药学学报

No.	Identification	Name	t_R /min	Formula	m/z	Error (ppm)	Fragment ion	Ref.
1	Deapio-platycoside E	AP1	15.62	C₆₄H₁₀₄O₃₄	1 415.630 9	-1.13	1 005.486 3; 843.424 2	[14]
2	Platycoside E	AP2	17.40	C₆₉H₁₁₂O₃₈	1 547.673 8	-0.65	1 005.449 5; 519.320 6	[3]
3	Platycodin D3	AP3	23.85	C₆₃H₁₀₂O₃₃	1 385.619 3	-1.95	843.407 1; 1 253.549 5	[2]
4	3″-O-Acetyl platycodin D3	AP4	24.87	C₆₅H₁₀₄O₃₄	1 427.629 3	-2.24	1 385.582 4; 843.413 1	[15]
5	Platycoside G2	AP5	27.28	C₅₉H₉₆O₃₀	1 283.589 6	-0.55	843.362 9; 519.270 3	[16]
6	Deapio-platycodin D2	AP6	30.14	C₅₈H₉₄O₂₉	1 253.577 3	-1.92	843.408 5; 681.381 6	[6]
7	Deapio-platycodin D	AP7	30.41	C₅₂H₈₄O₂₄	1 091.525 1	-1.65	681.360 3; 519.342 9	[17]
8	Platycodin D2	AP8	31.90	C₆₃H₁₀₂O₃₃	1 385.621 5	-0.37	843.407 1; 1 253.549 5	[18]
9	Platycodin D	AP9	32.23	C₅₇H₉₂O₂₈	1 223.565 8	-2.70	681.343 5; 1 091.511 0	[2]
10	Platycoside F	AP10	34.44	C₄₇H₇₆O₂₀	959.484 5	-0.10	681.374 2; 797.431 4	[2]
11	Platycodins K	AP11	35.42	C₅₉H₉₂O₃₀	1 279.558 2	-0.63	827.463 3; 1 147.544 7	[2]
12	Platycoside B	AP12	35.83	C₅₄H₈₆O₂₅	1 133.535 3	-1.85	681.393 5; 1 091.543 8	[18]
13	3-O-β-D-Gentiobiosyl platycodigenin methylester	AP13	36.75	C₄₃H₇₀O₁₇	857.456 0	3.62	797.613 4; 858.662 5	[19]
14	2″-O-Acetyl-platycodin D2	AP14	38.08	C₆₅H₁₀₄O₃₄	1 427.630 4	-1.47	1 385.623 3; 843.482 7	[16]
15	Platycoside L	AP15	52.52	C₄₂H₆₈O₁₇	843.435 4	-2.25	519.291 1; 681.346 9	[7]
16	Platycoside K	AP16	52.83	C₄₂H₆₈O₁₇	843.436 8	-0.59	519.291 3; 681.346 9	[7]
17	3-O-β-D-Glucopyranosyl platycodigenin	AP17	54.96	C₃₆H₅₈O₁₂	681.383 8	-1.03	519.295 4	[3]
18	Platycodigenin	AP18	57.93	C₃₀H₄₈O₇	519.332 1	0.96	501.136 8	[3]
19	Platycoside D	BP1	25.25	C₆₉H₁₁₂O₃₇	1 531.678 2	-1.11	827.428 4; 665.452 7	[20]
20	Polygalacin D2	BP2	32.88	C₆₃H₁₀₂O₃₂	1 369.626 2	-0.66	827.411 1; 665.394 5	[16]
21	Polygalacin D	BP3	33.74	C₅₇H₉₂O₂₇	1 207.573 6	-0.50	1 075.503 1; 665.361 5	[19]
22	3″-O-Acetyl polygalacin D	BP4	35.14	C₅₉H₉₄O₂₈	1 249.590 2	4.32	1 207.558 4; 665.376 7	[18]
23	Platycoside J	BP5	38.80	C₅₂H₈₄O₂₃	1 075.530 8	-1.12	665.363 0; 503.333 4	[18]
24	2″-O-Acetyl polygalacin D2	BP6	40.03	C₆₅H₁₀₄O₃₃	1 411.634 8	-1.98	1 369.654 7; 827.436 5	[21]
25	3-O-β-D-Laminaribiosyl polygalacic acid	BP7	55.97	C₄₂H₆₈O₁₆	827.442 0	-0.48	503.317 4; 665.378 4	[22]
26	3-O-β-D-Glucopyranosyl polygalacic acid	BP8	56.85	C₃₆H₅₈O₁₁	665.388 2	-1.95	647.233 6; 503.334 3	[14]
27	Methyl-3-O-β-D-glucopyranosyl polygalaeate	BP9	62.71	C₃₇H₆₀O₁₁	679.400 0	-7.66	633.371 3; 661.229 7	[19]
28	Polygalacic acid	BP10	64.50	C₃₀H₄₈O₆	503.337 2	-0.99	485.111 5; 503.195 3	[22]
29	Platyconic acid A	CP1	30.01	C₅₇H₉₀O₂₉	1 237.546 3	-1.70	827.433 9	[7]
30	Platyconic acid E	CP2	37.52	C₅₈H₉₂O₃₀	1 267.556 9	-1.66	1 117.583 2	[23]
31	2''-O-Acetyl platyconic acid A	CP3	43.07	C₅₉H₉₂O₃₀	1 279.555 1	-3.05	1 147.577 4; 827.463 3	[2]
32	Platyconic acid C	CP4	43.11	C₅₂H₈₂O₂₅	1 105.504 9	-1.09	943.521 9; 695.415 4	[23]
33	Platycoside O	DP1	36.61	C₅₃H₈₄O₂₅	1 119.520 6	-1.07	635.333 6; 1 119.178 6	[15]
34	Platyconic acid A methylester	DP2	39.80	C₅₈H₉₂O₂₉	1 251.560 4	-2.96	635.330 8; 1 089.517 9	[7]
35	Deapio-platyconic acid A lactone	EP1	33.29	C₅₂H₈₀O₂₄	1 087.494 9	-0.64	1 069.565 3	[7]
36	Platyconic acid A lactone	EP2	34.72	C₅₇H₈₈O₂₈	1 219.533 9	-3.20	677.324 7; 1 087.651 6	[7]
37	Platycoside M-2	EP3	50.80	C₄₇H₇₂O₂₀	955.459 3	6.28	937.188 6; 793.335 6	[24]
38	Platycoside M-1	EP4	53.36	C₃₆H₅₄O₁₂	677.353 0	-0.30	659.374 8	[18]
39	Platycogenic acid A lactone	EP5	53.73	C₃₀H₄₄O₇	515.301 3	1.94	495.030 2	[7]
40	3-O-β-D-Glucopyranosyl-(1→3)-β-D- glucopyranosyl-2β, 12α, 16α, 23α- tetrahydroxyoleanane-28(13)-lactone	FP1	51.19	C₄₃H₇₀O₁₆	841.459 0	1.19	679.347 6; 517.300 9	[25]
41	3-O-β-D-Glucopyranosyl-2β, 12α, 16α, 23, 24- pentahydroxyoleanane-28(13)-lactone	FP2	56.90	C₃₇H₆₀O₁₂	695.397 3	-4.03	533.301 0; 676.848 4	[25]
42	16-oxo-Platycodin D	GP1	37.46	C₅₇H₉₀O₂₈	1 221.551 1	-1.97	1 089.470 0; 679.342 2	[7]
43	Platycogenin A	HP1	53.90	C₄₂H₆₈O₁₆	827.441 7	-0.85	503.317 4; 665.378 4	[17]
44	Platycogenic acid C	HP2	59.78	C₃₀H₄₈O₆	503.335 6	-2.19	485.179 4	[7]

No.

Identification

Name

t_R /min

Formula

m/z

Error (ppm)

Fragment ion

Ref.

Deapio-platycoside E

AP1

15.62

C₆₄H₁₀₄O₃₄

1 415.630 9

-1.13

1 005.486 3; 843.424 2

[14]

Platycoside E

AP2

17.40

C₆₉H₁₁₂O₃₈

1 547.673 8

-0.65

1 005.449 5; 519.320 6

[3]

Platycodin D3

AP3

23.85

C₆₃H₁₀₂O₃₃

1 385.619 3

-1.95

843.407 1; 1 253.549 5

[2]

3″-O-Acetyl platycodin D3

AP4

24.87

C₆₅H₁₀₄O₃₄

1 427.629 3

-2.24

1 385.582 4; 843.413 1

[15]

Platycoside G2

AP5

27.28

C₅₉H₉₆O₃₀

1 283.589 6

-0.55

843.362 9; 519.270 3

[16]

Deapio-platycodin D2

AP6

30.14

C₅₈H₉₄O₂₉

1 253.577 3

-1.92

843.408 5; 681.381 6

[6]

Deapio-platycodin D

AP7

30.41

C₅₂H₈₄O₂₄

1 091.525 1

-1.65

681.360 3; 519.342 9

[17]

Platycodin D2

AP8

31.90

C₆₃H₁₀₂O₃₃

1 385.621 5

-0.37

843.407 1; 1 253.549 5

[18]

Platycodin D

AP9

32.23

C₅₇H₉₂O₂₈

1 223.565 8

-2.70

681.343 5; 1 091.511 0

[2]

Platycoside F

AP10

34.44

C₄₇H₇₆O₂₀

959.484 5

-0.10

681.374 2; 797.431 4

[2]

Platycodins K

AP11

35.42

C₅₉H₉₂O₃₀

1 279.558 2

-0.63

827.463 3; 1 147.544 7

[2]

Platycoside B

AP12

35.83

C₅₄H₈₆O₂₅

1 133.535 3

-1.85

681.393 5; 1 091.543 8

[18]

3-O-β-D-Gentiobiosyl platycodigenin methylester

AP13

36.75

C₄₃H₇₀O₁₇

857.456 0

3.62

797.613 4; 858.662 5

[19]

2″-O-Acetyl-platycodin D2

AP14

38.08

C₆₅H₁₀₄O₃₄

1 427.630 4

-1.47

1 385.623 3; 843.482 7

[16]

Platycoside L

AP15

52.52

C₄₂H₆₈O₁₇

843.435 4

-2.25

519.291 1; 681.346 9

[7]

Platycoside K

AP16

52.83

C₄₂H₆₈O₁₇

843.436 8

-0.59

519.291 3; 681.346 9

[7]

3-O-β-D-Glucopyranosyl platycodigenin

AP17

54.96

C₃₆H₅₈O₁₂

681.383 8

-1.03

519.295 4

[3]

Platycodigenin

AP18

57.93

C₃₀H₄₈O₇

519.332 1

0.96

501.136 8

[3]

Platycoside D

BP1

25.25

C₆₉H₁₁₂O₃₇

1 531.678 2

-1.11

827.428 4; 665.452 7

[20]

Polygalacin D2

BP2

32.88

C₆₃H₁₀₂O₃₂

1 369.626 2

-0.66

827.411 1; 665.394 5

[16]

Polygalacin D

BP3

33.74

C₅₇H₉₂O₂₇

1 207.573 6

-0.50

1 075.503 1; 665.361 5

[19]

3″-O-Acetyl polygalacin D

BP4

35.14

C₅₉H₉₄O₂₈

1 249.590 2

4.32

1 207.558 4; 665.376 7

[18]

Platycoside J

BP5

38.80

C₅₂H₈₄O₂₃

1 075.530 8

-1.12

665.363 0; 503.333 4

[18]

2″-O-Acetyl polygalacin D2

BP6

40.03

C₆₅H₁₀₄O₃₃

1 411.634 8

-1.98

1 369.654 7; 827.436 5

[21]

3-O-β-D-Laminaribiosyl polygalacic acid

BP7

55.97

C₄₂H₆₈O₁₆

827.442 0

-0.48

503.317 4; 665.378 4

[22]

3-O-β-D-Glucopyranosyl polygalacic acid

BP8

56.85

C₃₆H₅₈O₁₁

665.388 2

-1.95

647.233 6; 503.334 3

[14]

Methyl-3-O-β-D-glucopyranosyl polygalaeate

BP9

62.71

C₃₇H₆₀O₁₁

679.400 0

-7.66

633.371 3; 661.229 7

[19]

Polygalacic acid

BP10

64.50

C₃₀H₄₈O₆

503.337 2

-0.99

485.111 5; 503.195 3

[22]

Platyconic acid A

CP1

30.01

C₅₇H₉₀O₂₉

1 237.546 3

-1.70

827.433 9

[7]

Platyconic acid E

CP2

37.52

C₅₈H₉₂O₃₀

1 267.556 9

-1.66

1 117.583 2

[23]

2''-O-Acetyl platyconic acid A

CP3

43.07

C₅₉H₉₂O₃₀

1 279.555 1

-3.05

1 147.577 4; 827.463 3

[2]

Platyconic acid C

CP4

43.11

C₅₂H₈₂O₂₅

1 105.504 9

-1.09

943.521 9; 695.415 4

[23]

Platycoside O

DP1

36.61

C₅₃H₈₄O₂₅

1 119.520 6

-1.07

635.333 6; 1 119.178 6

[15]

Platyconic acid A methylester

DP2

39.80

C₅₈H₉₂O₂₉

1 251.560 4

-2.96

635.330 8; 1 089.517 9

[7]

Deapio-platyconic acid A lactone

EP1

33.29

C₅₂H₈₀O₂₄

1 087.494 9

-0.64

1 069.565 3

[7]

Platyconic acid A lactone

EP2

34.72

C₅₇H₈₈O₂₈

1 219.533 9

-3.20

677.324 7; 1 087.651 6

[7]

Platycoside M-2

EP3

50.80

C₄₇H₇₂O₂₀

955.459 3

6.28

937.188 6; 793.335 6

[24]

Platycoside M-1

EP4

53.36

C₃₆H₅₄O₁₂

677.353 0

-0.30

659.374 8

[18]

Platycogenic acid A lactone

EP5

53.73

C₃₀H₄₄O₇

515.301 3

1.94

495.030 2

[7]

3-O-β-D-Glucopyranosyl-(1→3)-β-D-
glucopyranosyl-2β, 12α, 16α, 23α-
tetrahydroxyoleanane-28(13)-lactone

FP1

51.19

C₄₃H₇₀O₁₆

841.459 0

1.19

679.347 6; 517.300 9

[25]

3-O-β-D-Glucopyranosyl-2β, 12α, 16α, 23, 24-
pentahydroxyoleanane-28(13)-lactone

FP2

56.90

C₃₇H₆₀O₁₂

695.397 3

-4.03

533.301 0; 676.848 4

[25]

16-oxo-Platycodin D

GP1

37.46

C₅₇H₉₀O₂₈

1 221.551 1

-1.97

1 089.470 0; 679.342 2

[7]

Platycogenin A

HP1

53.90

C₄₂H₆₈O₁₆

827.441 7

-0.85

503.317 4; 665.378 4

[17]

Platycogenic acid C

HP2

59.78

C₃₀H₄₈O₆

503.335 6

-2.19

485.179 4

[7]

No.	Identification	Name	t_R /min	Formula	m/z	Error (ppm)	Fragment ion	Ref.
1	Deapio-platycoside E	AP1	15.62	C₆₄H₁₀₄O₃₄	1 415.630 9	-1.13	1 005.486 3; 843.424 2	[14]
2	Platycoside E	AP2	17.40	C₆₉H₁₁₂O₃₈	1 547.673 8	-0.65	1 005.449 5; 519.320 6	[3]
3	Platycodin D3	AP3	23.85	C₆₃H₁₀₂O₃₃	1 385.619 3	-1.95	843.407 1; 1 253.549 5	[2]
4	3″-O-Acetyl platycodin D3	AP4	24.87	C₆₅H₁₀₄O₃₄	1 427.629 3	-2.24	1 385.582 4; 843.413 1	[15]
5	Platycoside G2	AP5	27.28	C₅₉H₉₆O₃₀	1 283.589 6	-0.55	843.362 9; 519.270 3	[16]
6	Deapio-platycodin D2	AP6	30.14	C₅₈H₉₄O₂₉	1 253.577 3	-1.92	843.408 5; 681.381 6	[6]
7	Deapio-platycodin D	AP7	30.41	C₅₂H₈₄O₂₄	1 091.525 1	-1.65	681.360 3; 519.342 9	[17]
8	Platycodin D2	AP8	31.90	C₆₃H₁₀₂O₃₃	1 385.621 5	-0.37	843.407 1; 1 253.549 5	[18]
9	Platycodin D	AP9	32.23	C₅₇H₉₂O₂₈	1 223.565 8	-2.70	681.343 5; 1 091.511 0	[2]
10	Platycoside F	AP10	34.44	C₄₇H₇₆O₂₀	959.484 5	-0.10	681.374 2; 797.431 4	[2]
11	Platycodins K	AP11	35.42	C₅₉H₉₂O₃₀	1 279.558 2	-0.63	827.463 3; 1 147.544 7	[2]
12	Platycoside B	AP12	35.83	C₅₄H₈₆O₂₅	1 133.535 3	-1.85	681.393 5; 1 091.543 8	[18]
13	3-O-β-D-Gentiobiosyl platycodigenin methylester	AP13	36.75	C₄₃H₇₀O₁₇	857.456 0	3.62	797.613 4; 858.662 5	[19]
14	2″-O-Acetyl-platycodin D2	AP14	38.08	C₆₅H₁₀₄O₃₄	1 427.630 4	-1.47	1 385.623 3; 843.482 7	[16]
15	Platycoside L	AP15	52.52	C₄₂H₆₈O₁₇	843.435 4	-2.25	519.291 1; 681.346 9	[7]
16	Platycoside K	AP16	52.83	C₄₂H₆₈O₁₇	843.436 8	-0.59	519.291 3; 681.346 9	[7]
17	3-O-β-D-Glucopyranosyl platycodigenin	AP17	54.96	C₃₆H₅₈O₁₂	681.383 8	-1.03	519.295 4	[3]
18	Platycodigenin	AP18	57.93	C₃₀H₄₈O₇	519.332 1	0.96	501.136 8	[3]
19	Platycoside D	BP1	25.25	C₆₉H₁₁₂O₃₇	1 531.678 2	-1.11	827.428 4; 665.452 7	[20]
20	Polygalacin D2	BP2	32.88	C₆₃H₁₀₂O₃₂	1 369.626 2	-0.66	827.411 1; 665.394 5	[16]
21	Polygalacin D	BP3	33.74	C₅₇H₉₂O₂₇	1 207.573 6	-0.50	1 075.503 1; 665.361 5	[19]
22	3″-O-Acetyl polygalacin D	BP4	35.14	C₅₉H₉₄O₂₈	1 249.590 2	4.32	1 207.558 4; 665.376 7	[18]
23	Platycoside J	BP5	38.80	C₅₂H₈₄O₂₃	1 075.530 8	-1.12	665.363 0; 503.333 4	[18]
24	2″-O-Acetyl polygalacin D2	BP6	40.03	C₆₅H₁₀₄O₃₃	1 411.634 8	-1.98	1 369.654 7; 827.436 5	[21]
25	3-O-β-D-Laminaribiosyl polygalacic acid	BP7	55.97	C₄₂H₆₈O₁₆	827.442 0	-0.48	503.317 4; 665.378 4	[22]
26	3-O-β-D-Glucopyranosyl polygalacic acid	BP8	56.85	C₃₆H₅₈O₁₁	665.388 2	-1.95	647.233 6; 503.334 3	[14]
27	Methyl-3-O-β-D-glucopyranosyl polygalaeate	BP9	62.71	C₃₇H₆₀O₁₁	679.400 0	-7.66	633.371 3; 661.229 7	[19]
28	Polygalacic acid	BP10	64.50	C₃₀H₄₈O₆	503.337 2	-0.99	485.111 5; 503.195 3	[22]
29	Platyconic acid A	CP1	30.01	C₅₇H₉₀O₂₉	1 237.546 3	-1.70	827.433 9	[7]
30	Platyconic acid E	CP2	37.52	C₅₈H₉₂O₃₀	1 267.556 9	-1.66	1 117.583 2	[23]
31	2''-O-Acetyl platyconic acid A	CP3	43.07	C₅₉H₉₂O₃₀	1 279.555 1	-3.05	1 147.577 4; 827.463 3	[2]
32	Platyconic acid C	CP4	43.11	C₅₂H₈₂O₂₅	1 105.504 9	-1.09	943.521 9; 695.415 4	[23]
33	Platycoside O	DP1	36.61	C₅₃H₈₄O₂₅	1 119.520 6	-1.07	635.333 6; 1 119.178 6	[15]
34	Platyconic acid A methylester	DP2	39.80	C₅₈H₉₂O₂₉	1 251.560 4	-2.96	635.330 8; 1 089.517 9	[7]
35	Deapio-platyconic acid A lactone	EP1	33.29	C₅₂H₈₀O₂₄	1 087.494 9	-0.64	1 069.565 3	[7]
36	Platyconic acid A lactone	EP2	34.72	C₅₇H₈₈O₂₈	1 219.533 9	-3.20	677.324 7; 1 087.651 6	[7]
37	Platycoside M-2	EP3	50.80	C₄₇H₇₂O₂₀	955.459 3	6.28	937.188 6; 793.335 6	[24]
38	Platycoside M-1	EP4	53.36	C₃₆H₅₄O₁₂	677.353 0	-0.30	659.374 8	[18]
39	Platycogenic acid A lactone	EP5	53.73	C₃₀H₄₄O₇	515.301 3	1.94	495.030 2	[7]
40	3-O-β-D-Glucopyranosyl-(1→3)-β-D- glucopyranosyl-2β, 12α, 16α, 23α- tetrahydroxyoleanane-28(13)-lactone	FP1	51.19	C₄₃H₇₀O₁₆	841.459 0	1.19	679.347 6; 517.300 9	[25]
41	3-O-β-D-Glucopyranosyl-2β, 12α, 16α, 23, 24- pentahydroxyoleanane-28(13)-lactone	FP2	56.90	C₃₇H₆₀O₁₂	695.397 3	-4.03	533.301 0; 676.848 4	[25]
42	16-oxo-Platycodin D	GP1	37.46	C₅₇H₉₀O₂₈	1 221.551 1	-1.97	1 089.470 0; 679.342 2	[7]
43	Platycogenin A	HP1	53.90	C₄₂H₆₈O₁₆	827.441 7	-0.85	503.317 4; 665.378 4	[17]
44	Platycogenic acid C	HP2	59.78	C₃₀H₄₈O₆	503.335 6	-2.19	485.179 4	[7]

No.

Identification

Name

t_R /min

Formula

m/z

Error (ppm)

Fragment ion

Ref.

Deapio-platycoside E

AP1

15.62

C₆₄H₁₀₄O₃₄

1 415.630 9

-1.13

1 005.486 3; 843.424 2

[14]

Platycoside E

AP2

17.40

C₆₉H₁₁₂O₃₈

1 547.673 8

-0.65

1 005.449 5; 519.320 6

[3]

Platycodin D3

AP3

23.85

C₆₃H₁₀₂O₃₃

1 385.619 3

-1.95

843.407 1; 1 253.549 5

[2]

3″-O-Acetyl platycodin D3

AP4

24.87

C₆₅H₁₀₄O₃₄

1 427.629 3

-2.24

1 385.582 4; 843.413 1

[15]

Platycoside G2

AP5

27.28

C₅₉H₉₆O₃₀

1 283.589 6

-0.55

843.362 9; 519.270 3

[16]

Deapio-platycodin D2

AP6

30.14

C₅₈H₉₄O₂₉

1 253.577 3

-1.92

843.408 5; 681.381 6

[6]

Deapio-platycodin D

AP7

30.41

C₅₂H₈₄O₂₄

1 091.525 1

-1.65

681.360 3; 519.342 9

[17]

Platycodin D2

AP8

31.90

C₆₃H₁₀₂O₃₃

1 385.621 5

-0.37

843.407 1; 1 253.549 5

[18]

Platycodin D

AP9

32.23

C₅₇H₉₂O₂₈

1 223.565 8

-2.70

681.343 5; 1 091.511 0

[2]

Platycoside F

AP10

34.44

C₄₇H₇₆O₂₀

959.484 5

-0.10

681.374 2; 797.431 4

[2]

Platycodins K

AP11

35.42

C₅₉H₉₂O₃₀

1 279.558 2

-0.63

827.463 3; 1 147.544 7

[2]

Platycoside B

AP12

35.83

C₅₄H₈₆O₂₅

1 133.535 3

-1.85

681.393 5; 1 091.543 8

[18]

3-O-β-D-Gentiobiosyl platycodigenin methylester

AP13

36.75

C₄₃H₇₀O₁₇

857.456 0

3.62

797.613 4; 858.662 5

[19]

2″-O-Acetyl-platycodin D2

AP14

38.08

C₆₅H₁₀₄O₃₄

1 427.630 4

-1.47

1 385.623 3; 843.482 7

[16]

Platycoside L

AP15

52.52

C₄₂H₆₈O₁₇

843.435 4

-2.25

519.291 1; 681.346 9

[7]

Platycoside K

AP16

52.83

C₄₂H₆₈O₁₇

843.436 8

-0.59

519.291 3; 681.346 9

[7]

3-O-β-D-Glucopyranosyl platycodigenin

AP17

54.96

C₃₆H₅₈O₁₂

681.383 8

-1.03

519.295 4

[3]

Platycodigenin

AP18

57.93

C₃₀H₄₈O₇

519.332 1

0.96

501.136 8

[3]

Platycoside D

BP1

25.25

C₆₉H₁₁₂O₃₇

1 531.678 2

-1.11

827.428 4; 665.452 7

[20]

Polygalacin D2

BP2

32.88

C₆₃H₁₀₂O₃₂

1 369.626 2

-0.66

827.411 1; 665.394 5

[16]

Polygalacin D

BP3

33.74

C₅₇H₉₂O₂₇

1 207.573 6

-0.50

1 075.503 1; 665.361 5

[19]

3″-O-Acetyl polygalacin D

BP4

35.14

C₅₉H₉₄O₂₈

1 249.590 2

4.32

1 207.558 4; 665.376 7

[18]

Platycoside J

BP5

38.80

C₅₂H₈₄O₂₃

1 075.530 8

-1.12

665.363 0; 503.333 4

[18]

2″-O-Acetyl polygalacin D2

BP6

40.03

C₆₅H₁₀₄O₃₃

1 411.634 8

-1.98

1 369.654 7; 827.436 5

[21]

3-O-β-D-Laminaribiosyl polygalacic acid

BP7

55.97

C₄₂H₆₈O₁₆

827.442 0

-0.48

503.317 4; 665.378 4

[22]

3-O-β-D-Glucopyranosyl polygalacic acid

BP8

56.85

C₃₆H₅₈O₁₁

665.388 2

-1.95

647.233 6; 503.334 3

[14]

Methyl-3-O-β-D-glucopyranosyl polygalaeate

BP9

62.71

C₃₇H₆₀O₁₁

679.400 0

-7.66

633.371 3; 661.229 7

[19]

Polygalacic acid

BP10

64.50

C₃₀H₄₈O₆

503.337 2

-0.99

485.111 5; 503.195 3

[22]

Platyconic acid A

CP1

30.01

C₅₇H₉₀O₂₉

1 237.546 3

-1.70

827.433 9

[7]

Platyconic acid E

CP2

37.52

C₅₈H₉₂O₃₀

1 267.556 9

-1.66

1 117.583 2

[23]

2''-O-Acetyl platyconic acid A

CP3

43.07

C₅₉H₉₂O₃₀

1 279.555 1

-3.05

1 147.577 4; 827.463 3

[2]

Platyconic acid C

CP4

43.11

C₅₂H₈₂O₂₅

1 105.504 9

-1.09

943.521 9; 695.415 4

[23]

Platycoside O

DP1

36.61

C₅₃H₈₄O₂₅

1 119.520 6

-1.07

635.333 6; 1 119.178 6

[15]

Platyconic acid A methylester

DP2

39.80

C₅₈H₉₂O₂₉

1 251.560 4

-2.96

635.330 8; 1 089.517 9

[7]

Deapio-platyconic acid A lactone

EP1

33.29

C₅₂H₈₀O₂₄

1 087.494 9

-0.64

1 069.565 3

[7]

Platyconic acid A lactone

EP2

34.72

C₅₇H₈₈O₂₈

1 219.533 9

-3.20

677.324 7; 1 087.651 6

[7]

Platycoside M-2

EP3

50.80

C₄₇H₇₂O₂₀

955.459 3

6.28

937.188 6; 793.335 6

[24]

Platycoside M-1

EP4

53.36

C₃₆H₅₄O₁₂

677.353 0

-0.30

659.374 8

[18]

Platycogenic acid A lactone

EP5

53.73

C₃₀H₄₄O₇

515.301 3

1.94

495.030 2

[7]

3-O-β-D-Glucopyranosyl-(1→3)-β-D-
glucopyranosyl-2β, 12α, 16α, 23α-
tetrahydroxyoleanane-28(13)-lactone

FP1

51.19

C₄₃H₇₀O₁₆

841.459 0

1.19

679.347 6; 517.300 9

[25]

3-O-β-D-Glucopyranosyl-2β, 12α, 16α, 23, 24-
pentahydroxyoleanane-28(13)-lactone

FP2

56.90

C₃₇H₆₀O₁₂

695.397 3

-4.03

533.301 0; 676.848 4

[25]

16-oxo-Platycodin D

GP1

37.46

C₅₇H₉₀O₂₈

1 221.551 1

-1.97

1 089.470 0; 679.342 2

[7]

Platycogenin A

HP1

53.90

C₄₂H₆₈O₁₆

827.441 7

-0.85

503.317 4; 665.378 4

[17]

Platycogenic acid C

HP2

59.78

C₃₀H₄₈O₆

503.335 6

-2.19

485.179 4

[7]

No.	Identification	Name	Formula	t_R/min	m/z	Error (ppm)	Peak intensity	Fragment ion
1	Deapio-platycodin D2	AP6-M1	C₅₈H₉₄O₂₉	30.20	1 253.586 2	5.19	857	843.473 5; 1 091.610 4
2	Deapio-platycodin D	AP7-M2	C₅₂H₈₄O₂₄	30.40	1 091.526 0	-0.82	2 608	681.323 9; 1 091.467 5
3	Platycodin D2	AP8-M3	C₆₃H₁₀₂O₃₃	31.96	1 385.619 1	-2.09	2 519	843.450 8; 1 223.914 9
4	Platycodin D	AP9-M4	C₅₇H₉₂O₂₈	32.16	1 223.565 9	-2.62	13 791	681.411 1; 1 091.693 1
5	Hydroxylated platycoside metabolite	AM5	C₅₇H₉₂O₂₉	32.62	1 239.581 9	14.37	402	-
6	PD-api-xyl-rha dehydrogenated metabolite	AM6	C₄₁H₆₄O₁₆	52.44	811.425 3	17.51	16 640	-
7	PD-glc-api-xyl hydroxylated metabolite	AM7	C₄₁H₆₆O₁₆	54.83	813.418 8	-9.12	29 671	-
8	3-O-β-D-Glucopyranosyl platycodigenin	AP17-M8	C₃₆H₅₈O₁₂	54.98	681.382 8	-2.50	921	-
9	PD-api-xyl-rha methylated metabolite	AM9	C₄₂H₆₈O₁₆	56.26	827.436 5	-7.13	26 141	-
10	Platycodigenin	AP18-M10	C₃₀H₄₈O₇	57.88	519.333 5	3.66	6 506	-
11	Platycodigenin dehydrogenated metabolite	AM11	C₃₀H₄₆O₇	58.45	517.316 0	0	18 016	496.991 3; 449.078 3
12	Polygalacin D2	BP2-M1	C₆₃H₁₀₂O₃₂	32.96	1 369.626 2	-0.66	2 235	827.350 7; 503.441 0
13	Polygalacin D	BP3-M2	C₅₇H₉₂O₂₇	33.75	1 207.578 6	3.65	1 851	665.373 2; 1 207.292 0
14	Polygalacin D-glc-api-xyl dehydroxylated metabolite	BM3	C₄₁H₆₆O₁₃	58.02	765.453 1	14.51	32 883
15	Polygalacin D-glc-api-xyl-rha	BM4	C₃₅H₅₆O₁₀	61.31	635.375 9	-4.88	39 541	403.283 1; 571.327 5
16	Polygalacin D-api-xyl-rha dehydroxylated metabolite	BM5	C₄₁H₆₆O₁₄	61.48	781.422 7	-18.18	45 908	-
17	Polygalacin D-glc-api-xyl-rha-ara dehydrogenated metabolite	BM6	C₃₀H₄₆O₆	64.93	501.321 0	-0.20	11 100	-
18	Polygalacin D-glc-api-xyl-rha methylated metabolite	BM7	C₃₆H₅₈O₁₀	64.96	649.388 8	-8.94	27 070	-
19	Polygalacin D-api-xyl-rha acetylated metabolite	BM8	C₄₃H₆₈O₁₆	64.98	839.444 5	2.50	14 119	-
20	Polygalacin D-glc-api-xyl-rha glucuronicated metabolite	BM9	C₄₁H₆₄O₁₆	65.13	811.410 8	-0.37	13 749	-
21	Polygalacin D-glc-api-xyl-rha-ara decarboxylated metabolite	BM10	C₂₉H₄₈O₄	65.22	459.347 3	1.53	28 030	-
22	Polygalacin D-glc-api-xyl-rha-ara acetylated metabolite	BM11	C₃₂H₅₀O₇	65.67	545.346 4	-1.65	237 331	527.273 4; 501.260 1
23	Polygalacin D-glc-api-xyl-rha-ara methylated metabolite	BM12	C₃₁H₅₀O₆	65.73	517.350 5	-3.68	55 733	-
24	Polygalacin D-glc-api-xyl-rha-ara hydroxylated metabolite	BM13	C₃₀H₄₈O₇	66.22	519.331 8	0.39	12 470	-
25	Polygalacin D-glc-api-xyl-rha dehydrogenated metabolite	BM14	C₃₅H₅₄O₁₀	66.94	633.360 9	-3.79	23 734	-
26	Platyconic acid E	CP2-M1	C₅₈H₉₂O₃₀	37.53	1 267.555 8	-2.53	1 897	859.463 3; 841.466 0
27	Platyconic acid A-api-xyl-rha-ara	CM2	C₃₆H₅₆O₁₃	58.17	695.350 8	-18.56	136 178	635.296 5; 480.274 2
28	Platyconic acid A-glc-api-xyl-rha	CM3	C₃₅H₅₄O₁₂	58.63	665.351 5	-2.56	39 887	-
29	Platyconic acid A-api-xyl-rha-ara hydroxylation metabolite	CM4	C₃₆H₅₆O₁₄	58.82	711.352 6	-8.44	122 922	-
30	Platyconic acid A-glc-api-xyl-rha dehydroxylated metabolite	CM5	C₃₅H₅₄O₁₁	61.80	649.351 6	-10.17	10 843	-
31	Platycoside O	DP1-M1	C₅₃H₈₄O₂₅	36.62	1 119.521 0	-0.71	2 468	1 085.304 8; 1 119.383 9
32	Platycoside O-glc-xyl	DM2	C₄₂H₆₆O₁₆	54.87	825.427 7	-0.12	27 787	-
33	Platycoside O-glc-xyl dehydroxylated metabolite	DM3	C₄₂H₆₆O₁₅	55.59	809.435 4	3.09	27 042	-
34	Platycoside O-xyl-rha-ara methylated	DM4	C₃₈H₆₀O₁₃	58.88	723.390 9	-7.19	27 696	-
35	Platycoside O-xyl-rha acetylated metabolite	DM5	C₄₄H₆₈O₁₈	68.85	883.439 6	7.13	5 578	865.475 2; 465.221 0
36	Platycoside O-xyl-rha-ara dehydroxylated metabolite	DM6	C₃₇H₅₈O₁₂	68.91	693.397 5	17.17	29 302	-
37	Platycogenic acid A lactone	EP5-M1	C₃₀H₄₄O₇	53.84	515.304 3	7.77	190 527	279.236 5; 495.045 8
38	Platycoside M1-glc dehydroxylated metabolite	EM2	C₃₀H₄₄O₆	59.12	499.303 3	-4.21	21 565	-
39	Platycoside M1-glc hydroxylated metabolite	EM3	C₃₀H₄₄O₈	59.69	531.303 8	16.20	116 812	-
40	Platycoside M1-glc methylated metabolite	EM4	C₃₁H₄₆O₇	60.91	529.312 2	-7.18	27 747	-
41	Platycoside M1-glc dehydroxylated metabolite and D-methylated	EM5	C₃₀H₄₄O₆	68.94	499.308 8	7.30	73 393	-
42	3-O-β-D-Glucopyranosyl-(1→3)-β-D-glucopyranosyl-2β, 12α, 16α, 23α-tetrahydroxyoleanane-28(13)-lactone(F1) dehydroxylated metabolite	FM1	C₄₃H₇₀O₁₅	56.92	825.459 4	-8.12	31 450	-
43	3-O-β-D-Glucopyranosyl-2β, 12α, 16α, 23, 24-pentahydroxyoleanane-28(13)-lactone(F2)-glcdehydrogenated metabolite	FM2	C₃₁H₄₈O₇	60.09	531.328 8	-5.27	61 396	-
44	F1 methylated metabolite	FM3	C₄₄H₇₂O₁₆	60.77	855.476 1	2.81	36 600	-
45	F1-glc methylated metabolite	FM4	C₃₈H₆₂O₁₁	61.70	693.415 0	-8.37	49 989	633.346 9; 508.321 8
46	F2-glc methylated metabolite	FM5	C₃₂H₅₂O₇	64.15	547.363 0	0.18	49 200	-
47	F1-2glc dehydroxylated metabolite	FM6	C₃₁H₅₀O₅	67.04	501.358 2	1.40	17 722	-
48	F1-2glc acetylated metabolite	FM7	C₃₃H₅₂O₇	67.43	559.363 5	1.07	48 216	559.280 2; 541.382 6
49	F1-2glc methylated metabolite	FM8	C₃₂H₅₂O₆	68.81	531.363 3	-8.85	13 228
50	16-oxo-Platycodin D	GP1-M1	C₅₇H₉₀O₂₈	37.46	1 221.551 3	-1.80	4 237	469.098 4; 635.470 4
51	16-oxo-Platycodin D-glc-api-xyl methylated metabolite	GM2	C₄₂H₆₆O₁₅	53.07	809.434 6	3.46	9 101	-
52	16-oxo-Platycodin D-api-xyl-rha methylated metabolite	GM3	C₄₂H₆₆O₁₆	53.83	825.418 3	-10.18	10 027	-
53	16-oxo-Platycodin D-glc-api-xyl methylated and deglycosylated metabolite	GM4	C₄₂H₆₆O₁₅	55.04	809.426 0	-7.17	16 453	-
54	16-oxo-Platycodin D-glc-api-xyl-rha-ara decarboxylated metabolite	GM5	C₂₉H₄₆O₅	60.21	473.326 4	0.42	55 603	-
55	16-oxo-Platycodin D-glc-api-xyl-rha-ara acetylated metabolite	GM6	C₃₂H₄₈O₈	64.70	559.325 7	-1.43	48 881	-
56	Platycogenin A-2glc dehydroxylated metabolite	HM1	C₃₀H₄₈O₅	64.54	487.342 1	0.62	11 627	-
57	Platycogenin A-2glc decarboxylated metabolite	HM2	C₂₉H₄₈O₄	65.70	459.347 0	0.22	14 265	-

No.

Identification

Name

Formula

t_R/min

m/z

Error (ppm)

Peak intensity

Fragment ion

Deapio-platycodin D2

AP6-M1

C₅₈H₉₄O₂₉

30.20

1 253.586 2

5.19

857

843.473 5;
1 091.610 4

Deapio-platycodin D

AP7-M2

C₅₂H₈₄O₂₄

30.40

1 091.526 0

-0.82

2 608

681.323 9;
1 091.467 5

Platycodin D2

AP8-M3

C₆₃H₁₀₂O₃₃

31.96

1 385.619 1

-2.09

2 519

843.450 8;
1 223.914 9

Platycodin D

AP9-M4

C₅₇H₉₂O₂₈

32.16

1 223.565 9

-2.62

13 791

681.411 1;
1 091.693 1

Hydroxylated platycoside metabolite

AM5

C₅₇H₉₂O₂₉

32.62

1 239.581 9

14.37

402

PD-api-xyl-rha dehydrogenated metabolite

AM6

C₄₁H₆₄O₁₆

52.44

811.425 3

17.51

16 640

PD-glc-api-xyl hydroxylated metabolite

AM7

C₄₁H₆₆O₁₆

54.83

813.418 8

-9.12

29 671

3-O-β-D-Glucopyranosyl platycodigenin

AP17-M8

C₃₆H₅₈O₁₂

54.98

681.382 8

-2.50

921

PD-api-xyl-rha methylated metabolite

AM9

C₄₂H₆₈O₁₆

56.26

827.436 5

-7.13

26 141

Platycodigenin

AP18-M10

C₃₀H₄₈O₇

57.88

519.333 5

3.66

6 506

Platycodigenin dehydrogenated metabolite

AM11

C₃₀H₄₆O₇

58.45

517.316 0

18 016

496.991 3;
449.078 3

Polygalacin D2

BP2-M1

C₆₃H₁₀₂O₃₂

32.96

1 369.626 2

-0.66

2 235

827.350 7;
503.441 0

Polygalacin D

BP3-M2

C₅₇H₉₂O₂₇

33.75

1 207.578 6

3.65

1 851

665.373 2;
1 207.292 0

Polygalacin D-glc-api-xyl dehydroxylated metabolite

BM3

C₄₁H₆₆O₁₃

58.02

765.453 1

14.51

32 883

Polygalacin D-glc-api-xyl-rha

BM4

C₃₅H₅₆O₁₀

61.31

635.375 9

-4.88

39 541

403.283 1;
571.327 5

Polygalacin D-api-xyl-rha dehydroxylated metabolite

BM5

C₄₁H₆₆O₁₄

61.48

781.422 7

-18.18

45 908

Polygalacin D-glc-api-xyl-rha-ara dehydrogenated metabolite

BM6

C₃₀H₄₆O₆

64.93

501.321 0

-0.20

11 100

Polygalacin D-glc-api-xyl-rha methylated metabolite

BM7

C₃₆H₅₈O₁₀

64.96

649.388 8

-8.94

27 070

Polygalacin D-api-xyl-rha acetylated metabolite

BM8

C₄₃H₆₈O₁₆

64.98

839.444 5

2.50

14 119

Polygalacin D-glc-api-xyl-rha glucuronicated metabolite

BM9

C₄₁H₆₄O₁₆

65.13

811.410 8

-0.37

13 749

Polygalacin D-glc-api-xyl-rha-ara decarboxylated metabolite

BM10

C₂₉H₄₈O₄

65.22

459.347 3

1.53

28 030

Polygalacin D-glc-api-xyl-rha-ara acetylated metabolite

BM11

C₃₂H₅₀O₇

65.67

545.346 4

-1.65

237 331

527.273 4;
501.260 1

Polygalacin D-glc-api-xyl-rha-ara methylated metabolite

BM12

C₃₁H₅₀O₆

65.73

517.350 5

-3.68

55 733

Polygalacin D-glc-api-xyl-rha-ara hydroxylated metabolite

BM13

C₃₀H₄₈O₇

66.22

519.331 8

0.39

12 470

Polygalacin D-glc-api-xyl-rha dehydrogenated metabolite

BM14

C₃₅H₅₄O₁₀

66.94

633.360 9

-3.79

23 734

Platyconic acid E

CP2-M1

C₅₈H₉₂O₃₀

37.53

1 267.555 8

-2.53

1 897

859.463 3;
841.466 0

Platyconic acid A-api-xyl-rha-ara

CM2

C₃₆H₅₆O₁₃

58.17

695.350 8

-18.56

136 178

635.296 5;
480.274 2

Platyconic acid A-glc-api-xyl-rha

CM3

C₃₅H₅₄O₁₂

58.63

665.351 5

-2.56

39 887

Platyconic acid A-api-xyl-rha-ara hydroxylation metabolite

CM4

C₃₆H₅₆O₁₄

58.82

711.352 6

-8.44

122 922

Platyconic acid A-glc-api-xyl-rha dehydroxylated metabolite

CM5

C₃₅H₅₄O₁₁

61.80

649.351 6

-10.17

10 843

Platycoside O

DP1-M1

C₅₃H₈₄O₂₅

36.62

1 119.521 0

-0.71

2 468

1 085.304 8;
1 119.383 9

Platycoside O-glc-xyl

DM2

C₄₂H₆₆O₁₆

54.87

825.427 7

-0.12

27 787

Platycoside O-glc-xyl dehydroxylated metabolite

DM3

C₄₂H₆₆O₁₅

55.59

809.435 4

3.09

27 042

Platycoside O-xyl-rha-ara methylated

DM4

C₃₈H₆₀O₁₃

58.88

723.390 9

-7.19

27 696

Platycoside O-xyl-rha acetylated metabolite

DM5

C₄₄H₆₈O₁₈

68.85

883.439 6

7.13

5 578

865.475 2;
465.221 0

Platycoside O-xyl-rha-ara dehydroxylated metabolite

DM6

C₃₇H₅₈O₁₂

68.91

693.397 5

17.17

29 302

Platycogenic acid A lactone

EP5-M1

C₃₀H₄₄O₇

53.84

515.304 3

7.77

190 527

279.236 5;
495.045 8

Platycoside M1-glc dehydroxylated metabolite

EM2

C₃₀H₄₄O₆

59.12

499.303 3

-4.21

21 565

Platycoside M1-glc hydroxylated metabolite

EM3

C₃₀H₄₄O₈

59.69

531.303 8

16.20

116 812

Platycoside M1-glc methylated metabolite

EM4

C₃₁H₄₆O₇

60.91

529.312 2

-7.18

27 747

Platycoside M1-glc dehydroxylated metabolite and D-methylated

EM5

C₃₀H₄₄O₆

68.94

499.308 8

7.30

73 393

3-O-β-D-Glucopyranosyl-(1→3)-β-D-glucopyranosyl-2β, 12α, 16α, 23α-tetrahydroxyoleanane-28(13)-lactone(F1) dehydroxylated metabolite

FM1

C₄₃H₇₀O₁₅

56.92

825.459 4

-8.12

31 450

3-O-β-D-Glucopyranosyl-2β, 12α, 16α, 23, 24-pentahydroxyoleanane-28(13)-lactone(F2)-glcdehydrogenated metabolite

FM2

C₃₁H₄₈O₇

60.09

531.328 8

-5.27

61 396

F1 methylated metabolite

FM3

C₄₄H₇₂O₁₆

60.77

855.476 1

2.81

36 600

F1-glc methylated metabolite

FM4

C₃₈H₆₂O₁₁

61.70

693.415 0

-8.37

49 989

633.346 9;
508.321 8

F2-glc methylated metabolite

FM5

C₃₂H₅₂O₇

64.15

547.363 0

0.18

49 200

F1-2glc dehydroxylated metabolite

FM6

C₃₁H₅₀O₅

67.04

501.358 2

1.40

17 722

F1-2glc acetylated metabolite

FM7

C₃₃H₅₂O₇

67.43

559.363 5

1.07

48 216

559.280 2;
541.382 6

F1-2glc methylated metabolite

FM8

C₃₂H₅₂O₆

68.81

531.363 3

-8.85

13 228

16-oxo-Platycodin D

GP1-M1

C₅₇H₉₀O₂₈

37.46

1 221.551 3

-1.80

4 237

469.098 4;
635.470 4

16-oxo-Platycodin D-glc-api-xyl methylated metabolite

GM2

C₄₂H₆₆O₁₅

53.07

809.434 6

3.46

9 101

16-oxo-Platycodin D-api-xyl-rha methylated metabolite

GM3

C₄₂H₆₆O₁₆

53.83

825.418 3

-10.18

10 027

16-oxo-Platycodin D-glc-api-xyl methylated and deglycosylated metabolite

GM4

C₄₂H₆₆O₁₅

55.04

809.426 0

-7.17

16 453

16-oxo-Platycodin D-glc-api-xyl-rha-ara decarboxylated metabolite

GM5

C₂₉H₄₆O₅

60.21

473.326 4

0.42

55 603

16-oxo-Platycodin D-glc-api-xyl-rha-ara acetylated metabolite

GM6

C₃₂H₄₈O₈

64.70

559.325 7

-1.43

48 881

Platycogenin A-2glc dehydroxylated metabolite

HM1

C₃₀H₄₈O₅

64.54

487.342 1

0.62

11 627

Platycogenin A-2glc decarboxylated metabolite

HM2

C₂₉H₄₈O₄

65.70

459.347 0

0.22

14 265

No.	Identification	Name	Formula	t_R/min	m/z	Error (ppm)	Peak intensity	Fragment ion
1	Deapio-platycodin D2	AP6-M1	C₅₈H₉₄O₂₉	30.20	1 253.586 2	5.19	857	843.473 5; 1 091.610 4
2	Deapio-platycodin D	AP7-M2	C₅₂H₈₄O₂₄	30.40	1 091.526 0	-0.82	2 608	681.323 9; 1 091.467 5
3	Platycodin D2	AP8-M3	C₆₃H₁₀₂O₃₃	31.96	1 385.619 1	-2.09	2 519	843.450 8; 1 223.914 9
4	Platycodin D	AP9-M4	C₅₇H₉₂O₂₈	32.16	1 223.565 9	-2.62	13 791	681.411 1; 1 091.693 1
5	Hydroxylated platycoside metabolite	AM5	C₅₇H₉₂O₂₉	32.62	1 239.581 9	14.37	402	-
6	PD-api-xyl-rha dehydrogenated metabolite	AM6	C₄₁H₆₄O₁₆	52.44	811.425 3	17.51	16 640	-
7	PD-glc-api-xyl hydroxylated metabolite	AM7	C₄₁H₆₆O₁₆	54.83	813.418 8	-9.12	29 671	-
8	3-O-β-D-Glucopyranosyl platycodigenin	AP17-M8	C₃₆H₅₈O₁₂	54.98	681.382 8	-2.50	921	-
9	PD-api-xyl-rha methylated metabolite	AM9	C₄₂H₆₈O₁₆	56.26	827.436 5	-7.13	26 141	-
10	Platycodigenin	AP18-M10	C₃₀H₄₈O₇	57.88	519.333 5	3.66	6 506	-
11	Platycodigenin dehydrogenated metabolite	AM11	C₃₀H₄₆O₇	58.45	517.316 0	0	18 016	496.991 3; 449.078 3
12	Polygalacin D2	BP2-M1	C₆₃H₁₀₂O₃₂	32.96	1 369.626 2	-0.66	2 235	827.350 7; 503.441 0
13	Polygalacin D	BP3-M2	C₅₇H₉₂O₂₇	33.75	1 207.578 6	3.65	1 851	665.373 2; 1 207.292 0
14	Polygalacin D-glc-api-xyl dehydroxylated metabolite	BM3	C₄₁H₆₆O₁₃	58.02	765.453 1	14.51	32 883
15	Polygalacin D-glc-api-xyl-rha	BM4	C₃₅H₅₆O₁₀	61.31	635.375 9	-4.88	39 541	403.283 1; 571.327 5
16	Polygalacin D-api-xyl-rha dehydroxylated metabolite	BM5	C₄₁H₆₆O₁₄	61.48	781.422 7	-18.18	45 908	-
17	Polygalacin D-glc-api-xyl-rha-ara dehydrogenated metabolite	BM6	C₃₀H₄₆O₆	64.93	501.321 0	-0.20	11 100	-
18	Polygalacin D-glc-api-xyl-rha methylated metabolite	BM7	C₃₆H₅₈O₁₀	64.96	649.388 8	-8.94	27 070	-
19	Polygalacin D-api-xyl-rha acetylated metabolite	BM8	C₄₃H₆₈O₁₆	64.98	839.444 5	2.50	14 119	-
20	Polygalacin D-glc-api-xyl-rha glucuronicated metabolite	BM9	C₄₁H₆₄O₁₆	65.13	811.410 8	-0.37	13 749	-
21	Polygalacin D-glc-api-xyl-rha-ara decarboxylated metabolite	BM10	C₂₉H₄₈O₄	65.22	459.347 3	1.53	28 030	-
22	Polygalacin D-glc-api-xyl-rha-ara acetylated metabolite	BM11	C₃₂H₅₀O₇	65.67	545.346 4	-1.65	237 331	527.273 4; 501.260 1
23	Polygalacin D-glc-api-xyl-rha-ara methylated metabolite	BM12	C₃₁H₅₀O₆	65.73	517.350 5	-3.68	55 733	-
24	Polygalacin D-glc-api-xyl-rha-ara hydroxylated metabolite	BM13	C₃₀H₄₈O₇	66.22	519.331 8	0.39	12 470	-
25	Polygalacin D-glc-api-xyl-rha dehydrogenated metabolite	BM14	C₃₅H₅₄O₁₀	66.94	633.360 9	-3.79	23 734	-
26	Platyconic acid E	CP2-M1	C₅₈H₉₂O₃₀	37.53	1 267.555 8	-2.53	1 897	859.463 3; 841.466 0
27	Platyconic acid A-api-xyl-rha-ara	CM2	C₃₆H₅₆O₁₃	58.17	695.350 8	-18.56	136 178	635.296 5; 480.274 2
28	Platyconic acid A-glc-api-xyl-rha	CM3	C₃₅H₅₄O₁₂	58.63	665.351 5	-2.56	39 887	-
29	Platyconic acid A-api-xyl-rha-ara hydroxylation metabolite	CM4	C₃₆H₅₆O₁₄	58.82	711.352 6	-8.44	122 922	-
30	Platyconic acid A-glc-api-xyl-rha dehydroxylated metabolite	CM5	C₃₅H₅₄O₁₁	61.80	649.351 6	-10.17	10 843	-
31	Platycoside O	DP1-M1	C₅₃H₈₄O₂₅	36.62	1 119.521 0	-0.71	2 468	1 085.304 8; 1 119.383 9
32	Platycoside O-glc-xyl	DM2	C₄₂H₆₆O₁₆	54.87	825.427 7	-0.12	27 787	-
33	Platycoside O-glc-xyl dehydroxylated metabolite	DM3	C₄₂H₆₆O₁₅	55.59	809.435 4	3.09	27 042	-
34	Platycoside O-xyl-rha-ara methylated	DM4	C₃₈H₆₀O₁₃	58.88	723.390 9	-7.19	27 696	-
35	Platycoside O-xyl-rha acetylated metabolite	DM5	C₄₄H₆₈O₁₈	68.85	883.439 6	7.13	5 578	865.475 2; 465.221 0
36	Platycoside O-xyl-rha-ara dehydroxylated metabolite	DM6	C₃₇H₅₈O₁₂	68.91	693.397 5	17.17	29 302	-
37	Platycogenic acid A lactone	EP5-M1	C₃₀H₄₄O₇	53.84	515.304 3	7.77	190 527	279.236 5; 495.045 8
38	Platycoside M1-glc dehydroxylated metabolite	EM2	C₃₀H₄₄O₆	59.12	499.303 3	-4.21	21 565	-
39	Platycoside M1-glc hydroxylated metabolite	EM3	C₃₀H₄₄O₈	59.69	531.303 8	16.20	116 812	-
40	Platycoside M1-glc methylated metabolite	EM4	C₃₁H₄₆O₇	60.91	529.312 2	-7.18	27 747	-
41	Platycoside M1-glc dehydroxylated metabolite and D-methylated	EM5	C₃₀H₄₄O₆	68.94	499.308 8	7.30	73 393	-
42	3-O-β-D-Glucopyranosyl-(1→3)-β-D-glucopyranosyl-2β, 12α, 16α, 23α-tetrahydroxyoleanane-28(13)-lactone(F1) dehydroxylated metabolite	FM1	C₄₃H₇₀O₁₅	56.92	825.459 4	-8.12	31 450	-
43	3-O-β-D-Glucopyranosyl-2β, 12α, 16α, 23, 24-pentahydroxyoleanane-28(13)-lactone(F2)-glcdehydrogenated metabolite	FM2	C₃₁H₄₈O₇	60.09	531.328 8	-5.27	61 396	-
44	F1 methylated metabolite	FM3	C₄₄H₇₂O₁₆	60.77	855.476 1	2.81	36 600	-
45	F1-glc methylated metabolite	FM4	C₃₈H₆₂O₁₁	61.70	693.415 0	-8.37	49 989	633.346 9; 508.321 8
46	F2-glc methylated metabolite	FM5	C₃₂H₅₂O₇	64.15	547.363 0	0.18	49 200	-
47	F1-2glc dehydroxylated metabolite	FM6	C₃₁H₅₀O₅	67.04	501.358 2	1.40	17 722	-
48	F1-2glc acetylated metabolite	FM7	C₃₃H₅₂O₇	67.43	559.363 5	1.07	48 216	559.280 2; 541.382 6
49	F1-2glc methylated metabolite	FM8	C₃₂H₅₂O₆	68.81	531.363 3	-8.85	13 228
50	16-oxo-Platycodin D	GP1-M1	C₅₇H₉₀O₂₈	37.46	1 221.551 3	-1.80	4 237	469.098 4; 635.470 4
51	16-oxo-Platycodin D-glc-api-xyl methylated metabolite	GM2	C₄₂H₆₆O₁₅	53.07	809.434 6	3.46	9 101	-
52	16-oxo-Platycodin D-api-xyl-rha methylated metabolite	GM3	C₄₂H₆₆O₁₆	53.83	825.418 3	-10.18	10 027	-
53	16-oxo-Platycodin D-glc-api-xyl methylated and deglycosylated metabolite	GM4	C₄₂H₆₆O₁₅	55.04	809.426 0	-7.17	16 453	-
54	16-oxo-Platycodin D-glc-api-xyl-rha-ara decarboxylated metabolite	GM5	C₂₉H₄₆O₅	60.21	473.326 4	0.42	55 603	-
55	16-oxo-Platycodin D-glc-api-xyl-rha-ara acetylated metabolite	GM6	C₃₂H₄₈O₈	64.70	559.325 7	-1.43	48 881	-
56	Platycogenin A-2glc dehydroxylated metabolite	HM1	C₃₀H₄₈O₅	64.54	487.342 1	0.62	11 627	-
57	Platycogenin A-2glc decarboxylated metabolite	HM2	C₂₉H₄₈O₄	65.70	459.347 0	0.22	14 265	-

No.

Identification

Name

Formula

t_R/min

m/z

Error (ppm)

Peak intensity

Fragment ion

Deapio-platycodin D2

AP6-M1

C₅₈H₉₄O₂₉

30.20

1 253.586 2

5.19

857

843.473 5;
1 091.610 4

Deapio-platycodin D

AP7-M2

C₅₂H₈₄O₂₄

30.40

1 091.526 0

-0.82

2 608

681.323 9;
1 091.467 5

Platycodin D2

AP8-M3

C₆₃H₁₀₂O₃₃

31.96

1 385.619 1

-2.09

2 519

843.450 8;
1 223.914 9

Platycodin D

AP9-M4

C₅₇H₉₂O₂₈

32.16

1 223.565 9

-2.62

13 791

681.411 1;
1 091.693 1

Hydroxylated platycoside metabolite

AM5

C₅₇H₉₂O₂₉

32.62

1 239.581 9

14.37

402

PD-api-xyl-rha dehydrogenated metabolite

AM6

C₄₁H₆₄O₁₆

52.44

811.425 3

17.51

16 640

PD-glc-api-xyl hydroxylated metabolite

AM7

C₄₁H₆₆O₁₆

54.83

813.418 8

-9.12

29 671

3-O-β-D-Glucopyranosyl platycodigenin

AP17-M8

C₃₆H₅₈O₁₂

54.98

681.382 8

-2.50

921

PD-api-xyl-rha methylated metabolite

AM9

C₄₂H₆₈O₁₆

56.26

827.436 5

-7.13

26 141

Platycodigenin

AP18-M10

C₃₀H₄₈O₇

57.88

519.333 5

3.66

6 506

Platycodigenin dehydrogenated metabolite

AM11

C₃₀H₄₆O₇

58.45

517.316 0

18 016

496.991 3;
449.078 3

Polygalacin D2

BP2-M1

C₆₃H₁₀₂O₃₂

32.96

1 369.626 2

-0.66

2 235

827.350 7;
503.441 0

Polygalacin D

BP3-M2

C₅₇H₉₂O₂₇

33.75

1 207.578 6

3.65

1 851

665.373 2;
1 207.292 0

Polygalacin D-glc-api-xyl dehydroxylated metabolite

BM3

C₄₁H₆₆O₁₃

58.02

765.453 1

14.51

32 883

Polygalacin D-glc-api-xyl-rha

BM4

C₃₅H₅₆O₁₀

61.31

635.375 9

-4.88

39 541

403.283 1;
571.327 5

Polygalacin D-api-xyl-rha dehydroxylated metabolite

BM5

C₄₁H₆₆O₁₄

61.48

781.422 7

-18.18

45 908

Polygalacin D-glc-api-xyl-rha-ara dehydrogenated metabolite

BM6

C₃₀H₄₆O₆

64.93

501.321 0

-0.20

11 100

Polygalacin D-glc-api-xyl-rha methylated metabolite

BM7

C₃₆H₅₈O₁₀

64.96

649.388 8

-8.94

27 070

Polygalacin D-api-xyl-rha acetylated metabolite

BM8

C₄₃H₆₈O₁₆

64.98

839.444 5

2.50

14 119

Polygalacin D-glc-api-xyl-rha glucuronicated metabolite

BM9

C₄₁H₆₄O₁₆

65.13

811.410 8

-0.37

13 749

Polygalacin D-glc-api-xyl-rha-ara decarboxylated metabolite

BM10

C₂₉H₄₈O₄

65.22

459.347 3

1.53

28 030

Polygalacin D-glc-api-xyl-rha-ara acetylated metabolite

BM11

C₃₂H₅₀O₇

65.67

545.346 4

-1.65

237 331

527.273 4;
501.260 1

Polygalacin D-glc-api-xyl-rha-ara methylated metabolite

BM12

C₃₁H₅₀O₆

65.73

517.350 5

-3.68

55 733

Polygalacin D-glc-api-xyl-rha-ara hydroxylated metabolite

BM13

C₃₀H₄₈O₇

66.22

519.331 8

0.39

12 470

Polygalacin D-glc-api-xyl-rha dehydrogenated metabolite

BM14

C₃₅H₅₄O₁₀

66.94

633.360 9

-3.79

23 734

Platyconic acid E

CP2-M1

C₅₈H₉₂O₃₀

37.53

1 267.555 8

-2.53

1 897

859.463 3;
841.466 0

Platyconic acid A-api-xyl-rha-ara

CM2

C₃₆H₅₆O₁₃

58.17

695.350 8

-18.56

136 178

635.296 5;
480.274 2

Platyconic acid A-glc-api-xyl-rha

CM3

C₃₅H₅₄O₁₂

58.63

665.351 5

-2.56

39 887

Platyconic acid A-api-xyl-rha-ara hydroxylation metabolite

CM4

C₃₆H₅₆O₁₄

58.82

711.352 6

-8.44

122 922

Platyconic acid A-glc-api-xyl-rha dehydroxylated metabolite

CM5

C₃₅H₅₄O₁₁

61.80

649.351 6

-10.17

10 843

Platycoside O

DP1-M1

C₅₃H₈₄O₂₅

36.62

1 119.521 0

-0.71

2 468

1 085.304 8;
1 119.383 9

Platycoside O-glc-xyl

DM2

C₄₂H₆₆O₁₆

54.87

825.427 7

-0.12

27 787

Platycoside O-glc-xyl dehydroxylated metabolite

DM3

C₄₂H₆₆O₁₅

55.59

809.435 4

3.09

27 042

Platycoside O-xyl-rha-ara methylated

DM4

C₃₈H₆₀O₁₃

58.88

723.390 9

-7.19

27 696

Platycoside O-xyl-rha acetylated metabolite

DM5

C₄₄H₆₈O₁₈

68.85

883.439 6

7.13

5 578

865.475 2;
465.221 0

Platycoside O-xyl-rha-ara dehydroxylated metabolite

DM6

C₃₇H₅₈O₁₂

68.91

693.397 5

17.17

29 302

Platycogenic acid A lactone

EP5-M1

C₃₀H₄₄O₇

53.84

515.304 3

7.77

190 527

279.236 5;
495.045 8

Platycoside M1-glc dehydroxylated metabolite

EM2

C₃₀H₄₄O₆

59.12

499.303 3

-4.21

21 565

Platycoside M1-glc hydroxylated metabolite

EM3

C₃₀H₄₄O₈

59.69

531.303 8

16.20

116 812

Platycoside M1-glc methylated metabolite

EM4

C₃₁H₄₆O₇

60.91

529.312 2

-7.18

27 747

Platycoside M1-glc dehydroxylated metabolite and D-methylated

EM5

C₃₀H₄₄O₆

68.94

499.308 8

7.30

73 393

3-O-β-D-Glucopyranosyl-(1→3)-β-D-glucopyranosyl-2β, 12α, 16α, 23α-tetrahydroxyoleanane-28(13)-lactone(F1) dehydroxylated metabolite

FM1

C₄₃H₇₀O₁₅

56.92

825.459 4

-8.12

31 450

3-O-β-D-Glucopyranosyl-2β, 12α, 16α, 23, 24-pentahydroxyoleanane-28(13)-lactone(F2)-glcdehydrogenated metabolite

FM2

C₃₁H₄₈O₇

60.09

531.328 8

-5.27

61 396

F1 methylated metabolite

FM3

C₄₄H₇₂O₁₆

60.77

855.476 1

2.81

36 600

F1-glc methylated metabolite

FM4

C₃₈H₆₂O₁₁

61.70

693.415 0

-8.37

49 989

633.346 9;
508.321 8

F2-glc methylated metabolite

FM5

C₃₂H₅₂O₇

64.15

547.363 0

0.18

49 200

F1-2glc dehydroxylated metabolite

FM6

C₃₁H₅₀O₅

67.04

501.358 2

1.40

17 722

F1-2glc acetylated metabolite

FM7

C₃₃H₅₂O₇

67.43

559.363 5

1.07

48 216

559.280 2;
541.382 6

F1-2glc methylated metabolite

FM8

C₃₂H₅₂O₆

68.81

531.363 3

-8.85

13 228

16-oxo-Platycodin D

GP1-M1

C₅₇H₉₀O₂₈

37.46

1 221.551 3

-1.80

4 237

469.098 4;
635.470 4

16-oxo-Platycodin D-glc-api-xyl methylated metabolite

GM2

C₄₂H₆₆O₁₅

53.07

809.434 6

3.46

9 101

16-oxo-Platycodin D-api-xyl-rha methylated metabolite

GM3

C₄₂H₆₆O₁₆

53.83

825.418 3

-10.18

10 027

16-oxo-Platycodin D-glc-api-xyl methylated and deglycosylated metabolite

GM4

C₄₂H₆₆O₁₅

55.04

809.426 0

-7.17

16 453

16-oxo-Platycodin D-glc-api-xyl-rha-ara decarboxylated metabolite

GM5

C₂₉H₄₆O₅

60.21

473.326 4

0.42

55 603

16-oxo-Platycodin D-glc-api-xyl-rha-ara acetylated metabolite

GM6

C₃₂H₄₈O₈

64.70

559.325 7

-1.43

48 881

Platycogenin A-2glc dehydroxylated metabolite

HM1

C₃₀H₄₈O₅

64.54

487.342 1

0.62

11 627

Platycogenin A-2glc decarboxylated metabolite

HM2

C₂₉H₄₈O₄

65.70

459.347 0

0.22

14 265

基于肠道菌转化介导的桔梗总皂苷入血代谢产物鉴定研究

PDF下载

吴茜娃 ¹ , 张欣雨 ¹ , 钟渊涵 ¹ , 张雪梅 ¹ , 周瑜 ² , 冯艳 ¹ , 秦倩 ¹ , 张寿文 ¹ , 钟国跃 ¹ , 曾金祥 ¹^,^*

药学学报 | 研究论文 2024,59(11): 3141-3152

收起

药学学报 | 研究论文 2024, 59(11): 3141-3152

基于肠道菌转化介导的桔梗总皂苷入血代谢产物鉴定研究

全屏

吴茜娃¹, 张欣雨¹, 钟渊涵¹, 张雪梅¹, 周瑜², 冯艳¹, 秦倩¹, 张寿文¹, 钟国跃¹, 曾金祥¹^,^*

作者信息

1.江西中医药大学中药资源与民族药研究中心, 江西南昌 330004

2.九江学院生命科学学院, 江西九江 332005

通讯作者:

^*曾金祥, E-mail: zjx@jxutcm.edu.cn

Identify the metabolites of total saponins of Platycodonis Radix in blood based on intestinal bacteria-mediated method

Xi-wa WU¹, Xin-yu ZHANG¹, Yuan-han ZHONG¹, Xue-mei ZHANG¹, Yu ZHOU², Yan FENG¹, Qian QIN¹, Shou-wen ZHANG¹, Guo-yue ZHONG¹, Jin-xiang ZENG¹^,^*

Affiliations

1. Research Center of Chinese Medicine Resources and Ethnic Minority Medicine, Jiangxi University of Chinese Medicine, Nanchang 330004, China

2. College of Pharmacy and Life Sciences, Jiujiang University, Jiujiang 332005, China

出版时间: 2024-11-12 doi: 10.16438/j.0513-4870.2024-0377

文章导航

摘要

收起

桔梗总皂苷入血产物的鉴定具有重要意义, 但仍存在很大挑战。本研究采用超高效液相色谱-线性离子阱-静电场轨道阱高分辨质谱法(UPLC-LTQ-Orbitrap-MS), 应用Compound Discoverer 3.2与Trace finder 2.1软件, 首先从桔梗总皂苷中鉴定出8个类型共44个原形成分。在此基础上, 以所鉴定的原形成分及其肠道菌转化逐级脱糖产物为分子模板构建肠道菌介导鉴定新方法, 进一步从含药血浆中鉴定出来源于44个原形成分的57个入血产物。这些入血产物包括12个原形成分和45个代谢产物, 且血中原形成分同时是其他原形成分的脱糖基代谢产物。本研究表明肠道菌介导新方法可有效鉴定桔梗总皂苷入血产物, 揭示不同含量与口服生物利用度桔梗皂苷原形成分在血中的存在形式, 并可阐明中药原形成分及其代谢产物的一对多与多对一网络。所有动物实验方案均获得江西中医药大学实验动物伦理委员会批准(编号: JZLLSC-202100322)。

关键词

桔梗皂苷 / 原形成分 / 代谢产物 / 肠道菌介导方法

Abstract

收起

The identification of the components absorbed in serum of platycosides in total saponins fraction of Platycodonis Radix is great significance, but there are still great challenges. In this study, 8 types of 44 primordial components from Platycodon saponins were firstly identified using the ultra-performance liquid chromatography-linear ion trap electrostatic field orbitrap high resolution mass spectrometry (UPLC-LTQ-Orbitrap-MS) equipped with the software of Compound Discoverer 3.2 and Trace finder 2.1. Then, the platycosides and their deglycosylated metabolites were used as the template molecules to construct the intestinal microbiota mediated method to identify the primary components and the prototypes in serum. As results, 57 components originating from 44 prototypes of platycosides were identified from drug-containing plasma. Those compounds consist of 12 prototypes of platycosides and 45 metabolites, while the prototypes in serum are also deglycosylated metabolites of other platycosides. The results showed that the intestinal microbiota mediated method could be applied to identify the metabolites of platycosides in total saponins fraction of Platycodonis Radix; and reveal the potential existing forms of prototypes of platycosides in plasma; In addition, it could clearly illustrate the one to many and many to one network of the prototypes and metabolites of platycosides. All animal protocols were approved by the Animal Ethics Committee of Jiangxi University of Traditional Chinese Medicine (No.JZLLSC-202100322).

Key words

platycoside / prototype / metabolite / intestinal microbiota mediated method

引用本文

吴茜娃, 张欣雨, 钟渊涵, 张雪梅, 周瑜, 冯艳, 秦倩, 张寿文, 钟国跃, 曾金祥. 基于肠道菌转化介导的桔梗总皂苷入血代谢产物鉴定研究. 药学学报, 2024 , 59 (11) : 3141 -3152 . DOI: 10.16438/j.0513-4870.2024-0377

Xi-wa WU, Xin-yu ZHANG, Yuan-han ZHONG, Xue-mei ZHANG, Yu ZHOU, Yan FENG, Qian QIN, Shou-wen ZHANG, Guo-yue ZHONG, Jin-xiang ZENG. Identify the metabolites of total saponins of Platycodonis Radix in blood based on intestinal bacteria-mediated method[J]. Acta Pharmaceutica Sinica, 2024 , 59 (11) : 3141 -3152 . DOI: 10.16438/j.0513-4870.2024-0377

正文

收起

桔梗为桔梗科植物桔梗Platycodon grandiflorum (Jacq.) A. DC.的干燥根, 广泛分布于中国、朝鲜、日本、俄罗斯远东地区和西伯利亚东南部^[1], 具有多种药理作用和保健功效, 主要活性部位为桔梗总皂苷^{[2, 3]}。大量研究表明, 桔梗皂苷D^{[4, 5]}、桔梗皂苷A^[6]、桔梗皂苷E^[7]、桔梗皂苷D₃^[7]和去芹糖桔梗皂苷D₃^[8]等主要皂苷成分具有较好的镇咳、祛痰、抗炎、抗肿瘤等药理活性^[8], 提示桔梗总皂苷具有很好的现代化新药研究与开发价值。

不过, 这些桔梗总皂苷所含成分口服生物利用度往往较低, 在体内难以直接与靶点结合, 故其代谢物才有可能是体内的显效形式^[9]。但迄今为止, 已鉴定的桔梗总皂苷血中产物仍主要为含量相对较高的原形皂苷成分, 而代谢产物仅2到3个^[10], 严重制约后续药效物质及作用机制的合理阐释。已有研究表明低口服生物利用度的中药成分进入肠道后, 不可避免与肠道菌作用, 进而被其代谢转化^[11]。课题组前期研究显示, 桔梗皂苷肠道菌转化代谢物的活性高于其原形成分^[12]; 且桔梗皂苷部分原形成分与其代谢产物之间还存在一对多、多对一的网络关系^[13]。但这些研究仍采用体外肠道菌转化方法鉴定代谢产物, 且代谢产物是否可入血液成为潜在显效形式仍不清楚。

基于低口服生物利用度的中药成分进入肠道后, 不可避免与肠道菌作用之特征, 本研究提出了一种肠道菌介导的血清药物化学方法, 用以鉴定桔梗皂苷入血产物: 首先采用UHPLC-LTQ-Orbitrap-MS技术及Xcalibur 2.1和TraceFinder 4.1软件鉴定桔梗总皂苷原形成分; 然后以原形成分之肠道菌转化逐级脱糖产物为分子模板, 运用Trace Finder 4.1及Compound Discoverer 3.2软件对桔梗总皂苷入血产物进行靶向鉴定; 最后, 基于代谢产物相同母核反向追踪血中代谢产物的原形成分来源, 并构建原形成分与代谢产物之间的网络关系。本研究结果首次显示, 桔梗总皂苷所有不同口服生物利用度与含量原形皂苷成分均可以在血中产生代谢产物, 且原形成分-代谢产物之间存在一对多与多对一的网络关系。

仪器与材料

收起

仪器 LTQ Orbitrap VELOS Pro型线性离子阱-静电场轨道阱联用质谱仪, 配备Ultimate 3000超高效液相色谱系统(美国赛默飞公司); ZORBAX RRHD Eclipse Plus C18色谱柱(100 mm × 2.1 mm, 1.8 µm; 美国安捷伦公司); 5430R型高速冷冻离心机(德国Eppendorf公司); R-210型旋转蒸发仪(瑞士Buchi公司); CP214型电子分析天平(上海奥豪斯仪器有限公司); UV-1800型紫外分光光度计(日本Shimadzu公司); QL-901型涡旋仪(海门市其林贝尔仪器制造有限公司); SCIENTZ-10N冷冻干燥机(宁波新芝生物科技股份有限公司); Milli-Q水净化系统(美国Millipore公司)。

药物与试剂 桔梗产自内蒙古赤峰牛家营子镇, 经江西中医药大学中药资源与民族药研究中心慕泽泾副研究员鉴定为桔梗科植物桔梗Platycodon grandiflorum (Jacq.) A.DC.的干燥根。桔梗皂苷D (platycodin D, PD) 纯度98.66%, 批号MUST-20051510, 购自成都曼斯特生物科技有限公司。乙腈(质谱级, 德国Merck公司)、甲酸(色谱级, 上海阿拉丁试剂有限公司); 水为Milli-Q超纯水, 其余试剂均为分析纯。

动物实验动物购自江西中医药大学实验动物科技中心, 许可证号为SCXK (Gan) 2018-0003。实验动物为雄性SPF级SD大鼠, 体质量为180~220 g。饲养温度为21~25 ℃, 相对湿度为50%~60%, 明暗循环12 h。动物实验经江西中医药大学实验动物伦理委员会批准, 批准号为JZLLSC-202100322。

桔梗总皂苷样品的制备 桔梗药材烘干粉碎后过二号筛, 称取100 g置于圆底烧瓶, 并加入70%乙醇800 mL静置过夜, 回流提取3次, 每次1 h, 合并滤液置于旋转蒸发仪浓缩。残渣加适量蒸馏水加热溶解, 用等量水饱和的正丁醇萃取3次, 合并上层萃取液后分别用等量的氨试液和正丁醇饱和的水溶液洗涤, 之后取上清液。将所得上清液回收溶剂后真空冷冻干燥, 所得固体粉末即桔梗总皂苷(得率为1.3%), 密封置于-20 ℃保存。UHPLC-LTQ-Orbitrap MS分析时取上述桔梗总皂苷50 mg以甲醇溶解, 定容至25 mL。取适量标准品PD以甲醇溶解。样品及标准品均用注射器经0.22 μm滤膜过滤后进样分析。

含药血浆样本的采集 取6只SD大鼠为给药组, 每只大鼠用桔梗总皂苷灌胃, 给药剂量1 g kg^-1; 单次灌胃后禁食不禁水, 给药60 min后对大鼠眼眶取血0.5 mL, 各鼠血浆样品等体积混匀后, 置于含肝素钠EP管中, 4 ℃以4 000 r·min^-1离心5 min取上清液, 即得含药血浆样本, 样本置于-80 ℃保存备用。

空白血浆样本的采集 取6只SD大鼠为空白组, 每只大鼠给予相同剂量的生理盐水, 灌胃60 min眼眶取血0.5 mL, 各鼠血浆样品等体积混匀后, 置于含肝素钠EP管中, 4 ℃以4 000 r·min^-1离心5 min取上清液, 即得空白血浆样本, 样本置于-80 ℃保存备用。

血浆样本的处理与分析 取血浆样本于4 ℃解冻, 各取100 µL分别置于离心管中, 加3倍量正丁醇沉淀蛋白, 涡旋混合1 min, 将混合物于4 ℃以13 000 r·min^-1离心10 min后取上清液。然后用N₂气流干燥上清液, 将获得的残渣于200 μL甲醇中复溶, 将溶液涡旋混合1 min, 并于4 ℃下以13 000 r·min^-1离心10 min取上清液, 以获得用于UHPLC-LTQ-Orbitrap MS分析的最终样品。

色谱条件 ZORBAX RRHD Eclipse Plus C18色谱柱(100 mm × 2.1 mm, 1.8 µm; 美国安捷伦公司); 流动相为0.1%甲酸水(A)-乙腈(B)。梯度洗脱条件: 0~30 min, 15%~24% B; 30~45 min, 24% B; 45~62 min, 24%~71% B; 62~67 min, 71%~95% B; 67~67.1 min, 95%~15% B; 67.1~70 min, 15% B; 流速0.3 mL·min^-1, 进样量1 μL; 柱温40 ℃。

质谱条件 采用电喷雾离子源(ESI), 毛细管温度320 ℃, 鞘气流速35 arb; 辅助气流速10 arb, 以负离子模式采集, 喷雾电压-3.5 kV, 毛细管电压为-5 V, 管透镜电压为-110 V, 样品一级质谱采用全扫描模式, 扫描范围m/z 400~2 000 Da, 检测分辨率30 000, 二级质谱数据采用数据依赖性扫描模式, 选取上一级丰度最高的6个峰进行碰撞诱导解离(collision induced dissociation, CID) 碎片扫描。

数据分析 采用Xcalibur 2.1软件和TraceFinder 4.1软件对目标物进行筛查, 初步筛选出相关化合物, 结合文献进行药材成分鉴定。采用Compound Discoverer 3.2软件, 以桔梗总皂苷原形成分及其逐级脱糖产物为分子模板对入血成分进行靶向鉴定, 同分异构体成分的保留时间根据ClogP值来确定。由于血浆中噪音较高, 把入血成分鉴定的质量误差容限设置为20 ppm, 信号强度设置为至少超过空白血浆10倍。

结果

收起

1 桔梗总皂苷化学成分鉴定

采用UHPLC-LTQ-Orbitrap-MS技术, 对桔梗总皂苷进行定性分析, 样品在负离子模式下的总离子流图(total ion chromatogram, TIC) 见图 1, 应用Xcalibur 2.1软件对各成分的保留时间、准分子离子峰和二级碎片进行提取分析, 并结合标准品及相关文献推测其结构, 结果共鉴定出44个桔梗皂苷主要原形成分, 详情见表 1^{[2, 3, 6, 7, 14-25]}。

进一步分析桔梗皂苷成分结构类型可知, 桔梗总皂苷部位中含有全部8类, 总计44个桔梗皂苷成分, 其中A类型18个, B类型10个, C类型4个, D类型2个, E类型5个, F类型2个, G类型1个, H类型2个。这些成分中, 大部分成分在C-3位及C-28位均含有双糖链。大量研究显示, 肠道菌群可产生大量肠道酶, 可使桔梗皂苷成分发生脱糖、脱水、羟基化、甲基化、氧化等代谢反应^{[9, 10]}。这些双糖链易于被肠道菌转化之特征, 无疑使低口服生物利用度的桔梗皂苷原形成分难以被直接吸收入血而被检出。

2 桔梗总皂苷入血产物鉴定

有研究显示, 桔梗皂苷成分的双糖链可经肠道菌转化发生脱糖反应^{[9, 10]}。这提示, 以桔梗皂苷成分逐级脱糖产物为分子模板, 可基于Ⅰ相与Ⅱ相代谢产物规律靶向鉴定其血中代谢产物。基于此, 采用UHPLC-LTQ-Orbitrap-MS技术, 进一步获取了SD大鼠灌胃桔梗总皂苷前、后血浆中成分的TIC图, 结果见图 2。应用Xcalibur 2.1、TraceFinder 4.1及Compound Discoverer 3.2软件, 结合桔梗总皂苷TIC色谱图成分保留时间和相关文献, 对桔梗总皂苷入血产物进行了鉴定。结果共鉴定出57个桔梗总皂苷入血产物, 各成分的保留时间、准分子离子峰和二级碎片及鉴定结果见图 2、表 2。表内产物名称中, A~H表示化合物结构类别, P表示原形成分, M表示代谢产物, 各产物依次编号。

由表 2可知, 57个入血成分中, 仅包含12个原形成分, 但包含45个肠道菌转化代谢产物, 且其代谢途径主要为甲基化、羟化反应、脱羟反应Ⅰ相代谢反应。这说明, 以肠道菌转化产物逐级脱糖产物为分子模板, 显著提高了桔梗总皂苷血中代谢产物的鉴定能力。

3 桔梗皂苷代谢产物之原形成分的逆向追踪

阐明代谢产物的原形成分来源, 可有效说明桔梗皂苷原形成分在血中的潜在形式, 并说明其与口服生物利用度与含量的潜在关系, 进而为揭示原形成分的起效机制提供重要依据。已有研究显示, 桔梗皂苷成分的双糖链可经肠道菌转化发生脱糖反应, 而基于代谢产物的相同母核可反向追溯其潜在原形^{[9, 15]}。本研究基于相同母核反向追溯了代谢产物的原形成分, 结果见图 3~6, 图中蓝色标记为成分结构分类特征基团, A~H代表不同的化合物类型, P表示原形桔梗皂苷, M表示代谢产物, 红色标记为原形桔梗皂苷, 绿色标记为代谢产物, 双色标记表示其同时为原形与代谢产物, 黑色标记表示它们为过渡态分子模板探针。

3.1 A型桔梗皂苷及其代谢产物的原形成分反向追踪结果

A型桔梗皂苷成分在C-4位连接2个羟甲基。如图 3所示, 5个A型代谢产物可反向追踪至全部18个A型原形成分。从代谢路径看, 其主要由18个原形成分在肠道菌作用下发生多步脱糖、甲基化、乙酰化、羟基化及脱氢等转化反应所致, 并形成AP2、AP5、AP11及AP14等主要转化路径。且由转化路径可知, AP7~10及AP17、AP18等6个血中成分既是原形成分, 也是代谢产物。另外, 进入血中的原形成分AP7~10虽然口服生物利用度很低, 但因含量相对较高而可直接入血; 另2个原形成分AP17、AP18虽然含量相对较低, 但口服生物利用度高, 也可在血中被检测到; 其他低含量低口服生物利用度的原形成分则难以在血中被检测到。此外, 由图 3还可发现, 无论成分口服生物利用度及含量高低如何, 均可在血中检测到其代谢产物。这说明, A型原形成分在血中的存在形式与肠道菌转化、口服生物利用度及其含量均具有密切相关性, 肠道菌介导方法可揭示不同口服生物利用度及含量全部A型原形成分在血中的存在形式及其来源, 进而为A型成分活性与作用机制的合理阐释提供充分依据。

3.2 B类型桔梗皂苷成分及其代谢产物的原形成分反向追踪结果

B型桔梗皂苷成分在C-4位连接1个甲基和1个羟甲基。如图 4所示, 12个B型代谢产物可反向追踪至全部10个B型原形成分。从代谢路径看, 其主要由10个原形成分在肠道菌作用下发生多步脱糖、甲基化、乙酰化、羟基化及脱氢等转化反应所致, 并形成BP1、BP4、BP6及BP9等主要转化路径。且由转化路径可知, 进入血中的BP2及BP3同样是含量相对较高的低口服生物利用度原形成分。而其他低含量原形成分, 则不管口服生物利用度如何, 均以代谢产物形式入血。这说明, 肠道菌介导方法同样可揭示不同口服生物利用度及含量全部B型原形成分在血中的存在形式及其来源, 进而为合理阐释B型原形成分活性与作用机制提供重要支撑。

3.3 C~E类型桔梗皂苷及其代谢产物的原形成分反向追踪结果

C~E型桔梗皂苷原形成分各自数目相对较少, 且口服生物利用度大多较低, 故放在一起讨论。

C型成分在C-4位连接1个羧基和1个羟甲基。如图 5A所示, 4个C型代谢产物可反向追踪至全部4个C型原形成分。从代谢路径看, 其主要由4个C型原形成分在肠道菌作用下发生脱酰、脱糖及羟基化等转化反应所致, 并形成CP2及CP32条主要转化路径。

D型桔梗皂苷成分在C-4位连接1个甲酸甲酯基和1个羟甲基。如图 5B所示, 6个D型代谢产物可反向追踪至全部2个D型原形成分。从代谢路径分析, 其主要由原形成分DP2脱糖产生另一原形成分DP1, 之后再经脱糖、脱羟、甲基化或乙酰化等肠道菌转化反应所致, 主要形成DP2转化路径。

E型桔梗皂苷成分C-4位连接1个羟甲基与1个羧基。如图 5C所示, 4个E型代谢产物可反向追踪至全部5个E型原形成分。由代谢路径分析, 其主要由5个原形成分经多步脱糖, 再经羟基化及甲基化等肠道菌转化反应所致, 并形成EP2转化路径。另外, 由转化路径可知, 原形成分EP3、EP4等高口服生物利用度原形成分, 因其含量较低, 同样难以在血中被检测到。

因此, C~E型皂苷成分的反向追踪结果同样说明, 肠道菌介导方法完全可阐明此3类全部原形成分在血中存在的形式及其来源, 且口服生物利用度及含量对这3类成分在血中的存在形式同样具有重要影响。

3.4 F~H类型桔梗皂苷及其代谢产物的原形成分反向追踪结果

F~H型桔梗皂苷原形成分总数相对较少, 但口服生物利用度大多较高, 故也放在一起讨论。

F型桔梗皂苷成分C-13羧基与C-17位羟基缩合成酯。如图 6A所示, 8个F型代谢产物可反向追踪至全部2个F型原形成分。从代谢路径看, 其主要由2个原形成分在肠道菌作用下发生脱糖、脱氢、脱羟、甲基化及乙酰化等转化反应所致。另一方面, 这2个原形成分尽管口服生物利用度相对较高, 但结合丰度分析显示其含量相对较低, 故仍难在血中被检测到。

G型桔梗皂苷成分C-4位连接双羟甲基且C-16位连接酮基。如图 6B所示, G型皂苷原形成分GP1除本身可直接入血外, 还可产生其他5个代谢产物。其主要由GP1经脱糖、乙酰化、甲基化及脱羧等肠道菌转化反应产生所致。另外, 从分子结构及丰度分析, GP1具有相对较低的口服生物利用度与较高的含量, 故其仍可直接入血而被检测到。

H型桔梗皂苷成分C-4位连接两个甲基, 且C-21位连接羟基或葡萄糖分子。由图 6C可知, 2个H型代谢产物可反向追踪至全部2个H型原形成分。从代谢路径看, 2个代谢产物由原形成分HP1经过脱糖转化为另一原形成分HP2, 之后再发生脱羟、脱羧等肠道菌作用所致。另外, 从分子结构及丰度分析, 虽然这两个H型原形成分具有较高的口服生物利用度, 但因含量相对较低, 在血中同样难以检测到其原形成分。

因此, F~H型皂苷成分的反向追踪结果再次说明, 肠道菌介导方法完全可阐明此3类全部原形成分在血中存在的形式及其来源, 且肠道菌介导、口服生物利用度及含量对这3类原形成分在血中的存在形式具有重要影响。

讨论

收起

桔梗皂苷成分口服生物利用度低, 难以被直接吸收入血, 且进入血中的原形成分往往难以与体内靶标结合, 提示血中代谢产物才可能是其显效形式^{[9, 15]}。但迄今为止, 桔梗总皂苷血中成分的鉴定仍主要集中在主要原形成分, 代谢产物的鉴定仅为2到3个^{[3, 10]}, 极大制约其药效物质及作用机制阐释。本文基于UHPLC-LTQ-Orbitrap-MS技术, 首先采用Xcalibur 2.1软件和TraceFinder 4.1软件对原形成分进行鉴定。然后基于肠道菌介导方法, 采用Compound Discoverer 3.2软件设定以桔梗总皂苷原形成分及其逐级脱糖产物为分子模板基于Ⅰ相及Ⅱ相代谢反应对入血产物进行靶向鉴定。结果除鉴定出12种原形成分外, 还鉴定出了45种代谢产物。这说明肠道菌介导方法极大地提高了桔梗皂苷血中产物的鉴定效率, 为桔梗药效物质阐释提供了重要物质基础。

另一方面, 原形成分与代谢产物之间一对多、多对一的网络关系是中药最具特色的作用机制。本研究先对桔梗总皂苷原形成分进行鉴定, 再以其肠道菌转化逐级脱糖基产物为分子模板, 鉴定血中代谢产物; 并进一步基于相同母核反向追踪了其潜在原形, 进而成功构建了8类44个桔梗皂苷原形成分与45个代谢产物之间的一对多、多对一网络关系。大量研究已经表明, 桔梗皂苷成分的双糖链可在肠道菌转化作用下逐步水解形成脱糖基产物; 且可进一步发生羟基化、加氧、脱氢、甲基化等肠道菌转化反应。因此, 桔梗皂苷成分长双糖链经脱糖再进一步转化形成其他原形成分再生成Ⅰ相及Ⅱ相代谢产物具有严密的逻辑性, 基于此逻辑构建原形成分与代谢产物之间的网络关系是合理的。显然, 这些网络为揭示低口服生物利用度桔梗皂苷原形成分通过其代谢产物产生的潜在药效叠加作用提供了重要依据。同时, 这也提示经过酸、碱、酶及肠道菌群等水解桔梗总皂苷成分后, 再使用微乳与自微乳、脂质体以及纳米粒等新型药物传递系统无疑可大大提高其成分的口服生物利用, 进而为基于桔梗总皂苷的新型高口服生物利用度新药的开发提供了新的思路。

此外, 这些血中产物同时也显示: 不仅低口服生物利用度原形成分可产生入血代谢产物, 高口服生物利用度原形成分如H类皂苷成分HP1、HP2以及A类成分AP18也可以产生入血代谢产物; 同时, 血中原形成分主要为高含量的低口服生物利用度成分, 且其同时还是其他桔梗皂苷原形成分的脱糖基代谢产物; 低含量的桔梗皂苷原形成分则不论口服生物利用度如何, 均可被肠道菌转化产生入血代谢产物。这说明, 桔梗皂苷原形成分在血中的存在形式不仅与桔梗总皂苷原形成分的口服生物利用度相关, 还与其含量密切相关。这一发现为认识中药药效物质提供了全新视角。

总之, 本文基于肠道菌介导的血清药物化学方法, 鉴定了桔梗总皂苷在血中的代谢产物, 揭示了桔梗皂苷原形成分血中存在形式与原形成分口服生物利用度及含量的潜在关系, 说明了原形成分与其代谢产物一对多、多对一的网络关系。其结果提示不同口服生物利用度及含量桔梗皂苷原形成分均有可能通过其血中代谢产物发挥潜在药效, 可为准确阐释桔梗总皂苷药效物质提供重要参考依据。

作者贡献: 吴茜娃和曾金祥构思并设计了实验, 吴茜娃、张欣雨、钟渊涵、张雪梅、冯艳进行论文整体实验和数据分析, 周瑜、秦倩、张寿文、钟国跃协助实验开展与数据分析, 吴茜娃、张欣雨与曾金祥撰写并修改了论文。

利益冲突: 所有作者均声明不存在利益冲突。

基金

收起

国家自然科学基金项目(82160736)
江西中医药大学科技创新团队项目(CXTD22002)

参考文献

收起

文献

收起

参考文献引证文献

排序方式：

[1]

Zhang S, Chai X, Hou G, et al. Platycodon grandiflorum (Jacq.) A. DC. : a review of phytochemistry, pharmacology, toxicology and traditional use [J]. Phytomedicine, 2022, 106: 154422.

[2]

Huang W, Zhou H, Yuan M, et al. Comprehensive characterization of the chemical constituents in Platycodon grandiflorum by an integrated liquid chromatography-mass spectrometry strategy [J]. J Chromatogr A, 2021, 1654: 462477.

[3]

Yau LF, Huang H, Tong TT, et al. Characterization of deglycosylated metabolites of platycosides reveals their biotransformation after oral administration [J]. Food Chem, 2022, 393: 133383.

[4]

Lee SK, ParK KK, Kim HJ, et al. Platycodin D blocks breast cancer-induced bone destruction by inhibiting osteoclastogenesis and the growth of breast cancer cells [J]. Cell Physiol Biochem, 2015, 36: 1809-1820.

[5]

Wang C, Schuller Levis GB, Lee EB, et al. Platycodin D and D3 isolated from the root of Platycodon grandiflorum modulate the production of nitric oxide and secretion of TNF-alpha in activated RAW 264.7 cells [J]. Int Immunopharmacol, 2004, 4: 1039-1049.

[6]

Choi JH, Jin SW, Kim HG, et al. Saponins, especially platyconic acid A, from Platycodon grandiflorum reduce airway inflammation in ovalbumin-induced mice and PMA-exposed A549 cells [J]. J Agric Food Chem, 2015, 63: 1468-1476.

[7]

Lee DY, Choi BR, Lee JW, et al. Simultaneous determination of various platycosides in four Platycodon grandiflorum cultivars by UPLC-QTOF/MS [J]. Appl Biol Chem, 2019, 62: 47.

[8]

Ryu J, Lee HJ, Park SH, et al. Effects of the root of Platycodon grandiflorum on airway mucin hypersecretion in vivo and platycodin D (3) and deapi-platycodin on production and secretion of airway mucin in vitro [J]. Phytomedicine, 2014, 21: 529-533.

[9]

Zhang C, Wang X, Zhong Y, et al. Active microbial metabolites study on antitussive and expectorant effects and metabolic mechanisms of platycosides fraction of Platycodonis Radix [J]. J Chromatogr B Analyt Technol Biomed Life Sci, 2022, 1195: 123171.

[10]

Zhang X, Jiang Z, Zhang L, et al. Identification of prototype compounds and their metabolites in rats serum from Xuefu Zhuyu Decoction by UPLC-Q-TOF/MS [J]. Chin Herb Med, 2022, 15: 139-150.

[11]

Gong X, Li X, Bo A, et al. The interactions between gut microbiota and bioactive ingredients of traditional Chinese medicines: a review [J]. Pharmacol Res, 2020, 157: 104824.

[12]

Ju JH, Lee TE, Lee J, et al. Improved bioactivity of 3-O-β-D-glucopyranosyl platycosides in biotransformed Platycodon grandiflorum root extract by pectinase from Aspergillus aculeatus [J]. J Microbiol Biotechnol, 2021, 31: 847-854.

[13]

Zhong YH, Liang J, Qin Q, et al. The activities and mechanisms of intestinal microbiota metabolites of TCM herbal ingredients could be illustrated by a strategy integrating spectrum effects, network pharmacology, metabolomics and molecular docking analysis: platycodin D as an example [J]. Phytomedicine, 2023, 115: 154831.

[14]

Ha YW, Na YC, Ha IJ, et al. Liquid chromatography/mass spectrometry-based structural analysis of new platycoside metabolites transformed by human intestinal bacteria [J]. J Pharm Biomed Anal, 2010, 51: 202-209.

[15]

Fu WW, Fu JN, Zhang WM, et al. Platycoside O, a new triterpenoid saponin from the roots of Platycodon grandiflorum [J]. Molecules, 2011, 16: 4371-4378.

[16]

Na YC, Ha YW, Kim YS, et al. Structural analysis of platycosides in Platycodi Radix by liquid chromatography/electrospray ionization-tandem mass spectrometry [J]. J Chromatogr A, 2008, 1189: 467-475.

[17]

Ma XQ, Li SM, Chan CL, et al. Influence of sulfur fumigation on glycoside profile in Platycodonis Radix (Jiegeng) [J]. Chin Med, 2016, 11: 32.

[18]

Deng Y, Ye X, Chen Y, et al. Chemical characteristics of Platycodon grandiflorum and its mechanism in lung cancer treatment [J]. Front Pharmacol, 2021, 11: 609825.

[19]

Hiroshi I, Kazou T. Saponins from roots of Platycodon grandiflorum. Part 1. Structure of prosapogenin [J]. J Chem Soc, 1981, 12: 295

[20]

Nikaido T, Koike K, Mitsunaga K, et al. Two new triterpenoid saponins from Platycodon grandiflorum [J]. Chem Pharm Bull (Tokyo), 1999, 47: 903-904.

[21]

Yu J, Chang X, Peng H, et al. A strategy based on isocratic and linear gradient high speed counter current chromatography for the comprehensive separation of platycosides from Platycodi Radix [J]. Anal Methods, 2021, 13: 477-483.

[22]

Fu W, Hou W, Dou D, et al. Saponins of polygalacic acid type from Platycodon gradiflorm [J]. Acta Pharm Sin (药学学报), 2006, 41: 358-360.

[23]

Motonori F, Daigo I, Yasuaki H, et al. Eight new oleanane-type triterpenoid saponins from platycodon root [J]. Heterocycles, 2010, 81: 2793-2806.

[24]

Fu WW, Shimizu N, Takeda T, et al. New A-ring lactone triterpenoid saponins from the roots of Platycodon grandiflorum [J]. Chem Pharm Bull (Tokyo), 2006, 54: 1285-1287.

[25]

Zhang L, Liu ZH, Tian JK. Cytotoxic triterpenoid saponins from the roots of Platycodon grandiflorum [J]. Molecules, 2007, 12: 832-841.

2024年第59卷第11期

PDF下载

195

引用本文

BibTeX

文章信息

doi: 10.16438/j.0513-4870.2024-0377

接收时间：2024-04-18
首发时间：2025-11-24
出版时间：2024-11-12

补充材料

相关文章

文章信息

作者

出版历史

收稿日期：2024-04-18
修回日期：2024-08-15

基金

国家自然科学基金项目(82160736)

江西中医药大学科技创新团队项目(CXTD22002)

作者信息

1.江西中医药大学中药资源与民族药研究中心, 江西南昌 330004

2.九江学院生命科学学院, 江西九江 332005

通讯作者:

^*曾金祥, E-mail: zjx@jxutcm.edu.cn

参考文献

分享链接

https://castjournals.cast.org.cn/joweb/yxxb/CN/10.16438/j.0513-4870.2024-0377

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.	Identification	Name	t_R /min	Formula	m/z	Error (ppm)	Fragment ion	Ref.
1	Deapio-platycoside E	AP1	15.62	C₆₄H₁₀₄O₃₄	1 415.630 9	-1.13	1 005.486 3; 843.424 2	[14]
2	Platycoside E	AP2	17.40	C₆₉H₁₁₂O₃₈	1 547.673 8	-0.65	1 005.449 5; 519.320 6	[3]
3	Platycodin D3	AP3	23.85	C₆₃H₁₀₂O₃₃	1 385.619 3	-1.95	843.407 1; 1 253.549 5	[2]
4	3″-O-Acetyl platycodin D3	AP4	24.87	C₆₅H₁₀₄O₃₄	1 427.629 3	-2.24	1 385.582 4; 843.413 1	[15]
5	Platycoside G2	AP5	27.28	C₅₉H₉₆O₃₀	1 283.589 6	-0.55	843.362 9; 519.270 3	[16]
6	Deapio-platycodin D2	AP6	30.14	C₅₈H₉₄O₂₉	1 253.577 3	-1.92	843.408 5; 681.381 6	[6]
7	Deapio-platycodin D	AP7	30.41	C₅₂H₈₄O₂₄	1 091.525 1	-1.65	681.360 3; 519.342 9	[17]
8	Platycodin D2	AP8	31.90	C₆₃H₁₀₂O₃₃	1 385.621 5	-0.37	843.407 1; 1 253.549 5	[18]
9	Platycodin D	AP9	32.23	C₅₇H₉₂O₂₈	1 223.565 8	-2.70	681.343 5; 1 091.511 0	[2]
10	Platycoside F	AP10	34.44	C₄₇H₇₆O₂₀	959.484 5	-0.10	681.374 2; 797.431 4	[2]
11	Platycodins K	AP11	35.42	C₅₉H₉₂O₃₀	1 279.558 2	-0.63	827.463 3; 1 147.544 7	[2]
12	Platycoside B	AP12	35.83	C₅₄H₈₆O₂₅	1 133.535 3	-1.85	681.393 5; 1 091.543 8	[18]
13	3-O-β-D-Gentiobiosyl platycodigenin methylester	AP13	36.75	C₄₃H₇₀O₁₇	857.456 0	3.62	797.613 4; 858.662 5	[19]
14	2″-O-Acetyl-platycodin D2	AP14	38.08	C₆₅H₁₀₄O₃₄	1 427.630 4	-1.47	1 385.623 3; 843.482 7	[16]
15	Platycoside L	AP15	52.52	C₄₂H₆₈O₁₇	843.435 4	-2.25	519.291 1; 681.346 9	[7]
16	Platycoside K	AP16	52.83	C₄₂H₆₈O₁₇	843.436 8	-0.59	519.291 3; 681.346 9	[7]
17	3-O-β-D-Glucopyranosyl platycodigenin	AP17	54.96	C₃₆H₅₈O₁₂	681.383 8	-1.03	519.295 4	[3]
18	Platycodigenin	AP18	57.93	C₃₀H₄₈O₇	519.332 1	0.96	501.136 8	[3]
19	Platycoside D	BP1	25.25	C₆₉H₁₁₂O₃₇	1 531.678 2	-1.11	827.428 4; 665.452 7	[20]
20	Polygalacin D2	BP2	32.88	C₆₃H₁₀₂O₃₂	1 369.626 2	-0.66	827.411 1; 665.394 5	[16]
21	Polygalacin D	BP3	33.74	C₅₇H₉₂O₂₇	1 207.573 6	-0.50	1 075.503 1; 665.361 5	[19]
22	3″-O-Acetyl polygalacin D	BP4	35.14	C₅₉H₉₄O₂₈	1 249.590 2	4.32	1 207.558 4; 665.376 7	[18]
23	Platycoside J	BP5	38.80	C₅₂H₈₄O₂₃	1 075.530 8	-1.12	665.363 0; 503.333 4	[18]
24	2″-O-Acetyl polygalacin D2	BP6	40.03	C₆₅H₁₀₄O₃₃	1 411.634 8	-1.98	1 369.654 7; 827.436 5	[21]
25	3-O-β-D-Laminaribiosyl polygalacic acid	BP7	55.97	C₄₂H₆₈O₁₆	827.442 0	-0.48	503.317 4; 665.378 4	[22]
26	3-O-β-D-Glucopyranosyl polygalacic acid	BP8	56.85	C₃₆H₅₈O₁₁	665.388 2	-1.95	647.233 6; 503.334 3	[14]
27	Methyl-3-O-β-D-glucopyranosyl polygalaeate	BP9	62.71	C₃₇H₆₀O₁₁	679.400 0	-7.66	633.371 3; 661.229 7	[19]
28	Polygalacic acid	BP10	64.50	C₃₀H₄₈O₆	503.337 2	-0.99	485.111 5; 503.195 3	[22]
29	Platyconic acid A	CP1	30.01	C₅₇H₉₀O₂₉	1 237.546 3	-1.70	827.433 9	[7]
30	Platyconic acid E	CP2	37.52	C₅₈H₉₂O₃₀	1 267.556 9	-1.66	1 117.583 2	[23]
31	2''-O-Acetyl platyconic acid A	CP3	43.07	C₅₉H₉₂O₃₀	1 279.555 1	-3.05	1 147.577 4; 827.463 3	[2]
32	Platyconic acid C	CP4	43.11	C₅₂H₈₂O₂₅	1 105.504 9	-1.09	943.521 9; 695.415 4	[23]
33	Platycoside O	DP1	36.61	C₅₃H₈₄O₂₅	1 119.520 6	-1.07	635.333 6; 1 119.178 6	[15]
34	Platyconic acid A methylester	DP2	39.80	C₅₈H₉₂O₂₉	1 251.560 4	-2.96	635.330 8; 1 089.517 9	[7]
35	Deapio-platyconic acid A lactone	EP1	33.29	C₅₂H₈₀O₂₄	1 087.494 9	-0.64	1 069.565 3	[7]
36	Platyconic acid A lactone	EP2	34.72	C₅₇H₈₈O₂₈	1 219.533 9	-3.20	677.324 7; 1 087.651 6	[7]
37	Platycoside M-2	EP3	50.80	C₄₇H₇₂O₂₀	955.459 3	6.28	937.188 6; 793.335 6	[24]
38	Platycoside M-1	EP4	53.36	C₃₆H₅₄O₁₂	677.353 0	-0.30	659.374 8	[18]
39	Platycogenic acid A lactone	EP5	53.73	C₃₀H₄₄O₇	515.301 3	1.94	495.030 2	[7]
40	3-O-β-D-Glucopyranosyl-(1→3)-β-D- glucopyranosyl-2β, 12α, 16α, 23α- tetrahydroxyoleanane-28(13)-lactone	FP1	51.19	C₄₃H₇₀O₁₆	841.459 0	1.19	679.347 6; 517.300 9	[25]
41	3-O-β-D-Glucopyranosyl-2β, 12α, 16α, 23, 24- pentahydroxyoleanane-28(13)-lactone	FP2	56.90	C₃₇H₆₀O₁₂	695.397 3	-4.03	533.301 0; 676.848 4	[25]
42	16-oxo-Platycodin D	GP1	37.46	C₅₇H₉₀O₂₈	1 221.551 1	-1.97	1 089.470 0; 679.342 2	[7]
43	Platycogenin A	HP1	53.90	C₄₂H₆₈O₁₆	827.441 7	-0.85	503.317 4; 665.378 4	[17]
44	Platycogenic acid C	HP2	59.78	C₃₀H₄₈O₆	503.335 6	-2.19	485.179 4	[7]

No.

Identification

Name

t_R /min

Formula

m/z

Error (ppm)

Fragment ion

Ref.

Deapio-platycoside E

AP1

15.62

C₆₄H₁₀₄O₃₄

1 415.630 9

-1.13

1 005.486 3; 843.424 2

[14]

Platycoside E

AP2

17.40

C₆₉H₁₁₂O₃₈

1 547.673 8

-0.65

1 005.449 5; 519.320 6

[3]

Platycodin D3

AP3

23.85

C₆₃H₁₀₂O₃₃

1 385.619 3

-1.95

843.407 1; 1 253.549 5

[2]

3″-O-Acetyl platycodin D3

AP4

24.87

C₆₅H₁₀₄O₃₄

1 427.629 3

-2.24

1 385.582 4; 843.413 1

[15]

Platycoside G2

AP5

27.28

C₅₉H₉₆O₃₀

1 283.589 6

-0.55

843.362 9; 519.270 3

[16]

Deapio-platycodin D2

AP6

30.14

C₅₈H₉₄O₂₉

1 253.577 3

-1.92

843.408 5; 681.381 6

[6]

Deapio-platycodin D

AP7

30.41

C₅₂H₈₄O₂₄

1 091.525 1

-1.65

681.360 3; 519.342 9

[17]

Platycodin D2

AP8

31.90

C₆₃H₁₀₂O₃₃

1 385.621 5

-0.37

843.407 1; 1 253.549 5

[18]

Platycodin D

AP9

32.23

C₅₇H₉₂O₂₈

1 223.565 8

-2.70

681.343 5; 1 091.511 0

[2]

Platycoside F

AP10

34.44

C₄₇H₇₆O₂₀

959.484 5

-0.10

681.374 2; 797.431 4

[2]

Platycodins K

AP11

35.42

C₅₉H₉₂O₃₀

1 279.558 2

-0.63

827.463 3; 1 147.544 7

[2]

Platycoside B

AP12

35.83

C₅₄H₈₆O₂₅

1 133.535 3

-1.85

681.393 5; 1 091.543 8

[18]

3-O-β-D-Gentiobiosyl platycodigenin methylester

AP13

36.75

C₄₃H₇₀O₁₇

857.456 0

3.62

797.613 4; 858.662 5

[19]

2″-O-Acetyl-platycodin D2

AP14

38.08

C₆₅H₁₀₄O₃₄

1 427.630 4

-1.47

1 385.623 3; 843.482 7

[16]

Platycoside L

AP15

52.52

C₄₂H₆₈O₁₇

843.435 4

-2.25

519.291 1; 681.346 9

[7]

Platycoside K

AP16

52.83

C₄₂H₆₈O₁₇

843.436 8

-0.59

519.291 3; 681.346 9

[7]

3-O-β-D-Glucopyranosyl platycodigenin

AP17

54.96

C₃₆H₅₈O₁₂

681.383 8

-1.03

519.295 4

[3]

Platycodigenin

AP18

57.93

C₃₀H₄₈O₇

519.332 1

0.96

501.136 8

[3]

Platycoside D

BP1

25.25

C₆₉H₁₁₂O₃₇

1 531.678 2

-1.11

827.428 4; 665.452 7

[20]

Polygalacin D2

BP2

32.88

C₆₃H₁₀₂O₃₂

1 369.626 2

-0.66

827.411 1; 665.394 5

[16]

Polygalacin D

BP3

33.74

C₅₇H₉₂O₂₇

1 207.573 6

-0.50

1 075.503 1; 665.361 5

[19]

3″-O-Acetyl polygalacin D

BP4

35.14

C₅₉H₉₄O₂₈

1 249.590 2

4.32

1 207.558 4; 665.376 7

[18]

Platycoside J

BP5

38.80

C₅₂H₈₄O₂₃

1 075.530 8

-1.12

665.363 0; 503.333 4

[18]

2″-O-Acetyl polygalacin D2

BP6

40.03

C₆₅H₁₀₄O₃₃

1 411.634 8

-1.98

1 369.654 7; 827.436 5

[21]

3-O-β-D-Laminaribiosyl polygalacic acid

BP7

55.97

C₄₂H₆₈O₁₆

827.442 0

-0.48

503.317 4; 665.378 4

[22]

3-O-β-D-Glucopyranosyl polygalacic acid

BP8

56.85

C₃₆H₅₈O₁₁

665.388 2

-1.95

647.233 6; 503.334 3

[14]

Methyl-3-O-β-D-glucopyranosyl polygalaeate

BP9

62.71

C₃₇H₆₀O₁₁

679.400 0

-7.66

633.371 3; 661.229 7

[19]

Polygalacic acid

BP10

64.50

C₃₀H₄₈O₆

503.337 2

-0.99

485.111 5; 503.195 3

[22]

Platyconic acid A

CP1

30.01

C₅₇H₉₀O₂₉

1 237.546 3

-1.70

827.433 9

[7]

Platyconic acid E

CP2

37.52

C₅₈H₉₂O₃₀

1 267.556 9

-1.66

1 117.583 2

[23]

2''-O-Acetyl platyconic acid A

CP3

43.07

C₅₉H₉₂O₃₀

1 279.555 1

-3.05

1 147.577 4; 827.463 3

[2]

Platyconic acid C

CP4

43.11

C₅₂H₈₂O₂₅

1 105.504 9

-1.09

943.521 9; 695.415 4

[23]

Platycoside O

DP1

36.61

C₅₃H₈₄O₂₅

1 119.520 6

-1.07

635.333 6; 1 119.178 6

[15]

Platyconic acid A methylester

DP2

39.80

C₅₈H₉₂O₂₉

1 251.560 4

-2.96

635.330 8; 1 089.517 9

[7]

Deapio-platyconic acid A lactone

EP1

33.29

C₅₂H₈₀O₂₄

1 087.494 9

-0.64

1 069.565 3

[7]

Platyconic acid A lactone

EP2

34.72

C₅₇H₈₈O₂₈

1 219.533 9

-3.20

677.324 7; 1 087.651 6

[7]

Platycoside M-2

EP3

50.80

C₄₇H₇₂O₂₀

955.459 3

6.28

937.188 6; 793.335 6

[24]

Platycoside M-1

EP4

53.36

C₃₆H₅₄O₁₂

677.353 0

-0.30

659.374 8

[18]

Platycogenic acid A lactone

EP5

53.73

C₃₀H₄₄O₇

515.301 3

1.94

495.030 2

[7]

3-O-β-D-Glucopyranosyl-(1→3)-β-D-
glucopyranosyl-2β, 12α, 16α, 23α-
tetrahydroxyoleanane-28(13)-lactone

FP1

51.19

C₄₃H₇₀O₁₆

841.459 0

1.19

679.347 6; 517.300 9

[25]

3-O-β-D-Glucopyranosyl-2β, 12α, 16α, 23, 24-
pentahydroxyoleanane-28(13)-lactone

FP2

56.90

C₃₇H₆₀O₁₂

695.397 3

-4.03

533.301 0; 676.848 4

[25]

16-oxo-Platycodin D

GP1

37.46

C₅₇H₉₀O₂₈

1 221.551 1

-1.97

1 089.470 0; 679.342 2

[7]

Platycogenin A

HP1

53.90

C₄₂H₆₈O₁₆

827.441 7

-0.85

503.317 4; 665.378 4

[17]

Platycogenic acid C

HP2

59.78

C₃₀H₄₈O₆

503.335 6

-2.19

485.179 4

[7]

No.	Identification	Name	Formula	t_R/min	m/z	Error (ppm)	Peak intensity	Fragment ion
1	Deapio-platycodin D2	AP6-M1	C₅₈H₉₄O₂₉	30.20	1 253.586 2	5.19	857	843.473 5; 1 091.610 4
2	Deapio-platycodin D	AP7-M2	C₅₂H₈₄O₂₄	30.40	1 091.526 0	-0.82	2 608	681.323 9; 1 091.467 5
3	Platycodin D2	AP8-M3	C₆₃H₁₀₂O₃₃	31.96	1 385.619 1	-2.09	2 519	843.450 8; 1 223.914 9
4	Platycodin D	AP9-M4	C₅₇H₉₂O₂₈	32.16	1 223.565 9	-2.62	13 791	681.411 1; 1 091.693 1
5	Hydroxylated platycoside metabolite	AM5	C₅₇H₉₂O₂₉	32.62	1 239.581 9	14.37	402	-
6	PD-api-xyl-rha dehydrogenated metabolite	AM6	C₄₁H₆₄O₁₆	52.44	811.425 3	17.51	16 640	-
7	PD-glc-api-xyl hydroxylated metabolite	AM7	C₄₁H₆₆O₁₆	54.83	813.418 8	-9.12	29 671	-
8	3-O-β-D-Glucopyranosyl platycodigenin	AP17-M8	C₃₆H₅₈O₁₂	54.98	681.382 8	-2.50	921	-
9	PD-api-xyl-rha methylated metabolite	AM9	C₄₂H₆₈O₁₆	56.26	827.436 5	-7.13	26 141	-
10	Platycodigenin	AP18-M10	C₃₀H₄₈O₇	57.88	519.333 5	3.66	6 506	-
11	Platycodigenin dehydrogenated metabolite	AM11	C₃₀H₄₆O₇	58.45	517.316 0	0	18 016	496.991 3; 449.078 3
12	Polygalacin D2	BP2-M1	C₆₃H₁₀₂O₃₂	32.96	1 369.626 2	-0.66	2 235	827.350 7; 503.441 0
13	Polygalacin D	BP3-M2	C₅₇H₉₂O₂₇	33.75	1 207.578 6	3.65	1 851	665.373 2; 1 207.292 0
14	Polygalacin D-glc-api-xyl dehydroxylated metabolite	BM3	C₄₁H₆₆O₁₃	58.02	765.453 1	14.51	32 883
15	Polygalacin D-glc-api-xyl-rha	BM4	C₃₅H₅₆O₁₀	61.31	635.375 9	-4.88	39 541	403.283 1; 571.327 5
16	Polygalacin D-api-xyl-rha dehydroxylated metabolite	BM5	C₄₁H₆₆O₁₄	61.48	781.422 7	-18.18	45 908	-
17	Polygalacin D-glc-api-xyl-rha-ara dehydrogenated metabolite	BM6	C₃₀H₄₆O₆	64.93	501.321 0	-0.20	11 100	-
18	Polygalacin D-glc-api-xyl-rha methylated metabolite	BM7	C₃₆H₅₈O₁₀	64.96	649.388 8	-8.94	27 070	-
19	Polygalacin D-api-xyl-rha acetylated metabolite	BM8	C₄₃H₆₈O₁₆	64.98	839.444 5	2.50	14 119	-
20	Polygalacin D-glc-api-xyl-rha glucuronicated metabolite	BM9	C₄₁H₆₄O₁₆	65.13	811.410 8	-0.37	13 749	-
21	Polygalacin D-glc-api-xyl-rha-ara decarboxylated metabolite	BM10	C₂₉H₄₈O₄	65.22	459.347 3	1.53	28 030	-
22	Polygalacin D-glc-api-xyl-rha-ara acetylated metabolite	BM11	C₃₂H₅₀O₇	65.67	545.346 4	-1.65	237 331	527.273 4; 501.260 1
23	Polygalacin D-glc-api-xyl-rha-ara methylated metabolite	BM12	C₃₁H₅₀O₆	65.73	517.350 5	-3.68	55 733	-
24	Polygalacin D-glc-api-xyl-rha-ara hydroxylated metabolite	BM13	C₃₀H₄₈O₇	66.22	519.331 8	0.39	12 470	-
25	Polygalacin D-glc-api-xyl-rha dehydrogenated metabolite	BM14	C₃₅H₅₄O₁₀	66.94	633.360 9	-3.79	23 734	-
26	Platyconic acid E	CP2-M1	C₅₈H₉₂O₃₀	37.53	1 267.555 8	-2.53	1 897	859.463 3; 841.466 0
27	Platyconic acid A-api-xyl-rha-ara	CM2	C₃₆H₅₆O₁₃	58.17	695.350 8	-18.56	136 178	635.296 5; 480.274 2
28	Platyconic acid A-glc-api-xyl-rha	CM3	C₃₅H₅₄O₁₂	58.63	665.351 5	-2.56	39 887	-
29	Platyconic acid A-api-xyl-rha-ara hydroxylation metabolite	CM4	C₃₆H₅₆O₁₄	58.82	711.352 6	-8.44	122 922	-
30	Platyconic acid A-glc-api-xyl-rha dehydroxylated metabolite	CM5	C₃₅H₅₄O₁₁	61.80	649.351 6	-10.17	10 843	-
31	Platycoside O	DP1-M1	C₅₃H₈₄O₂₅	36.62	1 119.521 0	-0.71	2 468	1 085.304 8; 1 119.383 9
32	Platycoside O-glc-xyl	DM2	C₄₂H₆₆O₁₆	54.87	825.427 7	-0.12	27 787	-
33	Platycoside O-glc-xyl dehydroxylated metabolite	DM3	C₄₂H₆₆O₁₅	55.59	809.435 4	3.09	27 042	-
34	Platycoside O-xyl-rha-ara methylated	DM4	C₃₈H₆₀O₁₃	58.88	723.390 9	-7.19	27 696	-
35	Platycoside O-xyl-rha acetylated metabolite	DM5	C₄₄H₆₈O₁₈	68.85	883.439 6	7.13	5 578	865.475 2; 465.221 0
36	Platycoside O-xyl-rha-ara dehydroxylated metabolite	DM6	C₃₇H₅₈O₁₂	68.91	693.397 5	17.17	29 302	-
37	Platycogenic acid A lactone	EP5-M1	C₃₀H₄₄O₇	53.84	515.304 3	7.77	190 527	279.236 5; 495.045 8
38	Platycoside M1-glc dehydroxylated metabolite	EM2	C₃₀H₄₄O₆	59.12	499.303 3	-4.21	21 565	-
39	Platycoside M1-glc hydroxylated metabolite	EM3	C₃₀H₄₄O₈	59.69	531.303 8	16.20	116 812	-
40	Platycoside M1-glc methylated metabolite	EM4	C₃₁H₄₆O₇	60.91	529.312 2	-7.18	27 747	-
41	Platycoside M1-glc dehydroxylated metabolite and D-methylated	EM5	C₃₀H₄₄O₆	68.94	499.308 8	7.30	73 393	-
42	3-O-β-D-Glucopyranosyl-(1→3)-β-D-glucopyranosyl-2β, 12α, 16α, 23α-tetrahydroxyoleanane-28(13)-lactone(F1) dehydroxylated metabolite	FM1	C₄₃H₇₀O₁₅	56.92	825.459 4	-8.12	31 450	-
43	3-O-β-D-Glucopyranosyl-2β, 12α, 16α, 23, 24-pentahydroxyoleanane-28(13)-lactone(F2)-glcdehydrogenated metabolite	FM2	C₃₁H₄₈O₇	60.09	531.328 8	-5.27	61 396	-
44	F1 methylated metabolite	FM3	C₄₄H₇₂O₁₆	60.77	855.476 1	2.81	36 600	-
45	F1-glc methylated metabolite	FM4	C₃₈H₆₂O₁₁	61.70	693.415 0	-8.37	49 989	633.346 9; 508.321 8
46	F2-glc methylated metabolite	FM5	C₃₂H₅₂O₇	64.15	547.363 0	0.18	49 200	-
47	F1-2glc dehydroxylated metabolite	FM6	C₃₁H₅₀O₅	67.04	501.358 2	1.40	17 722	-
48	F1-2glc acetylated metabolite	FM7	C₃₃H₅₂O₇	67.43	559.363 5	1.07	48 216	559.280 2; 541.382 6
49	F1-2glc methylated metabolite	FM8	C₃₂H₅₂O₆	68.81	531.363 3	-8.85	13 228
50	16-oxo-Platycodin D	GP1-M1	C₅₇H₉₀O₂₈	37.46	1 221.551 3	-1.80	4 237	469.098 4; 635.470 4
51	16-oxo-Platycodin D-glc-api-xyl methylated metabolite	GM2	C₄₂H₆₆O₁₅	53.07	809.434 6	3.46	9 101	-
52	16-oxo-Platycodin D-api-xyl-rha methylated metabolite	GM3	C₄₂H₆₆O₁₆	53.83	825.418 3	-10.18	10 027	-
53	16-oxo-Platycodin D-glc-api-xyl methylated and deglycosylated metabolite	GM4	C₄₂H₆₆O₁₅	55.04	809.426 0	-7.17	16 453	-
54	16-oxo-Platycodin D-glc-api-xyl-rha-ara decarboxylated metabolite	GM5	C₂₉H₄₆O₅	60.21	473.326 4	0.42	55 603	-
55	16-oxo-Platycodin D-glc-api-xyl-rha-ara acetylated metabolite	GM6	C₃₂H₄₈O₈	64.70	559.325 7	-1.43	48 881	-
56	Platycogenin A-2glc dehydroxylated metabolite	HM1	C₃₀H₄₈O₅	64.54	487.342 1	0.62	11 627	-
57	Platycogenin A-2glc decarboxylated metabolite	HM2	C₂₉H₄₈O₄	65.70	459.347 0	0.22	14 265	-

No.

Identification

Name

Formula

t_R/min

m/z

Error (ppm)

Peak intensity

Fragment ion

Deapio-platycodin D2

AP6-M1

C₅₈H₉₄O₂₉

30.20

1 253.586 2

5.19

857

843.473 5;
1 091.610 4

Deapio-platycodin D

AP7-M2

C₅₂H₈₄O₂₄

30.40

1 091.526 0

-0.82

2 608

681.323 9;
1 091.467 5

Platycodin D2

AP8-M3

C₆₃H₁₀₂O₃₃

31.96

1 385.619 1

-2.09

2 519

843.450 8;
1 223.914 9

Platycodin D

AP9-M4

C₅₇H₉₂O₂₈

32.16

1 223.565 9

-2.62

13 791

681.411 1;
1 091.693 1

Hydroxylated platycoside metabolite

AM5

C₅₇H₉₂O₂₉

32.62

1 239.581 9

14.37

402

PD-api-xyl-rha dehydrogenated metabolite

AM6

C₄₁H₆₄O₁₆

52.44

811.425 3

17.51

16 640

PD-glc-api-xyl hydroxylated metabolite

AM7

C₄₁H₆₆O₁₆

54.83

813.418 8

-9.12

29 671

3-O-β-D-Glucopyranosyl platycodigenin

AP17-M8

C₃₆H₅₈O₁₂

54.98

681.382 8

-2.50

921

PD-api-xyl-rha methylated metabolite

AM9

C₄₂H₆₈O₁₆

56.26

827.436 5

-7.13

26 141

Platycodigenin

AP18-M10

C₃₀H₄₈O₇

57.88

519.333 5

3.66

6 506

Platycodigenin dehydrogenated metabolite

AM11

C₃₀H₄₆O₇

58.45

517.316 0

18 016

496.991 3;
449.078 3

Polygalacin D2

BP2-M1

C₆₃H₁₀₂O₃₂

32.96

1 369.626 2

-0.66

2 235

827.350 7;
503.441 0

Polygalacin D

BP3-M2

C₅₇H₉₂O₂₇

33.75

1 207.578 6

3.65

1 851

665.373 2;
1 207.292 0

Polygalacin D-glc-api-xyl dehydroxylated metabolite

BM3

C₄₁H₆₆O₁₃

58.02

765.453 1

14.51

32 883

Polygalacin D-glc-api-xyl-rha

BM4

C₃₅H₅₆O₁₀

61.31

635.375 9

-4.88

39 541

403.283 1;
571.327 5

Polygalacin D-api-xyl-rha dehydroxylated metabolite

BM5

C₄₁H₆₆O₁₄

61.48

781.422 7

-18.18

45 908

Polygalacin D-glc-api-xyl-rha-ara dehydrogenated metabolite

BM6

C₃₀H₄₆O₆

64.93

501.321 0

-0.20

11 100

Polygalacin D-glc-api-xyl-rha methylated metabolite

BM7

C₃₆H₅₈O₁₀

64.96

649.388 8

-8.94

27 070

Polygalacin D-api-xyl-rha acetylated metabolite

BM8

C₄₃H₆₈O₁₆

64.98

839.444 5

2.50

14 119

Polygalacin D-glc-api-xyl-rha glucuronicated metabolite

BM9

C₄₁H₆₄O₁₆

65.13

811.410 8

-0.37

13 749

Polygalacin D-glc-api-xyl-rha-ara decarboxylated metabolite

BM10

C₂₉H₄₈O₄

65.22

459.347 3

1.53

28 030

Polygalacin D-glc-api-xyl-rha-ara acetylated metabolite

BM11

C₃₂H₅₀O₇

65.67

545.346 4

-1.65

237 331

527.273 4;
501.260 1

Polygalacin D-glc-api-xyl-rha-ara methylated metabolite

BM12

C₃₁H₅₀O₆

65.73

517.350 5

-3.68

55 733

Polygalacin D-glc-api-xyl-rha-ara hydroxylated metabolite

BM13

C₃₀H₄₈O₇

66.22

519.331 8

0.39

12 470

Polygalacin D-glc-api-xyl-rha dehydrogenated metabolite

BM14

C₃₅H₅₄O₁₀

66.94

633.360 9

-3.79

23 734

Platyconic acid E

CP2-M1

C₅₈H₉₂O₃₀

37.53

1 267.555 8

-2.53

1 897

859.463 3;
841.466 0

Platyconic acid A-api-xyl-rha-ara

CM2

C₃₆H₅₆O₁₃

58.17

695.350 8

-18.56

136 178

635.296 5;
480.274 2

Platyconic acid A-glc-api-xyl-rha

CM3

C₃₅H₅₄O₁₂

58.63

665.351 5

-2.56

39 887

Platyconic acid A-api-xyl-rha-ara hydroxylation metabolite

CM4

C₃₆H₅₆O₁₄

58.82

711.352 6

-8.44

122 922

Platyconic acid A-glc-api-xyl-rha dehydroxylated metabolite

CM5

C₃₅H₅₄O₁₁

61.80

649.351 6

-10.17

10 843

Platycoside O

DP1-M1

C₅₃H₈₄O₂₅

36.62

1 119.521 0

-0.71

2 468

1 085.304 8;
1 119.383 9

Platycoside O-glc-xyl

DM2

C₄₂H₆₆O₁₆

54.87

825.427 7

-0.12

27 787

Platycoside O-glc-xyl dehydroxylated metabolite

DM3

C₄₂H₆₆O₁₅

55.59

809.435 4

3.09

27 042

Platycoside O-xyl-rha-ara methylated

DM4

C₃₈H₆₀O₁₃

58.88

723.390 9

-7.19

27 696

Platycoside O-xyl-rha acetylated metabolite

DM5

C₄₄H₆₈O₁₈

68.85

883.439 6

7.13

5 578

865.475 2;
465.221 0

Platycoside O-xyl-rha-ara dehydroxylated metabolite

DM6

C₃₇H₅₈O₁₂

68.91

693.397 5

17.17

29 302

Platycogenic acid A lactone

EP5-M1

C₃₀H₄₄O₇

53.84

515.304 3

7.77

190 527

279.236 5;
495.045 8

Platycoside M1-glc dehydroxylated metabolite

EM2

C₃₀H₄₄O₆

59.12

499.303 3

-4.21

21 565

Platycoside M1-glc hydroxylated metabolite

EM3

C₃₀H₄₄O₈

59.69

531.303 8

16.20

116 812

Platycoside M1-glc methylated metabolite

EM4

C₃₁H₄₆O₇

60.91

529.312 2

-7.18

27 747

Platycoside M1-glc dehydroxylated metabolite and D-methylated

EM5

C₃₀H₄₄O₆

68.94

499.308 8

7.30

73 393

3-O-β-D-Glucopyranosyl-(1→3)-β-D-glucopyranosyl-2β, 12α, 16α, 23α-tetrahydroxyoleanane-28(13)-lactone(F1) dehydroxylated metabolite

FM1

C₄₃H₇₀O₁₅

56.92

825.459 4

-8.12

31 450

3-O-β-D-Glucopyranosyl-2β, 12α, 16α, 23, 24-pentahydroxyoleanane-28(13)-lactone(F2)-glcdehydrogenated metabolite

FM2

C₃₁H₄₈O₇

60.09

531.328 8

-5.27

61 396

F1 methylated metabolite

FM3

C₄₄H₇₂O₁₆

60.77

855.476 1

2.81

36 600

F1-glc methylated metabolite

FM4

C₃₈H₆₂O₁₁

61.70

693.415 0

-8.37

49 989

633.346 9;
508.321 8

F2-glc methylated metabolite

FM5

C₃₂H₅₂O₇

64.15

547.363 0

0.18

49 200

F1-2glc dehydroxylated metabolite

FM6

C₃₁H₅₀O₅

67.04

501.358 2

1.40

17 722

F1-2glc acetylated metabolite

FM7

C₃₃H₅₂O₇

67.43

559.363 5

1.07

48 216

559.280 2;
541.382 6

F1-2glc methylated metabolite

FM8

C₃₂H₅₂O₆

68.81

531.363 3

-8.85

13 228

16-oxo-Platycodin D

GP1-M1

C₅₇H₉₀O₂₈

37.46

1 221.551 3

-1.80

4 237

469.098 4;
635.470 4

16-oxo-Platycodin D-glc-api-xyl methylated metabolite

GM2

C₄₂H₆₆O₁₅

53.07

809.434 6

3.46

9 101

16-oxo-Platycodin D-api-xyl-rha methylated metabolite

GM3

C₄₂H₆₆O₁₆

53.83

825.418 3

-10.18

10 027

16-oxo-Platycodin D-glc-api-xyl methylated and deglycosylated metabolite

GM4

C₄₂H₆₆O₁₅

55.04

809.426 0

-7.17

16 453

16-oxo-Platycodin D-glc-api-xyl-rha-ara decarboxylated metabolite

GM5

C₂₉H₄₆O₅

60.21

473.326 4

0.42

55 603

16-oxo-Platycodin D-glc-api-xyl-rha-ara acetylated metabolite

GM6

C₃₂H₄₈O₈

64.70

559.325 7

-1.43

48 881

Platycogenin A-2glc dehydroxylated metabolite

HM1

C₃₀H₄₈O₅

64.54

487.342 1

0.62

11 627

Platycogenin A-2glc decarboxylated metabolite

HM2

C₂₉H₄₈O₄

65.70

459.347 0

0.22

14 265