253.194 7
90^a	26.56	C₂₇H₄₅NO₂	Compound 56 isomer^[29]	416.351 7	-1.44	[M+H]⁺	399.326 2, 273.220 7, 255.210 5
91^a	27.55	C₂₇H₃₉NO₂	Veratramine^[18]	410.304 9	0.49	[M+H]⁺	392.294 3, 297.221 5, 267.174 0, 249.179 1
Flavones
92^a	2.57	C₁₆H₁₂O₇	Isorhamnetin^[8]	317.059 7	0.00	[M+H]⁺	317.059 7, 302.032 6, 285.035 8
93^a	2.79	C₃₃H₄₀O₂₁	Quercetin-3-O-rutinosyl-7-O-glucoside^[24]	771.198 4	-0.65	[M-H]^-	301.032 5, 271.024 8, 255.029 8
94^b	2.83	C₃₅H₄₂O₂₃	Quercetin-3-O-rutinosyl-7-O-glucoside+O+hex+AA^[32]	829.159 2	-6.27	[M-H]^-	771.198 7, 301.032 7, 271.024 8, 255.030 0
95^a	3.82	C₄₂H₄₆O₂₂	Kaempferol 3-[2-(6-coumaroylglucosyl)-rhamnoside]7-glucoside^[18]	901.241 0	0.22	[M-H]^-	609.139 3, 285.036 0, 255.029 8
96^a	3.83	C₃₃H₄₀O₂₀	Kaempferol 3-rutinoside 4′-glucoside^[16]	757.217 3	-1.58	[M+H]⁺	449.106 4, 303.049 5, 287.054 6, 258.051 1
97^b	4.46	C₄₃H₄₈O₂₄	3-(2-Feruloylsophoroside)^[34]	947.229	-7.71	[M-H]^-	785.193 5, 609.147 6, 446.085 1, 285.030 1
98^a	4.50	C₂₇H₃₀O₁₇	Quercetin 3, 4-diglucoside^[23]	625.141 2	0.32	[M-H]^-	301.033 6, 300.027 6, 283.024 7, 255.029 8
99^e	4.60	C₂₉H₃₂O₁₉	Unknown flavone 1	683.099 3	-0.73	[M-H]^-	625.141 2, 301.033 9, 271.024 8
100^b	4.62	C₃₁H₃₄O₁₈	Isoscutellarein 7-O-[2, 6-di-O-acetyl]allosyl(1→2)glucoside^[32]	693.128 4	1.73	[M-H]^-	625.141 9, 301.034 2, 271.024 8, 255.029 9
101^b	4.64	C₃₁H₃₅O₁₉	Peonidin, 3-(6-malonyl-glucoside), 5-glucoside^[32]	710.118 0	-4.08	[M-H]^-	625.141 4, 301.826 9, 271.907 2
102^e	5.04	C₃₁H₃₅O₁₈	Unknown flavone 2	694.119 8	-6.05	[M-H]^-	609.146 5, 301.032 0, 271.024 8
103^a	5.14	C₂₉H₃₂O₁₈	Euphorbianin^[32]	667.104 9	-0.15	[M-H]^-	609.145 6, 477.043 4, 300.027 6
104^e	5.19	C₁₈H₁₂O₇	Unknown flavone 3	341.082 4	-9.38	[M+H]⁺	301.142 0, 285.039 1, 257.036 9
105^b	5.36	C₃₁H₃₄O₁₇	Pelargonidin 3, 5-di-(6-acetylglucoside)^[34]	677.133 5	-0.74	[M-H]^-	609.146 6, 271.024 7, 255.030 0
106^a	5.98	C₂₇H₃₀O₁₆	Kaempferol-3-O-sophoroside^[20]	611.163 7	4.91	[M+H]⁺	449.109 5, 303.048 9, 287.054 7
107^e	6.10	C₂₇H₃₂O₁₇	Unknown flavone 4	629.171 2	3.66	[M+H]⁺	445.154 1, 385.134 6, 303.092 7, 285.081 6
108^a	6.12	C₂₁H₂₀O₁₀	Trihydroxy flavone C-glc^[12]	433.112 5	-1.15	[M+H]⁺	369.124 4, 287.054 7, 213.054 2
109^b	6.14	C₃₁H₃₅O₁₇	Pelargonidin 3, 5-di-(6-acetylglucoside)^[32]	678.125 2	-5.60	[M-H]^-	593.151 3, 273.123 2, 255.029 9
110^b	6.14	C₃₁H₃₄O₁₆	Crassirhizomoside B^[32]	661.139 1	-8.02	[M-H]^-	593.152 7, 447.093 0, 431.096 9
111^a	6.33	C₂₆H₂₈O₁₄	Apigenin 6-C-glucosyl-O-arabinoside^[24]	563.140 4	-0.36	[M-H]^-	417.084 1, 255.030 0, 227.035 2
112^e	6.81	C₃₁H₄₀O₁₅	Unknown flavone 5	651.109	-1.54	[M-H]^-	593.150 1, 284.033 1, 255.030 8
113^a	7.03	C₂₁H₂₀O₁₂	Hyperoside^[12]	463.087 6	-1.08	[M-H]^-	301.034 3, 271.024 9, 255.029 8
114^a	7.24	C₂₉H₃₆O₁₆	Tetrahydroxymethoxyflavone O-dihex^[12]	641.207 9	-0.47	[M+H]⁺	317.065 2, 302.041 8, 285.038 7, 229.048 9
115^b	7.40	C₄₃H₄₈O₂₃	Kaempferol-3-neohesperidoside-7-(2-ferulylglucoside)^[32]	931.249 2	-3.01	[M-H]^-	785.193 5, 609.148 3, 430.089 5, 285.039 8
116^e	7.45	C₄₃H₄₈O₂₃	Unknown flavone 6	933.265 9	-8.61	[M+H]⁺	583.413 1, 433.113 9, 287.055 6, 258.052 3
117^a	7.49	C₂₁H₂₀O₁₂	Quercetin-3-O-galactoside^[13]	465.100 2	-5.38	[M+H]⁺	303.049 7, 285.038 6, 165.016 8, 85.027 1
118^b	7.51	C₂₅H₂₅O₁₄	Cyanidin 3-(6-succinyl-glucoside)^[34]	548.117 1	0.00	[M-H]^-	463.084 4, 447.197 5, 285.084 4, 255.083 9
119^a	9.26	C₂₁H₂₀O₁₁	Kaempferol-3-O-glucoside^[24]	447.093 4	0.45	[M-H]^-	447.093 4, 285.038 7, 255.029 9, 227.035 0
120^a	10.43	C₂₁H₂₂O₁₂	Glucodistylin^[23]	449.107 4	0.89	[M+H]⁺	449.107 4, 287.054 6, 258.051 5, 213.054 2
121^a	11.37	C₂₂H₂₂O₁₂	Tetrahydroxymethoxyflavone 3-O-hex^[12]	479.118 0	-0.83	[M+H]⁺	479.118 0, 393.186 2, 317.065 1, 285.038 6
122^a	17.25	C₁₅H₁₀O₇	Quercetion^[24]	301.035 5	0.33	[M-H]^-	271.025 0, 255.041 1, 163.015 9, 83.027 6
123^e	18.91	C₃₁H₃₄O₁₅	Unknown flavone 7	647.197 0	1.89	[M-H]^-	595.383 5, 577.374 8, 393.202 2, 316.167 9
124^a	26.03	C₂₇H₃₀O₁₆	Rutin^[26]	609.146 4	0.49	[M-H]^-	429.206 6, 380.366 4, 315.050 0, 275.201 7
125^a	26.65	C₂₇H₃₀O₁₅	Kaempferol-3-O-glucoside-7-O-rhamnoside^[20]	593.151 2	0.17	[M-H]^-	418.226 8, 299.043 8, 225.007 5
126^a	31.39	C₂₇H₃₀O₁₄	Kaempferitrin^[16]	577.156 8	0.69	[M-H]^-	428.284 1, 299.044 6, 225.007 5
Others
127^a	0.96	C₁₂H₂₂O₁₁	Sucrose^[8]	341.108 9	-0.59	[M-H]^-	179.056 2, 119.036 0, 89.024 4
128^a	0.97	C₆H₉N₃O₂	Histidine^[22]	156.076 6	-1.28	[M+H]⁺	131.974 4, 110.071 6
129^a	1.02	C₆H₁₂O₇	Galacturonic acid^[11]	195.050 9	-0.51	[M-H]^-	177.040 5, 159.029 9
130^a	1.07	C₉H₁₁NO₃	Tyrosine^[11]	182.081 0	-0.55	[M+H]⁺	165.045 7, 136.075 8, 107.049 7
131^a	1.16	C₆H₅NO₂	Nicotinic acid^[22]	124.039 6	2.42	[M+H]⁺	106.029 4, 80.050 0, 78.034 4
132^a	1.17	C₁₂H₂₁NO₆	9-Amino-1, 3, 9-nonane dicarboxylic acid^[11]	276.144 4	1.09	[M+H]⁺	258.133 6, 230.138 7, 161.068 3
133^a	1.10	C₆H₁₁NO₂	Pipecolic acid^[8]	130.049 8	-9.22	[M+H]⁺	84.044 8, 67.053 7, 62.024 6, 56.048 9
134^a	1.13	C₅H₇NO₃	Pyroglutamic acid^[8]	130.050 1	1.54	[M+H]⁺	84.044 9, 69.070 5, 56.050 1
135^a	1.63	C₁₀H₁₃N₄O₃	Histidyl asparagine^[11]	238.106 7	2.94	[M+H]⁺	192.102 2, 120.995 9, 103.054 6
136^a	1.73	C₁₂H₁₅NO₅	Serine^[11]	254.102 1	-0.39	[M+H]⁺	208.058 2, 136.990 6, 119.118 4
137^a	1.87	C₁₁H₁₂N₂O₂	Tryptophan^[8]	205.097 2	0.49	[M+H]⁺	188.070 7, 170.060 1, 159.091 8
138^a	1.87	C₁₁H₉NO₂	Indole-3-acrylic acid^[11]	188.070 3	-1.60	[M+H]⁺	146.060 2, 186.065 4
139^a	1.92	C₇H₆O₄	Protocatechuic acid^[8]	153.019 4	2.61	[M-H]^-	109.029 5, 91.018 9, 81.034 6
140^a	2.48	C₁₆H₁₈O₉	Chlorogenic acid^[8]	355.100 1	-6.20	[M+H]⁺	181.050 1, 145.026 7, 135.041 6, 117.033 7
141^a	3.08	C₁₆H₁₈O₉	Neochlorogenic acid^[11]	353.089 9	-2.27	[M-H]^-	191.056 2, 179.035 2, 162.027 8
142^a	3.13	C₁₆H₂₄O₁₀	Vitamin B₂^[8]	377.144 9	1.86	[M+H]⁺	243.087 3, 172.086 6, 99.044 3,
143^a	3.34	C₉H₈O₄	Caffeic acid^[8]	179.034 7	-1.12	[M-H]^-	135.044 6, 112.984 9, 89.023 5
144^a	3.49	C₁₆H₁₈O₈	p-Coumaroylquinic acid^[8]	339.106 9	-1.47	[M+H]⁺	147.043 9, 119.049 2, 91.054 5
145^a	4.01	C₅H₅N₅	Adenine^[8]	136.061 8	0.73	[M+H]⁺	119.049 3, 94.065 5, 92.049 7
146^a	5.44	C₉H₈O₃	p-Coumaric acid^[8]	163.040 6	0.00	[M-H]^-	119.051 1, 91.053 7
147^a	5.56	C₈H₁₆N₂O₃	Glycyl-L-leucine^[11]	189.121 8	-7.93	[M+H]⁺	171.149 0, 130.086 2, 84.081 2
148^a	7.42	C₁₀H₁₀O₄	Isoferulic acid^[8]	195.063 9	-6.66	[M+H]⁺	177.054 4, 149.059 6, 117.033 5
149^a	8.24	C₅H₉NO₄	L-Glutamic acid^[8]	148.060 2	-1.35	[M+H]⁺	130.069 2, 103.054 4, 84.044 7
150^a	8.54	C₆H₁₂O₇	Glucuronic acid^[8]	197.063 9	-8.63	[M+H]⁺	179.106 4, 161.095 9, 133.101 1
151^a	8.58	C₈H₁₆N₂O₃	Compound 147 isomer^[11]	189.121 8	-7.93	[M+H]⁺	156.093 1, 129.070 0, 105.070 1
152^a	9.65	C₉H₁₂N₂O₆	Uridine^[22]	245.079 1	9.38	[M+H]⁺	203.123 7, 189.112 0, 135.080 1
153^a	11.67	C₁₂H₁₈O₂	Serdanolide^[8]	195.137 6	-1.54	[M+H]⁺	167.085 0, 135.044 0, 111.044 2
154^a	21.65	C₁₀H₁₀O₄	Ferulic acid^[22]	195.063 2	-9.74	[M+H]⁺	177.091 1, 149.067 2, 89.065 9
155^a	26.49	C₂₃H₂₄O₉	Diferuloylglycerol^[8]	445.147 9	-3.15	[M+H]⁺	271.205 2, 253.194 7
156^a	27.87	C₁₆H₃₀O	Muscone^[8]	239.235 7	-5.02	[M+H]⁺	183.116 6, 197.132 2, 119.085 7, 81.068 6
157^a	28.20	C₁₈H₃₅NO	Oleamide^[8]	282.278 7	-1.42	[M+H]⁺	247.241 6, 135.116 8, 121.101 2

No.	t_R /min	Molecular formula	Identification	Mass	Error (×10^-6)	Ion	Fragment ion
Saponins
1^a	2.96	C₂₇H₄₄O₄	Gitogenin^[28]	433.332 3	2.54	[M+H]⁺	415.320 8, 397.309 8, 271.205 3
2^a	3.94	C₂₇H₄₂O₅	Manogenin^[20]	447.306 9	-8.05	[M+H]⁺	429.119 1, 273.220 9, 255.210 2, 161.132 2
3^a	14.72	C₅₁H₈₂O₂₆	Solanigroside C^[31]	1 133.498 0	-0.53	[M+Na]⁺	971.444 8, 809.3927, 647.342 5, 467.137 5
4^a	15.70	C₅₇H₉₄O₂₈	Solanigroside Y5^[19]	1 271.591 8	2.16	[M+FA-H]^-	1 225.585 7, 1 063.538 0, 757.365 7, 431.310 6
5^a	16.65	C₂₇H₄₆O₄	25S-Furosta-5β, 3β, 20α, 26-triol^[23]	435.270 4	3.79	[M+H]⁺	417.266 5, 291.215 5, 273.221 5
6^b	16.89	C₅₆H₉₂O₂₈	Timosaponin H1^[33]	1 257.574 8	2.32	[M+FA-H]^-	1 211.570 9, 1 079.526 6, 1 049.519 7, 755.422 9, 593.369 9
7^a	16.91	C₃₃H₅₂O₈	Trillin^[17]	577.374 9	2.42	[M+H]⁺	415.320 5, 271.205 1, 253.194 8
8^a	16.93	C₅₁H₈₀O₂₆	Solanigroside Y3^[13]	1 131.482 2	-0.71	[M+Na]⁺	969.429 0, 807.377 8, 645.324 5
9^a	18.10	C₃₃H₅₄O₈	Tigogenin-hex^[10]	579.391 4	3.97	[M+H]⁺	579.391 4, 417.335 2, 399.335 2, 273.220 8
10^a	18.14	C₅₇H₉₄O₂₈	Trigoneoside XIIIa^[27]	1 227.589 4	-8.96	[M+H]⁺	904.140 3, 741.440 7, 579.388 1, 417.335 8
11^a	18.17	C₃₉H₆₄O₁₃	Timosaponin AⅢ^[28]	741.444 5	3.51	[M+H]⁺	579.388 2, 417.334 4, 273.220 8
12^a	18.23	C₅₇H₉₄O₂₇	Yuccaloiside B^[28]	1 193.604 7	8.21	[M-H₂O+H]⁺	1 031.536 3, 723.429 8, 577.372 4, 415.320 3
13^a	18.23	C₄₅H₇₄O₁₈	Shatavarin Ⅸ^[8]	903.494 1	-0.66	[M+H]⁺	741.439 1, 579.621 9, 417.335 6
14^a	18.23	C₅₇H₉₄O₂₇	Solanigroside Y6^[13]	1 255.595 2	2.69	[M+FA-H]^-	1 209.590 9, 1 047.538 0, 901.483 5, 755.423 2, 593.366 6, 431.316 0, 413.308 4
15^a	18.25	C₃₉H₆₂O₁₃	Diosgenin 3-O-cellobioside^[13]	739.427 4	1.49	[M+H]⁺	577.372 6, 415.320 1, 271.205 4, 253.194 7
16^b	18.41	C₅₁H₈₆O₂₄	Tomatoside A^[30]	1 117.520 4	5.61	[M+FA-H]^-	1 081.543 1, 919.492 0, 757.437 3, 595.384 9, 433.337 0
17^a	18.59	C₅₀H₈₂O₂₂	Degalactotigonin^[28]	1 035.544 9	7.63	[M+H]⁺	873.481 0, 741.441 0, 579.388 5, 417.335 8
18^a	18.70	C₅₆H₉₂O₂₇	Diurnoside^[25]	1 197.589 1	-0.58	[M+H]⁺	1035.534 3, 741.440 4, 579.388 2, 417.335 5
19^a	18.82	C₃₃H₅₂O₁₀	Chonglouoside SL-10^[12]	609.364 1	1.31	[M+H]⁺	609.364 1, 447.310 1, 429.299 6, 411, 288 5
20^a	18.89	C₅₁H₈₂O₂₂	Zingiberensis saponin^[35]	1 047.532 8	-4.01	[M+H]⁺	885.483 9, 723.433 2, 577.376 0, 415.320 5
21^b	18.91	C₅₁H₈₄O₂₃	25(27)-ene-Gurilioside H^[33]	1 109.501 8	8.65	[M+FA-H]^-	1 063.532 5, 917.474 9, 755.424 0, 575.373 3
22^a	19.14	C₅₁H₈₄O₂₂	Asparasaponin Ⅰ^[19]	1 031.544 2	2.04	[M-H₂O+H]⁺	869.487 4, 723.428 1, 577.372 7, 415.320 2
23^b	19.15	C₄₅H₇₆O₁₉	Timosaponin B Ⅱ^[14]	965.495 9	6.91	[M+FA-H]^-	919.490 9, 757.437 8, 595.385 5, 433.333 0, 330.488 9
24^a	19.21	C₄₅H₇₂O₁₇	Gracillin^[18]	885.481 9	-2.60	[M+H]⁺	723.429 6, 579.315 1, 415.320 1, 271.205 2
25^a	19.36	C₅₁H₈₄O₂₂	Zingiberensis saponin^[19]	1 049.549 6	-2.95	[M+H]⁺	869.488 0, 723.429 0, 577.372 4, 415.320 2
26^a	19.39	C₃₃H₅₀O₁₀	Kammogenin-glu^[20]	607.346 2	-2.31	[M+H]⁺	445.296 1, 427.273 0, 409.273 0
27^b	19.75	C₅₁H₈₄O₂₂	Compound 36 isomer^[35]	1 093.536 6	5.69	[M+FA-H]^-	1 047.538 2, 901.477 5, 575.372 6, 431.319 3
28^a	19.81	C₃₉H₆₂O₁₄	Pennogenin-rha^[12]	755.421 8	0.79	[M+H]⁺	579.389 3, 435.273 5, 399.324 5, 285.256 5
29^a	19.84	C₃₃H₅₂O₉	D-Glucuronic acid, (3β, 5β, 25R)-spirostan-3-yl ester^[20]	593.361 7	-9.10	[M+H]⁺	417.317 6, 399.325 3, 273.220 7
30^b	19.93	C₄₅H₇₆O₁₈	Aspacochioside A^[30]	949.485 7	6.18	[M+FA-H]^-	903.495 7, 757.444 2, 595.393 7, 433.330 5, 352.469 5
31^a	20.26	C₅₀H₈₂O₂₂	Melongoside F^[19]	1 033.522 1	-0.29	[M-H]^-	901.480 7, 739.4258, 577.374 6, 415.320 3
32^a	20.34	C₄₅H₇₄O₁₇	Shatavarin Ⅵ^[9]	887.491 1	-9.80	[M+H]⁺	725.443 7, 579.389 8, 417.336 2, 399.325 9
33^a	20.50	C₃₃H₅₀O₉	Spirost-9(11)-en-12-one^[20]	591.354 6	3.21	[M+H]⁺	429.300 1, 273.220 8, 255.210 3
34^a	20.51	C₃₉H₆₀O₁₄	β-Sitosterol-3-O-β-D-glucuronoside+glc^[8]	753.403 2	-3.05	[M+H]⁺	591.351 1, 273.221 0, 255.210 2
35^a	20.52	C₅₇H₉₆O₂₈	Trigoneoside XIIIb^[27]	1 227.606 1	3.75	[M+H]⁺	1065.540 9, 903.501 7, 741.443 1
36^b	20.82	C₅₁H₈₄O₂₂	Protodioscin^[35]	1 093.536 6	1.26	[M+FA-H]^-	1 047.536 5, 915.458 5, 885.449 5, 591.354 4, 429.303 5
37^a	20.84	C₂₇H₄₄O₃	Tigogenin^[15]	417.335 7	-1.44	[M+H]⁺	399.326 4, 273.220 8, 255.210 4, 161, 132 2
38^a	20.88	C₅₁H₈₂O₂₃	Deltoside^[19]	1 063.528 1	-3.76	[M+H]⁺	901.471 9, 739.429 5, 577.372 5, 415.320 0
39^a	21.14	C₂₇H₄₀O₅	Kammogenin^[20]	445.295 5	1.57	[M+H]⁺	445.295 5, 427.283 6, 409.273 8, 273.220 8, 255.213 0
40^b	21.26	C₅₀H₈₂O₂	Anemarrhenasaponin F^[33]	1 095.516 8	2.99	[M+FA-H]^-	1 049.517 5, 917.475 3, 887.464 7, 755.424 6, 593.369 6
41^a	21.77	C₂₇H₄₂O₃	Diosgenin^[19]	415.320 3	-0.72	[M+H]⁺	397.308 4, 271.205 3, 253.194 7
42^b	21.89	C₄₅H₇₄O₁₇	Deltonin^[35]	931.491 0	1.81	[M+FA-H]^-	885.485 3, 739.426 4, 575.357 2, 413.307 7
43^a	21.98	C₃₃H₅₀O₈	Ruscogenin-rha^[11]	575.357 7	-0.17	[M+H]⁺	415.320 3, 273.220 8, 255.210 1
44^a	22.28	C₂₇H₄₀O₄	9(11)-Dehydrohecogenin^[18]	429.301	2.56	[M+H]⁺	411.288 9, 384.297 0, 273.220 8
45^a	22.30	C₅₁H₈₈O₃₁	Solanigroside E^[19]	1 195.549 6	8.93	[M-H]^-	1 063.496 6, 931.450 1, 417.303 8
46^b	22.75	C₄₅H₇₂O₁₉	Chinenoside Ⅴ^[30]	961.463 9	-5.16	[M+FA-H]^-	915.459 2, 753.409 5, 607.349 2, 445.296 4, 417.292 5
47^b	22.83	C₅₀H₈₂O₂₂	Hamoside A^[33]	1 079.528 6	2.81	[M+FA-H]^-	1 033.521 0, 901.479 0, 871.470 6, 739.435 5, 577.374 9
48^b	23.01	C₄₅H₇₂O₁₈	Vaviloside B₁/B₂^[30]	945.469 8	-6.78	[M+FA-H]^-	899.464 7, 753.407 4, 607.349 1, 445.296 1
49^a	23.55	C₂₇H₄₂O₄	Yuccagenin^[35]	431.314 1	-3.25	[M+H]⁺	395.293 0, 273.220 9, 255.075 2
50^b	26.20	C₄₅H₇₀O₁₆	Sansevistatin 1^[30]	867.474 1	5.99	[M+H]⁺	721.414 6, 575.358 3, 413.307 9
51^b	26.27	C₂₇H₄₀O₃	Episceptrumgenin^[35]	413.326 8	-4.84	[M+H]⁺	395.292 9, 271.205 1, 253.194 8
52^a	26.29	C₅₆H₉₂O₂₈	Capsicosin E1^[28]	1 211.570 7	0.42	[M-H]^-	1 079.527 1, 593.369 7, 431.317 4
53^a	26.31	C₃₉H₆₂O₁₂	Prosapogenin A of dioscin^[35]	723.428 2	-4.42	[M+H]⁺	577.392 5, 415.320 0, 271.205 3
54^a	26.40	C₅₁H₈₆O₂₃	Shatavarin Ⅰ^[9]	1 065.550 2	2.44	[M-H]^-	903.491 8, 579.388 7, 417.335 4
55^b	27.35	C₄₅H₇₂O₁₇	Pennogenin 3-O-β-chacotrioside^[30]	929.475 1	5.27	[M+FA-H]^-	883.469 3, 737.412 4, 496.438 7, 417.401 9
56^b	28.66	C₄₄H₇₂O₁₆	Smilaxchinoside C^[30]	901.480 3	-2.88	[M+FA-H]^-	855.475 2, 723.433 2, 577.374 1, 415.325 6
57^b	28.98	C₅₁H₈₄O₂₃	Timosaponin B Ⅳ^[33]	1 109.501 8	7.33	[M+FA-H]^-	1 063.532 7, 901.480 0, 739.427 8, 577.374 6
58^b	29.22	C₅₀H₈₂O₂₂	Dongnoside E^[33]	1 079.528 6	0.86	[M+FA-H]^-	1 033.522 1, 871.469 5, 739.426 6, 577.374 6
59^a	29.42	C₃₉H₆₄O₁₂	Prosapogenin B^[15]	725.445 5	-2.07	[M+H]⁺	579.388 4, 417.335 7, 255.210 3
60^b	29.47	C₄₅H₇₄O₁₈	Protobioside^[35]	947.485 0	5.98	[M+FA-H]^-	901.479 7, 739.427 2, 577.374 5, 252.392 5
61^b	29.66	C₄₅H₇₄O₁₆	Indioside Ⅰ^[30]	915.496 0	-1.89	[M+FA-H]^-	869.490 1, 723.431 9, 577.375 2, 415.330 9
Alkaloids
62^c	5.02	C₄₅H₇₁NO₁₉	Alkaloid 1^[10]	930.467 8	-0.32	[M+H]⁺	930.467 8, 912.458 2, 894.446 2, 739.974 9
63^a	5.41	C₄₅H₇₃NO₁₈	Compound 74 isomer^[10]	916.489 1	0.00	[M+H]⁺	898.476 8, 829.415 6, 670.498 4, 410.306 1
64^a	6.41	C₄₅H₇₁NO₁₈	22α, 23α-Epoxysolasodine-hex-hex-hex^[10]	914.473 3	-0.55	[M+H]⁺	878.452 9, 732.396 7, 424.285 1, 287.201 3
65^a	9.18	C₃₃H₅₃NO₈	Solasodine-OH-hex^[10]	592.385 2	2.53	[M+H]⁺	574.373 0, 433.258 1, 271.205 1
66^a	9.24	C₃₉H₆₃NO₁₃	Solasodine-OH-hex-hex^[10]	754.435 9	-0.27	[M+H]⁺	718.416 3, 572.359 8, 410.304 8
67^a	11.59	C₄₅H₇₅NO₁₈	Dihydrosolasodine-2OH-hex-hex-rha^[10]	918.504 7	-0.22	[M+H]⁺	696.667 0, 396.679 9, 269.189 5
68^b	12.35	C₄₅H₇₅NO₁₇	Compound 70 isomer^[21]	902.509 0	-1.99	[M+H]⁺	884.453 4, 756.415 5, 448.305 3, 430.290 9
69^a	12.47	C₃₉H₆₅NO₁₃	Dihydrosolasodine-2OH-hex-rha^[10]	756.451 7	0.00	[M+H]⁺	738.442 1, 269.189 7, 251.178 9
70^b	12.90	C₄₅H₇₅NO₁₇	Dihydrosolasodine-2OH-rha-rha-hex^[21]	902.509 0	-1.99	[M+H]⁺	884.506 7, 725.094 5, 430.328 7
71^b	13.45	C₄₅H₇₃NO₁₇	Compound 76 isomer^[35]	900.493 7	-1.55	[M+H]⁺	864.472 3, 834.430 8, 702.418 1, 430.334 3
72^c	14.99	C₄₅H₆₉NO₁₅	Unknown alkaloid 1	864.474 0	2.31	[M+H]⁺	583.515 0, 455.002 0, 392.297 3
73^a	15.06	C₂₇H₄₃NO₄	(3β, 22α, 25R)-3, 12-Dihydroxy-spirosol-27-oic-acid^[31]	446.326 0	0.22	[M+H]⁺	428.315 9, 410.304 8, 395.279 3, 287.200 3
74^c	15.21	C₄₅H₇₃NO₁₈	Alkaloid 2^[10]	916.490 2	0.00	[M+H]⁺	832.430 1, 592.374 2, 446.326 0, 410.308 5
75^c	15.54	C₄₅H₇₁NO₁₆	Alkaloid 3^[10]	882.483	-0.68	[M+H]⁺	864.475 3, 795.405 1, 736.425 0, 410.305 0
76^b	15.64	C₄₅H₇₃NO₁₇	Peimisine+rha+hex+rha+OH^[35]	900.493 4	-1.89	[M+H]⁺	882.481 0, 558.377 9, 412.320 4
77^a	17.31	C₃₃H₅₅NO₇	δ-Tomatine^[29]	578.403 9	-2.07	[M+H]⁺	416.336 6, 273.205 5, 255.194 3
78^a	17.31	C₂₇H₄₅NO₂	Tomatidine^[29]	416.351 8	-1.20	[M+H]⁺	398.342 0, 273.221 3, 255.210 4
79^d	17.45	C₄₅H₇₃NO₁₆	Solasonine	884.498 7	-1.70	[M+H]⁺	738.430 8, 576.392 5, 414.338 3, 396.328 5
80^a	17.49	C₃₃H₅₃NO₇	γ-Solamargine^[29]	576.388 7	-1.21	[M+H]⁺	576.388 7, 414.336 6, 396.324 1, 271.205 0
81^a	17.52	C₃₉H₆₃NO₁₂	Solanigroside P^[35]	738.440 7	-2.17	[M+H]⁺	414.334 7, 253.194 6, 157.101 0
82^b	17.86	C₅₀H₈₁NO₁₉	Sycophantine^[35]	1 000.545 5	-2.10	[M+H]⁺	868.495 5, 722.420 9, 414.329 7, 396.326 3
83^a	18.10	C₄₅H₇₃NO₁₅	δ-Solanigrine^[35]	868.504 6	-0.69	[M+H]⁺	722.445 6, 576.388 3, 414.335 6
84^a	18.32	C₄₅H₇₅NO₁₆	Solaverbascine Solatrioside^[10]	886.514 6	-1.47	[M+H]⁺	868.469 8, 740.419 5, 594.357 8, 414.299 1
85^b	18.16	C₄₅H₇₃NO₁₅	α-Solanine^[31]	912.496 0	2.99	[M+FA-H]^-	866.490 6, 720.432 7, 412.331 2
86^a	20.02	C₃₉H₆₃NO₁₁	β2-Solanine^[35]	722.446 2	-1.52	[M+H]⁺	416.351 8, 253.193 7, 157.100 9
87^c	20.69	C₃₉H₆₅NO₁₁	Unknown alkaloid 2	724.461 2	-1.10	[M+H]⁺	704.451 2, 445.495 2, 398.344 4
88^a	21.98	C₃₃H₅₃NO₉	Solasodine-2OH-hex^[10]	608.275 1	3.62	[M+H]⁺	599.177 9, 529.257 8, 479.137 6, 447.312 6
89^d	25.01	C₂₇H₄₃NO₂	Solasodine	414.336 2	-0.97	[M+H]⁺	396.325 9, 271.204 7, 253.194 7
90^a	26.56	C₂₇H₄₅NO₂	Compound 56 isomer^[29]	416.351 7	-1.44	[M+H]⁺	399.326 2, 273.220 7, 255.210 5
91^a	27.55	C₂₇H₃₉NO₂	Veratramine^[18]	410.304 9	0.49	[M+H]⁺	392.294 3, 297.221 5, 267.174 0, 249.179 1
Flavones
92^a	2.57	C₁₆H₁₂O₇	Isorhamnetin^[8]	317.059 7	0.00	[M+H]⁺	317.059 7, 302.032 6, 285.035 8
93^a	2.79	C₃₃H₄₀O₂₁	Quercetin-3-O-rutinosyl-7-O-glucoside^[24]	771.198 4	-0.65	[M-H]^-	301.032 5, 271.024 8, 255.029 8
94^b	2.83	C₃₅H₄₂O₂₃	Quercetin-3-O-rutinosyl-7-O-glucoside+O+hex+AA^[32]	829.159 2	-6.27	[M-H]^-	771.198 7, 301.032 7, 271.024 8, 255.030 0
95^a	3.82	C₄₂H₄₆O₂₂	Kaempferol 3-[2-(6-coumaroylglucosyl)-rhamnoside]7-glucoside^[18]	901.241 0	0.22	[M-H]^-	609.139 3, 285.036 0, 255.029 8
96^a	3.83	C₃₃H₄₀O₂₀	Kaempferol 3-rutinoside 4′-glucoside^[16]	757.217 3	-1.58	[M+H]⁺	449.106 4, 303.049 5, 287.054 6, 258.051 1
97^b	4.46	C₄₃H₄₈O₂₄	3-(2-Feruloylsophoroside)^[34]	947.229	-7.71	[M-H]^-	785.193 5, 609.147 6, 446.085 1, 285.030 1
98^a	4.50	C₂₇H₃₀O₁₇	Quercetin 3, 4-diglucoside^[23]	625.141 2	0.32	[M-H]^-	301.033 6, 300.027 6, 283.024 7, 255.029 8
99^e	4.60	C₂₉H₃₂O₁₉	Unknown flavone 1	683.099 3	-0.73	[M-H]^-	625.141 2, 301.033 9, 271.024 8
100^b	4.62	C₃₁H₃₄O₁₈	Isoscutellarein 7-O-[2, 6-di-O-acetyl]allosyl(1→2)glucoside^[32]	693.128 4	1.73	[M-H]^-	625.141 9, 301.034 2, 271.024 8, 255.029 9
101^b	4.64	C₃₁H₃₅O₁₉	Peonidin, 3-(6-malonyl-glucoside), 5-glucoside^[32]	710.118 0	-4.08	[M-H]^-	625.141 4, 301.826 9, 271.907 2
102^e	5.04	C₃₁H₃₅O₁₈	Unknown flavone 2	694.119 8	-6.05	[M-H]^-	609.146 5, 301.032 0, 271.024 8
103^a	5.14	C₂₉H₃₂O₁₈	Euphorbianin^[32]	667.104 9	-0.15	[M-H]^-	609.145 6, 477.043 4, 300.027 6
104^e	5.19	C₁₈H₁₂O₇	Unknown flavone 3	341.082 4	-9.38	[M+H]⁺	301.142 0, 285.039 1, 257.036 9
105^b	5.36	C₃₁H₃₄O₁₇	Pelargonidin 3, 5-di-(6-acetylglucoside)^[34]	677.133 5	-0.74	[M-H]^-	609.146 6, 271.024 7, 255.030 0
106^a	5.98	C₂₇H₃₀O₁₆	Kaempferol-3-O-sophoroside^[20]	611.163 7	4.91	[M+H]⁺	449.109 5, 303.048 9, 287.054 7
107^e	6.10	C₂₇H₃₂O₁₇	Unknown flavone 4	629.171 2	3.66	[M+H]⁺	445.154 1, 385.134 6, 303.092 7, 285.081 6
108^a	6.12	C₂₁H₂₀O₁₀	Trihydroxy flavone C-glc^[12]	433.112 5	-1.15	[M+H]⁺	369.124 4, 287.054 7, 213.054 2
109^b	6.14	C₃₁H₃₅O₁₇	Pelargonidin 3, 5-di-(6-acetylglucoside)^[32]	678.125 2	-5.60	[M-H]^-	593.151 3, 273.123 2, 255.029 9
110^b	6.14	C₃₁H₃₄O₁₆	Crassirhizomoside B^[32]	661.139 1	-8.02	[M-H]^-	593.152 7, 447.093 0, 431.096 9
111^a	6.33	C₂₆H₂₈O₁₄	Apigenin 6-C-glucosyl-O-arabinoside^[24]	563.140 4	-0.36	[M-H]^-	417.084 1, 255.030 0, 227.035 2
112^e	6.81	C₃₁H₄₀O₁₅	Unknown flavone 5	651.109	-1.54	[M-H]^-	593.150 1, 284.033 1, 255.030 8
113^a	7.03	C₂₁H₂₀O₁₂	Hyperoside^[12]	463.087 6	-1.08	[M-H]^-	301.034 3, 271.024 9, 255.029 8
114^a	7.24	C₂₉H₃₆O₁₆	Tetrahydroxymethoxyflavone O-dihex^[12]	641.207 9	-0.47	[M+H]⁺	317.065 2, 302.041 8, 285.038 7, 229.048 9
115^b	7.40	C₄₃H₄₈O₂₃	Kaempferol-3-neohesperidoside-7-(2-ferulylglucoside)^[32]	931.249 2	-3.01	[M-H]^-	785.193 5, 609.148 3, 430.089 5, 285.039 8
116^e	7.45	C₄₃H₄₈O₂₃	Unknown flavone 6	933.265 9	-8.61	[M+H]⁺	583.413 1, 433.113 9, 287.055 6, 258.052 3
117^a	7.49	C₂₁H₂₀O₁₂	Quercetin-3-O-galactoside^[13]	465.100 2	-5.38	[M+H]⁺	303.049 7, 285.038 6, 165.016 8, 85.027 1
118^b	7.51	C₂₅H₂₅O₁₄	Cyanidin 3-(6-succinyl-glucoside)^[34]	548.117 1	0.00	[M-H]^-	463.084 4, 447.197 5, 285.084 4, 255.083 9
119^a	9.26	C₂₁H₂₀O₁₁	Kaempferol-3-O-glucoside^[24]	447.093 4	0.45	[M-H]^-	447.093 4, 285.038 7, 255.029 9, 227.035 0
120^a	10.43	C₂₁H₂₂O₁₂	Glucodistylin^[23]	449.107 4	0.89	[M+H]⁺	449.107 4, 287.054 6, 258.051 5, 213.054 2
121^a	11.37	C₂₂H₂₂O₁₂	Tetrahydroxymethoxyflavone 3-O-hex^[12]	479.118 0	-0.83	[M+H]⁺	479.118 0, 393.186 2, 317.065 1, 285.038 6
122^a	17.25	C₁₅H₁₀O₇	Quercetion^[24]	301.035 5	0.33	[M-H]^-	271.025 0, 255.041 1, 163.015 9, 83.027 6
123^e	18.91	C₃₁H₃₄O₁₅	Unknown flavone 7	647.197 0	1.89	[M-H]^-	595.383 5, 577.374 8, 393.202 2, 316.167 9
124^a	26.03	C₂₇H₃₀O₁₆	Rutin^[26]	609.146 4	0.49	[M-H]^-	429.206 6, 380.366 4, 315.050 0, 275.201 7
125^a	26.65	C₂₇H₃₀O₁₅	Kaempferol-3-O-glucoside-7-O-rhamnoside^[20]	593.151 2	0.17	[M-H]^-	418.226 8, 299.043 8, 225.007 5
126^a	31.39	C₂₇H₃₀O₁₄	Kaempferitrin^[16]	577.156 8	0.69	[M-H]^-	428.284 1, 299.044 6, 225.007 5
Others
127^a	0.96	C₁₂H₂₂O₁₁	Sucrose^[8]	341.108 9	-0.59	[M-H]^-	179.056 2, 119.036 0, 89.024 4
128^a	0.97	C₆H₉N₃O₂	Histidine^[22]	156.076 6	-1.28	[M+H]⁺	131.974 4, 110.071 6
129^a	1.02	C₆H₁₂O₇	Galacturonic acid^[11]	195.050 9	-0.51	[M-H]^-	177.040 5, 159.029 9
130^a	1.07	C₉H₁₁NO₃	Tyrosine^[11]	182.081 0	-0.55	[M+H]⁺	165.045 7, 136.075 8, 107.049 7
131^a	1.16	C₆H₅NO₂	Nicotinic acid^[22]	124.039 6	2.42	[M+H]⁺	106.029 4, 80.050 0, 78.034 4
132^a	1.17	C₁₂H₂₁NO₆	9-Amino-1, 3, 9-nonane dicarboxylic acid^[11]	276.144 4	1.09	[M+H]⁺	258.133 6, 230.138 7, 161.068 3
133^a	1.10	C₆H₁₁NO₂	Pipecolic acid^[8]	130.049 8	-9.22	[M+H]⁺	84.044 8, 67.053 7, 62.024 6, 56.048 9
134^a	1.13	C₅H₇NO₃	Pyroglutamic acid^[8]	130.050 1	1.54	[M+H]⁺	84.044 9, 69.070 5, 56.050 1
135^a	1.63	C₁₀H₁₃N₄O₃	Histidyl asparagine^[11]	238.106 7	2.94	[M+H]⁺	192.102 2, 120.995 9, 103.054 6
136^a	1.73	C₁₂H₁₅NO₅	Serine^[11]	254.102 1	-0.39	[M+H]⁺	208.058 2, 136.990 6, 119.118 4
137^a	1.87	C₁₁H₁₂N₂O₂	Tryptophan^[8]	205.097 2	0.49	[M+H]⁺	188.070 7, 170.060 1, 159.091 8
138^a	1.87	C₁₁H₉NO₂	Indole-3-acrylic acid^[11]	188.070 3	-1.60	[M+H]⁺	146.060 2, 186.065 4
139^a	1.92	C₇H₆O₄	Protocatechuic acid^[8]	153.019 4	2.61	[M-H]^-	109.029 5, 91.018 9, 81.034 6
140^a	2.48	C₁₆H₁₈O₉	Chlorogenic acid^[8]	355.100 1	-6.20	[M+H]⁺	181.050 1, 145.026 7, 135.041 6, 117.033 7
141^a	3.08	C₁₆H₁₈O₉	Neochlorogenic acid^[11]	353.089 9	-2.27	[M-H]^-	191.056 2, 179.035 2, 162.027 8
142^a	3.13	C₁₆H₂₄O₁₀	Vitamin B₂^[8]	377.144 9	1.86	[M+H]⁺	243.087 3, 172.086 6, 99.044 3,
143^a	3.34	C₉H₈O₄	Caffeic acid^[8]	179.034 7	-1.12	[M-H]^-	135.044 6, 112.984 9, 89.023 5
144^a	3.49	C₁₆H₁₈O₈	p-Coumaroylquinic acid^[8]	339.106 9	-1.47	[M+H]⁺	147.043 9, 119.049 2, 91.054 5
145^a	4.01	C₅H₅N₅	Adenine^[8]	136.061 8	0.73	[M+H]⁺	119.049 3, 94.065 5, 92.049 7
146^a	5.44	C₉H₈O₃	p-Coumaric acid^[8]	163.040 6	0.00	[M-H]^-	119.051 1, 91.053 7
147^a	5.56	C₈H₁₆N₂O₃	Glycyl-L-leucine^[11]	189.121 8	-7.93	[M+H]⁺	171.149 0, 130.086 2, 84.081 2
148^a	7.42	C₁₀H₁₀O₄	Isoferulic acid^[8]	195.063 9	-6.66	[M+H]⁺	177.054 4, 149.059 6, 117.033 5
149^a	8.24	C₅H₉NO₄	L-Glutamic acid^[8]	148.060 2	-1.35	[M+H]⁺	130.069 2, 103.054 4, 84.044 7
150^a	8.54	C₆H₁₂O₇	Glucuronic acid^[8]	197.063 9	-8.63	[M+H]⁺	179.106 4, 161.095 9, 133.101 1
151^a	8.58	C₈H₁₆N₂O₃	Compound 147 isomer^[11]	189.121 8	-7.93	[M+H]⁺	156.093 1, 129.070 0, 105.070 1
152^a	9.65	C₉H₁₂N₂O₆	Uridine^[22]	245.079 1	9.38	[M+H]⁺	203.123 7, 189.112 0, 135.080 1
153^a	11.67	C₁₂H₁₈O₂	Serdanolide^[8]	195.137 6	-1.54	[M+H]⁺	167.085 0, 135.044 0, 111.044 2
154^a	21.65	C₁₀H₁₀O₄	Ferulic acid^[22]	195.063 2	-9.74	[M+H]⁺	177.091 1, 149.067 2, 89.065 9
155^a	26.49	C₂₃H₂₄O₉	Diferuloylglycerol^[8]	445.147 9	-3.15	[M+H]⁺	271.205 2, 253.194 7
156^a	27.87	C₁₆H₃₀O	Muscone^[8]	239.235 7	-5.02	[M+H]⁺	183.116 6, 197.132 2, 119.085 7, 81.068 6
157^a	28.20	C₁₈H₃₅NO	Oleamide^[8]	282.278 7	-1.42	[M+H]⁺	247.241 6, 135.116 8, 121.101 2

Aglycone	Adduct ion	Characteristic ion
Diosgenin	[M+H]⁺	415.320 3, 397.308 4, 271.205 3, 253.194 7
Tigogenin	[M+H]⁺	417.335 7, 399.326 4, 273.220 8, 255.210 4
Furosta-5β, 3β, 20α, 26-triol	[M+H]⁺	435.270 4, 417.266 5, 291.215 5, 273.221 5

Aglycone	Adduct ion	Characteristic ion
Diosgenin	[M+H]⁺	415.320 3, 397.308 4, 271.205 3, 253.194 7
Tigogenin	[M+H]⁺	417.335 7, 399.326 4, 273.220 8, 255.210 4
Furosta-5β, 3β, 20α, 26-triol	[M+H]⁺	435.270 4, 417.266 5, 291.215 5, 273.221 5

Aglycone	Adduct ion	Characteristic ion
Veratramine	[M+H]⁺	410.304 9, 392.294 3, 295.221 5, 267.174, 249.179 1
Solasodine	[M+H]⁺	414.336 2, 396.325 9, 271.204 7, 253.194 7
Tomatidine	[M+H]⁺	416.351 8, 398.342 1, 273.221 3, 255.210 4
Spirosol-5-ene-3, 12-diol	[M+H]⁺	430.331 2, 412.320 7, 394.313 1, 271.205 6

Aglycone	Adduct ion	Characteristic ion
Veratramine	[M+H]⁺	410.304 9, 392.294 3, 295.221 5, 267.174, 249.179 1
Solasodine	[M+H]⁺	414.336 2, 396.325 9, 271.204 7, 253.194 7
Tomatidine	[M+H]⁺	416.351 8, 398.342 1, 273.221 3, 255.210 4
Spirosol-5-ene-3, 12-diol	[M+H]⁺	430.331 2, 412.320 7, 394.313 1, 271.205 6

基于UHPLC-Q Exactive MS的分子网络技术快速分析龙葵叶物质成分

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董现龙 , 杨琳娇 , 秦雪梅 , 李震宇 ^*

药学学报 | 研究论文 2023,58(4): 1003-1013

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药学学报 | 研究论文 2023, 58(4): 1003-1013

基于UHPLC-Q Exactive MS的分子网络技术快速分析龙葵叶物质成分

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董现龙, 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 the chemical compounds in the leaves of Solanum nigrum L. based on UHPLC-Q Exactive MS and molecular network technology

Xian-long DONG, 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: 2023-04-12 doi: 10.16438/j.0513-4870.2022-1162

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摘要

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龙葵(Solanum nigrum L.) 全草均可入药。本研究采用UHPLC-Q Exactive高分辨质谱结合GNPS分子网络(global natural products social molecular networking), 对龙葵叶的化学成分进行快速表征。通过与文献报道数据比较, 并结合质谱裂解特征规律分析, 以及GNPS分子网络中已知和未知节点的关联分析, 从龙葵叶中共鉴定157个化合物, 包括甾体生物碱30个, 甾体皂苷61个, 黄酮类35个, 氨基酸、有机酸等其他类型化合物31个。与龙葵果和龙葵茎相比, 龙葵叶中甾体皂苷、甾体生物碱、黄酮类成分的种类均较为丰富, 本研究结果为龙葵药材资源的精准利用奠定了基础。

关键词

UHPLC-Q Exactive MS / 龙葵 / GNPS分子网络 / 甾体生物碱 / 甾体皂苷 / 黄酮

Abstract

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The whole herb of Solanum nigrum L. can be used as the herbal drug. In this study, UHPLC-Q Exactive high resolution mass combined with GNPS molecular network was used for the rapid characterization of the components in the leaves of S. nigrum L. A total of 157 compounds were identified, including 30 steroid alkaloids, 61 steroid saponins, 35 flavonoids, and 31 other compounds (amino acids and organic acids), by comparison with the data reported in the literature, and mass fragmentation characteristics analysis, as well as the correlation of known and unknown nodes in the GNPS molecular network. Compared with the fruits and stems, the leaves of S. nigrum L was rich in a variety of steroidal saponins, steroidal alkaloids, and flavonoids, and the results lay the foundation for the precise resources utilization of S. nigrum L.

Key words

UHPLC-Q Exactive MS / Solanum nigrum L. / GNPS molecular network / steroid alkaloids / steroid saponins / flavonoids

引用本文

董现龙, 杨琳娇, 秦雪梅, 李震宇. 基于UHPLC-Q Exactive MS的分子网络技术快速分析龙葵叶物质成分. 药学学报, 2023 , 58 (4) : 1003 -1013 . DOI: 10.16438/j.0513-4870.2022-1162

Xian-long DONG, Lin-jiao YANG, Xue-mei QIN, Zhen-yu LI. Rapid identification of the chemical compounds in the leaves of Solanum nigrum L. based on UHPLC-Q Exactive MS and molecular network technology[J]. Acta Pharmaceutica Sinica, 2023 , 58 (4) : 1003 -1013 . DOI: 10.16438/j.0513-4870.2022-1162

正文

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龙葵为茄科茄属植物(Solanum nigrum L.), 具有清解热毒、消肿散结、消炎利尿的功效。文献^[1]研究表明龙葵的化学成分主要为甾体皂苷类生物碱、龙葵多糖、矿物质、维生素、色素、氨基酸等。龙葵全草均可入药, 现有的化学研究^[2]大多针对全草, 结果表明龙葵中含有多种甾体生物碱、甾体皂苷和黄酮类成分等。已有文献表明, 对于全草类中药材, 不同的部位的化学成分和生物活性存在差异, 如薄荷^[3]和蒲公英^[4]。文献^{[5, 6]}报道龙葵叶具有显著的抗氧化作用, 对谷氨酸诱导星形胶质细胞的氧化损伤具有保护作用; 此外, 龙葵叶对束缚应激导致的肝脏损伤具有保护作用。然而, 目前尚未开展单独针对龙葵叶化学成分的研究。

UHPLC-Q Exactive高分辨质谱技术具有高分辨率、高灵敏度、用时短、扫描范围广等特点, 现已广泛运用到药用植物的化学成分快速鉴定研究中。GNPS分子网络^{[7, 8]}是近年发展起来的天然产物可视化鉴定技术, 结构类似的天然产物具有相似的特征碎片离子, 根据相似度可以生成可视化的分子网络图, 每一个节点表示一个化合物。借助分子网络技术, 可以根据已知的化合物发现潜在的未知同类型成分。目前, 液质联用结合分子网络技术已经成功的运用到多种药用植物成分的快速分析和鉴定中, 如炮附片^[7]、芦笋^[8]和黄山药^[9]等。

本课题组前期已对龙葵果^[10]和龙葵茎^[11]分别进行了化学成分解析, 本研究基于UHPLC-Q Exactive高分辨质谱技术和GNPS分子网络技术对龙葵叶的化学成分进行快速解析。

材料与方法

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仪器 Thermo Fisher U3000超高效液相色谱仪, 配置在线脱气机、四元梯度泵、柱温箱、自动进样器, Thermo Scientific^TM Q Exactive组合型四极杆Orbitrap质谱仪(美国Thermo Fisher Scientific公司); 十万分之一天平(梅特勒-托利多仪器有限公司); KQ5200E超声波清洗器和XK-80A快速混匀器(江苏新康医疗器械有限公司)。

试剂与样品 龙葵2019年8月采集于山西省五台县蒋坊乡, 由山西药科职业学院刘林凤教授鉴定为茄科茄属植物龙葵的全草。甲醇(分析纯, 天津市大茂化学试剂厂), 甲酸、乙腈(色谱纯, 美国Thermo公司), 超纯水由Milli-Q Integral Water Purification System (美国Millipore公司) 制备。澳洲茄胺对照品(批号19121-58-5, 纯度94.5%)、澳洲茄碱对照品(批号20318-30-3, 纯度≥ 95%) 均购买于上海安奈德化学技术中心。

色谱条件 Waters Acquity UPLC HSS T3色谱柱(100 mm × 2.1 mm, 1.8 µm), 流动相0.1%甲酸水溶液(A)-乙腈(B); 梯度洗脱(0~15 min, 5%~20% B; 15~20 min, 20%~35% B; 20~30 min, 35%~55% B)。柱温为35 ℃, 流速为0.25 mL·min^-1, 进样量为1 μL。

质谱条件 Full MS/DD MS 2 (TOPN): 采用电喷雾离子源(HESI); 扫描方式采用正负离子同时扫描; 毛细管温度为320 ℃; 鞘气体积流量为35 psi (1 psi ≈6.9 kPa), 辅助气体积流量为10 psi; 正离子模式下喷雾电压为3.5 kV, 负离子模式喷雾电压下为2.5 kV, 透镜电压为55 kPa; 探头加温器温度为300 ℃; 最大喷雾电流为100 V; 碰撞能量梯度为20、40、60 eV; 扫描质量范围为m/z 80~1 200 Da, 质量分辨率70 000。

供试品溶液的制备 取龙葵叶粉碎, 精密称取粉末0.50 g, 置于10 mL玻璃管中, 加50%甲醇溶液6.0 mL, 涡旋1 min, 超声提取25 min, 放冷至室温, 3 500 r·min^-1离心25 min, 取上清液经0.22 µm微孔滤膜滤过, 用于UHPLC-Q Exactive MS分析。

GNPS分子网络建立 利用Reifycs-Abf Conventor软件将原始质谱数据转换为abf格式的文件, 然后利用MS-DIAL处理abf的数据, 将abf格式的数据输出为GNPS网站所需要的mgf格式, 处理好的数据利用WinSCP软件将待分析数据连接到GNPS平台(http://gnps.ucsd.edu), 分别建立GNPS网络。数据分析在Cytoscape 3.7.2软件中进行。

化合物结构解析 采用Thermo Xcalibur 3.2软件对采集到的原始质谱数据进行分析处理。通过分析目标化合物的一级和二级质谱数据, 结合文献报道的质谱数据和标准品对照, 以及HMDB、Pubchem和SciFinder等数据库进行化合物结构鉴定。

结果

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1 龙葵叶化学成分的定性分析

正、负模式下的龙葵叶的总离子流图分别如图 1所示, 根据文献^[8-35]报道的数据以及GNPS分子网络共鉴定出157个化合物(表 1)。

1.1 采用UHPLC-Q Exactive MS表征龙葵中的皂苷类和生物碱类成分

甾体皂苷是龙葵中的重要活性成分。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41个, 其中包括以薯蓣皂苷元(diosgenin, 图 2A) 为苷元的甾体皂苷11个, 以替告皂苷元(tigogenin, 图 2B) 为苷元的甾体皂苷14个, 以furosta-5β, 3β, 20α, 26-triol (图 2C) 为苷元的甾体皂苷2个, 以去9(11)-去氢海柯皂苷元[9(11)-dehydrohecogenin] 为苷元的甾体皂苷4个, 以卡莫皂苷元(kammogenin) 为苷元的甾体皂苷2个, 以曼诺皂苷元(manogenin) 为苷元的甾体皂苷1个, 以丝蓝皂苷元(yuccagenin) 为苷元的甾体皂苷3个, 以及其他类型皂苷4个, 包括solanigroside C^[2]、dihydrosolanigroside C^[12]、shatavarin I和solanigroside Y5^[13]。

龙葵中皂苷类化合物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)生成苷元离子, 即相应的皂苷元。在正离子模式下, 以替告皂苷元为苷元的龙葵皂苷脱去糖基后会产生m/z 417.335 7 [M+H]⁺, 进一步失去H₂O分子产生碎片m/z 399.326 4 [M+H-H₂O]⁺, 随后失去侧链C₈H₁₆O₂得到特征碎片m/z 255.210 4 [M+H-H₂O-C₈H₁₆O₂]⁺, 或直接失去侧链C₈H₁₆O₂得到特征碎片m/z 273.220 8 [M+H-C₈H₁₆O₂]⁺ (表 2)。薯蓣皂苷元比替告皂苷元多了C5, C6位的不饱和双键, 因此薯蓣皂苷元和替告皂苷元有相似的裂解规律。正离子模式下, 以薯蓣皂苷元为苷元的皂苷在脱去糖基后产生m/z 415.320 3 [M+H]⁺, 然后依次失去H₂O、C₈H₁₆O₂得到碎片m/z 397.308 4 [M+H-H₂O]⁺、m/z 253.194 7 [M+H-H₂O-C₈H₁₆O₂]⁺, 或直接失去C₈H₁₆O₂得到特征碎片m/z 271.205 3 [M+H-C₈H₁₆O₂]⁺。furosta-5β, 3β, 20α, 26-triol为呋甾烷醇型甾体皂苷, 该皂苷元在F环处为开环结构^[14], 正离子模式下, 以furosta-5β, 3β, 20α, 26-triol为苷元的皂苷在脱去糖基后产生m/z 435.270 4 [M+H]⁺, 然后依次失去H₂O、C₈H₁₆O₂、H₂O得到碎片m/z 417.266 5 [M+H-H₂O]⁺、m/z 273.221 5 [M+H-H₂O-C₈H₁₆O₂]⁺, 或直接失去C₈H₁₆O₂得到特征碎片m/z 291.215 5 [M+H-C₈H₁₆O₂]⁺。

除了甾体皂苷类, 龙葵中还富含甾体生物碱类成分。通过文献报道、数据库比对共解析出22个生物碱化合物, 其中包括以藜芦胺(veratramine, 图 3A) 为苷元的甾体生物碱5个, 以澳洲茄胺(solasodine, 图 3B) 为苷元的甾体生物碱8个、番茄碱(tomatidine, 图 3C) 为苷元的甾体生物碱5个, 以spirosol-5-ene-3, 12-diol (图 3D) 为苷元的甾体生物碱2个, 以及其他类型苷元的甾体生物碱2个。这4类生物碱苷元的特征离子碎片如表 3所示。

龙葵生物碱类化合物具有如下质谱裂解规律(表 3)。澳洲茄胺比番茄碱多了C5, C6位的不饱和双键, spirosol-5-ene-3, 12-diol比澳洲茄胺多了一个羟基取代, 因此spirosol-5-ene-3, 12-diol、澳洲茄胺和番茄碱为苷元的甾体生物碱具有相似的裂解规律(表 2)。如以番茄碱为苷元的生物碱在正离子模式下脱去糖基后产生m/z 416.351 8 [M+H]⁺, 然后依次失去H₂O、C₈H₁₇NO得到碎片m/z 398.342 1 [M+H-H₂O]⁺、m/z 255.210 4 [M+H-H₂O-C₈H₁₇NO]⁺, 或直接失去C₈H₁₇NO得到特征碎片m/z 273.221 3 [M+H-C₈H₁₇NO]⁺。藜芦胺结构与其他生物碱苷元不同, 其裂解规律也有区别。正离子模式下, 以藜芦胺为苷元的生物碱在脱去糖基后产生m/z 410.304 9 [M+H]⁺, 然后失去C₂₂-C₂₇部分(C₆H₁₂NO) 得到碎片m/z 295.221 5 [M+H-C₆H₁₂NO]⁺, 进而得到m/z 267.174 0 [M+H-C₆H₁₂NO-2CH₂]⁺。此外, m/z 410.304 9 [M+H]⁺还可依次失去H₂O和C₈H₁₃O得到m/z 392.294 3 [M+H-H₂O]⁺和m/z 249.179 1 [M+H-H₂O-C₈H₁₇NO]⁺, 或直接失去C₈H₁₇NO得到m/z 267.174 0 [M+H-C₈H₁₇NO]⁺。

由于龙葵中皂苷类成分和生物碱成分结构相似, 所以皂苷类化合物和生物碱类化合物聚集在同一个分子网络图中。如图 4所示, 分子网络中包含15个生物碱类节点和56个皂苷类节点。

化合物50在分子网络中的准分子离子为m/z 867.474 1 [M+H]⁺, 与纤细薯蓣皂苷(gracillin, 分子离子为m/z 885.481 9 [M+H]⁺, 分子式为C₄₅H₇₂O₁₇) 之间存在m/z 18.01的质量差, 对应2个H和1个O, 故推测化合物50的分子式为C₄₅H₇₀O₁₆。从质谱图中提取该化合物的二级碎片信息, 在正离子模式下, 二级质谱图中化合物50呈现的裂解途径为m/z 867.474 1→m/z 721.414 6→m/z 575.358 3→m/z 413.307 9, 质量数依次相差m/z 162.05、146.05、146.05, 提示该化合物50可能是以episceptrumgenin为苷元, 以hex、rha和rha为糖基取代基, 推测化合物50为sansevistatin Ⅰ (图 5A)。通过分子网络技术, 共推测20个皂苷类化合物, 其中2个皂苷化合物为episceptrumgenin的衍生物, 而另外18个皂苷化合物为furosta-5β, 3β, 20α, 26-triol的衍生物, 20个皂苷化合物均为首次在龙葵中报道。

化合物82在分子网络中的准分子离子为m/z 1 000.545 5 [M+H]⁺, 与澳洲茄边碱(δ-solanigrine, 分子离子为m/z 868.504 6 [M+H]⁺, 分子式为C₄₅H₇₃NO₁₅) 之间存在m/z 132.05的质量差, 对应1个木糖(C₄H₈O₄), 故推测其分子式为C₄₅H₇₃NO₁₇。化合物82的裂解途径与澳洲茄边碱相似, 推测其以澳洲茄胺为苷元, 具有2个rha、1个hex和1个xyl为取代基的生物碱化合物, 可能为sycophantine (图 5B)。通过分子网络技术, 解析出4个生物碱节点, 由于存在同分异构体, 涉及6个首次在龙葵中报道的生物碱化合物, 包括以澳洲茄胺为苷元的1个, 以番茄碱为苷元的1个, 以贝母辛(peimisine) 为苷元的2个, 以spirosol-5-ene-3, 12-diol为苷元的2个。

1.2 黄酮类

龙葵除了皂苷、生物碱类化合物外, 还含有黄酮类物质。龙葵黄酮类化合物多以异鼠李素、槲皮素和山柰酚为母核。通过文献比对和质谱裂解规律的分析, 鉴定出黄酮类化合物19个, 其中包括以槲皮素为母核的化合物有6个, 以山柰酚为母核的化合物9种, 以异鼠李素为母核的化合物有4个。

化合物97在分子网络中的准分子离子为m/z 947.229 0 [M-H]^-, 化合物97与已鉴定的化合物95 (C₄₂H₄₆O₂₂, m/z 901.241 0 [M-H]^-) 之间存在m/z 46.001的质量差, 差值对应1个CH₂O和1个O, 推测化合物97的分子式为C₄₃H₄₈O₂₄。根据其裂解途径(图 6): m/z 947.229 0 [M-H]^-、m/z 785.193 5 [M-H-hex]^-、m/z 609.147 6 [M-H-hex-ferulic acid]^-、m/z 447.085 1 [M-H-hex-FA-hex]^-、285.030 1 [M-H-hex-FA-hex-hex]^-, 255.029 9 [M-H-hex-FA-hex-hex-CO-H]^-, 推测母核为山柰酚, 并具有3个hex和1个阿魏酸(ferulic acid) 取代基, 结构可能为3-(2-feruloylsophoroside)。通过分子网络技术, 鉴定了9个黄酮节点(图 7), 这9个黄酮类分子式均为首次在龙葵中报道, 包括以槲皮素图为母核的2个, 以山柰酚图为母核的5个, 以贝母辛为母核的1个, 以异鼠李糖苷为母核的1个。

1.3 其他化合物

龙葵中除了皂苷、黄酮、生物碱等化合物外还存在氨基酸类、酚酸类等化合物^[11], 这些化合物分别为: 12个氨基酸类化合物(包括组氨酸、缬氨酸、丝氨酸和色氨酸等); 2个核苷类化合物(包括尿苷, 腺嘌呤); 7个酚酸类化合物(包括绿原酸、新绿原酸和咖啡酸等); 2个维生素类化合物(烟酸、维生素B₂); 2个糖醛酸类化合物(葡萄糖醛酸、半乳糖醛酸); 2个内酯类化合物(包括瑟丹内酯、对香豆酸); 还包括蔗糖、酰胺等其他类化合物, 共计31个化合物。

讨论

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本研究采用UHPLC-Q Exactive MS结合GNPS分子网络技术对龙葵叶的化学成分进行了鉴定, 共鉴定化合物157个, 包括生物碱30个、皂苷化合物61个、黄酮化合物35个、氨基酸类和酚酸类等化合物31个。其中通过与文献报道的数据比较鉴定出122个化合物, 借助GNPS分子网络技术后进一步解析了35个化合物, 均为首次在龙葵中报道的化合物, 包括6个生物碱类、20个甾体皂苷、9个黄酮。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, 基于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^[8], 能够加速促进未知化合物的指认。本研究将UHPLC-Q Exactive MS与GNPS分子网络技术结合, 实现了对龙葵叶的化学成分进行快速、全面地鉴定。

课题组前期从龙葵茎^[11]中共鉴定化合物89个, 包括甾体生物碱5个、黄酮1个、甾体皂苷28个, 以及其他类型化合物55个; 从龙葵果^[10]中鉴定化合物170个, 包括甾体生物碱114个、黄酮2个、5种甾体皂苷5个, 以及其他结构化合物49个。可见, 龙葵果富含多种甾体生物碱成分, 而龙葵茎富含多种甾体皂苷成分。与龙葵果和龙葵茎相比, 龙葵叶中甾体皂苷、甾体生物碱、黄酮类成分的种类均较为丰富。从化学多样性来看, 龙葵茎、叶、果3个不同的部位各有特点。研究结果为龙葵药材资源的精准利用奠定了基础。然而, 目前的结果仅仅是化学成分种类的比较, 在后续的工作中还将通过代谢组学结合多指标含量测定对3个不同的部位进行含量的比较。

作者贡献: 董现龙、杨琳娇负责实验研究工作及数据分析处理, 并撰写稿件; 秦雪梅参与文章的监督和修改; 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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山西省现代农业产业技术体系建设专项资金资助(2021-11)

参考文献

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2023年第58卷第4期

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doi: 10.16438/j.0513-4870.2022-1162

接收时间：2022-11-01
首发时间：2025-11-21
出版时间：2023-04-12

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收稿日期：2022-11-01
修回日期：2023-03-14

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山西省现代农业产业技术体系建设专项资金资助(2021-11)

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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	Molecular formula	Identification	Mass	Error (×10^-6)	Ion	Fragment ion
Saponins
1^a	2.96	C₂₇H₄₄O₄	Gitogenin^[28]	433.332 3	2.54	[M+H]⁺	415.320 8, 397.309 8, 271.205 3
2^a	3.94	C₂₇H₄₂O₅	Manogenin^[20]	447.306 9	-8.05	[M+H]⁺	429.119 1, 273.220 9, 255.210 2, 161.132 2
3^a	14.72	C₅₁H₈₂O₂₆	Solanigroside C^[31]	1 133.498 0	-0.53	[M+Na]⁺	971.444 8, 809.3927, 647.342 5, 467.137 5
4^a	15.70	C₅₇H₉₄O₂₈	Solanigroside Y5^[19]	1 271.591 8	2.16	[M+FA-H]^-	1 225.585 7, 1 063.538 0, 757.365 7, 431.310 6
5^a	16.65	C₂₇H₄₆O₄	25S-Furosta-5β, 3β, 20α, 26-triol^[23]	435.270 4	3.79	[M+H]⁺	417.266 5, 291.215 5, 273.221 5
6^b	16.89	C₅₆H₉₂O₂₈	Timosaponin H1^[33]	1 257.574 8	2.32	[M+FA-H]^-	1 211.570 9, 1 079.526 6, 1 049.519 7, 755.422 9, 593.369 9
7^a	16.91	C₃₃H₅₂O₈	Trillin^[17]	577.374 9	2.42	[M+H]⁺	415.320 5, 271.205 1, 253.194 8
8^a	16.93	C₅₁H₈₀O₂₆	Solanigroside Y3^[13]	1 131.482 2	-0.71	[M+Na]⁺	969.429 0, 807.377 8, 645.324 5
9^a	18.10	C₃₃H₅₄O₈	Tigogenin-hex^[10]	579.391 4	3.97	[M+H]⁺	579.391 4, 417.335 2, 399.335 2, 273.220 8
10^a	18.14	C₅₇H₉₄O₂₈	Trigoneoside XIIIa^[27]	1 227.589 4	-8.96	[M+H]⁺	904.140 3, 741.440 7, 579.388 1, 417.335 8
11^a	18.17	C₃₉H₆₄O₁₃	Timosaponin AⅢ^[28]	741.444 5	3.51	[M+H]⁺	579.388 2, 417.334 4, 273.220 8
12^a	18.23	C₅₇H₉₄O₂₇	Yuccaloiside B^[28]	1 193.604 7	8.21	[M-H₂O+H]⁺	1 031.536 3, 723.429 8, 577.372 4, 415.320 3
13^a	18.23	C₄₅H₇₄O₁₈	Shatavarin Ⅸ^[8]	903.494 1	-0.66	[M+H]⁺	741.439 1, 579.621 9, 417.335 6
14^a	18.23	C₅₇H₉₄O₂₇	Solanigroside Y6^[13]	1 255.595 2	2.69	[M+FA-H]^-	1 209.590 9, 1 047.538 0, 901.483 5, 755.423 2, 593.366 6, 431.316 0, 413.308 4
15^a	18.25	C₃₉H₆₂O₁₃	Diosgenin 3-O-cellobioside^[13]	739.427 4	1.49	[M+H]⁺	577.372 6, 415.320 1, 271.205 4, 253.194 7
16^b	18.41	C₅₁H₈₆O₂₄	Tomatoside A^[30]	1 117.520 4	5.61	[M+FA-H]^-	1 081.543 1, 919.492 0, 757.437 3, 595.384 9, 433.337 0
17^a	18.59	C₅₀H₈₂O₂₂	Degalactotigonin^[28]	1 035.544 9	7.63	[M+H]⁺	873.481 0, 741.441 0, 579.388 5, 417.335 8
18^a	18.70	C₅₆H₉₂O₂₇	Diurnoside^[25]	1 197.589 1	-0.58	[M+H]⁺	1035.534 3, 741.440 4, 579.388 2, 417.335 5
19^a	18.82	C₃₃H₅₂O₁₀	Chonglouoside SL-10^[12]	609.364 1	1.31	[M+H]⁺	609.364 1, 447.310 1, 429.299 6, 411, 288 5
20^a	18.89	C₅₁H₈₂O₂₂	Zingiberensis saponin^[35]	1 047.532 8	-4.01	[M+H]⁺	885.483 9, 723.433 2, 577.376 0, 415.320 5
21^b	18.91	C₅₁H₈₄O₂₃	25(27)-ene-Gurilioside H^[33]	1 109.501 8	8.65	[M+FA-H]^-	1 063.532 5, 917.474 9, 755.424 0, 575.373 3
22^a	19.14	C₅₁H₈₄O₂₂	Asparasaponin Ⅰ^[19]	1 031.544 2	2.04	[M-H₂O+H]⁺	869.487 4, 723.428 1, 577.372 7, 415.320 2
23^b	19.15	C₄₅H₇₆O₁₉	Timosaponin B Ⅱ^[14]	965.495 9	6.91	[M+FA-H]^-	919.490 9, 757.437 8, 595.385 5, 433.333 0, 330.488 9
24^a	19.21	C₄₅H₇₂O₁₇	Gracillin^[18]	885.481 9	-2.60	[M+H]⁺	723.429 6, 579.315 1, 415.320 1, 271.205 2
25^a	19.36	C₅₁H₈₄O₂₂	Zingiberensis saponin^[19]	1 049.549 6	-2.95	[M+H]⁺	869.488 0, 723.429 0, 577.372 4, 415.320 2
26^a	19.39	C₃₃H₅₀O₁₀	Kammogenin-glu^[20]	607.346 2	-2.31	[M+H]⁺	445.296 1, 427.273 0, 409.273 0
27^b	19.75	C₅₁H₈₄O₂₂	Compound 36 isomer^[35]	1 093.536 6	5.69	[M+FA-H]^-	1 047.538 2, 901.477 5, 575.372 6, 431.319 3
28^a	19.81	C₃₉H₆₂O₁₄	Pennogenin-rha^[12]	755.421 8	0.79	[M+H]⁺	579.389 3, 435.273 5, 399.324 5, 285.256 5
29^a	19.84	C₃₃H₅₂O₉	D-Glucuronic acid, (3β, 5β, 25R)-spirostan-3-yl ester^[20]	593.361 7	-9.10	[M+H]⁺	417.317 6, 399.325 3, 273.220 7
30^b	19.93	C₄₅H₇₆O₁₈	Aspacochioside A^[30]	949.485 7	6.18	[M+FA-H]^-	903.495 7, 757.444 2, 595.393 7, 433.330 5, 352.469 5
31^a	20.26	C₅₀H₈₂O₂₂	Melongoside F^[19]	1 033.522 1	-0.29	[M-H]^-	901.480 7, 739.4258, 577.374 6, 415.320 3
32^a	20.34	C₄₅H₇₄O₁₇	Shatavarin Ⅵ^[9]	887.491 1	-9.80	[M+H]⁺	725.443 7, 579.389 8, 417.336 2, 399.325 9
33^a	20.50	C₃₃H₅₀O₉	Spirost-9(11)-en-12-one^[20]	591.354 6	3.21	[M+H]⁺	429.300 1, 273.220 8, 255.210 3
34^a	20.51	C₃₉H₆₀O₁₄	β-Sitosterol-3-O-β-D-glucuronoside+glc^[8]	753.403 2	-3.05	[M+H]⁺	591.351 1, 273.221 0, 255.210 2
35^a	20.52	C₅₇H₉₆O₂₈	Trigoneoside XIIIb^[27]	1 227.606 1	3.75	[M+H]⁺	1065.540 9, 903.501 7, 741.443 1
36^b	20.82	C₅₁H₈₄O₂₂	Protodioscin^[35]	1 093.536 6	1.26	[M+FA-H]^-	1 047.536 5, 915.458 5, 885.449 5, 591.354 4, 429.303 5
37^a	20.84	C₂₇H₄₄O₃	Tigogenin^[15]	417.335 7	-1.44	[M+H]⁺	399.326 4, 273.220 8, 255.210 4, 161, 132 2
38^a	20.88	C₅₁H₈₂O₂₃	Deltoside^[19]	1 063.528 1	-3.76	[M+H]⁺	901.471 9, 739.429 5, 577.372 5, 415.320 0
39^a	21.14	C₂₇H₄₀O₅	Kammogenin^[20]	445.295 5	1.57	[M+H]⁺	445.295 5, 427.283 6, 409.273 8, 273.220 8, 255.213 0
40^b	21.26	C₅₀H₈₂O₂	Anemarrhenasaponin F^[33]	1 095.516 8	2.99	[M+FA-H]^-	1 049.517 5, 917.475 3, 887.464 7, 755.424 6, 593.369 6
41^a	21.77	C₂₇H₄₂O₃	Diosgenin^[19]	415.320 3	-0.72	[M+H]⁺	397.308 4, 271.205 3, 253.194 7
42^b	21.89	C₄₅H₇₄O₁₇	Deltonin^[35]	931.491 0	1.81	[M+FA-H]^-	885.485 3, 739.426 4, 575.357 2, 413.307 7
43^a	21.98	C₃₃H₅₀O₈	Ruscogenin-rha^[11]	575.357 7	-0.17	[M+H]⁺	415.320 3, 273.220 8, 255.210 1
44^a	22.28	C₂₇H₄₀O₄	9(11)-Dehydrohecogenin^[18]	429.301	2.56	[M+H]⁺	411.288 9, 384.297 0, 273.220 8
45^a	22.30	C₅₁H₈₈O₃₁	Solanigroside E^[19]	1 195.549 6	8.93	[M-H]^-	1 063.496 6, 931.450 1, 417.303 8
46^b	22.75	C₄₅H₇₂O₁₉	Chinenoside Ⅴ^[30]	961.463 9	-5.16	[M+FA-H]^-	915.459 2, 753.409 5, 607.349 2, 445.296 4, 417.292 5
47^b	22.83	C₅₀H₈₂O₂₂	Hamoside A^[33]	1 079.528 6	2.81	[M+FA-H]^-	1 033.521 0, 901.479 0, 871.470 6, 739.435 5, 577.374 9
48^b	23.01	C₄₅H₇₂O₁₈	Vaviloside B₁/B₂^[30]	945.469 8	-6.78	[M+FA-H]^-	899.464 7, 753.407 4, 607.349 1, 445.296 1
49^a	23.55	C₂₇H₄₂O₄	Yuccagenin^[35]	431.314 1	-3.25	[M+H]⁺	395.293 0, 273.220 9, 255.075 2
50^b	26.20	C₄₅H₇₀O₁₆	Sansevistatin 1^[30]	867.474 1	5.99	[M+H]⁺	721.414 6, 575.358 3, 413.307 9
51^b	26.27	C₂₇H₄₀O₃	Episceptrumgenin^[35]	413.326 8	-4.84	[M+H]⁺	395.292 9, 271.205 1, 253.194 8
52^a	26.29	C₅₆H₉₂O₂₈	Capsicosin E1^[28]	1 211.570 7	0.42	[M-H]^-	1 079.527 1, 593.369 7, 431.317 4
53^a	26.31	C₃₉H₆₂O₁₂	Prosapogenin A of dioscin^[35]	723.428 2	-4.42	[M+H]⁺	577.392 5, 415.320 0, 271.205 3
54^a	26.40	C₅₁H₈₆O₂₃	Shatavarin Ⅰ^[9]	1 065.550 2	2.44	[M-H]^-	903.491 8, 579.388 7, 417.335 4
55^b	27.35	C₄₅H₇₂O₁₇	Pennogenin 3-O-β-chacotrioside^[30]	929.475 1	5.27	[M+FA-H]^-	883.469 3, 737.412 4, 496.438 7, 417.401 9
56^b	28.66	C₄₄H₇₂O₁₆	Smilaxchinoside C^[30]	901.480 3	-2.88	[M+FA-H]^-	855.475 2, 723.433 2, 577.374 1, 415.325 6
57^b	28.98	C₅₁H₈₄O₂₃	Timosaponin B Ⅳ^[33]	1 109.501 8	7.33	[M+FA-H]^-	1 063.532 7, 901.480 0, 739.427 8, 577.374 6
58^b	29.22	C₅₀H₈₂O₂₂	Dongnoside E^[33]	1 079.528 6	0.86	[M+FA-H]^-	1 033.522 1, 871.469 5, 739.426 6, 577.374 6
59^a	29.42	C₃₉H₆₄O₁₂	Prosapogenin B^[15]	725.445 5	-2.07	[M+H]⁺	579.388 4, 417.335 7, 255.210 3
60^b	29.47	C₄₅H₇₄O₁₈	Protobioside^[35]	947.485 0	5.98	[M+FA-H]^-	901.479 7, 739.427 2, 577.374 5, 252.392 5
61^b	29.66	C₄₅H₇₄O₁₆	Indioside Ⅰ^[30]	915.496 0	-1.89	[M+FA-H]^-	869.490 1, 723.431 9, 577.375 2, 415.330 9
Alkaloids
62^c	5.02	C₄₅H₇₁NO₁₉	Alkaloid 1^[10]	930.467 8	-0.32	[M+H]⁺	930.467 8, 912.458 2, 894.446 2, 739.974 9
63^a	5.41	C₄₅H₇₃NO₁₈	Compound 74 isomer^[10]	916.489 1	0.00	[M+H]⁺	898.476 8, 829.415 6, 670.498 4, 410.306 1
64^a	6.41	C₄₅H₇₁NO₁₈	22α, 23α-Epoxysolasodine-hex-hex-hex^[10]	914.473 3	-0.55	[M+H]⁺	878.452 9, 732.396 7, 424.285 1, 287.201 3
65^a	9.18	C₃₃H₅₃NO₈	Solasodine-OH-hex^[10]	592.385 2	2.53	[M+H]⁺	574.373 0, 433.258 1, 271.205 1
66^a	9.24	C₃₉H₆₃NO₁₃	Solasodine-OH-hex-hex^[10]	754.435 9	-0.27	[M+H]⁺	718.416 3, 572.359 8, 410.304 8
67^a	11.59	C₄₅H₇₅NO₁₈	Dihydrosolasodine-2OH-hex-hex-rha^[10]	918.504 7	-0.22	[M+H]⁺	696.667 0, 396.679 9, 269.189 5
68^b	12.35	C₄₅H₇₅NO₁₇	Compound 70 isomer^[21]	902.509 0	-1.99	[M+H]⁺	884.453 4, 756.415 5, 448.305 3, 430.290 9
69^a	12.47	C₃₉H₆₅NO₁₃	Dihydrosolasodine-2OH-hex-rha^[10]	756.451 7	0.00	[M+H]⁺	738.442 1, 269.189 7, 251.178 9
70^b	12.90	C₄₅H₇₅NO₁₇	Dihydrosolasodine-2OH-rha-rha-hex^[21]	902.509 0	-1.99	[M+H]⁺	884.506 7, 725.094 5, 430.328 7
71^b	13.45	C₄₅H₇₃NO₁₇	Compound 76 isomer^[35]	900.493 7	-1.55	[M+H]⁺	864.472 3, 834.430 8, 702.418 1, 430.334 3
72^c	14.99	C₄₅H₆₉NO₁₅	Unknown alkaloid 1	864.474 0	2.31	[M+H]⁺	583.515 0, 455.002 0, 392.297 3
73^a	15.06	C₂₇H₄₃NO₄	(3β, 22α, 25R)-3, 12-Dihydroxy-spirosol-27-oic-acid^[31]	446.326 0	0.22	[M+H]⁺	428.315 9, 410.304 8, 395.279 3, 287.200 3
74^c	15.21	C₄₅H₇₃NO₁₈	Alkaloid 2^[10]	916.490 2	0.00	[M+H]⁺	832.430 1, 592.374 2, 446.326 0, 410.308 5
75^c	15.54	C₄₅H₇₁NO₁₆	Alkaloid 3^[10]	882.483	-0.68	[M+H]⁺	864.475 3, 795.405 1, 736.425 0, 410.305 0
76^b	15.64	C₄₅H₇₃NO₁₇	Peimisine+rha+hex+rha+OH^[35]	900.493 4	-1.89	[M+H]⁺	882.481 0, 558.377 9, 412.320 4
77^a	17.31	C₃₃H₅₅NO₇	δ-Tomatine^[29]	578.403 9	-2.07	[M+H]⁺	416.336 6, 273.205 5, 255.194 3
78^a	17.31	C₂₇H₄₅NO₂	Tomatidine^[29]	416.351 8	-1.20	[M+H]⁺	398.342 0, 273.221 3, 255.210 4
79^d	17.45	C₄₅H₇₃NO₁₆	Solasonine	884.498 7	-1.70	[M+H]⁺	738.430 8, 576.392 5, 414.338 3, 396.328 5
80^a	17.49	C₃₃H₅₃NO₇	γ-Solamargine^[29]	576.388 7	-1.21	[M+H]⁺	576.388 7, 414.336 6, 396.324 1, 271.205 0
81^a	17.52	C₃₉H₆₃NO₁₂	Solanigroside P^[35]	738.440 7	-2.17	[M+H]⁺	414.334 7, 253.194 6, 157.101 0
82^b	17.86	C₅₀H₈₁NO₁₉	Sycophantine^[35]	1 000.545 5	-2.10	[M+H]⁺	868.495 5, 722.420 9, 414.329 7, 396.326 3
83^a	18.10	C₄₅H₇₃NO₁₅	δ-Solanigrine^[35]	868.504 6	-0.69	[M+H]⁺	722.445 6, 576.388 3, 414.335 6
84^a	18.32	C₄₅H₇₅NO₁₆	Solaverbascine Solatrioside^[10]	886.514 6	-1.47	[M+H]⁺	868.469 8, 740.419 5, 594.357 8, 414.299 1
85^b	18.16	C₄₅H₇₃NO₁₅	α-Solanine^[31]	912.496 0	2.99	[M+FA-H]^-	866.490 6, 720.432 7, 412.331 2
86^a	20.02	C₃₉H₆₃NO₁₁	β2-Solanine^[35]	722.446 2	-1.52	[M+H]⁺	416.351 8, 253.193 7, 157.100 9
87^c	20.69	C₃₉H₆₅NO₁₁	Unknown alkaloid 2	724.461 2	-1.10	[M+H]⁺	704.451 2, 445.495 2, 398.344 4
88^a	21.98	C₃₃H₅₃NO₉	Solasodine-2OH-hex^[10]	608.275 1	3.62	[M+H]⁺	599.177 9, 529.257 8, 479.137 6, 447.312 6
89^d	25.01	C₂₇H₄₃NO₂	Solasodine	414.336 2	-0.97	[M+H]⁺	396.325 9, 271.204 7, 253.194 7
90^a	26.56	C₂₇H₄₅NO₂	Compound 56 isomer^[29]	416.351 7	-1.44	[M+H]⁺	399.326 2, 273.220 7, 255.210 5
91^a	27.55	C₂₇H₃₉NO₂	Veratramine^[18]	410.304 9	0.49	[M+H]⁺	392.294 3, 297.221 5, 267.174 0, 249.179 1
Flavones
92^a	2.57	C₁₆H₁₂O₇	Isorhamnetin^[8]	317.059 7	0.00	[M+H]⁺	317.059 7, 302.032 6, 285.035 8
93^a	2.79	C₃₃H₄₀O₂₁	Quercetin-3-O-rutinosyl-7-O-glucoside^[24]	771.198 4	-0.65	[M-H]^-	301.032 5, 271.024 8, 255.029 8
94^b	2.83	C₃₅H₄₂O₂₃	Quercetin-3-O-rutinosyl-7-O-glucoside+O+hex+AA^[32]	829.159 2	-6.27	[M-H]^-	771.198 7, 301.032 7, 271.024 8, 255.030 0
95^a	3.82	C₄₂H₄₆O₂₂	Kaempferol 3-[2-(6-coumaroylglucosyl)-rhamnoside]7-glucoside^[18]	901.241 0	0.22	[M-H]^-	609.139 3, 285.036 0, 255.029 8
96^a	3.83	C₃₃H₄₀O₂₀	Kaempferol 3-rutinoside 4′-glucoside^[16]	757.217 3	-1.58	[M+H]⁺	449.106 4, 303.049 5, 287.054 6, 258.051 1
97^b	4.46	C₄₃H₄₈O₂₄	3-(2-Feruloylsophoroside)^[34]	947.229	-7.71	[M-H]^-	785.193 5, 609.147 6, 446.085 1, 285.030 1
98^a	4.50	C₂₇H₃₀O₁₇	Quercetin 3, 4-diglucoside^[23]	625.141 2	0.32	[M-H]^-	301.033 6, 300.027 6, 283.024 7, 255.029 8
99^e	4.60	C₂₉H₃₂O₁₉	Unknown flavone 1	683.099 3	-0.73	[M-H]^-	625.141 2, 301.033 9, 271.024 8
100^b	4.62	C₃₁H₃₄O₁₈	Isoscutellarein 7-O-[2, 6-di-O-acetyl]allosyl(1→2)glucoside^[32]	693.128 4	1.73	[M-H]^-	625.141 9, 301.034 2, 271.024 8, 255.029 9
101^b	4.64	C₃₁H₃₅O₁₉	Peonidin, 3-(6-malonyl-glucoside), 5-glucoside^[32]	710.118 0	-4.08	[M-H]^-	625.141 4, 301.826 9, 271.907 2
102^e	5.04	C₃₁H₃₅O₁₈	Unknown flavone 2	694.119 8	-6.05	[M-H]^-	609.146 5, 301.032 0, 271.024 8
103^a	5.14	C₂₉H₃₂O₁₈	Euphorbianin^[32]	667.104 9	-0.15	[M-H]^-	609.145 6, 477.043 4, 300.027 6
104^e	5.19	C₁₈H₁₂O₇	Unknown flavone 3	341.082 4	-9.38	[M+H]⁺	301.142 0, 285.039 1, 257.036 9
105^b	5.36	C₃₁H₃₄O₁₇	Pelargonidin 3, 5-di-(6-acetylglucoside)^[34]	677.133 5	-0.74	[M-H]^-	609.146 6, 271.024 7, 255.030 0
106^a	5.98	C₂₇H₃₀O₁₆	Kaempferol-3-O-sophoroside^[20]	611.163 7	4.91	[M+H]⁺	449.109 5, 303.048 9, 287.054 7
107^e	6.10	C₂₇H₃₂O₁₇	Unknown flavone 4	629.171 2	3.66	[M+H]⁺	445.154 1, 385.134 6, 303.092 7, 285.081 6
108^a	6.12	C₂₁H₂₀O₁₀	Trihydroxy flavone C-glc^[12]	433.112 5	-1.15	[M+H]⁺	369.124 4, 287.054 7, 213.054 2
109^b	6.14	C₃₁H₃₅O₁₇	Pelargonidin 3, 5-di-(6-acetylglucoside)^[32]	678.125 2	-5.60	[M-H]^-	593.151 3, 273.123 2, 255.029 9
110^b	6.14	C₃₁H₃₄O₁₆	Crassirhizomoside B^[32]	661.139 1	-8.02	[M-H]^-	593.152 7, 447.093 0, 431.096 9
111^a	6.33	C₂₆H₂₈O₁₄	Apigenin 6-C-glucosyl-O-arabinoside^[24]	563.140 4	-0.36	[M-H]^-	417.084 1, 255.030 0, 227.035 2
112^e	6.81	C₃₁H₄₀O₁₅	Unknown flavone 5	651.109	-1.54	[M-H]^-	593.150 1, 284.033 1, 255.030 8
113^a	7.03	C₂₁H₂₀O₁₂	Hyperoside^[12]	463.087 6	-1.08	[M-H]^-	301.034 3, 271.024 9, 255.029 8
114^a	7.24	C₂₉H₃₆O₁₆	Tetrahydroxymethoxyflavone O-dihex^[12]	641.207 9	-0.47	[M+H]⁺	317.065 2, 302.041 8, 285.038 7, 229.048 9
115^b	7.40	C₄₃H₄₈O₂₃	Kaempferol-3-neohesperidoside-7-(2-ferulylglucoside)^[32]	931.249 2	-3.01	[M-H]^-	785.193 5, 609.148 3, 430.089 5, 285.039 8
116^e	7.45	C₄₃H₄₈O₂₃	Unknown flavone 6	933.265 9	-8.61	[M+H]⁺	583.413 1, 433.113 9, 287.055 6, 258.052 3
117^a	7.49	C₂₁H₂₀O₁₂	Quercetin-3-O-galactoside^[13]	465.100 2	-5.38	[M+H]⁺	303.049 7, 285.038 6, 165.016 8, 85.027 1
118^b	7.51	C₂₅H₂₅O₁₄	Cyanidin 3-(6-succinyl-glucoside)^[34]	548.117 1	0.00	[M-H]^-	463.084 4, 447.197 5, 285.084 4, 255.083 9
119^a	9.26	C₂₁H₂₀O₁₁	Kaempferol-3-O-glucoside^[24]	447.093 4	0.45	[M-H]^-	447.093 4, 285.038 7, 255.029 9, 227.035 0
120^a	10.43	C₂₁H₂₂O₁₂	Glucodistylin^[23]	449.107 4	0.89	[M+H]⁺	449.107 4, 287.054 6, 258.051 5, 213.054 2
121^a	11.37	C₂₂H₂₂O₁₂	Tetrahydroxymethoxyflavone 3-O-hex^[12]	479.118 0	-0.83	[M+H]⁺	479.118 0, 393.186 2, 317.065 1, 285.038 6
122^a	17.25	C₁₅H₁₀O₇	Quercetion^[24]	301.035 5	0.33	[M-H]^-	271.025 0, 255.041 1, 163.015 9, 83.027 6
123^e	18.91	C₃₁H₃₄O₁₅	Unknown flavone 7	647.197 0	1.89	[M-H]^-	595.383 5, 577.374 8, 393.202 2, 316.167 9
124^a	26.03	C₂₇H₃₀O₁₆	Rutin^[26]	609.146 4	0.49	[M-H]^-	429.206 6, 380.366 4, 315.050 0, 275.201 7
125^a	26.65	C₂₇H₃₀O₁₅	Kaempferol-3-O-glucoside-7-O-rhamnoside^[20]	593.151 2	0.17	[M-H]^-	418.226 8, 299.043 8, 225.007 5
126^a	31.39	C₂₇H₃₀O₁₄	Kaempferitrin^[16]	577.156 8	0.69	[M-H]^-	428.284 1, 299.044 6, 225.007 5
Others
127^a	0.96	C₁₂H₂₂O₁₁	Sucrose^[8]	341.108 9	-0.59	[M-H]^-	179.056 2, 119.036 0, 89.024 4
128^a	0.97	C₆H₉N₃O₂	Histidine^[22]	156.076 6	-1.28	[M+H]⁺	131.974 4, 110.071 6
129^a	1.02	C₆H₁₂O₇	Galacturonic acid^[11]	195.050 9	-0.51	[M-H]^-	177.040 5, 159.029 9
130^a	1.07	C₉H₁₁NO₃	Tyrosine^[11]	182.081 0	-0.55	[M+H]⁺	165.045 7, 136.075 8, 107.049 7
131^a	1.16	C₆H₅NO₂	Nicotinic acid^[22]	124.039 6	2.42	[M+H]⁺	106.029 4, 80.050 0, 78.034 4
132^a	1.17	C₁₂H₂₁NO₆	9-Amino-1, 3, 9-nonane dicarboxylic acid^[11]	276.144 4	1.09	[M+H]⁺	258.133 6, 230.138 7, 161.068 3
133^a	1.10	C₆H₁₁NO₂	Pipecolic acid^[8]	130.049 8	-9.22	[M+H]⁺	84.044 8, 67.053 7, 62.024 6, 56.048 9
134^a	1.13	C₅H₇NO₃	Pyroglutamic acid^[8]	130.050 1	1.54	[M+H]⁺	84.044 9, 69.070 5, 56.050 1
135^a	1.63	C₁₀H₁₃N₄O₃	Histidyl asparagine^[11]	238.106 7	2.94	[M+H]⁺	192.102 2, 120.995 9, 103.054 6
136^a	1.73	C₁₂H₁₅NO₅	Serine^[11]	254.102 1	-0.39	[M+H]⁺	208.058 2, 136.990 6, 119.118 4
137^a	1.87	C₁₁H₁₂N₂O₂	Tryptophan^[8]	205.097 2	0.49	[M+H]⁺	188.070 7, 170.060 1, 159.091 8
138^a	1.87	C₁₁H₉NO₂	Indole-3-acrylic acid^[11]	188.070 3	-1.60	[M+H]⁺	146.060 2, 186.065 4
139^a	1.92	C₇H₆O₄	Protocatechuic acid^[8]	153.019 4	2.61	[M-H]^-	109.029 5, 91.018 9, 81.034 6
140^a	2.48	C₁₆H₁₈O₉	Chlorogenic acid^[8]	355.100 1	-6.20	[M+H]⁺	181.050 1, 145.026 7, 135.041 6, 117.033 7
141^a	3.08	C₁₆H₁₈O₉	Neochlorogenic acid^[11]	353.089 9	-2.27	[M-H]^-	191.056 2, 179.035 2, 162.027 8
142^a	3.13	C₁₆H₂₄O₁₀	Vitamin B₂^[8]	377.144 9	1.86	[M+H]⁺	243.087 3, 172.086 6, 99.044 3,
143^a	3.34	C₉H₈O₄	Caffeic acid^[8]	179.034 7	-1.12	[M-H]^-	135.044 6, 112.984 9, 89.023 5
144^a	3.49	C₁₆H₁₈O₈	p-Coumaroylquinic acid^[8]	339.106 9	-1.47	[M+H]⁺	147.043 9, 119.049 2, 91.054 5
145^a	4.01	C₅H₅N₅	Adenine^[8]	136.061 8	0.73	[M+H]⁺	119.049 3, 94.065 5, 92.049 7
146^a	5.44	C₉H₈O₃	p-Coumaric acid^[8]	163.040 6	0.00	[M-H]^-	119.051 1, 91.053 7
147^a	5.56	C₈H₁₆N₂O₃	Glycyl-L-leucine^[11]	189.121 8	-7.93	[M+H]⁺	171.149 0, 130.086 2, 84.081 2
148^a	7.42	C₁₀H₁₀O₄	Isoferulic acid^[8]	195.063 9	-6.66	[M+H]⁺	177.054 4, 149.059 6, 117.033 5
149^a	8.24	C₅H₉NO₄	L-Glutamic acid^[8]	148.060 2	-1.35	[M+H]⁺	130.069 2, 103.054 4, 84.044 7
150^a	8.54	C₆H₁₂O₇	Glucuronic acid^[8]	197.063 9	-8.63	[M+H]⁺	179.106 4, 161.095 9, 133.101 1
151^a	8.58	C₈H₁₆N₂O₃	Compound 147 isomer^[11]	189.121 8	-7.93	[M+H]⁺	156.093 1, 129.070 0, 105.070 1
152^a	9.65	C₉H₁₂N₂O₆	Uridine^[22]	245.079 1	9.38	[M+H]⁺	203.123 7, 189.112 0, 135.080 1
153^a	11.67	C₁₂H₁₈O₂	Serdanolide^[8]	195.137 6	-1.54	[M+H]⁺	167.085 0, 135.044 0, 111.044 2
154^a	21.65	C₁₀H₁₀O₄	Ferulic acid^[22]	195.063 2	-9.74	[M+H]⁺	177.091 1, 149.067 2, 89.065 9
155^a	26.49	C₂₃H₂₄O₉	Diferuloylglycerol^[8]	445.147 9	-3.15	[M+H]⁺	271.205 2, 253.194 7
156^a	27.87	C₁₆H₃₀O	Muscone^[8]	239.235 7	-5.02	[M+H]⁺	183.116 6, 197.132 2, 119.085 7, 81.068 6
157^a	28.20	C₁₈H₃₅NO	Oleamide^[8]	282.278 7	-1.42	[M+H]⁺	247.241 6, 135.116 8, 121.101 2

No.

t_R /min

Molecular formula

Identification

Mass

Error (×10^-6)

Ion

Fragment ion

Saponins

1^a

2.96

C₂₇H₄₄O₄

Gitogenin^[28]

433.332 3

2.54

[M+H]⁺

415.320 8, 397.309 8, 271.205 3

2^a

3.94

C₂₇H₄₂O₅

Manogenin^[20]

447.306 9

-8.05

[M+H]⁺

429.119 1, 273.220 9, 255.210 2, 161.132 2

3^a

14.72

C₅₁H₈₂O₂₆

Solanigroside C^[31]

1 133.498 0

-0.53

[M+Na]⁺

971.444 8, 809.3927, 647.342 5, 467.137 5

4^a

15.70

C₅₇H₉₄O₂₈

Solanigroside Y5^[19]

1 271.591 8

2.16

[M+FA-H]^-

1 225.585 7, 1 063.538 0, 757.365 7, 431.310 6

5^a

16.65

C₂₇H₄₆O₄

25S-Furosta-5β, 3β, 20α, 26-triol^[23]

435.270 4

3.79

[M+H]⁺

417.266 5, 291.215 5, 273.221 5

6^b

16.89

C₅₆H₉₂O₂₈

Timosaponin H1^[33]

1 257.574 8

2.32

[M+FA-H]^-

1 211.570 9, 1 079.526 6, 1 049.519 7, 755.422 9, 593.369 9

7^a

16.91

C₃₃H₅₂O₈

Trillin^[17]

577.374 9

2.42

[M+H]⁺

415.320 5, 271.205 1, 253.194 8

8^a

16.93

C₅₁H₈₀O₂₆

Solanigroside Y3^[13]

1 131.482 2

-0.71

[M+Na]⁺

969.429 0, 807.377 8, 645.324 5

9^a

18.10

C₃₃H₅₄O₈

Tigogenin-hex^[10]

579.391 4

3.97

[M+H]⁺

579.391 4, 417.335 2, 399.335 2, 273.220 8

10^a

18.14

C₅₇H₉₄O₂₈

Trigoneoside XIIIa^[27]

1 227.589 4

-8.96

[M+H]⁺

904.140 3, 741.440 7, 579.388 1, 417.335 8

11^a

18.17

C₃₉H₆₄O₁₃

Timosaponin AⅢ^[28]

741.444 5

3.51

[M+H]⁺

579.388 2, 417.334 4, 273.220 8

12^a

18.23

C₅₇H₉₄O₂₇

Yuccaloiside B^[28]

1 193.604 7

8.21

[M-H₂O+H]⁺

1 031.536 3, 723.429 8, 577.372 4, 415.320 3

13^a

18.23

C₄₅H₇₄O₁₈

Shatavarin Ⅸ^[8]

903.494 1

-0.66

[M+H]⁺

741.439 1, 579.621 9, 417.335 6

14^a

18.23

C₅₇H₉₄O₂₇

Solanigroside Y6^[13]

1 255.595 2

2.69

[M+FA-H]^-

1 209.590 9, 1 047.538 0, 901.483 5, 755.423 2, 593.366 6, 431.316 0, 413.308 4

15^a

18.25

C₃₉H₆₂O₁₃

Diosgenin 3-O-cellobioside^[13]

739.427 4

1.49

[M+H]⁺

577.372 6, 415.320 1, 271.205 4, 253.194 7

16^b

18.41

C₅₁H₈₆O₂₄

Tomatoside A^[30]

1 117.520 4

5.61

[M+FA-H]^-

1 081.543 1, 919.492 0, 757.437 3, 595.384 9, 433.337 0

17^a

18.59

C₅₀H₈₂O₂₂

Degalactotigonin^[28]

1 035.544 9

7.63

[M+H]⁺

873.481 0, 741.441 0, 579.388 5, 417.335 8

18^a

18.70

C₅₆H₉₂O₂₇

Diurnoside^[25]

1 197.589 1

-0.58

[M+H]⁺

1035.534 3, 741.440 4, 579.388 2, 417.335 5

19^a

18.82

C₃₃H₅₂O₁₀

Chonglouoside SL-10^[12]

609.364 1

1.31

[M+H]⁺

609.364 1, 447.310 1, 429.299 6, 411, 288 5

20^a

18.89

C₅₁H₈₂O₂₂

Zingiberensis saponin^[35]

1 047.532 8

-4.01

[M+H]⁺

885.483 9, 723.433 2, 577.376 0, 415.320 5

21^b

18.91

C₅₁H₈₄O₂₃

25(27)-ene-Gurilioside H^[33]

1 109.501 8

8.65

[M+FA-H]^-

1 063.532 5, 917.474 9, 755.424 0, 575.373 3

22^a

19.14

C₅₁H₈₄O₂₂

Asparasaponin Ⅰ^[19]

1 031.544 2

2.04

[M-H₂O+H]⁺

869.487 4, 723.428 1, 577.372 7, 415.320 2

23^b

19.15

C₄₅H₇₆O₁₉

Timosaponin B Ⅱ^[14]

965.495 9

6.91

[M+FA-H]^-

919.490 9, 757.437 8, 595.385 5, 433.333 0, 330.488 9

24^a

19.21

C₄₅H₇₂O₁₇

Gracillin^[18]

885.481 9

-2.60

[M+H]⁺

723.429 6, 579.315 1, 415.320 1, 271.205 2

25^a

19.36

C₅₁H₈₄O₂₂

Zingiberensis saponin^[19]

1 049.549 6

-2.95

[M+H]⁺

869.488 0, 723.429 0, 577.372 4, 415.320 2

26^a

19.39

C₃₃H₅₀O₁₀

Kammogenin-glu^[20]

607.346 2

-2.31

[M+H]⁺

445.296 1, 427.273 0, 409.273 0

27^b

19.75

C₅₁H₈₄O₂₂

Compound 36 isomer^[35]

1 093.536 6

5.69

[M+FA-H]^-

1 047.538 2, 901.477 5, 575.372 6, 431.319 3

28^a

19.81

C₃₉H₆₂O₁₄

Pennogenin-rha^[12]

755.421 8

0.79

[M+H]⁺

579.389 3, 435.273 5, 399.324 5, 285.256 5

29^a

19.84

C₃₃H₅₂O₉

D-Glucuronic acid, (3β, 5β, 25R)-spirostan-3-yl ester^[20]

593.361 7

-9.10

[M+H]⁺

417.317 6, 399.325 3, 273.220 7

30^b

19.93

C₄₅H₇₆O₁₈

Aspacochioside A^[30]

949.485 7

6.18

[M+FA-H]^-

903.495 7, 757.444 2, 595.393 7, 433.330 5, 352.469 5

31^a

20.26

C₅₀H₈₂O₂₂

Melongoside F^[19]

1 033.522 1

-0.29

[M-H]^-

901.480 7, 739.4258, 577.374 6, 415.320 3

32^a

20.34

C₄₅H₇₄O₁₇

Shatavarin Ⅵ^[9]

887.491 1

-9.80

[M+H]⁺

725.443 7, 579.389 8, 417.336 2, 399.325 9

33^a

20.50

C₃₃H₅₀O₉

Spirost-9(11)-en-12-one^[20]

591.354 6

3.21

[M+H]⁺

429.300 1, 273.220 8, 255.210 3

34^a

20.51

C₃₉H₆₀O₁₄

β-Sitosterol-3-O-β-D-glucuronoside+glc^[8]

753.403 2

-3.05

[M+H]⁺

591.351 1, 273.221 0, 255.210 2

35^a

20.52

C₅₇H₉₆O₂₈

Trigoneoside XIIIb^[27]

1 227.606 1

3.75

[M+H]⁺

1065.540 9, 903.501 7, 741.443 1

36^b

20.82

C₅₁H₈₄O₂₂

Protodioscin^[35]

1 093.536 6

1.26

[M+FA-H]^-

1 047.536 5, 915.458 5, 885.449 5, 591.354 4, 429.303 5

37^a

20.84

C₂₇H₄₄O₃

Tigogenin^[15]

417.335 7

-1.44

[M+H]⁺

399.326 4, 273.220 8, 255.210 4, 161, 132 2

38^a

20.88

C₅₁H₈₂O₂₃

Deltoside^[19]

1 063.528 1

-3.76

[M+H]⁺

901.471 9, 739.429 5, 577.372 5, 415.320 0

39^a

21.14

C₂₇H₄₀O₅

Kammogenin^[20]

445.295 5

1.57

[M+H]⁺

445.295 5, 427.283 6, 409.273 8, 273.220 8, 255.213 0

40^b

21.26

C₅₀H₈₂O₂

Anemarrhenasaponin F^[33]

1 095.516 8

2.99

[M+FA-H]^-

1 049.517 5, 917.475 3, 887.464 7, 755.424 6, 593.369 6

41^a

21.77

C₂₇H₄₂O₃

Diosgenin^[19]

415.320 3

-0.72

[M+H]⁺

397.308 4, 271.205 3, 253.194 7

42^b

21.89

C₄₅H₇₄O₁₇

Deltonin^[35]

931.491 0

1.81

[M+FA-H]^-

885.485 3, 739.426 4, 575.357 2, 413.307 7

43^a

21.98

C₃₃H₅₀O₈

Ruscogenin-rha^[11]

575.357 7

-0.17

[M+H]⁺

415.320 3, 273.220 8, 255.210 1

44^a

22.28

C₂₇H₄₀O₄

9(11)-Dehydrohecogenin^[18]

429.301

2.56

[M+H]⁺

411.288 9, 384.297 0, 273.220 8

45^a

22.30

C₅₁H₈₈O₃₁

Solanigroside E^[19]

1 195.549 6

8.93

[M-H]^-

1 063.496 6, 931.450 1, 417.303 8

46^b

22.75

C₄₅H₇₂O₁₉

Chinenoside Ⅴ^[30]

961.463 9

-5.16

[M+FA-H]^-

915.459 2, 753.409 5, 607.349 2, 445.296 4, 417.292 5

47^b

22.83

C₅₀H₈₂O₂₂

Hamoside A^[33]

1 079.528 6

2.81

[M+FA-H]^-

1 033.521 0, 901.479 0, 871.470 6, 739.435 5, 577.374 9

48^b

23.01

C₄₅H₇₂O₁₈

Vaviloside B₁/B₂^[30]

945.469 8

-6.78

[M+FA-H]^-

899.464 7, 753.407 4, 607.349 1, 445.296 1

49^a

23.55

C₂₇H₄₂O₄

Yuccagenin^[35]

431.314 1

-3.25

[M+H]⁺

395.293 0, 273.220 9, 255.075 2

50^b

26.20

C₄₅H₇₀O₁₆

Sansevistatin 1^[30]

867.474 1

5.99

[M+H]⁺

721.414 6, 575.358 3, 413.307 9

51^b

26.27

C₂₇H₄₀O₃

Episceptrumgenin^[35]

413.326 8

-4.84

[M+H]⁺

395.292 9, 271.205 1, 253.194 8

52^a

26.29

C₅₆H₉₂O₂₈

Capsicosin E1^[28]

1 211.570 7

0.42

[M-H]^-

1 079.527 1, 593.369 7, 431.317 4

53^a

26.31

C₃₉H₆₂O₁₂

Prosapogenin A of dioscin^[35]

723.428 2

-4.42

[M+H]⁺

577.392 5, 415.320 0, 271.205 3

54^a

26.40

C₅₁H₈₆O₂₃

Shatavarin Ⅰ^[9]

1 065.550 2

2.44

[M-H]^-

903.491 8, 579.388 7, 417.335 4

55^b

27.35

C₄₅H₇₂O₁₇

Pennogenin 3-O-β-chacotrioside^[30]

929.475 1

5.27

[M+FA-H]^-

883.469 3, 737.412 4, 496.438 7, 417.401 9

56^b

28.66

C₄₄H₇₂O₁₆

Smilaxchinoside C^[30]

901.480 3

-2.88

[M+FA-H]^-

855.475 2, 723.433 2, 577.374 1, 415.325 6

57^b

28.98

C₅₁H₈₄O₂₃

Timosaponin B Ⅳ^[33]

1 109.501 8

7.33

[M+FA-H]^-

1 063.532 7, 901.480 0, 739.427 8, 577.374 6

58^b

29.22

C₅₀H₈₂O₂₂

Dongnoside E^[33]

1 079.528 6

0.86

[M+FA-H]^-

1 033.522 1, 871.469 5, 739.426 6, 577.374 6

59^a

29.42

C₃₉H₆₄O₁₂

Prosapogenin B^[15]

725.445 5

-2.07

[M+H]⁺

579.388 4, 417.335 7, 255.210 3

60^b

29.47

C₄₅H₇₄O₁₈

Protobioside^[35]

947.485 0

5.98

[M+FA-H]^-

901.479 7, 739.427 2, 577.374 5, 252.392 5

61^b

29.66

C₄₅H₇₄O₁₆

Indioside Ⅰ^[30]

915.496 0

-1.89

[M+FA-H]^-

869.490 1, 723.431 9, 577.375 2, 415.330 9

Alkaloids

62^c

5.02

C₄₅H₇₁NO₁₉

Alkaloid 1^[10]

930.467 8

-0.32

[M+H]⁺

930.467 8, 912.458 2, 894.446 2, 739.974 9

63^a

5.41

C₄₅H₇₃NO₁₈

Compound 74 isomer^[10]

916.489 1

0.00

[M+H]⁺

898.476 8, 829.415 6, 670.498 4, 410.306 1

64^a

6.41

C₄₅H₇₁NO₁₈

22α, 23α-Epoxysolasodine-hex-hex-hex^[10]

914.473 3

-0.55

[M+H]⁺

878.452 9, 732.396 7, 424.285 1, 287.201 3

65^a

9.18

C₃₃H₅₃NO₈

Solasodine-OH-hex^[10]

592.385 2

2.53

[M+H]⁺

574.373 0, 433.258 1, 271.205 1

66^a

9.24

C₃₉H₆₃NO₁₃

Solasodine-OH-hex-hex^[10]

754.435 9

-0.27

[M+H]⁺

718.416 3, 572.359 8, 410.304 8

67^a

11.59

C₄₅H₇₅NO₁₈

Dihydrosolasodine-2OH-hex-hex-rha^[10]

918.504 7

-0.22

[M+H]⁺

696.667 0, 396.679 9, 269.189 5

68^b

12.35

C₄₅H₇₅NO₁₇

Compound 70 isomer^[21]

902.509 0

-1.99

[M+H]⁺

884.453 4, 756.415 5, 448.305 3, 430.290 9

69^a

12.47

C₃₉H₆₅NO₁₃

Dihydrosolasodine-2OH-hex-rha^[10]

756.451 7

0.00

[M+H]⁺

738.442 1, 269.189 7, 251.178 9

70^b

12.90

C₄₅H₇₅NO₁₇

Dihydrosolasodine-2OH-rha-rha-hex^[21]

902.509 0

-1.99

[M+H]⁺

884.506 7, 725.094 5, 430.328 7

71^b

13.45

C₄₅H₇₃NO₁₇

Compound 76 isomer^[35]

900.493 7

-1.55

[M+H]⁺

864.472 3, 834.430 8, 702.418 1, 430.334 3

72^c

14.99

C₄₅H₆₉NO₁₅

Unknown alkaloid 1

864.474 0

2.31

[M+H]⁺

583.515 0, 455.002 0, 392.297 3

73^a

15.06

C₂₇H₄₃NO₄

(3β, 22α, 25R)-3, 12-Dihydroxy-spirosol-27-oic-acid^[31]

446.326 0

0.22

[M+H]⁺

428.315 9, 410.304 8, 395.279 3, 287.200 3

74^c

15.21

C₄₅H₇₃NO₁₈

Alkaloid 2^[10]

916.490 2

0.00

[M+H]⁺

832.430 1, 592.374 2, 446.326 0, 410.308 5

75^c

15.54

C₄₅H₇₁NO₁₆

Alkaloid 3^[10]

882.483

-0.68

[M+H]⁺

864.475 3, 795.405 1, 736.425 0, 410.305 0

76^b

15.64

C₄₅H₇₃NO₁₇

Peimisine+rha+hex+rha+OH^[35]

900.493 4

-1.89

[M+H]⁺

882.481 0, 558.377 9, 412.320 4

77^a

17.31

C₃₃H₅₅NO₇

δ-Tomatine^[29]

578.403 9

-2.07

[M+H]⁺

416.336 6, 273.205 5, 255.194 3

78^a

17.31

C₂₇H₄₅NO₂

Tomatidine^[29]

416.351 8

-1.20

[M+H]⁺

398.342 0, 273.221 3, 255.210 4

79^d

17.45

C₄₅H₇₃NO₁₆

Solasonine

884.498 7

-1.70

[M+H]⁺

738.430 8, 576.392 5, 414.338 3, 396.328 5

80^a

17.49

C₃₃H₅₃NO₇

γ-Solamargine^[29]

576.388 7

-1.21

[M+H]⁺

576.388 7, 414.336 6, 396.324 1, 271.205 0

81^a

17.52

C₃₉H₆₃NO₁₂

Solanigroside P^[35]

738.440 7

-2.17

[M+H]⁺

414.334 7, 253.194 6, 157.101 0

82^b

17.86

C₅₀H₈₁NO₁₉

Sycophantine^[35]

1 000.545 5

-2.10

[M+H]⁺

868.495 5, 722.420 9, 414.329 7, 396.326 3

83^a

18.10

C₄₅H₇₃NO₁₅

δ-Solanigrine^[35]

868.504 6

-0.69

[M+H]⁺

722.445 6, 576.388 3, 414.335 6

84^a

18.32

C₄₅H₇₅NO₁₆

Solaverbascine Solatrioside^[10]

886.514 6

-1.47

[M+H]⁺

868.469 8, 740.419 5, 594.357 8, 414.299 1

85^b

18.16

C₄₅H₇₃NO₁₅

α-Solanine^[31]

912.496 0

2.99

[M+FA-H]^-

866.490 6, 720.432 7, 412.331 2

86^a

20.02

C₃₉H₆₃NO₁₁

β2-Solanine^[35]

722.446 2

-1.52

[M+H]⁺

416.351 8, 253.193 7, 157.100 9

87^c

20.69

C₃₉H₆₅NO₁₁

Unknown alkaloid 2

724.461 2

-1.10

[M+H]⁺

704.451 2, 445.495 2, 398.344 4

88^a

21.98

C₃₃H₅₃NO₉

Solasodine-2OH-hex^[10]

608.275 1

3.62

[M+H]⁺

599.177 9, 529.257 8, 479.137 6, 447.312 6

89^d

25.01

C₂₇H₄₃NO₂

Solasodine

414.336 2

-0.97

[M+H]⁺

396.325 9, 271.204 7, 253.194 7

90^a

26.56

C₂₇H₄₅NO₂

Compound 56 isomer^[29]

416.351 7

-1.44

[M+H]⁺

399.326 2, 273.220 7, 255.210 5

91^a

27.55

C₂₇H₃₉NO₂

Veratramine^[18]

410.304 9

0.49

[M+H]⁺

392.294 3, 297.221 5, 267.174 0, 249.179 1

Flavones

92^a

2.57

C₁₆H₁₂O₇

Isorhamnetin^[8]

317.059 7

0.00

[M+H]⁺

317.059 7, 302.032 6, 285.035 8

93^a

2.79

C₃₃H₄₀O₂₁

Quercetin-3-O-rutinosyl-7-O-glucoside^[24]

771.198 4

-0.65

[M-H]^-

301.032 5, 271.024 8, 255.029 8

94^b

2.83

C₃₅H₄₂O₂₃

Quercetin-3-O-rutinosyl-7-O-glucoside+O+hex+AA^[32]

829.159 2

-6.27

[M-H]^-

771.198 7, 301.032 7, 271.024 8, 255.030 0

95^a

3.82

C₄₂H₄₆O₂₂

Kaempferol 3-[2-(6-coumaroylglucosyl)-rhamnoside]7-glucoside^[18]

901.241 0

0.22

[M-H]^-

609.139 3, 285.036 0, 255.029 8

96^a

3.83

C₃₃H₄₀O₂₀

Kaempferol 3-rutinoside 4′-glucoside^[16]

757.217 3

-1.58

[M+H]⁺

449.106 4, 303.049 5, 287.054 6, 258.051 1

97^b

4.46

C₄₃H₄₈O₂₄

3-(2-Feruloylsophoroside)^[34]

947.229

-7.71

[M-H]^-

785.193 5, 609.147 6, 446.085 1, 285.030 1

98^a

4.50

C₂₇H₃₀O₁₇

Quercetin 3, 4-diglucoside^[23]

625.141 2

0.32

[M-H]^-

301.033 6, 300.027 6, 283.024 7, 255.029 8

99^e

4.60

C₂₉H₃₂O₁₉

Unknown flavone 1

683.099 3

-0.73

[M-H]^-

625.141 2, 301.033 9, 271.024 8

100^b

4.62

C₃₁H₃₄O₁₈

Isoscutellarein 7-O-[2, 6-di-O-acetyl]allosyl(1→2)glucoside^[32]

693.128 4

1.73

[M-H]^-

625.141 9, 301.034 2, 271.024 8, 255.029 9

101^b

4.64

C₃₁H₃₅O₁₉

Peonidin, 3-(6-malonyl-glucoside), 5-glucoside^[32]

710.118 0

-4.08

[M-H]^-

625.141 4, 301.826 9, 271.907 2

102^e

5.04

C₃₁H₃₅O₁₈

Unknown flavone 2

694.119 8

-6.05

[M-H]^-

609.146 5, 301.032 0, 271.024 8

103^a

5.14

C₂₉H₃₂O₁₈

Euphorbianin^[32]

667.104 9

-0.15

[M-H]^-

609.145 6, 477.043 4, 300.027 6

104^e

5.19

C₁₈H₁₂O₇

Unknown flavone 3

341.082 4

-9.38

[M+H]⁺

301.142 0, 285.039 1, 257.036 9

105^b

5.36

C₃₁H₃₄O₁₇

Pelargonidin 3, 5-di-(6-acetylglucoside)^[34]

677.133 5

-0.74

[M-H]^-

609.146 6, 271.024 7, 255.030 0

106^a

5.98

C₂₇H₃₀O₁₆

Kaempferol-3-O-sophoroside^[20]

611.163 7

4.91

[M+H]⁺

449.109 5, 303.048 9, 287.054 7

107^e

6.10

C₂₇H₃₂O₁₇

Unknown flavone 4

629.171 2

3.66

[M+H]⁺

445.154 1, 385.134 6, 303.092 7, 285.081 6

108^a

6.12

C₂₁H₂₀O₁₀

Trihydroxy flavone C-glc^[12]

433.112 5

-1.15

[M+H]⁺

369.124 4, 287.054 7, 213.054 2

109^b

6.14

C₃₁H₃₅O₁₇

Pelargonidin 3, 5-di-(6-acetylglucoside)^[32]

678.125 2

-5.60

[M-H]^-

593.151 3, 273.123 2, 255.029 9

110^b

6.14

C₃₁H₃₄O₁₆

Crassirhizomoside B^[32]

661.139 1

-8.02

[M-H]^-

593.152 7, 447.093 0, 431.096 9

111^a

6.33

C₂₆H₂₈O₁₄

Apigenin 6-C-glucosyl-O-arabinoside^[24]

563.140 4

-0.36

[M-H]^-

417.084 1, 255.030 0, 227.035 2

112^e

6.81

C₃₁H₄₀O₁₅

Unknown flavone 5

651.109

-1.54

[M-H]^-

593.150 1, 284.033 1, 255.030 8

113^a

7.03

C₂₁H₂₀O₁₂

Hyperoside^[12]

463.087 6

-1.08

[M-H]^-

301.034 3, 271.024 9, 255.029 8

114^a

7.24

C₂₉H₃₆O₁₆

Tetrahydroxymethoxyflavone O-dihex^[12]

641.207 9

-0.47

[M+H]⁺

317.065 2, 302.041 8, 285.038 7, 229.048 9

115^b

7.40

C₄₃H₄₈O₂₃

Kaempferol-3-neohesperidoside-7-(2-ferulylglucoside)^[32]

931.249 2

-3.01

[M-H]^-

785.193 5, 609.148 3, 430.089 5, 285.039 8

116^e

7.45

C₄₃H₄₈O₂₃

Unknown flavone 6

933.265 9

-8.61

[M+H]⁺

583.413 1, 433.113 9, 287.055 6, 258.052 3

117^a

7.49

C₂₁H₂₀O₁₂

Quercetin-3-O-galactoside^[13]

465.100 2

-5.38

[M+H]⁺

303.049 7, 285.038 6, 165.016 8, 85.027 1

118^b

7.51

C₂₅H₂₅O₁₄

Cyanidin 3-(6-succinyl-glucoside)^[34]

548.117 1

0.00

[M-H]^-

463.084 4, 447.197 5, 285.084 4, 255.083 9

119^a

9.26

C₂₁H₂₀O₁₁

Kaempferol-3-O-glucoside^[24]

447.093 4

0.45

[M-H]^-

447.093 4, 285.038 7, 255.029 9, 227.035 0

120^a

10.43

C₂₁H₂₂O₁₂

Glucodistylin^[23]

449.107 4

0.89

[M+H]⁺

449.107 4, 287.054 6, 258.051 5, 213.054 2

121^a

11.37

C₂₂H₂₂O₁₂

Tetrahydroxymethoxyflavone 3-O-hex^[12]

479.118 0

-0.83

[M+H]⁺

479.118 0, 393.186 2, 317.065 1, 285.038 6

122^a

17.25

C₁₅H₁₀O₇

Quercetion^[24]

301.035 5

0.33

[M-H]^-

271.025 0, 255.041 1, 163.015 9, 83.027 6

123^e

18.91

C₃₁H₃₄O₁₅

Unknown flavone 7

647.197 0

1.89

[M-H]^-

595.383 5, 577.374 8, 393.202 2, 316.167 9

124^a

26.03

C₂₇H₃₀O₁₆

Rutin^[26]

609.146 4

0.49

[M-H]^-

429.206 6, 380.366 4, 315.050 0, 275.201 7

125^a

26.65

C₂₇H₃₀O₁₅

Kaempferol-3-O-glucoside-7-O-rhamnoside^[20]

593.151 2

0.17

[M-H]^-

418.226 8, 299.043 8, 225.007 5

126^a

31.39

C₂₇H₃₀O₁₄

Kaempferitrin^[16]

577.156 8

0.69

[M-H]^-

428.284 1, 299.044 6, 225.007 5

Others

127^a

0.96

C₁₂H₂₂O₁₁

Sucrose^[8]

341.108 9

-0.59

[M-H]^-

179.056 2, 119.036 0, 89.024 4

128^a

0.97

C₆H₉N₃O₂

Histidine^[22]

156.076 6

-1.28

[M+H]⁺

131.974 4, 110.071 6

129^a

1.02

C₆H₁₂O₇

Galacturonic acid^[11]

195.050 9

-0.51

[M-H]^-

177.040 5, 159.029 9

130^a

1.07

C₉H₁₁NO₃

Tyrosine^[11]

182.081 0

-0.55

[M+H]⁺

165.045 7, 136.075 8, 107.049 7

131^a

1.16

C₆H₅NO₂

Nicotinic acid^[22]

124.039 6

2.42

[M+H]⁺

106.029 4, 80.050 0, 78.034 4

132^a

1.17

C₁₂H₂₁NO₆

9-Amino-1, 3, 9-nonane dicarboxylic acid^[11]

276.144 4

1.09

[M+H]⁺

258.133 6, 230.138 7, 161.068 3

133^a

1.10

C₆H₁₁NO₂

Pipecolic acid^[8]

130.049 8

-9.22

[M+H]⁺

84.044 8, 67.053 7, 62.024 6, 56.048 9

134^a

1.13

C₅H₇NO₃

Pyroglutamic acid^[8]

130.050 1

1.54

[M+H]⁺

84.044 9, 69.070 5, 56.050 1

135^a

1.63

C₁₀H₁₃N₄O₃

Histidyl asparagine^[11]

238.106 7

2.94

[M+H]⁺

192.102 2, 120.995 9, 103.054 6

136^a

1.73

C₁₂H₁₅NO₅

Serine^[11]

254.102 1

-0.39

[M+H]⁺

208.058 2, 136.990 6, 119.118 4

137^a

1.87

C₁₁H₁₂N₂O₂

Tryptophan^[8]

205.097 2

0.49

[M+H]⁺

188.070 7, 170.060 1, 159.091 8

138^a

1.87

C₁₁H₉NO₂

Indole-3-acrylic acid^[11]

188.070 3

-1.60

[M+H]⁺

146.060 2, 186.065 4

139^a

1.92

C₇H₆O₄

Protocatechuic acid^[8]

153.019 4

2.61

[M-H]^-

109.029 5, 91.018 9, 81.034 6

140^a

2.48

C₁₆H₁₈O₉

Chlorogenic acid^[8]

355.100 1

-6.20

[M+H]⁺

181.050 1, 145.026 7, 135.041 6, 117.033 7

141^a

3.08

C₁₆H₁₈O₉

Neochlorogenic acid^[11]

353.089 9

-2.27

[M-H]^-

191.056 2, 179.035 2, 162.027 8

142^a

3.13

C₁₆H₂₄O₁₀

Vitamin B₂^[8]

377.144 9

1.86

[M+H]⁺

243.087 3, 172.086 6, 99.044 3,

143^a

3.34

C₉H₈O₄

Caffeic acid^[8]

179.034 7

-1.12

[M-H]^-

135.044 6, 112.984 9, 89.023 5

144^a

3.49

C₁₆H₁₈O₈

p-Coumaroylquinic acid^[8]

339.106 9

-1.47

[M+H]⁺

147.043 9, 119.049 2, 91.054 5

145^a

4.01

C₅H₅N₅

Adenine^[8]

136.061 8

0.73

[M+H]⁺

119.049 3, 94.065 5, 92.049 7

146^a

5.44

C₉H₈O₃

p-Coumaric acid^[8]

163.040 6

0.00

[M-H]^-

119.051 1, 91.053 7

147^a

5.56

C₈H₁₆N₂O₃

Glycyl-L-leucine^[11]

189.121 8

-7.93

[M+H]⁺

171.149 0, 130.086 2, 84.081 2

148^a

7.42

C₁₀H₁₀O₄

Isoferulic acid^[8]

195.063 9

-6.66

[M+H]⁺

177.054 4, 149.059 6, 117.033 5

149^a

8.24

C₅H₉NO₄

L-Glutamic acid^[8]

148.060 2

-1.35

[M+H]⁺

130.069 2, 103.054 4, 84.044 7

150^a

8.54

C₆H₁₂O₇

Glucuronic acid^[8]

197.063 9

-8.63

[M+H]⁺

179.106 4, 161.095 9, 133.101 1

151^a

8.58

C₈H₁₆N₂O₃

Compound 147 isomer^[11]

189.121 8

-7.93

[M+H]⁺

156.093 1, 129.070 0, 105.070 1

152^a

9.65

C₉H₁₂N₂O₆

Uridine^[22]

245.079 1

9.38

[M+H]⁺

203.123 7, 189.112 0, 135.080 1

153^a

11.67

C₁₂H₁₈O₂

Serdanolide^[8]

195.137 6

-1.54

[M+H]⁺

167.085 0, 135.044 0, 111.044 2

154^a

21.65

C₁₀H₁₀O₄

Ferulic acid^[22]

195.063 2

-9.74

[M+H]⁺

177.091 1, 149.067 2, 89.065 9

155^a

26.49

C₂₃H₂₄O₉

Diferuloylglycerol^[8]

445.147 9

-3.15

[M+H]⁺

271.205 2, 253.194 7

156^a

27.87

C₁₆H₃₀O

Muscone^[8]

239.235 7

-5.02

[M+H]⁺

183.116 6, 197.132 2, 119.085 7, 81.068 6

157^a

28.20

C₁₈H₃₅NO

Oleamide^[8]

282.278 7

-1.42

[M+H]⁺

247.241 6, 135.116 8, 121.101 2

Aglycone	Adduct ion	Characteristic ion
Diosgenin	[M+H]⁺	415.320 3, 397.308 4, 271.205 3, 253.194 7
Tigogenin	[M+H]⁺	417.335 7, 399.326 4, 273.220 8, 255.210 4
Furosta-5β, 3β, 20α, 26-triol	[M+H]⁺	435.270 4, 417.266 5, 291.215 5, 273.221 5

Aglycone

Adduct ion

Characteristic ion

Diosgenin

[M+H]⁺

415.320 3, 397.308 4, 271.205 3, 253.194 7

Tigogenin

[M+H]⁺

417.335 7, 399.326 4, 273.220 8, 255.210 4

Furosta-5β, 3β, 20α, 26-triol

[M+H]⁺

435.270 4, 417.266 5, 291.215 5, 273.221 5

Aglycone	Adduct ion	Characteristic ion
Veratramine	[M+H]⁺	410.304 9, 392.294 3, 295.221 5, 267.174, 249.179 1
Solasodine	[M+H]⁺	414.336 2, 396.325 9, 271.204 7, 253.194 7
Tomatidine	[M+H]⁺	416.351 8, 398.342 1, 273.221 3, 255.210 4
Spirosol-5-ene-3, 12-diol	[M+H]⁺	430.331 2, 412.320 7, 394.313 1, 271.205 6

Aglycone

Adduct ion

Characteristic ion

Veratramine

[M+H]⁺

410.304 9, 392.294 3, 295.221 5, 267.174, 249.179 1

Solasodine

[M+H]⁺

414.336 2, 396.325 9, 271.204 7, 253.194 7

Tomatidine

[M+H]⁺

416.351 8, 398.342 1, 273.221 3, 255.210 4

Spirosol-5-ene-3, 12-diol

[M+H]⁺

430.331 2, 412.320 7, 394.313 1, 271.205 6