药学学报

No.	Species	Planting field	Medicinal part	Collection date
GB-1	G. burmanicum	Nanning, Guangxi	Leaf	2021-07
GB-2	G. burmanicum	Nanning, Guangxi	Leaf	2021-07
GB-3	G. burmanicum	Ankang, Shaanxi	Leaf	2021-09
GB-4	G. burmanicum	Ankang, Shaanxi	Leaf	2021-09
GB-5	G. burmanicum	Ankang, Shaanxi	Stem	2024-06
GB-6	G. burmanicum	Ankang, Shaanxi	Stem	2024-06
GB-7	G. burmanicum	Ankang, Shaanxi	Leaf	2024-06
GB-8	G. burmanicum	Ankang, Shaanxi	Leaf	2024-06
GL-1	G. longipes	Ankang, Shaanxi	Stem, leaf	2021-07
GL-2	G. longipes	Ankang, Shaanxi	Stem, leaf	2021-07
GL-3	G. longipes	Guangyuan, Sichuan	Root	2021
GL-4	G. longipes	Guangyuan, Sichuan	Root	2021

No.	Species	Planting field	Medicinal part	Collection date
GB-1	G. burmanicum	Nanning, Guangxi	Leaf	2021-07
GB-2	G. burmanicum	Nanning, Guangxi	Leaf	2021-07
GB-3	G. burmanicum	Ankang, Shaanxi	Leaf	2021-09
GB-4	G. burmanicum	Ankang, Shaanxi	Leaf	2021-09
GB-5	G. burmanicum	Ankang, Shaanxi	Stem	2024-06
GB-6	G. burmanicum	Ankang, Shaanxi	Stem	2024-06
GB-7	G. burmanicum	Ankang, Shaanxi	Leaf	2024-06
GB-8	G. burmanicum	Ankang, Shaanxi	Leaf	2024-06
GL-1	G. longipes	Ankang, Shaanxi	Stem, leaf	2021-07
GL-2	G. longipes	Ankang, Shaanxi	Stem, leaf	2021-07
GL-3	G. longipes	Guangyuan, Sichuan	Root	2021
GL-4	G. longipes	Guangyuan, Sichuan	Root	2021

No.	t_R/min	[M+HCOO]^-/[M-H]^-	Theoretical value	Error/ppm	Formula	Compound	Ion fragment
1	2.36	609.145 3	609.145 6	-0.49	C₂₇H₃₀O₁₆	Rutin^[17]	300.026 4, 271.023 7, 255.028 4, 243.028 6, 151.002 5
2	2.50	463.087 4	463.087 7	-0.65	C₂₁H₂₀O₁₂	Isoquercitrin^[17]	300.062 5, 271.023 2, 255.027 5, 227.033 5
3	2.67	593.151 0	593.150 6	0.67	C₂₇H₃₀O₁₅	Kaempferol-3-O-β-D-rutinoside^[17]	285.039 6, 255.028 7, 227.033 8, 211.387 0, 163.003 3
4	2.76	623.161 7	623.161 2	0.80	C₂₈H₃₂O₁₆	Isorhamnetin-3-O-neohespeidoside or isomer	315.050 5, 300.026 2, 271.024 4, 255.028 6, 243.028 4, 151.001 3
5	3.04	517.193 4	517.192 1	2.51	C₂₃H₃₄O₁₃	Jioglutoside B or isomer	299.012 9, 285.030 4, 271.023 2, 255.027 5, 227.034 6
6	3.42	607.166 4	607.166 3	0.16	C₂₈H₃₂O₁₅	Kaempferol-3-O-β-D-glucopyranosyl-2′-O-α-L-rhamnoside	607.165 0, 299.052 6, 284.031 0, 255.029 0, 227.032 8
7	3.70	623.160 9	623.161 2	-0.48	C₂₈H₃₂O₁₆	Isorhamnetin-3-O-β-D-rutinoside^[17]	451.327 8, 315.047 6, 299.018 6, 271.023 6, 243.027 9, 165.017 2
8	4.16	301.034 6	301.034 8	-0.66	C₁₅H₁₀O₇	Quercetin^[18]	271.022 3, 178.997 2, 151.002 2
9	4.42	637.177 3	637.176 9	0.63	C₂₉H₃₄O₁₆	Ombuoside^[17]	329.065 5, 314.041 7, 299.018 2, 271.023 9, 243.028 1
10	5.13	1 107.564 0/1 061.556 9	1 061.553 2	3.49	C₅₂H₈₆O₂₂	3β, 21, 25-Trihydroxy-20, 24-epoxydrammar-19-oxo-3-O-[α-L-rhamnopyranosyl(1→2)][β-D-xylopyranosyl(1→3)]-α-L-arabinpyranosyl-21-O-β-D-glucopyranoside^[15]	929.510 5, 783.447 2, 621.399 9, 489.358 6, 299.018 1, 271.023 0
11	5.62	285.039 7	285.039 9	-0.70	C₁₅H₁₀O₆	Kaempferol	271.023 8, 255.025 7, 227.035 3, 199.032 8
12	5.79	959.488 0/913.479 6	913.479 7	-0.11	C₄₆H₇₄O₁₈	(3β, 20ξ, 21ξ, 23ξ)-3, 20, 21, 26-Tetrahydroxy-19-oxo-21, 23-epoxydamane-24-ene-3-O-[α-L-rhamnopyranosyl(1→2)][β-D-xylopyranosyl(1→3)]-α-L-arabinopyranoside^[19]	681.386 2, 535.327 4, 403.284 8, 375.288 7
13	6.38	999.480 5	999.480 1	0.45	C₄₉H₇₆O₂₁	Malonyl-(3β, 20ξ, 21ξ, 23ξ)-3, 20, 21, 26-tetrahydroxy-19-oxo-21, 23-epoxydamane-24-en-3-O-[α-L-rhamnopyranosyl(1→2)][β-D-xylopyranosyl(1→3)]-α-L-arabinopyranoside	955.488 8, 913.478 0, 781.433 9, 681.385 3, 535.326 6, 403.284 2, 375.287 5, 299.016 5
14	6.54	1 001.496 0/955.491 3	955.490 3	1.05	C₄₈H₇₆O₁₉	Acetyl-(3β, 20ξ, 21ξ, 23ξ)-3, 20, 21, 26-tetrahydroxy-19-oxo-21, 23-epoxydamane-24-en-3-O-[α-L-rhamnopyranosyl(1→2)][β-D-xylopyranosyl(1→3)]-α-L-arabinopyranoside	913.480 7, 781.433 4, 681.385 4, 535.326 8, 403.284 4, 375.288 8, 299.018 1, 271.023 7
15	6.92	1 001.496 0/955.490 8	955.490 3	0.52	C₄₈H₇₆O₁₉	Acetyl-(3β, 20ξ, 21ξ, 23ξ)-3, 20, 21, 26-tetrahydroxy-19-oxo-21, 23-epoxydamane-24-en-3-O-[α-L-rhamnopyranosyl(1→2)][β-D-xylopyranosyl(1→3)]-α-L-arabinopyranoside	913.472 7, 781.433 9, 681.385 6, 535.326 2, 403.284 1, 375.288 1, 299.018 2, 271.021 0
16	7.15	945.507 6/899.497 6	899.500 4	-3.11	C₄₆H₇₆O₁₇	3β, 19, 20, 21, 23-Pentahydroxy-21, 24-cyclodammarane-25-en-3-O-[α-L-rhamnopyranosyl(1→2)][β-D-xylopyranosyl(1→3)]-α-L-arabinopyranoside^[20]	767.457 7, 621.398 9, 489.357 3, 299.018 5, 271.022 1
17#	7.36	945.507 0/899.502 0	899.500 4	1.78	C₄₆H₇₆O₁₇	3β, 20, 21, 26-Tetrahydroxy-21, 23-epoxydamane-24-en-3-O-[α-L-rhamnopyranosyl(1→2)][β-D-xylopyranosyl(1→3)]-α-L-arabinopyranoside	767.476 3, 667.402 9, 521.346 7, 389.304 8, 299.016 9, 271.024 4
18	7.65	985.501 2	985.500 8	0.41	C₄₉H₇₈O₂₀	Acetyl-3β, 19, 20, 21, 23-pentahydroxy-21, 24-cyclodammarane-25-en-3-O-[α-L-rhamnopyranosyl(1→2)][β-D-xylpyranosyl(1→3)]-α-L-arabinopyranoside	941.504 7, 899.492 1, 767.457 5, 621.399 7, 489.357 3
29	7.93	985.502 4	985.500 8	1.62	C₄₉H₇₈O₂₀	Malonyl-3β, 20, 21, 26-tetrahydroxy-21, 23-epoxydammarane-24-en-3-O-[α-L-rhamnopyranosyl(1→2)][β-D-xylpyranosyl(1→3)]-α-L-arabinopyranoside	941.507 5, 899.486 4, 767.457 9, 667.405 5, 521.348 3, 389.305 5, 299.017 6
20^*	8.75	1 091.565 6/1 045.559 9	1 045.558 3	1.53	C₅₂H₈₆O₂₁	Gypenoside XLIX^[15]	913.517 2, 751.464 5, 605.405 0, 473.362 1, 389.273 7
21^*	8.89	1 093.581 3/1 047.574 1	1 047.574 0	0.10	C₅₂H₈₈C₂₁	3β, 19, 20S, 21-Tetrahydroxydammar-24-ene-3-O-[α-L-rhamnopyranosyl(1→2)][β-D-xylopyranosyl(1→3)]-α-L-arabinopyranosyl-21-O-β-D-glucopyranoside^[19]	915.530 9, 753.478 4, 607.418 5, 475.376 6
22	9.46	1 131.560 9	1 131.558 7	1.94	C₅₅H₈₈O₂₄	Malonyl-gypenoside XLIX	1 087.571 7, 1 045.558 8, 913.516 6, 751.463 9, 605.405 7, 473.358 7
23	9.79	299.018 6	299.019 2	-2.01	C₁₅H₈O₇	Dehydroquercetin or isomer	271.023 5, 243.025 2, 227.032 9, 215.028 5, 199.038 7
24#	10.25	959.522 2/913.516 8	913.516 1	0.77	C₄₇H₇₈O₁₇	3β, 20, 21-Trihydroxydamane-19-oxo-24-ene-3-O-[α-L-rhamnopyranosyl(1→2)][β-D-glucopyranosyl(1→3)]-α-L-arabinopyranoside	751.464 8, 605.401 6, 473.360 3
25#	10.44	961.537 0/915.529 7	915.531 7	-2.18	C₄₇H₈₀O₁₇	3β, 19, 20, 21-Tetrahydroxydamane-24-ene-3-O-[α-L-rhamnopyranosyl(1→2)][β-D-glucopyranosyl(1→3)]-α-L-arabinopyranoside	753.275 3, 607.416 9, 475.388 7
26	11.40	999.516 1	999.516 5	-0.40	C₅₀H₈₂O₂₀	Malonyl-3β, 20, 21-trihydroxydamane-19-oxo-24-ene-3-O-[α-L-rhamnopyranosyl(1→2)][β-D-glucopyranosyl(1→3)]-α-L-arabinopyranoside	955.526 4, 913, 5 135, 751.459 8, 681.387 8, 535.325 7, 403.282 3, 375.290 2
27	11.99	1 077.587 3/1 031.579 5	1 031.579 1	0.39	C₅₂H₈₈O₂₀	3, 20, 21-Trihydroxydama-24-en-3-O-[α-L-rhamnopyranosyl(1→2)][β-D-xylpyranosyl(1→3)]-α-L-arabinopyranosyl-21-O-β-D-glucoside^[21]	899.536 9, 737.484 4, 591.423 2, 459.386 7
28	12.14	1 013.497 7	1 013.495 7	1.97	C₅₀H₇₈O₂₁	Malonyl-3β, 20, 21-trihydroxy-19-oxo-21, 23-epoxydammarane-24-en-3-O-[α-L-rhamnopyranosyl(1→2)][β-D-glucopyranosyl(1→3)]-α-L-arabinopyranoside	969.506 0, 927.502 6, 765.446 2, 681.384 6, 535.325 1, 403.283 8, 375.292 1, 299.016 9
29	12.49	329.065 9	329.066 1	-0.61	C₁₇H₁₄O₇	Quercetin 3, 4′-dimethyl ether or isomer	314.039 7, 299.018 1, 271.022 6, 243.029 5
30#	12.68	945.506 6/899.501 9	899.500 4	1.67	C₄₆H₇₆O₁₇	3β, 19, 20, 21-Tetrahydroxy-21, 23-epoxydammarane-24-en-3-O-[α-L-rhamnopyranosyl(1→2)][β-D-xylopyranosyl(1→3)]-α-L-arabinopyranoside	767.465 3, 683.401 2, 537.340 2, 405.298 6, 375.288 4, 299.012 2
31^*	12.87	943.492 6/897.486 9	897.484 8	2.34	C₄₆H₇₄O₁₇	Gypenoside A^[15]	765.445 1, 681.386 7, 535.328 2, 403.284 9, 375.289 8, 329.247 8
32	13.73	983.488 6	983.485 2	3.46	C₄₉H₇₆O₂₀	Malonyl-gypenoside A	939.498 7, 897.486 1, 765.443 2, 681.386 2, 535.327 6, 403.284 4, 375.289 4, 259.080 0
33	14.37	983.487 9	983.485 2	2.75	C₄₉H₇₆O₂₀	Malonyl-gypenoside A	939.497 4, 897.486 3, 765.442 2, 681.384 9, 535.326 7, 403.285 1, 375.288 6
34^*	14.86	929.511 9/883.502 4	883.505 5	-3.51	C₄₆H₇₆O₁₆	Gylongiposide Ⅰ^[19]	751.459 9, 605.403 2, 473.363 2, 389.269 7, 299.017 7
35	15.10	985.501 6/939.496 6	939.495 3	1.38	C₄₈H₇₆O₁₈	Acetyl-gypenoside A	897.485 2, 765.441 5, 681.385 4, 535.327 0, 403.284 6, 375.288 1
36	15.56	971.519 0/925.517 4	925.516 1	1.40	C₄₈H₇₈O₁₇	Acetyl-gylongiposide Ⅰ	883.505 7, 751.462 9, 605.404 0, 473.360 2
37	15.99	999.516 5	999.516 5	0.00	C₅₀H₈₀O₂₀	Malonyl-3β, 19, 20, 21-tetrahydroxy-21, 23-epoxydammarane-24-ene-3-O-[α-L-rhamnose(1→2)][β-D-xylopyranosyl(1→3)]-β-D-glucopyranoside	955.533 1, 913.509 6, 781.468 5, 697.424 3, 551.358 9, 389.303 9, 299.016 6, 271.021 3
38#	16.76	929.512 3/883.505 2	883.505 5	-0.34	C₄₆H₇₆O₁₆	3β, 20, 21-Trihydroxy-21, 23-epoxydammarane-24-ene-3-O-[α-L-rhamnopyranosyl(1→2)][β-D-xylopyranosyl(1→3)]-α-L-arabinopyranoside	751.462 5, 667.452 0, 521.347 4, 389.305 3, 345.275 6, 299.015 7
39	17.18	969.508 7	969.505 9	2.89	C₄₉H₇₈O₁₉	Malonyl-3β, 20, 21-trihydroxy-21, 23-epoxydammarane-24-ene-3-O-[α-L-rhamnopyranosyl(1→2)][β-D-xylopyranosyl(1→3)]-α-L-arabinopyranoside	925.518 5, 883.507 8, 751.463 1, 667.407 0, 521.348 5, 389.306 0
40	18.01	969.506 6	969.505 9	0.72	C₄₉H₇₈O₁₉	Malonyl-3β, 20, 21-trihydroxy-21, 23-epoxydammarane-24-en-3-O-[α-L-rhamnopyranosyl(1→2)][β-D-xylopyranosyl(1→3)]-α-L-arabinopyranoside	925, 5 161, 883.501 8, 751.456 2, 667.403 7, 521.345 0, 389.304 5
41	18.88	971.520 8/925.515 2	925.516 1	-0.97	C₄₈H₇₈O₁₇	Acetyl-3β, 20, 21-trihydroxy-21, 23-epoxydammarane-24-en-3-O-[α-L-rhamnopyranosyl(1→2)][β-D-xylopyranosyl(1→3)]-α-L-arabinopyranoside	883.505 1, 751.456 2, 667.404 8, 521.344 0, 389.304 1, 299.022 1
42	21.37	999.514 8	999.516 5	-1.70	C₅₀H₈₀O₂₀	Malonyl-3β, 19, 20, 21-tetrahydroxy-21, 23-epoxydamane-24-ene-3-O-[α-L-rhamnopyranosyl(1→2)][β-D-glucopyranosyl(1→3)]-α-L-arabinopyranoside	955.531 7, 913.516 8, 883.537 3, 751.465 1, 667.400 9, 521.346 3, 389.303 2
43	21.68	999.516 6	999.516 5	0.10	C₅₀H₈₀O₂₀	Malonyl-3β, 20, 21-trihydroxydammarane-19-oxo-24-ene-3-O-[α-L-rhamnopyranosyl(1→2)][β-D-xylopyranosyl(1→3)]-β-D-glucopyranoside	955.525 0, 913.510 6, 781.473 6, 635.408 9, 473.362 3
44#	22.71	929.510 8/883.505 7	883.505 5	0.23	C₄₆H₇₆O₁₆	3β, 20, 21-Trihydroxydammarane-19-oxo-24-ene-3-O-[α-L-rhamnopyranosyl(1→2)][β-D-xylopyranosyl(1→3)]-α-L-arabinopyranoside	751.463 7, 605.400 0, 473.360 9
45	22.82	969.507 6	969.505 9	1.75	C₄₉H₇₈O₁₉	Malonyl-3β, 20, 21-trihydroxydammarane-19-oxo-24-ene-3-O-[α-L-rhamnopyranosyl(1→2)][β-D-xylopyranosyl(1→3)]-α-L-arabinopyranoside	925.511 7, 883.506 6, 751.464 2, 605.404 2, 473.361 8
46	23.77	969.506 0	969.505 9	0.10	C₄₉H₇₈O₂₀	Malonyl-3β, 20, 21-trihydroxydammarane-19-oxo-24-ene-3-O-[α-L-rhamnopyranosyl(1→2)][β-D-xylopyranosyl(1→3)]-α-L-arabinopyranoside	925.517 9, 883.505 8, 751.460 9, 605.375 9, 473.356 9
47	24.56	969.503 0	969.505 9	-2.99	C₄₉H₇₈O₂₁	Malonyl-3β, 20, 21-trihydroxydammarane-19-oxo-24-ene-3-O-[α-L-rhamnopyranosyl(1→2)][β-D-xylopyranosyl(1→3)]-α-L-arabinopyranoside	925.515 8, 883.501 2, 751.459 4, 605.389 2, 473.354 7, 427.347 1

No.	t_R/min	[M+HCOO]^-/[M-H]^-	Theoretical value	Error/ppm	Formula	Compound	Ion fragment
1	2.36	609.145 3	609.145 6	-0.49	C₂₇H₃₀O₁₆	Rutin^[17]	300.026 4, 271.023 7, 255.028 4, 243.028 6, 151.002 5
2	2.50	463.087 4	463.087 7	-0.65	C₂₁H₂₀O₁₂	Isoquercitrin^[17]	300.062 5, 271.023 2, 255.027 5, 227.033 5
3	2.67	593.151 0	593.150 6	0.67	C₂₇H₃₀O₁₅	Kaempferol-3-O-β-D-rutinoside^[17]	285.039 6, 255.028 7, 227.033 8, 211.387 0, 163.003 3
4	2.76	623.161 7	623.161 2	0.80	C₂₈H₃₂O₁₆	Isorhamnetin-3-O-neohespeidoside or isomer	315.050 5, 300.026 2, 271.024 4, 255.028 6, 243.028 4, 151.001 3
5	3.04	517.193 4	517.192 1	2.51	C₂₃H₃₄O₁₃	Jioglutoside B or isomer	299.012 9, 285.030 4, 271.023 2, 255.027 5, 227.034 6
6	3.42	607.166 4	607.166 3	0.16	C₂₈H₃₂O₁₅	Kaempferol-3-O-β-D-glucopyranosyl-2′-O-α-L-rhamnoside	607.165 0, 299.052 6, 284.031 0, 255.029 0, 227.032 8
7	3.70	623.160 9	623.161 2	-0.48	C₂₈H₃₂O₁₆	Isorhamnetin-3-O-β-D-rutinoside^[17]	451.327 8, 315.047 6, 299.018 6, 271.023 6, 243.027 9, 165.017 2
8	4.16	301.034 6	301.034 8	-0.66	C₁₅H₁₀O₇	Quercetin^[18]	271.022 3, 178.997 2, 151.002 2
9	4.42	637.177 3	637.176 9	0.63	C₂₉H₃₄O₁₆	Ombuoside^[17]	329.065 5, 314.041 7, 299.018 2, 271.023 9, 243.028 1
10	5.13	1 107.564 0/1 061.556 9	1 061.553 2	3.49	C₅₂H₈₆O₂₂	3β, 21, 25-Trihydroxy-20, 24-epoxydrammar-19-oxo-3-O-[α-L-rhamnopyranosyl(1→2)][β-D-xylopyranosyl(1→3)]-α-L-arabinpyranosyl-21-O-β-D-glucopyranoside^[15]	929.510 5, 783.447 2, 621.399 9, 489.358 6, 299.018 1, 271.023 0
11	5.62	285.039 7	285.039 9	-0.70	C₁₅H₁₀O₆	Kaempferol	271.023 8, 255.025 7, 227.035 3, 199.032 8
12	5.79	959.488 0/913.479 6	913.479 7	-0.11	C₄₆H₇₄O₁₈	(3β, 20ξ, 21ξ, 23ξ)-3, 20, 21, 26-Tetrahydroxy-19-oxo-21, 23-epoxydamane-24-ene-3-O-[α-L-rhamnopyranosyl(1→2)][β-D-xylopyranosyl(1→3)]-α-L-arabinopyranoside^[19]	681.386 2, 535.327 4, 403.284 8, 375.288 7
13	6.38	999.480 5	999.480 1	0.45	C₄₉H₇₆O₂₁	Malonyl-(3β, 20ξ, 21ξ, 23ξ)-3, 20, 21, 26-tetrahydroxy-19-oxo-21, 23-epoxydamane-24-en-3-O-[α-L-rhamnopyranosyl(1→2)][β-D-xylopyranosyl(1→3)]-α-L-arabinopyranoside	955.488 8, 913.478 0, 781.433 9, 681.385 3, 535.326 6, 403.284 2, 375.287 5, 299.016 5
14	6.54	1 001.496 0/955.491 3	955.490 3	1.05	C₄₈H₇₆O₁₉	Acetyl-(3β, 20ξ, 21ξ, 23ξ)-3, 20, 21, 26-tetrahydroxy-19-oxo-21, 23-epoxydamane-24-en-3-O-[α-L-rhamnopyranosyl(1→2)][β-D-xylopyranosyl(1→3)]-α-L-arabinopyranoside	913.480 7, 781.433 4, 681.385 4, 535.326 8, 403.284 4, 375.288 8, 299.018 1, 271.023 7
15	6.92	1 001.496 0/955.490 8	955.490 3	0.52	C₄₈H₇₆O₁₉	Acetyl-(3β, 20ξ, 21ξ, 23ξ)-3, 20, 21, 26-tetrahydroxy-19-oxo-21, 23-epoxydamane-24-en-3-O-[α-L-rhamnopyranosyl(1→2)][β-D-xylopyranosyl(1→3)]-α-L-arabinopyranoside	913.472 7, 781.433 9, 681.385 6, 535.326 2, 403.284 1, 375.288 1, 299.018 2, 271.021 0
16	7.15	945.507 6/899.497 6	899.500 4	-3.11	C₄₆H₇₆O₁₇	3β, 19, 20, 21, 23-Pentahydroxy-21, 24-cyclodammarane-25-en-3-O-[α-L-rhamnopyranosyl(1→2)][β-D-xylopyranosyl(1→3)]-α-L-arabinopyranoside^[20]	767.457 7, 621.398 9, 489.357 3, 299.018 5, 271.022 1
17#	7.36	945.507 0/899.502 0	899.500 4	1.78	C₄₆H₇₆O₁₇	3β, 20, 21, 26-Tetrahydroxy-21, 23-epoxydamane-24-en-3-O-[α-L-rhamnopyranosyl(1→2)][β-D-xylopyranosyl(1→3)]-α-L-arabinopyranoside	767.476 3, 667.402 9, 521.346 7, 389.304 8, 299.016 9, 271.024 4
18	7.65	985.501 2	985.500 8	0.41	C₄₉H₇₈O₂₀	Acetyl-3β, 19, 20, 21, 23-pentahydroxy-21, 24-cyclodammarane-25-en-3-O-[α-L-rhamnopyranosyl(1→2)][β-D-xylpyranosyl(1→3)]-α-L-arabinopyranoside	941.504 7, 899.492 1, 767.457 5, 621.399 7, 489.357 3
29	7.93	985.502 4	985.500 8	1.62	C₄₉H₇₈O₂₀	Malonyl-3β, 20, 21, 26-tetrahydroxy-21, 23-epoxydammarane-24-en-3-O-[α-L-rhamnopyranosyl(1→2)][β-D-xylpyranosyl(1→3)]-α-L-arabinopyranoside	941.507 5, 899.486 4, 767.457 9, 667.405 5, 521.348 3, 389.305 5, 299.017 6
20^*	8.75	1 091.565 6/1 045.559 9	1 045.558 3	1.53	C₅₂H₈₆O₂₁	Gypenoside XLIX^[15]	913.517 2, 751.464 5, 605.405 0, 473.362 1, 389.273 7
21^*	8.89	1 093.581 3/1 047.574 1	1 047.574 0	0.10	C₅₂H₈₈C₂₁	3β, 19, 20S, 21-Tetrahydroxydammar-24-ene-3-O-[α-L-rhamnopyranosyl(1→2)][β-D-xylopyranosyl(1→3)]-α-L-arabinopyranosyl-21-O-β-D-glucopyranoside^[19]	915.530 9, 753.478 4, 607.418 5, 475.376 6
22	9.46	1 131.560 9	1 131.558 7	1.94	C₅₅H₈₈O₂₄	Malonyl-gypenoside XLIX	1 087.571 7, 1 045.558 8, 913.516 6, 751.463 9, 605.405 7, 473.358 7
23	9.79	299.018 6	299.019 2	-2.01	C₁₅H₈O₇	Dehydroquercetin or isomer	271.023 5, 243.025 2, 227.032 9, 215.028 5, 199.038 7
24#	10.25	959.522 2/913.516 8	913.516 1	0.77	C₄₇H₇₈O₁₇	3β, 20, 21-Trihydroxydamane-19-oxo-24-ene-3-O-[α-L-rhamnopyranosyl(1→2)][β-D-glucopyranosyl(1→3)]-α-L-arabinopyranoside	751.464 8, 605.401 6, 473.360 3
25#	10.44	961.537 0/915.529 7	915.531 7	-2.18	C₄₇H₈₀O₁₇	3β, 19, 20, 21-Tetrahydroxydamane-24-ene-3-O-[α-L-rhamnopyranosyl(1→2)][β-D-glucopyranosyl(1→3)]-α-L-arabinopyranoside	753.275 3, 607.416 9, 475.388 7
26	11.40	999.516 1	999.516 5	-0.40	C₅₀H₈₂O₂₀	Malonyl-3β, 20, 21-trihydroxydamane-19-oxo-24-ene-3-O-[α-L-rhamnopyranosyl(1→2)][β-D-glucopyranosyl(1→3)]-α-L-arabinopyranoside	955.526 4, 913, 5 135, 751.459 8, 681.387 8, 535.325 7, 403.282 3, 375.290 2
27	11.99	1 077.587 3/1 031.579 5	1 031.579 1	0.39	C₅₂H₈₈O₂₀	3, 20, 21-Trihydroxydama-24-en-3-O-[α-L-rhamnopyranosyl(1→2)][β-D-xylpyranosyl(1→3)]-α-L-arabinopyranosyl-21-O-β-D-glucoside^[21]	899.536 9, 737.484 4, 591.423 2, 459.386 7
28	12.14	1 013.497 7	1 013.495 7	1.97	C₅₀H₇₈O₂₁	Malonyl-3β, 20, 21-trihydroxy-19-oxo-21, 23-epoxydammarane-24-en-3-O-[α-L-rhamnopyranosyl(1→2)][β-D-glucopyranosyl(1→3)]-α-L-arabinopyranoside	969.506 0, 927.502 6, 765.446 2, 681.384 6, 535.325 1, 403.283 8, 375.292 1, 299.016 9
29	12.49	329.065 9	329.066 1	-0.61	C₁₇H₁₄O₇	Quercetin 3, 4′-dimethyl ether or isomer	314.039 7, 299.018 1, 271.022 6, 243.029 5
30#	12.68	945.506 6/899.501 9	899.500 4	1.67	C₄₆H₇₆O₁₇	3β, 19, 20, 21-Tetrahydroxy-21, 23-epoxydammarane-24-en-3-O-[α-L-rhamnopyranosyl(1→2)][β-D-xylopyranosyl(1→3)]-α-L-arabinopyranoside	767.465 3, 683.401 2, 537.340 2, 405.298 6, 375.288 4, 299.012 2
31^*	12.87	943.492 6/897.486 9	897.484 8	2.34	C₄₆H₇₄O₁₇	Gypenoside A^[15]	765.445 1, 681.386 7, 535.328 2, 403.284 9, 375.289 8, 329.247 8
32	13.73	983.488 6	983.485 2	3.46	C₄₉H₇₆O₂₀	Malonyl-gypenoside A	939.498 7, 897.486 1, 765.443 2, 681.386 2, 535.327 6, 403.284 4, 375.289 4, 259.080 0
33	14.37	983.487 9	983.485 2	2.75	C₄₉H₇₆O₂₀	Malonyl-gypenoside A	939.497 4, 897.486 3, 765.442 2, 681.384 9, 535.326 7, 403.285 1, 375.288 6
34^*	14.86	929.511 9/883.502 4	883.505 5	-3.51	C₄₆H₇₆O₁₆	Gylongiposide Ⅰ^[19]	751.459 9, 605.403 2, 473.363 2, 389.269 7, 299.017 7
35	15.10	985.501 6/939.496 6	939.495 3	1.38	C₄₈H₇₆O₁₈	Acetyl-gypenoside A	897.485 2, 765.441 5, 681.385 4, 535.327 0, 403.284 6, 375.288 1
36	15.56	971.519 0/925.517 4	925.516 1	1.40	C₄₈H₇₈O₁₇	Acetyl-gylongiposide Ⅰ	883.505 7, 751.462 9, 605.404 0, 473.360 2
37	15.99	999.516 5	999.516 5	0.00	C₅₀H₈₀O₂₀	Malonyl-3β, 19, 20, 21-tetrahydroxy-21, 23-epoxydammarane-24-ene-3-O-[α-L-rhamnose(1→2)][β-D-xylopyranosyl(1→3)]-β-D-glucopyranoside	955.533 1, 913.509 6, 781.468 5, 697.424 3, 551.358 9, 389.303 9, 299.016 6, 271.021 3
38#	16.76	929.512 3/883.505 2	883.505 5	-0.34	C₄₆H₇₆O₁₆	3β, 20, 21-Trihydroxy-21, 23-epoxydammarane-24-ene-3-O-[α-L-rhamnopyranosyl(1→2)][β-D-xylopyranosyl(1→3)]-α-L-arabinopyranoside	751.462 5, 667.452 0, 521.347 4, 389.305 3, 345.275 6, 299.015 7
39	17.18	969.508 7	969.505 9	2.89	C₄₉H₇₈O₁₉	Malonyl-3β, 20, 21-trihydroxy-21, 23-epoxydammarane-24-ene-3-O-[α-L-rhamnopyranosyl(1→2)][β-D-xylopyranosyl(1→3)]-α-L-arabinopyranoside	925.518 5, 883.507 8, 751.463 1, 667.407 0, 521.348 5, 389.306 0
40	18.01	969.506 6	969.505 9	0.72	C₄₉H₇₈O₁₉	Malonyl-3β, 20, 21-trihydroxy-21, 23-epoxydammarane-24-en-3-O-[α-L-rhamnopyranosyl(1→2)][β-D-xylopyranosyl(1→3)]-α-L-arabinopyranoside	925, 5 161, 883.501 8, 751.456 2, 667.403 7, 521.345 0, 389.304 5
41	18.88	971.520 8/925.515 2	925.516 1	-0.97	C₄₈H₇₈O₁₇	Acetyl-3β, 20, 21-trihydroxy-21, 23-epoxydammarane-24-en-3-O-[α-L-rhamnopyranosyl(1→2)][β-D-xylopyranosyl(1→3)]-α-L-arabinopyranoside	883.505 1, 751.456 2, 667.404 8, 521.344 0, 389.304 1, 299.022 1
42	21.37	999.514 8	999.516 5	-1.70	C₅₀H₈₀O₂₀	Malonyl-3β, 19, 20, 21-tetrahydroxy-21, 23-epoxydamane-24-ene-3-O-[α-L-rhamnopyranosyl(1→2)][β-D-glucopyranosyl(1→3)]-α-L-arabinopyranoside	955.531 7, 913.516 8, 883.537 3, 751.465 1, 667.400 9, 521.346 3, 389.303 2
43	21.68	999.516 6	999.516 5	0.10	C₅₀H₈₀O₂₀	Malonyl-3β, 20, 21-trihydroxydammarane-19-oxo-24-ene-3-O-[α-L-rhamnopyranosyl(1→2)][β-D-xylopyranosyl(1→3)]-β-D-glucopyranoside	955.525 0, 913.510 6, 781.473 6, 635.408 9, 473.362 3
44#	22.71	929.510 8/883.505 7	883.505 5	0.23	C₄₆H₇₆O₁₆	3β, 20, 21-Trihydroxydammarane-19-oxo-24-ene-3-O-[α-L-rhamnopyranosyl(1→2)][β-D-xylopyranosyl(1→3)]-α-L-arabinopyranoside	751.463 7, 605.400 0, 473.360 9
45	22.82	969.507 6	969.505 9	1.75	C₄₉H₇₈O₁₉	Malonyl-3β, 20, 21-trihydroxydammarane-19-oxo-24-ene-3-O-[α-L-rhamnopyranosyl(1→2)][β-D-xylopyranosyl(1→3)]-α-L-arabinopyranoside	925.511 7, 883.506 6, 751.464 2, 605.404 2, 473.361 8
46	23.77	969.506 0	969.505 9	0.10	C₄₉H₇₈O₂₀	Malonyl-3β, 20, 21-trihydroxydammarane-19-oxo-24-ene-3-O-[α-L-rhamnopyranosyl(1→2)][β-D-xylopyranosyl(1→3)]-α-L-arabinopyranoside	925.517 9, 883.505 8, 751.460 9, 605.375 9, 473.356 9
47	24.56	969.503 0	969.505 9	-2.99	C₄₉H₇₈O₂₁	Malonyl-3β, 20, 21-trihydroxydammarane-19-oxo-24-ene-3-O-[α-L-rhamnopyranosyl(1→2)][β-D-xylopyranosyl(1→3)]-α-L-arabinopyranoside	925.515 8, 883.501 2, 751.459 4, 605.389 2, 473.354 7, 427.347 1

基于UHPLC-Q-TOF-MS技术的缅甸绞股蓝化学成分表征与鉴定

PDF下载

王美燕 ¹^,² , 李港 ² , 黄长亮 ¹^,² , 孙晴 ² , 南易 ² , 于德鑫 ² , 王秀 ² , 郭宝林 ³ , 梁海珍 ²^,^* , 马百平 ¹^,²^,^*

药学学报 | 研究论文 2025,60(5): 1499-1509

收起

药学学报 | 研究论文 2025, 60(5): 1499-1509

基于UHPLC-Q-TOF-MS技术的缅甸绞股蓝化学成分表征与鉴定

全屏

王美燕¹^,², 李港², 黄长亮¹^,², 孙晴², 南易², 于德鑫², 王秀², 郭宝林³, 梁海珍²^,^*, 马百平¹^,²^,^*

作者信息

1.广东药科大学, 广东广州 510006

2.军事科学院军事医学研究院, 北京 100850

3.中国医学科学院、北京协和医学院, 药用植物研究所, 北京 100193

通讯作者:

^*梁海珍, E-mail: lhzhcm@163.com

马百平, Tel: 86-10-66930265, E-mail: mabaiping@sina.com

Profiling and characterization of the chemical components in Gynostemma burmanicum based on UHPLC-Q-TOF-MS technology

Mei-yan WANG¹^,², Gang LI², Chang-liang HUANG¹^,², Qing SUN², Yi NAN², De-xin YU², Xiu WANG², Bao-lin GUO³, Hai-zhen LIANG²^,^*, Bai-ping MA¹^,²^,^*

Affiliations

1. Guangdong Pharmaceutical University, Guangzhou 510006, China

2. Academy of Military Medical Sciences, Academy of Military Sciences, Beijing 100850, China

3. Institute of Medicinal Plant Development, Chinese Academy of Medical Sciences and Peking Union Medical College, Beijing 100193, China

出版时间: 2025-05-12 doi: 10.16438/j.0513-4870.2024-1158

文章导航

摘要

收起

绞股蓝属植物资源丰富, 在我国分布广泛。绞股蓝属植物因含有丰富的达玛烷型三萜皂苷且药理活性多样而引起国内外广泛关注。目前对于绞股蓝属植物化学成分及药理活性研究主要集中于绞股蓝[Gynostemma pentaphyllum (Thunb.) Makino] 和长梗绞股蓝(G. longipes C. Y. Wu ex C. Y. Wu & S. K. Chen) 2个种, 对绞股蓝属其他种植物的研究则较少。本文采用超高效液相色谱-四极杆-飞行时间质谱联用技术, 系统阐明缅甸绞股蓝(G. burmanicum King ex Chakrav) 中的化学成分。首先对不同来源缅甸绞股蓝进行液质分析, 观察成分组成的一致性; 根据绞股蓝属来源达玛烷型三萜皂苷质谱裂解规律、丙二酰基及乙酰基皂苷成分裂解特点, 结合自建数据库及ChemSipder、SciFinder、PubChem在线数据库, 对表征的各个峰的结构进行鉴定; 通过液质基峰离子(base peak ion, BPI) 色谱图对比缅甸绞股蓝与长梗绞股蓝的成分异同。实验结果显示, 不同来源缅甸绞股蓝样品的成分组成一致性良好, 共从缅甸绞股蓝样品中鉴定化学成分47个, 包括12个黄酮和35个三萜皂苷类成分, 其中6个为新化合物。缅甸绞股蓝中的皂苷普遍存在丙二酰基和乙酰基化现象, 反相C18色谱分析时它们常常在相应的原型皂苷后相继出现。色谱图显示缅甸绞股蓝与长梗绞股蓝皂苷成分一致性良好, 且主要成分绞股蓝皂苷XLIX和绞股蓝皂苷A及其丙二酰基成分在2个种间含量相当。综上, 通过缅甸绞股蓝的液质分析, 明确了缅甸绞股蓝的成分组成及特点, 为缅甸绞股蓝的开发利用提供了实验依据。

关键词

UHPLC-Q-TOF-MS / 缅甸绞股蓝 / 三萜皂苷 / 丙二酰基 / 黄酮

Abstract

收起

The genus Gynostemma, with abundant plant resources, is widely distributed in China. Gynostemma plants have gathered widespread attention both domestically and internationally due to their abundant contents of diverse dammarane triterpenoid saponins and various promising pharmacological activities. At present, the studies on the chemical constituents and pharmacological activities of Gynostemma plants mainly focus on G. pentaphyllum (Thunb.) Makino and G. longipes C. Y. Wu ex C. Y. Wu & S. K. Chen, with less attention given to other species within genus. In this study, the chemical constituents of G. burmanicum King ex Chakrav were systematically identified by ultra-high performance liquid chromatography-quadrupole-time of flight-mass spectrometry (UHPLC-Q-TOF-MS). Firstly, the LC-MS analysis of G. burmanicum from different sources was carried out to evaluate the consistency. According to the mass spectrometry fragmentation pattern of dammarane triterpenoid saponins from Gynostemma, the fragmentation characteristics of malonylated and acetylated saponins, combined with the self-built database and online database such as ChemSipder, SciFinder, PubChem, the chemical components of G. burmanicum were identified. The similarities and differences in the components between G. burmanicum and G. longipes were further assessed by comparing their base peak chromatogram. The experimental results indicated a good consistency in the composition of G. burmanicum samples from different sources. A total of 47 chemical components were identified from G. burmanicum, including 12 flavonoids and 35 triterpenoid saponins, among which 6 were new compounds. Saponins in G. burmanicum generally exhibited malonylation and acetylation, appearing after the corresponding prototypical saponins on a reversed phase chromatography. The base peak ion (BPI) chromatograms showed that the saponins of G. burmanicum were highly consistent with those of G. longipes, with comparable contents of the main components gypenoside XLIX and gypenoside A and their malonylated derivatives. In summary, this study comprehensively clarified the chemical composition and characteristics of G. burmanicum, which provided an experimental basis for the development and utilization of G. burmanicum.

Key words

UHPLC-Q-TOF-MS / Gynostemma burmanicum / triterpenoid saponin / malonyl group / flavone

引用本文

王美燕, 李港, 黄长亮, 孙晴, 南易, 于德鑫, 王秀, 郭宝林, 梁海珍, 马百平. 基于UHPLC-Q-TOF-MS技术的缅甸绞股蓝化学成分表征与鉴定. 药学学报, 2025 , 60 (5) : 1499 -1509 . DOI: 10.16438/j.0513-4870.2024-1158

Mei-yan WANG, Gang LI, Chang-liang HUANG, Qing SUN, Yi NAN, De-xin YU, Xiu WANG, Bao-lin GUO, Hai-zhen LIANG, Bai-ping MA. Profiling and characterization of the chemical components in Gynostemma burmanicum based on UHPLC-Q-TOF-MS technology[J]. Acta Pharmaceutica Sinica, 2025 , 60 (5) : 1499 -1509 . DOI: 10.16438/j.0513-4870.2024-1158

正文

收起

绞股蓝属(Gynostemma) 隶属于葫芦科(Cucurbitaceae), 约有18种植物, 广泛分布于亚洲热带至东亚, 自喜马拉雅至日本、马来群岛和新几内亚岛。我国有16种2变种, 主产陕西南部和长江以南广大地区, 以西南地区最多, 如绞股蓝(G. pentaphyllum)、长梗绞股蓝(G. longipes)、扁果绞股蓝(G. compressum)、喙果绞股蓝(G. yixingense)、缅甸绞股蓝(G. burmanicum) 等^[1], 其中绞股蓝于1979年首次被报道含人参皂苷成分, 为除五加科植物以外富含人参皂苷的植物, 又被人们称为“南方人参”和“第二人参”^[2]。绞股蓝属植物含有三萜皂苷、黄酮及多糖类成分^[3], 达玛烷型三萜皂苷是其主要的特征性成分, 目前已报道328个^[3]。值得注意的是, 绞股蓝属不同种, 以及同种的不同群体中三萜皂苷类成分可能存在明显差异。如喙果绞股蓝中含原人参二醇型皂苷(PPD型) 和原人参三醇型皂苷(PPT型)^[4]; 扁果绞股蓝主要为1α-OH PPD型皂苷^[5]; 长梗绞股蓝中主要为C-19为醛基, 且C-17位侧链成环或为直链的皂苷^[6]; 心籽绞股蓝和毛绞股蓝常在C-21位有一个酯键且在其羟基端连接糖链^{[7, 8]}; 对于绞股蓝, 分布于广西、福建、云南的群体主要结构母核分别为PPD型^[9]、2α-OH PPD型^[10]和母核无OH取代型^[11]。绞股蓝属中复杂多样的三萜皂苷引起国内外学者广泛关注。现代药理研究显示绞股蓝属植物有降糖降脂、减肥、抗癌、抗炎、心脏保护、肝保护和神经保护等作用^[12]。国内对绞股蓝属植物开发利用较好的种主要为长梗绞股蓝和绞股蓝, 如以长梗绞股蓝为原料生产的绞股蓝总甙片、绞股蓝总苷胶囊等, 以绞股蓝为原料的绞股蓝茶、民间用药及多种保健食品, 对绞股蓝属其他种植物的研究则较少, 也有待开发利用。

缅甸绞股蓝(G. burmanicum King ex Chakrav.) 的叶片呈纸质, 具3小叶, 两面均被坚挺短梗毛, 在形态学上显著区别于绞股蓝属其他植物^[13], 广泛分布于越南、泰国及缅甸^{[13, 14]}, 在我国云南南部和西部也有分布。目前对缅甸绞股蓝化学成分的研究较少, 仅有9个三萜皂苷类化合物被报道从中分离得到^[14], 缺少对缅甸绞股蓝化学成分的全面认识。

综上, 本研究收集多个来源的绞股蓝植物样品, 利用超高效液相色谱-四极杆-飞行时间质谱联用(ultra-high performance liquid chromatography-quadrupole-time of flight-mass spectrometry, UHPLC-Q-TOF-MS) 技术对其全成分进行表征鉴定, 同时与长梗绞股蓝样品进行成分对比, 为后续缅甸绞股蓝的开发与利用提供依据。

材料与方法

收起

仪器及试样 Waters ACQUITY H-class超高效液相色谱仪、Synapt G2-S四极杆-飞行时间高分辨质谱仪、MasslynxV4.1软件、EZinfo 3.0软件(美国Waters公司); XS105DU/A十万分之一电子天平(德国梅特勒公司); DL-1000A超声波清洗器(上海之信仪器有限公司); 无水乙醇(国药集团); 蒸馏水(广州屈臣氏食品饮料有限公司); 质谱级乙腈(美国Fisher公司)。对照品绞股蓝皂苷XLIX、绞股蓝皂苷A、长梗绞股蓝皂苷Ⅰ以及(20S)-3β, 19, 20, 21-四羟基达玛-24-烯-3-O-[α-L-吡喃鼠李糖基(1→2)][β-D-吡喃木糖基(1→3)]-β-D-吡喃阿拉伯糖基-21-O-β-D-吡喃葡萄糖苷、(20R, 21R, 23R, 24R)-3β, 19, 20, 21, 23-五羟基-21, 24-环达玛烷-25-烯-3-O-[α-L-吡喃鼠李糖基(1→2)][β-D-吡喃木糖基(1→3)]-α-L-吡喃阿拉伯糖苷和(20S, 21S, 23S)-3β, 21, 26-四羟基-19-醛基-21, 23-环氧达玛烷-24-烯-3-O-[α-L-吡喃鼠李糖基(1→2)][β-D-吡喃木糖基(1→3)]-α-L-吡喃阿拉伯糖苷, 由实验室自制, 纯度大于95%。

植物样品 共收集8批缅甸绞股蓝植物样品, 经中国医学科学院药用植物研究所郭宝林教授鉴定为缅甸绞股蓝(Gynostemma burmanicum King ex Chakrav.)。其中缅甸绞股蓝均为云南种源, 在不同地区种植。采集后的药材经过快速清洗、烘箱60 ℃干燥、粉碎、过40目筛等操作后, 得药材粉末, 以供备用。根据课题组前期工作基础^[15], 分别选择两批具有代表性的陕西产长梗绞股蓝和四川产长梗绞股蓝用作对照药材。缅甸绞股蓝和长梗绞股蓝植物形态如图 1所示, 具体样品信息见表 1。

供试品的制备 取缅甸绞股蓝和长梗绞股蓝的干燥粉末0.1 g, 精密称定, 置具塞三角瓶中, 加入70%的乙醇溶液各10 mL, 称定重量, 超声提取30 min, 放冷, 补足重量, 摇匀, 静置10 min, 取上清液, 用0.22 μm微孔滤膜滤过, 即得供试品溶液。另取供试品各50 μL, 混合, 得QC样品, 用于检测仪器稳定性。

对照品的制备 取6个对照品适量, 于2 mL离心管中, 加入1 mL甲醇溶解成单个成分质量浓度为400~1 000 μg·mL^-1的混合对照品溶液, 0.22 μm滤膜过滤, 取续滤液, 即得对照品溶液。

分析条件优化

色谱条件 Waters BEH C18色谱柱(2.1 mm × 100 mm, 1.7 µm), 流动相为0.1%甲酸水(A)-乙腈(B), 梯度洗脱(0~2 min, 10%~25% B; 2~7 min, 25%~32% B; 7~10 min, 32%~33% B; 10~12 min, 33%~35% B; 12~22 min, 35%~46% B; 22~27 min, 46%~56% B; 27~28 min, 56%~95% B; 28~30 min, 95% B; 30~31 min, 95%~10% B; 31~33 min, 10% B); 柱温40 ℃; 流速0.50 mL·min^-1; 进样量3 µL。

质谱条件采用电喷雾离子源(ESI), 负离子模式扫描, 毛细管电压3 kV, 离子源温度为100 ℃, 脱溶剂气体为氮气, 脱溶剂温度为450 ℃, 脱溶剂气体流速为850 L·h^-1, 离子扫描范围m/z为100~1 500, 锥孔气体流量为50 L·h^-1, 碰撞气体为氩气, 碰撞能量为低能级6 eV, 高能级50~65 eV, 以亮氨酸脑啡肽用于液质校正。

数据处理与分析 Masslynx V4.1软件用于控制液相及质谱运行和基线离子流图分析。

结果

收起

1 缅甸绞股蓝样品间一致性观察

对不同来源、不同部位共8份缅甸绞股蓝定性分析, 结果显示样品间成分组成一致性良好, 主要成分明显, 个别成分含量存在一定差异。

2 缅甸绞股蓝代表样品中化学成分的表征

根据化合物的保留时间、绞股蓝属植物来源的三萜皂苷裂解规律、实验室已有绞股蓝三萜皂苷化学成分数据库, 结合ChemSpider、Scifinder、PubChem在线数据库及文献报道, 共从缅甸绞股蓝中鉴定47个成分, 其中黄酮类成分12个, 皂苷类成分35个, 其中包括新化合物6个。此外, 三萜皂苷类成分中丙二酰基及乙酰基现象普遍存在, 反相C18色谱分析时它们通常依次出现在相应原型皂苷之后。

2.1 黄酮类成分的鉴定

黄酮类化合物是绞股蓝中主要成分之一, 在本实验中的色谱条件下, 保留时间主要集中于2~6 min, 其中黄酮苷类物质主要在C-3位连接葡萄糖和芸香糖。

化合物1的保留时间为2.36 min, 低能级下可见准分子离子峰m/z 609.145 6 [M-H]^-, 推测分子式为C₂₇H₃₀O₁₆, 高能级模式下可见一系列碎片m/z 300.026 4、271.027 3和243.028 6, 推测分别脱去一分子芸香糖、CHO·、CO, 根据文献^{[16, 17]}对比, 鉴定化合物1为芦丁。化合物2的保留时间为2.50 min, 低能级下可见准分子离子峰m/z 463.087 4 [M-H]^-, 推测分子式为C₂₁H₂₀O₁₂, 高能级下碎片离子与化合物1一致, 推测化合物2母核与化合物1相同, C-3位连接葡萄糖, 根据文献^[17]对比, 鉴定化合物2为异槲皮素。化合物3的保留时间为2.67 min, 低能级可见准分子离子峰m/z 593.151 0 [M-H]^-, 推测分子式为C₂₇H₃₀O₁₅, 高能级可见一系列碎片m/z 285.309 6、255.028 7和227.033 8 (图 2), 推测分别脱去芸香糖、CH₂O和CO, 与文献^[17]报道裂解方式一致, 鉴定化合物为山柰酚-3-O-β-D-芸香糖苷。

2.2 三萜皂苷成分鉴定

达玛烷型三萜皂苷是绞股蓝属植物中主要的特征成分, 绞股蓝属不同种植物中三萜皂苷的具体结构通常存在较大差异, 其母核结构包括PPD、PPT、2α-OH PPD和C-17位侧链成环等多种类型^[4-11], 在此基础上连有葡萄糖、木糖、鼠李糖等单糖组合而成的不同糖链; 此外, 有众多文献报道绞股蓝属植物中的三萜皂苷上常有丙二酰基或乙酰基取代^[15]。本研究从缅甸绞股蓝中共鉴定出35个三萜皂苷类成分, 在此根据结构特点和裂解规律分为中性皂苷和丙二酰基/乙酰基皂苷进行阐述。

2.2.1 中性皂苷成分的鉴定

本研究中共鉴定出14个中性皂苷成分。该类成分在低能级下通常可观察到[M+HCOO]^-加合离子峰, 在高能级下可观察到[M-H]^-准分子离子峰和一系列脱糖碎片得母核m/z 473、475和489等, 脱糖顺序一般依次为木糖、鼠李糖和阿拉伯糖, 或木糖、葡萄糖、鼠李糖和阿拉伯糖。对于C-17位侧链成环的化合物, 可同时在脱糖时观察到丢失84 (C₅H₈O)、100 (C₅H₈O₂) 后的特征碎片, 得母核375、389和403。

化合物20在低能级下可观察到m/z 1 091.566 3 [M+HCOO]^-加合离子峰和m/z 1 045.559 9 [M-H]^-准分子离子峰, 高能级下可观察到一系列脱糖碎片913.527 1 [M-H-132]^-、751.464 5 [M-H-132-162]^-、605.405 0 [M-H-132-162-146]^-和473.362 1 [M-H-132-162-146-132]^-, 即分别脱去1分子五碳糖、六碳糖、甲基五碳糖和五碳糖得母核碎片离子, 裂解途径如图 3A所示, 推测糖基类型分别为木糖、葡萄糖、鼠李糖和阿拉伯糖, 根据化合物裂解碎片、保留时间及对照品, 化合物20鉴定为绞股蓝皂苷XLIX。

化合物31在低能级下观察到m/z 943.492 1 [M+HCOO]^-加合离子峰, 在高能级下可观察到m/z 897.487 9 [M-H]^-准分子离子峰及一系列碎片离子765.445 6 [M-H-132]^-、681.387 1 [M-H-132-84]^-、535.328 8 [M-H-132-84-146]^-和403.285 3 [M-H-132-84-146-132]^-, 即分别丢失1分子五碳糖、84 (C₅H₈O)、甲基五碳糖和五碳糖, 推测该化合物C-17位侧链成环, 母核连接木糖、葡萄糖和阿拉伯糖(图 3B), 结合化合物及对照品裂解特点, 化合物31鉴定为绞股蓝皂苷A。

化合物38在低能级下可观察到m/z 929.512 3 [M+HCOO]^-加合离子峰, 高能级下可观察到准分子离子峰m/z 883.505 2 [M-H]^-和一系列脱糖碎片及特征碎片751.462 5 [M-H-132]^-、667.452 0 [M-H-132-84]^-、521.347 2 [M-H-132-84-146]^-和389.305 3 [M-H-132-84-146]^-, 即脱去2分子五碳糖、1分子甲基五碳糖及C₅H₈O, 推测糖基为木糖、鼠李糖和阿拉伯糖, 且C-17位侧链成环。该化合物与长梗绞股蓝Ⅰ有相同分子量及糖链, 区别在于长梗绞股蓝Ⅰ在C-17位侧链为链状, 经Scifinder、PubChem及已有数据库对比, 推测化合物38为新化合物, 结构为3β, 20, 21-三羟基-21, 23-环氧达玛烷-24-烯-3-O-[α-L-吡喃鼠李糖基(1→2)][β-D-吡喃木糖基(1→3)]-β-D-吡喃阿拉伯糖苷。利用类似方法, 也鉴定了峰17的结构为3β, 20, 21, 26-四羟基-21, 23-环氧达玛烷-24-烯-3-O-[α-L-鼠李糖(1→2)][β-D-吡喃木糖基(1→3)]-α-L-吡喃阿拉伯糖苷; 峰24结构为3β, 20, 21-三羟基达玛烷-19-醛-24-烯3-O-[α-L-吡喃鼠李糖基(1→2)][β-D-吡喃葡萄糖(1→3)]-α-L-吡喃阿拉伯糖苷; 峰25结构为3β, 19, 20, 21-四羟基达玛烷-24-烯3-O-[α-L-吡喃鼠李糖基(1→2)][β-D-吡喃葡萄糖(1→3)]-α-L-吡喃阿拉伯糖苷; 峰30结构为3β, 19, 20, 21-四羟基-21, 23-环氧达玛烷-24-烯-3-O-[α-L-鼠李糖(1→2)][β-D-吡喃木糖基(1→3)]-α-L-吡喃阿拉伯糖苷; 峰44结构为3β, 20, 21-三羟基达玛烷-19-醛基-24-烯3-O-[α-L-吡喃鼠李糖基(1→2)]-[β-D-吡喃木糖基(1→3)]-α-L-吡喃阿拉伯糖苷, 经检索均为未见报道的新结构。

2.2.2 丙二酰基及乙酰基皂苷成分的鉴定

绞股蓝中普遍存在丙二酰基皂苷及乙酰基皂苷, 本研究共从缅甸绞股蓝中鉴定出21个此类成分, 包括16个丙二酰基皂苷和5个乙酰基皂苷。丙二酰基皂苷在ESI^-模式低能级下可见[M-H]^-准分子离子峰, 高能级下可依次脱去44 (CO₂) 和42 (C₂H₂O) 后得与原型成分准分子离子峰相同的碎片离子^[15], 后脱去一系列糖基得母核特征碎片。乙酰基成分在低能级下可观察到[M+HCOO]^-加合离子峰和[M-H]^-准分子离子峰, 高能级模式下可先脱去乙酰基^[15], 后脱糖基得母核特征碎片。

以绞股蓝皂苷A为例, 丙二酰基绞股蓝皂苷A (图 4峰32) 在低能级下可观察到准分子离子峰m/z 939.495 2 [M-H]^-, 高能级模式下可见丢失44和42后的碎片及脱糖碎片; 乙酰基绞股蓝A (图 4峰35) 在低能级下可见加合离子峰m/z 985.502 1 [M+HCOO]^-和准分子离子峰m/z 939.496 6 [M-H]^-, 高能级模式下先脱去乙酰基[M-H-C₂H₂O]^-, 后脱去糖基及C-17位侧链, 得到碎片离子m/z 403.285 4 [M-H-C₂H₂O-Xyl-C₅H₈O-Rha-Ara]^-。

缅甸绞股蓝中成分鉴定结果如表 2^{[5, 17-21]}所示, 从代表性成分结构特点(图 5) 可以看出, 缅甸绞股蓝中的三萜皂苷根据C-17位侧链是否环合可分为两类, C-17位侧链成环型(如化合物10、11和30) 和直链型(如化合物21、24和27) 三萜皂苷; 糖链通常连接在C-3位或C-21位, C-3位糖链中的单糖类型包括木糖、鼠李糖和阿拉伯糖, 少见葡萄糖, 糖链连接方式为阿拉伯糖连接在C-3位, 阿拉伯糖C-2′位及C-3′位分别连接鼠李糖和木糖/葡萄糖, 部分化合物, 如化合物38和44, 则在C-3直接连接葡萄糖, 后在葡萄糖C-2′和C-3′位分别连接鼠李糖和木糖; C-21位糖链主要以葡萄糖为主。缅甸绞股蓝中还普遍存在糖链中连有丙二酰基和乙酰基的皂苷, 常与原型成分相继出现。

3 缅甸绞股蓝和长梗绞股蓝的化学成分对比

从图 6可见, 缅甸绞股蓝与长梗绞股蓝样品间主成分一致性较好, 各成分含量存在一定差异。其中, 缅甸绞股蓝中绞股蓝皂苷XLIX、绞股蓝皂苷A及其丙二酰基成分含量相当或略高于长梗绞股蓝, 黄酮成分也相对丰富且含量不低。

讨论

收起

本研究收集了不同来源、不同年份、不同部位的缅甸绞股蓝样品8批以及陕西、四川产长梗绞股蓝4批共12批样品, 采用UHPLC-Q-TOF-MS技术进行分析, ESI^-模式采集, 对不同缅甸绞股蓝样品进行成分组成一致性观察, 了解缅甸绞股蓝成分组成的稳定性。根据绞股蓝属植物来源达玛烷型三萜皂苷的裂解规律, 结合实验室已有绞股蓝皂苷数据库及ChemSipder、SciFinder、PubChem在线数据库, 对缅甸绞股蓝中的主要成分进行结构鉴定, 并通过BPI图对比缅甸绞股蓝和长梗绞股蓝成分的异同。结果显示不同来源缅甸绞股蓝样品间成分组成一致性好, 共从缅甸绞股蓝中鉴定47个成分, 包括12个黄酮, 35个三萜皂苷, 其中6个为新化合物。BPI图结果显示, 缅甸绞股蓝与长梗绞股蓝的成分组成也具有良好的一致性。

绞股蓝属植物中达玛烷型三萜皂苷的具体结构差异较大, 变化主要在于母核上羟基的有无/多少/位置、糖基的类型及数量、糖链的连接位置等。缅甸绞股蓝中皂苷成分母核C-1、C-2及C-12位无羟基连接, C-19位可氧化成羟基或羰基, 在C-17位侧链成环或成链状。C-3和C-21位可连接糖链, 其中C-3位连接糖基类型包括木糖、鼠李糖和阿拉伯糖, 少见葡萄糖, 主要糖链为C-3内侧连接阿拉伯糖, 阿拉伯糖C-2′和C-3′分别连接鼠李糖和木糖/葡萄糖; C-21位糖链主要为葡萄糖。这类化合物结构特点与长梗绞股蓝^[19]中三萜皂苷类似。

与人参皂苷类似^[22], 丙二酰基和乙酰基皂苷在绞股蓝中也较为常见, 丙二酰基成分在质谱低能级模式下通常观察到[M-H]^-峰, 高能级模式下先依次丢失CO₂和乙酰基, 再脱糖得母核离子; 乙酰基成分在低能级模式下可观察到[M+HCOO]^-峰和[M-H]^-峰, 高能级下先丢失乙酰基, 后进行一系列脱糖得母核碎片离子。此外, 丙二酰基成分及乙酰基成分常与对应的原型皂苷相继出现。在反相C18色谱体系下的保留时间是乙酰基成分 > 丙二酰基成分 > 原型成分。根据丙二酰基及乙酰基成分裂解特点及保留时间规律, 可辅助绞股蓝皂苷类成分的鉴定, 并为丙二酰基成分和乙酰基成分的鉴定提供依据。由于丙二酰基成分不稳定, 难以获得丙二酰基成分单体化合物, 因此在结构鉴定时, 难以确定丙二酰基在糖基上的具体连接位置。

缅甸绞股蓝与长梗绞股蓝为绞股蓝属不同种植物, 在植物形态学上存在明显差异。长梗绞股蓝叶片呈鸟足状复叶, 具5~9小叶, 叶柄长4~8厘米; 缅甸绞股蓝叶呈纸质, 具3小叶, 两面均被坚挺短梗毛, 叶柄长3~6.5厘米^[13]。有意思的是, 对于不同种植物且形态学差异显著的情况下, 其成分组成及主要成分的一致性却很好。形成这一现象的原因可能为控制次生代谢产物合成的基因片段或者酶相同或相似^[23]。

目前各省中药材质量标准中收录的中药绞股蓝, 其基原植物主要为绞股蓝或长梗绞股蓝的全草^[24], 对于绞股蓝属的其他种植物则未见收录。以绞股蓝为原料的一系列成药, 如绞股蓝饮片、绞股蓝总苷片、绞股蓝总苷胶囊, 其主要成分就为绞股蓝皂苷XLIX和绞股蓝皂苷A^[25]。绞股蓝皂苷中丙二酰基成分不稳定, 在一定条件下可以脱去丙二酰基^{[26, 27]}, 生成相应的原型皂苷。缅甸绞股蓝与长梗绞股蓝相比, 其主成分绞股蓝皂苷XLIX和绞股蓝皂苷A及其丙二酰基皂苷含量相当或更高。此外, 缅甸绞股蓝茎体粗壮, 生长旺盛, 亩产量更高^[28]。综上, 以缅甸绞股蓝补充或替代长梗绞股蓝入药值得进一步研究, 这也为缅甸绞股蓝的资源利用提供了思路和实验依据。

作者贡献: 王美燕负责实验实施、数据分析及文章撰写; 李港负责文献调研及前期实验; 黄长亮、孙晴、南易、于德鑫和王秀参与实验; 郭宝林负责提供药材及文章审阅; 梁海珍和马百平负责实验设计、文章审阅及修改。

利益冲突: 作者声明无利益冲突。

基金

收起

国家自然科学基金面上项目(82074008)
国家自然科学基金青年项目(82404461)

参考文献

收起

文献

收起

参考文献引证文献

排序方式：

[1]

Editorial Committee of Flora of China, Chinese Academy of Sciences. Flora of China: Vol 73 (中国植物志: 第73卷) [M]. Beijing: Science Press, 1986: 265, 273.

[2]

Yang ZQ, Li M, Xu SY, et al. Enzymatic reaction pattern of saponins in Gynostemma pentaphyllum and identification of their transformed products [J]. China J Chin Mater Med (中国中药杂志), 2024, 49: 4925-4933.

[3]

Xie P, Luo HT, Pei WJ, et al. Saponins derived from Gynostemma pentaphyllum regulate triglyceride and cholesterol metabolism and the mechanisms: a review [J]. J Ethnopharmacol, 2024, 319: 117186.

[4]

Xiang WJ, Guo CY, Ma L, et al. Dammarane-type glycosides and long chain sesquiterpene glycosides from Gynostemma yixingense [J]. Fitoterapia, 2010, 81: 248-252.

[5]

Thi TTD, Thi TN, Huy TN, et al. Dammarane-type triterpenoids from Gynostemma compressum X. X. Chen & D. R. Liang (Cucurbitaceae) and their AMPK activation effect in 3T3-L1 cells [J]. Phytochemistry, 2022, 200: 113218.

[6]

Li Q, Pang X, Lu PX, et al. Four new dammarane-type triterpenoid saponins from Gynostemma longipes C. Y. Wu [J]. Acta Pharm Sin (药学学报), 2021, 56: 1670-1676.

[7]

Yin F, Zhang Y, Yang Z, et al. Triterpene saponins from Gynostemma cardiospermum [J]. J Nat Prod, 2006, 69: 1394-1398.

[8]

Yang Z, Chen Q, Hu L. Dammarane-type glycosides from Gynostemma pubescens [J]. Phytochemistry, 2007, 68: 1752-1761.

[9]

Yang G, Liang HZ, Zhang J, et al. Four new dammarane-type triterpenoid saponins from Gynostemma pentaphyllum (Thunb.) Makino [J]. Acta Pharm Sin (药学学报), 2024, 59: 2288-2294.

[10]

Liang HZ, Lu PX, Chu LL, et al. Dammarane-type saponins from Gynostemma pentaphyllum and their anti-aging activities via up-regulating mitochondria related proteins [J]. Phytochemistry, 2023, 213: 113744.

[11]

Li G, Yang G, Chen X J, et al. Eight new dammarane-type triterpenoid saponins from Gynostemma pentaphyllum [J]. Nat Prod Res, 2024, 31: 1-9.

[12]

Nguyen NH, Ha T, Yang JL, et al. Triterpenoids from the genus Gynostemma: chemistry and pharmacological activities [J]. J Ethnopharmacol, 2021, 268: 113574.

[13]

Editorial Committee of Flora of China, Chinese Academy of Sciences. Flora of China: Vol 73 (中国植物志: 第73卷) [M]. Beijing: Science Press, 1986: 269.

[14]

Than TKM, Pham TK, Pham TB, et al. New dammarane-type triterpenoid glycosides from Gynostemma burmanicum [J]. Nat Prod Res, 2020, 34: 217-224.

[15]

Zhang MM, Zhen W, Zhang J, et al. Qualitative analysis of Gynostemma longipes for medicinal usage [J]. China J Chin Mater Med (中国中药杂志), 2021, 46: 951-965.

[16]

Ablajan K. Study on the Mass Spectrometric Analytical Method of Flavonoid Glycosides (黄酮苷类天然产物的质谱分析方法研究) [D]. Beijing: China Union Medical University, 2006.

[17]

Wang YM, Wu YS, Wang SY, et al. Rapid identification of chemical composition and quality markers of Gynostemma pentaphylla by ultra-performance liquid chromatography combined with triple quadrupole mass spectrometry connected with high-performance liquid chromatography [J]. Spectrosc Lett, 2023, 56: 434-443.

[18]

Liu YT, Ji L, Chen LM, et al. Quality analysis of Xueshuan Xinmaining Tablets and Capsules based on UPLC-Q/TOF-MS and UPLC-QQQ-MS/MS [J]. China J Chin Mater Med (中国中药杂志), 2024, 49: 5193-5203.

[19]

Zhang MM. Isolation and Identification of Main Components, and Analysis of Chemical Compositions of Herba Gynostemmatis (中药绞股蓝的主要成分分离鉴定及成分组成分析) [D]. Tianjin: Tianjin University of Traditional Chinese Medicine, 2020.

[20]

Li Q. Studies on the Chemical Constituents of the Polar Fraction of Gynostemma longipes (长梗绞股蓝大极性部位化学成分研究) [D]. Guangzhou: Guangdong Pharmaceutical University, 2021.

[21]

Zheng W. The Chemical Composition Analysis of Herba Gynostemma based on Two-Dimensional Chromatography and Ion Mobility Mass Spectrometry (基于二维色谱及离子淌度质谱的中药绞股蓝成分分析) [D]. Beijing: Academy of Military Science, 2023.

[22]

Wang JM. Protective Effect of Malonyl Ginsenosides and Acetyl Ginsenoside Rg3 on Dextran Sulfate Sodium-Induced Ulcerative Colitis in Mice (丙二酰基人参皂苷及Ac-Rg3对DSS诱导小鼠急性肠炎的保护作用) [D]. Changchun: Jilin Agricultural University, 2023.

[23]

Liang TT. Screening and Functional Characterization of the Genes Related to Gypenoside Biosynthesis (绞股蓝皂苷生物合成相关基因的筛选与功能鉴定研究) [D]. Beijing: Peking Union Medical College, 2020.

[24]

Shanghai Health Bureau. Shanghai Chinese Herbal Medicine Processing Specification (上海市中药饮片炮制规范) [M]. Shanghai: Shanghai Science and Technology Press, 2018: 367.

[25]

Xu SM. Clinical Trial and Production Project of High-Dose Gynostemma pentaphyllum Total Glycosides Capsules (高剂量绞股蓝总甙胶囊临床试验及生产项目) [R]. Ankang: Ankang Beiyida Pharmaceutical Co., Ltd. 2022.

[26]

Li G, Lu PX, Liang HZ, et al. An effective and high-throughput sample preparation method involving demalonylation followed by an ultrahigh-performance liquid chromatography-charged aerosol detector for analyzing gypenoside XLIX and gypenoside A in Gynostemma longipes [J]. J Pharm Biomed Anal, 2023, 230: 115393.

[27]

Lu PX, Li G, Zheng W, et al. Determination of gypenoside XLIX and LVI in Gynostemma pentaphyllum from Fujian by ultra-high performance liquid chromatography-charged aerosol detector [J]. Chin J Chromatogr (色谱), 2022, 40: 833-842.

[28]

Ali MA, Al-Hemaid FM. Taxonomic significance of trichomes micromorphology in cucurbits [J]. Saudi J Biol Sci, 2011, 18: 87-92.

2025年第60卷第5期

PDF下载

235

引用本文

BibTeX

文章信息

doi: 10.16438/j.0513-4870.2024-1158

接收时间：2024-11-22
首发时间：2025-10-29
出版时间：2025-05-12

补充材料

相关文章

文章信息

作者

出版历史

收稿日期：2024-11-22
修回日期：2025-02-11

基金

国家自然科学基金面上项目(82074008)

国家自然科学基金青年项目(82404461)

作者信息

1.广东药科大学, 广东广州 510006

2.军事科学院军事医学研究院, 北京 100850

3.中国医学科学院、北京协和医学院, 药用植物研究所, 北京 100193

通讯作者:

^*梁海珍, E-mail: lhzhcm@163.com

马百平, Tel: 86-10-66930265, E-mail: mabaiping@sina.com

参考文献

分享链接

https://castjournals.cast.org.cn/joweb/yxxb/CN/10.16438/j.0513-4870.2024-1158

分享至

全文二维码

扫描看全文

引用本文

BibTeX

本文的引用情况

2种不同金属材料的力学参数

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

关闭全屏

BibTeX
EndNote
RefWorks
TxT

No.	Species	Planting field	Medicinal part	Collection date
GB-1	G. burmanicum	Nanning, Guangxi	Leaf	2021-07
GB-2	G. burmanicum	Nanning, Guangxi	Leaf	2021-07
GB-3	G. burmanicum	Ankang, Shaanxi	Leaf	2021-09
GB-4	G. burmanicum	Ankang, Shaanxi	Leaf	2021-09
GB-5	G. burmanicum	Ankang, Shaanxi	Stem	2024-06
GB-6	G. burmanicum	Ankang, Shaanxi	Stem	2024-06
GB-7	G. burmanicum	Ankang, Shaanxi	Leaf	2024-06
GB-8	G. burmanicum	Ankang, Shaanxi	Leaf	2024-06
GL-1	G. longipes	Ankang, Shaanxi	Stem, leaf	2021-07
GL-2	G. longipes	Ankang, Shaanxi	Stem, leaf	2021-07
GL-3	G. longipes	Guangyuan, Sichuan	Root	2021
GL-4	G. longipes	Guangyuan, Sichuan	Root	2021

No.

Species

Planting field

Medicinal part

Collection date

GB-1

G. burmanicum

Nanning, Guangxi

Leaf

2021-07

GB-2

G. burmanicum

Nanning, Guangxi

Leaf

2021-07

GB-3

G. burmanicum

Ankang, Shaanxi

Leaf

2021-09

GB-4

G. burmanicum

Ankang, Shaanxi

Leaf

2021-09

GB-5

G. burmanicum

Ankang, Shaanxi

Stem

2024-06

GB-6

G. burmanicum

Ankang, Shaanxi

Stem

2024-06

GB-7

G. burmanicum

Ankang, Shaanxi

Leaf

2024-06

GB-8

G. burmanicum

Ankang, Shaanxi

Leaf

2024-06

GL-1

G. longipes

Ankang, Shaanxi

Stem, leaf

2021-07

GL-2

G. longipes

Ankang, Shaanxi

Stem, leaf

2021-07

GL-3

G. longipes

Guangyuan, Sichuan

Root

2021

GL-4

G. longipes

Guangyuan, Sichuan

Root

2021

No.	t_R/min	[M+HCOO]^-/[M-H]^-	Theoretical value	Error/ppm	Formula	Compound	Ion fragment
1	2.36	609.145 3	609.145 6	-0.49	C₂₇H₃₀O₁₆	Rutin^[17]	300.026 4, 271.023 7, 255.028 4, 243.028 6, 151.002 5
2	2.50	463.087 4	463.087 7	-0.65	C₂₁H₂₀O₁₂	Isoquercitrin^[17]	300.062 5, 271.023 2, 255.027 5, 227.033 5
3	2.67	593.151 0	593.150 6	0.67	C₂₇H₃₀O₁₅	Kaempferol-3-O-β-D-rutinoside^[17]	285.039 6, 255.028 7, 227.033 8, 211.387 0, 163.003 3
4	2.76	623.161 7	623.161 2	0.80	C₂₈H₃₂O₁₆	Isorhamnetin-3-O-neohespeidoside or isomer	315.050 5, 300.026 2, 271.024 4, 255.028 6, 243.028 4, 151.001 3
5	3.04	517.193 4	517.192 1	2.51	C₂₃H₃₄O₁₃	Jioglutoside B or isomer	299.012 9, 285.030 4, 271.023 2, 255.027 5, 227.034 6
6	3.42	607.166 4	607.166 3	0.16	C₂₈H₃₂O₁₅	Kaempferol-3-O-β-D-glucopyranosyl-2′-O-α-L-rhamnoside	607.165 0, 299.052 6, 284.031 0, 255.029 0, 227.032 8
7	3.70	623.160 9	623.161 2	-0.48	C₂₈H₃₂O₁₆	Isorhamnetin-3-O-β-D-rutinoside^[17]	451.327 8, 315.047 6, 299.018 6, 271.023 6, 243.027 9, 165.017 2
8	4.16	301.034 6	301.034 8	-0.66	C₁₅H₁₀O₇	Quercetin^[18]	271.022 3, 178.997 2, 151.002 2
9	4.42	637.177 3	637.176 9	0.63	C₂₉H₃₄O₁₆	Ombuoside^[17]	329.065 5, 314.041 7, 299.018 2, 271.023 9, 243.028 1
10	5.13	1 107.564 0/1 061.556 9	1 061.553 2	3.49	C₅₂H₈₆O₂₂	3β, 21, 25-Trihydroxy-20, 24-epoxydrammar-19-oxo-3-O-[α-L-rhamnopyranosyl(1→2)][β-D-xylopyranosyl(1→3)]-α-L-arabinpyranosyl-21-O-β-D-glucopyranoside^[15]	929.510 5, 783.447 2, 621.399 9, 489.358 6, 299.018 1, 271.023 0
11	5.62	285.039 7	285.039 9	-0.70	C₁₅H₁₀O₆	Kaempferol	271.023 8, 255.025 7, 227.035 3, 199.032 8
12	5.79	959.488 0/913.479 6	913.479 7	-0.11	C₄₆H₇₄O₁₈	(3β, 20ξ, 21ξ, 23ξ)-3, 20, 21, 26-Tetrahydroxy-19-oxo-21, 23-epoxydamane-24-ene-3-O-[α-L-rhamnopyranosyl(1→2)][β-D-xylopyranosyl(1→3)]-α-L-arabinopyranoside^[19]	681.386 2, 535.327 4, 403.284 8, 375.288 7
13	6.38	999.480 5	999.480 1	0.45	C₄₉H₇₆O₂₁	Malonyl-(3β, 20ξ, 21ξ, 23ξ)-3, 20, 21, 26-tetrahydroxy-19-oxo-21, 23-epoxydamane-24-en-3-O-[α-L-rhamnopyranosyl(1→2)][β-D-xylopyranosyl(1→3)]-α-L-arabinopyranoside	955.488 8, 913.478 0, 781.433 9, 681.385 3, 535.326 6, 403.284 2, 375.287 5, 299.016 5
14	6.54	1 001.496 0/955.491 3	955.490 3	1.05	C₄₈H₇₆O₁₉	Acetyl-(3β, 20ξ, 21ξ, 23ξ)-3, 20, 21, 26-tetrahydroxy-19-oxo-21, 23-epoxydamane-24-en-3-O-[α-L-rhamnopyranosyl(1→2)][β-D-xylopyranosyl(1→3)]-α-L-arabinopyranoside	913.480 7, 781.433 4, 681.385 4, 535.326 8, 403.284 4, 375.288 8, 299.018 1, 271.023 7
15	6.92	1 001.496 0/955.490 8	955.490 3	0.52	C₄₈H₇₆O₁₉	Acetyl-(3β, 20ξ, 21ξ, 23ξ)-3, 20, 21, 26-tetrahydroxy-19-oxo-21, 23-epoxydamane-24-en-3-O-[α-L-rhamnopyranosyl(1→2)][β-D-xylopyranosyl(1→3)]-α-L-arabinopyranoside	913.472 7, 781.433 9, 681.385 6, 535.326 2, 403.284 1, 375.288 1, 299.018 2, 271.021 0
16	7.15	945.507 6/899.497 6	899.500 4	-3.11	C₄₆H₇₆O₁₇	3β, 19, 20, 21, 23-Pentahydroxy-21, 24-cyclodammarane-25-en-3-O-[α-L-rhamnopyranosyl(1→2)][β-D-xylopyranosyl(1→3)]-α-L-arabinopyranoside^[20]	767.457 7, 621.398 9, 489.357 3, 299.018 5, 271.022 1
17#	7.36	945.507 0/899.502 0	899.500 4	1.78	C₄₆H₇₆O₁₇	3β, 20, 21, 26-Tetrahydroxy-21, 23-epoxydamane-24-en-3-O-[α-L-rhamnopyranosyl(1→2)][β-D-xylopyranosyl(1→3)]-α-L-arabinopyranoside	767.476 3, 667.402 9, 521.346 7, 389.304 8, 299.016 9, 271.024 4
18	7.65	985.501 2	985.500 8	0.41	C₄₉H₇₈O₂₀	Acetyl-3β, 19, 20, 21, 23-pentahydroxy-21, 24-cyclodammarane-25-en-3-O-[α-L-rhamnopyranosyl(1→2)][β-D-xylpyranosyl(1→3)]-α-L-arabinopyranoside	941.504 7, 899.492 1, 767.457 5, 621.399 7, 489.357 3
29	7.93	985.502 4	985.500 8	1.62	C₄₉H₇₈O₂₀	Malonyl-3β, 20, 21, 26-tetrahydroxy-21, 23-epoxydammarane-24-en-3-O-[α-L-rhamnopyranosyl(1→2)][β-D-xylpyranosyl(1→3)]-α-L-arabinopyranoside	941.507 5, 899.486 4, 767.457 9, 667.405 5, 521.348 3, 389.305 5, 299.017 6
20^*	8.75	1 091.565 6/1 045.559 9	1 045.558 3	1.53	C₅₂H₈₆O₂₁	Gypenoside XLIX^[15]	913.517 2, 751.464 5, 605.405 0, 473.362 1, 389.273 7
21^*	8.89	1 093.581 3/1 047.574 1	1 047.574 0	0.10	C₅₂H₈₈C₂₁	3β, 19, 20S, 21-Tetrahydroxydammar-24-ene-3-O-[α-L-rhamnopyranosyl(1→2)][β-D-xylopyranosyl(1→3)]-α-L-arabinopyranosyl-21-O-β-D-glucopyranoside^[19]	915.530 9, 753.478 4, 607.418 5, 475.376 6
22	9.46	1 131.560 9	1 131.558 7	1.94	C₅₅H₈₈O₂₄	Malonyl-gypenoside XLIX	1 087.571 7, 1 045.558 8, 913.516 6, 751.463 9, 605.405 7, 473.358 7
23	9.79	299.018 6	299.019 2	-2.01	C₁₅H₈O₇	Dehydroquercetin or isomer	271.023 5, 243.025 2, 227.032 9, 215.028 5, 199.038 7
24#	10.25	959.522 2/913.516 8	913.516 1	0.77	C₄₇H₇₈O₁₇	3β, 20, 21-Trihydroxydamane-19-oxo-24-ene-3-O-[α-L-rhamnopyranosyl(1→2)][β-D-glucopyranosyl(1→3)]-α-L-arabinopyranoside	751.464 8, 605.401 6, 473.360 3
25#	10.44	961.537 0/915.529 7	915.531 7	-2.18	C₄₇H₈₀O₁₇	3β, 19, 20, 21-Tetrahydroxydamane-24-ene-3-O-[α-L-rhamnopyranosyl(1→2)][β-D-glucopyranosyl(1→3)]-α-L-arabinopyranoside	753.275 3, 607.416 9, 475.388 7
26	11.40	999.516 1	999.516 5	-0.40	C₅₀H₈₂O₂₀	Malonyl-3β, 20, 21-trihydroxydamane-19-oxo-24-ene-3-O-[α-L-rhamnopyranosyl(1→2)][β-D-glucopyranosyl(1→3)]-α-L-arabinopyranoside	955.526 4, 913, 5 135, 751.459 8, 681.387 8, 535.325 7, 403.282 3, 375.290 2
27	11.99	1 077.587 3/1 031.579 5	1 031.579 1	0.39	C₅₂H₈₈O₂₀	3, 20, 21-Trihydroxydama-24-en-3-O-[α-L-rhamnopyranosyl(1→2)][β-D-xylpyranosyl(1→3)]-α-L-arabinopyranosyl-21-O-β-D-glucoside^[21]	899.536 9, 737.484 4, 591.423 2, 459.386 7
28	12.14	1 013.497 7	1 013.495 7	1.97	C₅₀H₇₈O₂₁	Malonyl-3β, 20, 21-trihydroxy-19-oxo-21, 23-epoxydammarane-24-en-3-O-[α-L-rhamnopyranosyl(1→2)][β-D-glucopyranosyl(1→3)]-α-L-arabinopyranoside	969.506 0, 927.502 6, 765.446 2, 681.384 6, 535.325 1, 403.283 8, 375.292 1, 299.016 9
29	12.49	329.065 9	329.066 1	-0.61	C₁₇H₁₄O₇	Quercetin 3, 4′-dimethyl ether or isomer	314.039 7, 299.018 1, 271.022 6, 243.029 5
30#	12.68	945.506 6/899.501 9	899.500 4	1.67	C₄₆H₇₆O₁₇	3β, 19, 20, 21-Tetrahydroxy-21, 23-epoxydammarane-24-en-3-O-[α-L-rhamnopyranosyl(1→2)][β-D-xylopyranosyl(1→3)]-α-L-arabinopyranoside	767.465 3, 683.401 2, 537.340 2, 405.298 6, 375.288 4, 299.012 2
31^*	12.87	943.492 6/897.486 9	897.484 8	2.34	C₄₆H₇₄O₁₇	Gypenoside A^[15]	765.445 1, 681.386 7, 535.328 2, 403.284 9, 375.289 8, 329.247 8
32	13.73	983.488 6	983.485 2	3.46	C₄₉H₇₆O₂₀	Malonyl-gypenoside A	939.498 7, 897.486 1, 765.443 2, 681.386 2, 535.327 6, 403.284 4, 375.289 4, 259.080 0
33	14.37	983.487 9	983.485 2	2.75	C₄₉H₇₆O₂₀	Malonyl-gypenoside A	939.497 4, 897.486 3, 765.442 2, 681.384 9, 535.326 7, 403.285 1, 375.288 6
34^*	14.86	929.511 9/883.502 4	883.505 5	-3.51	C₄₆H₇₆O₁₆	Gylongiposide Ⅰ^[19]	751.459 9, 605.403 2, 473.363 2, 389.269 7, 299.017 7
35	15.10	985.501 6/939.496 6	939.495 3	1.38	C₄₈H₇₆O₁₈	Acetyl-gypenoside A	897.485 2, 765.441 5, 681.385 4, 535.327 0, 403.284 6, 375.288 1
36	15.56	971.519 0/925.517 4	925.516 1	1.40	C₄₈H₇₈O₁₇	Acetyl-gylongiposide Ⅰ	883.505 7, 751.462 9, 605.404 0, 473.360 2
37	15.99	999.516 5	999.516 5	0.00	C₅₀H₈₀O₂₀	Malonyl-3β, 19, 20, 21-tetrahydroxy-21, 23-epoxydammarane-24-ene-3-O-[α-L-rhamnose(1→2)][β-D-xylopyranosyl(1→3)]-β-D-glucopyranoside	955.533 1, 913.509 6, 781.468 5, 697.424 3, 551.358 9, 389.303 9, 299.016 6, 271.021 3
38#	16.76	929.512 3/883.505 2	883.505 5	-0.34	C₄₆H₇₆O₁₆	3β, 20, 21-Trihydroxy-21, 23-epoxydammarane-24-ene-3-O-[α-L-rhamnopyranosyl(1→2)][β-D-xylopyranosyl(1→3)]-α-L-arabinopyranoside	751.462 5, 667.452 0, 521.347 4, 389.305 3, 345.275 6, 299.015 7
39	17.18	969.508 7	969.505 9	2.89	C₄₉H₇₈O₁₉	Malonyl-3β, 20, 21-trihydroxy-21, 23-epoxydammarane-24-ene-3-O-[α-L-rhamnopyranosyl(1→2)][β-D-xylopyranosyl(1→3)]-α-L-arabinopyranoside	925.518 5, 883.507 8, 751.463 1, 667.407 0, 521.348 5, 389.306 0
40	18.01	969.506 6	969.505 9	0.72	C₄₉H₇₈O₁₉	Malonyl-3β, 20, 21-trihydroxy-21, 23-epoxydammarane-24-en-3-O-[α-L-rhamnopyranosyl(1→2)][β-D-xylopyranosyl(1→3)]-α-L-arabinopyranoside	925, 5 161, 883.501 8, 751.456 2, 667.403 7, 521.345 0, 389.304 5
41	18.88	971.520 8/925.515 2	925.516 1	-0.97	C₄₈H₇₈O₁₇	Acetyl-3β, 20, 21-trihydroxy-21, 23-epoxydammarane-24-en-3-O-[α-L-rhamnopyranosyl(1→2)][β-D-xylopyranosyl(1→3)]-α-L-arabinopyranoside	883.505 1, 751.456 2, 667.404 8, 521.344 0, 389.304 1, 299.022 1
42	21.37	999.514 8	999.516 5	-1.70	C₅₀H₈₀O₂₀	Malonyl-3β, 19, 20, 21-tetrahydroxy-21, 23-epoxydamane-24-ene-3-O-[α-L-rhamnopyranosyl(1→2)][β-D-glucopyranosyl(1→3)]-α-L-arabinopyranoside	955.531 7, 913.516 8, 883.537 3, 751.465 1, 667.400 9, 521.346 3, 389.303 2
43	21.68	999.516 6	999.516 5	0.10	C₅₀H₈₀O₂₀	Malonyl-3β, 20, 21-trihydroxydammarane-19-oxo-24-ene-3-O-[α-L-rhamnopyranosyl(1→2)][β-D-xylopyranosyl(1→3)]-β-D-glucopyranoside	955.525 0, 913.510 6, 781.473 6, 635.408 9, 473.362 3
44#	22.71	929.510 8/883.505 7	883.505 5	0.23	C₄₆H₇₆O₁₆	3β, 20, 21-Trihydroxydammarane-19-oxo-24-ene-3-O-[α-L-rhamnopyranosyl(1→2)][β-D-xylopyranosyl(1→3)]-α-L-arabinopyranoside	751.463 7, 605.400 0, 473.360 9
45	22.82	969.507 6	969.505 9	1.75	C₄₉H₇₈O₁₉	Malonyl-3β, 20, 21-trihydroxydammarane-19-oxo-24-ene-3-O-[α-L-rhamnopyranosyl(1→2)][β-D-xylopyranosyl(1→3)]-α-L-arabinopyranoside	925.511 7, 883.506 6, 751.464 2, 605.404 2, 473.361 8
46	23.77	969.506 0	969.505 9	0.10	C₄₉H₇₈O₂₀	Malonyl-3β, 20, 21-trihydroxydammarane-19-oxo-24-ene-3-O-[α-L-rhamnopyranosyl(1→2)][β-D-xylopyranosyl(1→3)]-α-L-arabinopyranoside	925.517 9, 883.505 8, 751.460 9, 605.375 9, 473.356 9
47	24.56	969.503 0	969.505 9	-2.99	C₄₉H₇₈O₂₁	Malonyl-3β, 20, 21-trihydroxydammarane-19-oxo-24-ene-3-O-[α-L-rhamnopyranosyl(1→2)][β-D-xylopyranosyl(1→3)]-α-L-arabinopyranoside	925.515 8, 883.501 2, 751.459 4, 605.389 2, 473.354 7, 427.347 1

No.

t_R/min

[M+HCOO]^-/[M-H]^-

Theoretical value

Error/ppm

Formula

Compound

Ion fragment

2.36

609.145 3

609.145 6

-0.49

C₂₇H₃₀O₁₆

Rutin^[17]

300.026 4, 271.023 7, 255.028 4, 243.028 6, 151.002 5

2.50

463.087 4

463.087 7

-0.65

C₂₁H₂₀O₁₂

Isoquercitrin^[17]

300.062 5, 271.023 2, 255.027 5, 227.033 5

2.67

593.151 0

593.150 6

0.67

C₂₇H₃₀O₁₅

Kaempferol-3-O-β-D-rutinoside^[17]

285.039 6, 255.028 7, 227.033 8, 211.387 0, 163.003 3

2.76

623.161 7

623.161 2

0.80

C₂₈H₃₂O₁₆

Isorhamnetin-3-O-neohespeidoside or isomer

315.050 5, 300.026 2, 271.024 4, 255.028 6, 243.028 4, 151.001 3

3.04

517.193 4

517.192 1

2.51

C₂₃H₃₄O₁₃

Jioglutoside B or isomer

299.012 9, 285.030 4, 271.023 2, 255.027 5, 227.034 6

3.42

607.166 4

607.166 3

0.16

C₂₈H₃₂O₁₅

Kaempferol-3-O-β-D-glucopyranosyl-2′-O-α-L-rhamnoside

607.165 0, 299.052 6, 284.031 0, 255.029 0, 227.032 8

3.70

623.160 9

623.161 2

-0.48

C₂₈H₃₂O₁₆

Isorhamnetin-3-O-β-D-rutinoside^[17]

451.327 8, 315.047 6, 299.018 6, 271.023 6, 243.027 9, 165.017 2

4.16

301.034 6

301.034 8

-0.66

C₁₅H₁₀O₇

Quercetin^[18]

271.022 3, 178.997 2, 151.002 2

4.42

637.177 3

637.176 9

0.63

C₂₉H₃₄O₁₆

Ombuoside^[17]

329.065 5, 314.041 7, 299.018 2, 271.023 9, 243.028 1

5.13

1 107.564 0/1 061.556 9

1 061.553 2

3.49

C₅₂H₈₆O₂₂

3β, 21, 25-Trihydroxy-20, 24-epoxydrammar-19-oxo-3-O-[α-L-rhamnopyranosyl(1→2)][β-D-xylopyranosyl(1→3)]-α-L-arabinpyranosyl-21-O-β-D-glucopyranoside^[15]

929.510 5, 783.447 2, 621.399 9, 489.358 6, 299.018 1, 271.023 0

5.62

285.039 7

285.039 9

-0.70

C₁₅H₁₀O₆

Kaempferol

271.023 8, 255.025 7, 227.035 3, 199.032 8

5.79

959.488 0/913.479 6

913.479 7

-0.11

C₄₆H₇₄O₁₈

(3β, 20ξ, 21ξ, 23ξ)-3, 20, 21, 26-Tetrahydroxy-19-oxo-21, 23-epoxydamane-24-ene-3-O-[α-L-rhamnopyranosyl(1→2)][β-D-xylopyranosyl(1→3)]-α-L-arabinopyranoside^[19]

681.386 2, 535.327 4, 403.284 8, 375.288 7

6.38

999.480 5

999.480 1

0.45

C₄₉H₇₆O₂₁

Malonyl-(3β, 20ξ, 21ξ, 23ξ)-3, 20, 21, 26-tetrahydroxy-19-oxo-21, 23-epoxydamane-24-en-3-O-[α-L-rhamnopyranosyl(1→2)][β-D-xylopyranosyl(1→3)]-α-L-arabinopyranoside

955.488 8, 913.478 0, 781.433 9, 681.385 3, 535.326 6, 403.284 2, 375.287 5, 299.016 5

6.54

1 001.496 0/955.491 3

955.490 3

1.05

C₄₈H₇₆O₁₉

Acetyl-(3β, 20ξ, 21ξ, 23ξ)-3, 20, 21, 26-tetrahydroxy-19-oxo-21, 23-epoxydamane-24-en-3-O-[α-L-rhamnopyranosyl(1→2)][β-D-xylopyranosyl(1→3)]-α-L-arabinopyranoside

913.480 7, 781.433 4, 681.385 4, 535.326 8, 403.284 4, 375.288 8, 299.018 1, 271.023 7

6.92

1 001.496 0/955.490 8

955.490 3

0.52

C₄₈H₇₆O₁₉

Acetyl-(3β, 20ξ, 21ξ, 23ξ)-3, 20, 21, 26-tetrahydroxy-19-oxo-21, 23-epoxydamane-24-en-3-O-[α-L-rhamnopyranosyl(1→2)][β-D-xylopyranosyl(1→3)]-α-L-arabinopyranoside

913.472 7, 781.433 9, 681.385 6, 535.326 2, 403.284 1, 375.288 1, 299.018 2, 271.021 0

7.15

945.507 6/899.497 6

899.500 4

-3.11

C₄₆H₇₆O₁₇

3β, 19, 20, 21, 23-Pentahydroxy-21, 24-cyclodammarane-25-en-3-O-[α-L-rhamnopyranosyl(1→2)][β-D-xylopyranosyl(1→3)]-α-L-arabinopyranoside^[20]

767.457 7, 621.398 9, 489.357 3, 299.018 5, 271.022 1

17#

7.36

945.507 0/899.502 0

899.500 4

1.78

C₄₆H₇₆O₁₇

3β, 20, 21, 26-Tetrahydroxy-21, 23-epoxydamane-24-en-3-O-[α-L-rhamnopyranosyl(1→2)][β-D-xylopyranosyl(1→3)]-α-L-arabinopyranoside

767.476 3, 667.402 9, 521.346 7, 389.304 8, 299.016 9, 271.024 4

7.65

985.501 2

985.500 8

0.41

C₄₉H₇₈O₂₀

Acetyl-3β, 19, 20, 21, 23-pentahydroxy-21, 24-cyclodammarane-25-en-3-O-[α-L-rhamnopyranosyl(1→2)][β-D-xylpyranosyl(1→3)]-α-L-arabinopyranoside

941.504 7, 899.492 1, 767.457 5, 621.399 7, 489.357 3

7.93

985.502 4

985.500 8

1.62

C₄₉H₇₈O₂₀

Malonyl-3β, 20, 21, 26-tetrahydroxy-21, 23-epoxydammarane-24-en-3-O-[α-L-rhamnopyranosyl(1→2)][β-D-xylpyranosyl(1→3)]-α-L-arabinopyranoside

941.507 5, 899.486 4, 767.457 9, 667.405 5, 521.348 3, 389.305 5, 299.017 6

20^*

8.75

1 091.565 6/1 045.559 9

1 045.558 3

1.53

C₅₂H₈₆O₂₁

Gypenoside XLIX^[15]

913.517 2, 751.464 5, 605.405 0, 473.362 1, 389.273 7

21^*

8.89

1 093.581 3/1 047.574 1

1 047.574 0

0.10

C₅₂H₈₈C₂₁

3β, 19, 20S, 21-Tetrahydroxydammar-24-ene-3-O-[α-L-rhamnopyranosyl(1→2)][β-D-xylopyranosyl(1→3)]-α-L-arabinopyranosyl-21-O-β-D-glucopyranoside^[19]

915.530 9, 753.478 4, 607.418 5, 475.376 6

9.46

1 131.560 9

1 131.558 7

1.94

C₅₅H₈₈O₂₄

Malonyl-gypenoside XLIX

1 087.571 7, 1 045.558 8, 913.516 6, 751.463 9, 605.405 7, 473.358 7

9.79

299.018 6

299.019 2

-2.01

C₁₅H₈O₇

Dehydroquercetin or isomer

271.023 5, 243.025 2, 227.032 9, 215.028 5, 199.038 7

24#

10.25

959.522 2/913.516 8

913.516 1

0.77

C₄₇H₇₈O₁₇

3β, 20, 21-Trihydroxydamane-19-oxo-24-ene-3-O-[α-L-rhamnopyranosyl(1→2)][β-D-glucopyranosyl(1→3)]-α-L-arabinopyranoside

751.464 8, 605.401 6, 473.360 3

25#

10.44

961.537 0/915.529 7

915.531 7

-2.18

C₄₇H₈₀O₁₇

3β, 19, 20, 21-Tetrahydroxydamane-24-ene-3-O-[α-L-rhamnopyranosyl(1→2)][β-D-glucopyranosyl(1→3)]-α-L-arabinopyranoside

753.275 3, 607.416 9, 475.388 7

11.40

999.516 1

999.516 5

-0.40

C₅₀H₈₂O₂₀

Malonyl-3β, 20, 21-trihydroxydamane-19-oxo-24-ene-3-O-[α-L-rhamnopyranosyl(1→2)][β-D-glucopyranosyl(1→3)]-α-L-arabinopyranoside

955.526 4, 913, 5 135, 751.459 8, 681.387 8, 535.325 7, 403.282 3, 375.290 2

11.99

1 077.587 3/1 031.579 5

1 031.579 1

0.39

C₅₂H₈₈O₂₀

3, 20, 21-Trihydroxydama-24-en-3-O-[α-L-rhamnopyranosyl(1→2)][β-D-xylpyranosyl(1→3)]-α-L-arabinopyranosyl-21-O-β-D-glucoside^[21]

899.536 9, 737.484 4, 591.423 2, 459.386 7

12.14

1 013.497 7

1 013.495 7

1.97

C₅₀H₇₈O₂₁

Malonyl-3β, 20, 21-trihydroxy-19-oxo-21, 23-epoxydammarane-24-en-3-O-[α-L-rhamnopyranosyl(1→2)][β-D-glucopyranosyl(1→3)]-α-L-arabinopyranoside

969.506 0, 927.502 6, 765.446 2, 681.384 6, 535.325 1, 403.283 8, 375.292 1, 299.016 9

12.49

329.065 9

329.066 1

-0.61

C₁₇H₁₄O₇

Quercetin 3, 4′-dimethyl ether or isomer

314.039 7, 299.018 1, 271.022 6, 243.029 5

30#

12.68

945.506 6/899.501 9

899.500 4

1.67

C₄₆H₇₆O₁₇

3β, 19, 20, 21-Tetrahydroxy-21, 23-epoxydammarane-24-en-3-O-[α-L-rhamnopyranosyl(1→2)][β-D-xylopyranosyl(1→3)]-α-L-arabinopyranoside

767.465 3, 683.401 2, 537.340 2, 405.298 6, 375.288 4, 299.012 2

31^*

12.87

943.492 6/897.486 9

897.484 8

2.34

C₄₆H₇₄O₁₇

Gypenoside A^[15]

765.445 1, 681.386 7, 535.328 2, 403.284 9, 375.289 8, 329.247 8

13.73

983.488 6

983.485 2

3.46

C₄₉H₇₆O₂₀

Malonyl-gypenoside A

939.498 7, 897.486 1, 765.443 2, 681.386 2, 535.327 6, 403.284 4, 375.289 4, 259.080 0

14.37

983.487 9

983.485 2

2.75

C₄₉H₇₆O₂₀

Malonyl-gypenoside A

939.497 4, 897.486 3, 765.442 2, 681.384 9, 535.326 7, 403.285 1, 375.288 6

34^*

14.86

929.511 9/883.502 4

883.505 5

-3.51

C₄₆H₇₆O₁₆

Gylongiposide Ⅰ^[19]

751.459 9, 605.403 2, 473.363 2, 389.269 7, 299.017 7

15.10

985.501 6/939.496 6

939.495 3

1.38

C₄₈H₇₆O₁₈

Acetyl-gypenoside A

897.485 2, 765.441 5, 681.385 4, 535.327 0, 403.284 6, 375.288 1

15.56

971.519 0/925.517 4

925.516 1

1.40

C₄₈H₇₈O₁₇

Acetyl-gylongiposide Ⅰ

883.505 7, 751.462 9, 605.404 0, 473.360 2

15.99

999.516 5

0.00

C₅₀H₈₀O₂₀

Malonyl-3β, 19, 20, 21-tetrahydroxy-21, 23-epoxydammarane-24-ene-3-O-[α-L-rhamnose(1→2)][β-D-xylopyranosyl(1→3)]-β-D-glucopyranoside

955.533 1, 913.509 6, 781.468 5, 697.424 3, 551.358 9, 389.303 9, 299.016 6, 271.021 3

38#

16.76

929.512 3/883.505 2

883.505 5

-0.34

C₄₆H₇₆O₁₆

3β, 20, 21-Trihydroxy-21, 23-epoxydammarane-24-ene-3-O-[α-L-rhamnopyranosyl(1→2)][β-D-xylopyranosyl(1→3)]-α-L-arabinopyranoside

751.462 5, 667.452 0, 521.347 4, 389.305 3, 345.275 6, 299.015 7

17.18

969.508 7

969.505 9

2.89

C₄₉H₇₈O₁₉

Malonyl-3β, 20, 21-trihydroxy-21, 23-epoxydammarane-24-ene-3-O-[α-L-rhamnopyranosyl(1→2)][β-D-xylopyranosyl(1→3)]-α-L-arabinopyranoside

925.518 5, 883.507 8, 751.463 1, 667.407 0, 521.348 5, 389.306 0

18.01

969.506 6

969.505 9

0.72

C₄₉H₇₈O₁₉

Malonyl-3β, 20, 21-trihydroxy-21, 23-epoxydammarane-24-en-3-O-[α-L-rhamnopyranosyl(1→2)][β-D-xylopyranosyl(1→3)]-α-L-arabinopyranoside

925, 5 161, 883.501 8, 751.456 2, 667.403 7, 521.345 0, 389.304 5

18.88

971.520 8/925.515 2

925.516 1

-0.97

C₄₈H₇₈O₁₇

Acetyl-3β, 20, 21-trihydroxy-21, 23-epoxydammarane-24-en-3-O-[α-L-rhamnopyranosyl(1→2)][β-D-xylopyranosyl(1→3)]-α-L-arabinopyranoside

883.505 1, 751.456 2, 667.404 8, 521.344 0, 389.304 1, 299.022 1

21.37

999.514 8

999.516 5

-1.70

C₅₀H₈₀O₂₀

Malonyl-3β, 19, 20, 21-tetrahydroxy-21, 23-epoxydamane-24-ene-3-O-[α-L-rhamnopyranosyl(1→2)][β-D-glucopyranosyl(1→3)]-α-L-arabinopyranoside

955.531 7, 913.516 8, 883.537 3, 751.465 1, 667.400 9, 521.346 3, 389.303 2

21.68

999.516 6

999.516 5

0.10

C₅₀H₈₀O₂₀

Malonyl-3β, 20, 21-trihydroxydammarane-19-oxo-24-ene-3-O-[α-L-rhamnopyranosyl(1→2)][β-D-xylopyranosyl(1→3)]-β-D-glucopyranoside

955.525 0, 913.510 6, 781.473 6, 635.408 9, 473.362 3

44#

22.71

929.510 8/883.505 7

883.505 5

0.23

C₄₆H₇₆O₁₆

3β, 20, 21-Trihydroxydammarane-19-oxo-24-ene-3-O-[α-L-rhamnopyranosyl(1→2)][β-D-xylopyranosyl(1→3)]-α-L-arabinopyranoside

751.463 7, 605.400 0, 473.360 9

22.82

969.507 6

969.505 9

1.75

C₄₉H₇₈O₁₉

Malonyl-3β, 20, 21-trihydroxydammarane-19-oxo-24-ene-3-O-[α-L-rhamnopyranosyl(1→2)][β-D-xylopyranosyl(1→3)]-α-L-arabinopyranoside

925.511 7, 883.506 6, 751.464 2, 605.404 2, 473.361 8

23.77

969.506 0

969.505 9

0.10

C₄₉H₇₈O₂₀

Malonyl-3β, 20, 21-trihydroxydammarane-19-oxo-24-ene-3-O-[α-L-rhamnopyranosyl(1→2)][β-D-xylopyranosyl(1→3)]-α-L-arabinopyranoside

925.517 9, 883.505 8, 751.460 9, 605.375 9, 473.356 9

24.56

969.503 0

969.505 9

-2.99

C₄₉H₇₈O₂₁

Malonyl-3β, 20, 21-trihydroxydammarane-19-oxo-24-ene-3-O-[α-L-rhamnopyranosyl(1→2)][β-D-xylopyranosyl(1→3)]-α-L-arabinopyranoside

925.515 8, 883.501 2, 751.459 4, 605.389 2, 473.354 7, 427.347 1