药学学报

No.	Compound	Formula	MW	R_t/min	Ion type	Classification	Ref.
1	Flakinin B	C₁₆H₂₄O₅	296.162 3	2.941	[M+H]⁺	Terpenoids	[15]
2	Dendronobilin N	C₁₅H₂₄O₄	268.167 4	2.987	[M+H]⁺	Terpenoids	[16]
3	Dendronobilin K	C₁₅H₂₄O₄	268.167 4	3.102	[M+H]⁺	Terpenoids	[16]
4	Aduncin	C₁₅H₁₈O₆	294.110 3	8.286	[M+H]⁺	Terpenoids	[17]
5	Dendroside D isomer 1	C₂₇H₄₄O₁₄	592.273 1	10.639	[M+H]⁺	Terpenoids	[18]
6	Dendroside D	C₂₇H₄₄O₁₄	592.273 1	10.287	[M+H]⁺	Terpenoids	[18]
7	Dendronobiloside C/D	C₂₇H₄₄O₁₂	560.283 2	10.363	[M+H]⁺	Terpenoids	[19]
8	Inosine isomer 1	C₁₀H₁₂N₄O₅	268.080 7	0.661	[M+H]⁺	Alkaloids	[20]
9	Inosine	C₁₀H₁₂N₄O₅	268.080 7	0.941	[M+H]⁺	Alkaloids	[20]
10	Dendrocrepine isomer 2	C₃₃H₄₄O₃N₂	516.335 1	2.457	[M+H]⁺	Alkaloids	[21]
11	Drepidamine	C₁₈H₂₅NO₂	287.188 5	3.125	[M+H]⁺	Alkaloids	[21]
12	Nobilonine	C₁₇H₂₇NO₃	293.199 0	2.609	[M+H]⁺	Alkaloids	[21]
13	Crepidine isomer 3	C₂₁H₂₉NO₃	343.214 7	2.682	[M+H]⁺	Alkaloids	[21]
14	Crepidatumines C	C₁₈H₂₅NO₂	287.188 5	2.722	[M+H]⁺	Alkaloids	[21]
15	Dendrocrepine isomer 1	C₃₃H₄₄O₃N₂	516.335 1	2.732	[M+H]⁺	Alkaloids	[21]
16	Crepidine	C₂₁H₂₉NO₃	343.214 7	2.777	[M+H]⁺	Alkaloids	[21]
17	Dendrocrepidine C	C₁₈H₂₅O₂N	287.188 5	2.823	[M+H]⁺	Alkaloids	[21]
18	N-Methyldendrobinium isomer 1	C₁₇H₂₈O₂N	278.212 0	2.858	[M]⁺	Alkaloids	[22]
19	Dendrocrepidine E	C₃₃H₄₅O₄N₂	533.337 9	3.417	[M+H]⁺	Alkaloids	[21]
20	Dendrocrepidine E isomer 1	C₃₃H₄₅O₄N₂	533.337 9	3.365	[M+H]⁺	Alkaloids	[21]
21	Dendrocrepine	C₃₃H₄₄O₃N₂	516.335 1	2.987	[M+H]⁺	Alkaloids	[21]
22	N-Methyldendrobinium isomer 2	C₁₇H₂₈O₂N	278.212 0	2.987	[M]⁺	Alkaloids	[22]
23	Crepidine isomer 2	C₂₁H₂₉NO₃	343.214 7	3.021	[M+H]⁺	Alkaloids	[21]
24	Shihunidine	C₁₂H₁₃NO₂	203.094 6	3.041	[M+H]⁺	Alkaloids	[23]
25	Ddendrocrepine isomer 3	C₃₃H₄₄O₃N₂	516.335 1	3.057	[M+H]⁺	Alkaloids	[21]
26	Dendrocrepidine B	C₂₀H₂₇NO₄	345.194 0	3.083	[M+H]⁺	Alkaloids	[21]
27	Homocrepidine B isomer 1	C₂₀H₂₇NO₄	345.194 0	3.323	[M+H]⁺	Alkaloids	[21]
28	N-Methyldendrobinium	C₁₇H₂₈O₂N	278.212 0	3.106	[M]⁺	Alkaloids	[22]
29	Dendrocrepidine D	C₁₇H₂₂NO₂	272.165 0	3.151	[M+H]⁺	Alkaloids	[21]
30	Homocrepidine B	C₁₈H₂₇NO₂	289.204 1	3.201	[M+H]⁺	Alkaloids	[21]
31	N-Isopentenyl-dendroxinium	C₂₂H₃₃NO₃	360.253 8	3.281	[M]⁺	Alkaloids	[21]
32	2-Hydroxydendrobine	C₁₆H₂₅NO₃	279.183 4	3.289	[M]⁺	Alkaloids	[24]
33	Crepidine isomer 3	C₂₁H₂₉NO₃	343.214 7	3.418	[M+H]⁺	Alkaloids	[21]
34	Crepidine isomer 1	C₂₁H₂₉NO₃	343.214 7	3.469	[M+H]⁺	Alkaloids	[21]
35	Crepidine isomer 5	C₂₁H₂₉NO₃	343.214 7	3.526	[M+H]⁺	Alkaloids	[21]
36	N-Isopentenyl-dendrobinium	C₂₁H₃₃NO₂	332.258 9	3.824	[M]⁺	Alkaloids	[21]
37	Mubironine B	C₁₅H₂₃O₂N	249.172 8	12.065	[M+H]⁺	Alkaloids	[15]
38	Dendrine	C₁₉H₂₉NO₄	335.209 6	5.981	[M]⁺	Alkaloids	[25]
39	6-Hydroxynobiline	C₁₇H₂₇O₄N	309.194 0	3.045	[M+H]⁺	Alkaloids	[26]
40	Dendrobine	C₁₆H₂₅O₂N	263.188 5	9.075	[M]⁺	Alkaloids	[27]
41	Dendroamine	C₁₆H₂₅O₃N	279.183 4	9.053	[M]⁺	Alkaloids	[28]
42	Gigantol isomer 1	C₁₆H₁₈O₄	274.120 5	3.891	[M+H]⁺	Bibenzyls	[29]
43	Gigantol	C₁₆H₁₈O₄	274.120 5	3.533	[M+H]⁺	Bibenzyls	[29]
44	Dendrocandin K	C₃₁H₃₀O₇	514.199 1	4.492	[M+H]⁺	Bibenzyls	[30]
45	Chrysotoxine	C₁₈H₂₂O₅	318.146 7	5.423	[M+H]⁺	Bibenzyls	[31]
46	Crepidatin	C₁₈H₂₂O₅	318.146 7	5.222	[M+H]⁺	Bibenzyls	[21]
47	Isoschaftoside isomer 1	C₂₆H₂₈O₁₄	564.147 9	2.659	[M+H]⁺	Flavonoids	[32]
48	Isoschaftoside	C₂₆H₂₈O₁₄	564.147 9	2.716	[M+H]⁺	Flavonoids	[32]
49	Kaempferol	C₁₅H₁₀O₆	286.047 7	2.747	[M+H]⁺	Flavonoids	[29]
50	Rutin	C₂₇H₃₀O₁₆	610.153 3	2.865	[M+H]⁺	Flavonoids	[29]
51	Quercetin	C₁₅H₁₀O₇	302.042 6	2.872	[M+H]⁺	Flavonoids	[29]
52	Dihydropinosylvin methyl ether	C₁₅H₁₆O₂	228.115 0	3.281	[M+H]⁺	Flavonoids	[29]
53	Violanthin	C₂₇H₃₀O₁₄	578.163 5	7.923	[M+H]⁺	Flavonoids	[33]
54	Schaftoside	C₂₆H₂₈O₁₄	564.147 9	2.609	[M+H]⁺	Flavonoids	[32]
55	Apigenin-6-C-α-L-arabinoside-8-C-β-D-xyloside	C₂₅H₂₆O₁₃	534.137 3	2.838	[M+H]⁺	Flavonoids	[34]
56	Glucosylvitexin	C₂₇H₃₀O₁₅	594.158 4	2.749	[M+H]⁺	Flavonoids	[35]
57	Confusarin	C₁₇H₁₆O₅	300.099 7	7.912	[M+H]⁺	Phenanthrenes	[36]
58	Denobilone B	C₁₅H₁₆O₄	260.104 8	7.682	[M+H]⁺	Phenanthrenes	[37]

No.	Compound	Formula	MW	R_t/min	Ion type	Classification	Ref.
1	Flakinin B	C₁₆H₂₄O₅	296.162 3	2.941	[M+H]⁺	Terpenoids	[15]
2	Dendronobilin N	C₁₅H₂₄O₄	268.167 4	2.987	[M+H]⁺	Terpenoids	[16]
3	Dendronobilin K	C₁₅H₂₄O₄	268.167 4	3.102	[M+H]⁺	Terpenoids	[16]
4	Aduncin	C₁₅H₁₈O₆	294.110 3	8.286	[M+H]⁺	Terpenoids	[17]
5	Dendroside D isomer 1	C₂₇H₄₄O₁₄	592.273 1	10.639	[M+H]⁺	Terpenoids	[18]
6	Dendroside D	C₂₇H₄₄O₁₄	592.273 1	10.287	[M+H]⁺	Terpenoids	[18]
7	Dendronobiloside C/D	C₂₇H₄₄O₁₂	560.283 2	10.363	[M+H]⁺	Terpenoids	[19]
8	Inosine isomer 1	C₁₀H₁₂N₄O₅	268.080 7	0.661	[M+H]⁺	Alkaloids	[20]
9	Inosine	C₁₀H₁₂N₄O₅	268.080 7	0.941	[M+H]⁺	Alkaloids	[20]
10	Dendrocrepine isomer 2	C₃₃H₄₄O₃N₂	516.335 1	2.457	[M+H]⁺	Alkaloids	[21]
11	Drepidamine	C₁₈H₂₅NO₂	287.188 5	3.125	[M+H]⁺	Alkaloids	[21]
12	Nobilonine	C₁₇H₂₇NO₃	293.199 0	2.609	[M+H]⁺	Alkaloids	[21]
13	Crepidine isomer 3	C₂₁H₂₉NO₃	343.214 7	2.682	[M+H]⁺	Alkaloids	[21]
14	Crepidatumines C	C₁₈H₂₅NO₂	287.188 5	2.722	[M+H]⁺	Alkaloids	[21]
15	Dendrocrepine isomer 1	C₃₃H₄₄O₃N₂	516.335 1	2.732	[M+H]⁺	Alkaloids	[21]
16	Crepidine	C₂₁H₂₉NO₃	343.214 7	2.777	[M+H]⁺	Alkaloids	[21]
17	Dendrocrepidine C	C₁₈H₂₅O₂N	287.188 5	2.823	[M+H]⁺	Alkaloids	[21]
18	N-Methyldendrobinium isomer 1	C₁₇H₂₈O₂N	278.212 0	2.858	[M]⁺	Alkaloids	[22]
19	Dendrocrepidine E	C₃₃H₄₅O₄N₂	533.337 9	3.417	[M+H]⁺	Alkaloids	[21]
20	Dendrocrepidine E isomer 1	C₃₃H₄₅O₄N₂	533.337 9	3.365	[M+H]⁺	Alkaloids	[21]
21	Dendrocrepine	C₃₃H₄₄O₃N₂	516.335 1	2.987	[M+H]⁺	Alkaloids	[21]
22	N-Methyldendrobinium isomer 2	C₁₇H₂₈O₂N	278.212 0	2.987	[M]⁺	Alkaloids	[22]
23	Crepidine isomer 2	C₂₁H₂₉NO₃	343.214 7	3.021	[M+H]⁺	Alkaloids	[21]
24	Shihunidine	C₁₂H₁₃NO₂	203.094 6	3.041	[M+H]⁺	Alkaloids	[23]
25	Ddendrocrepine isomer 3	C₃₃H₄₄O₃N₂	516.335 1	3.057	[M+H]⁺	Alkaloids	[21]
26	Dendrocrepidine B	C₂₀H₂₇NO₄	345.194 0	3.083	[M+H]⁺	Alkaloids	[21]
27	Homocrepidine B isomer 1	C₂₀H₂₇NO₄	345.194 0	3.323	[M+H]⁺	Alkaloids	[21]
28	N-Methyldendrobinium	C₁₇H₂₈O₂N	278.212 0	3.106	[M]⁺	Alkaloids	[22]
29	Dendrocrepidine D	C₁₇H₂₂NO₂	272.165 0	3.151	[M+H]⁺	Alkaloids	[21]
30	Homocrepidine B	C₁₈H₂₇NO₂	289.204 1	3.201	[M+H]⁺	Alkaloids	[21]
31	N-Isopentenyl-dendroxinium	C₂₂H₃₃NO₃	360.253 8	3.281	[M]⁺	Alkaloids	[21]
32	2-Hydroxydendrobine	C₁₆H₂₅NO₃	279.183 4	3.289	[M]⁺	Alkaloids	[24]
33	Crepidine isomer 3	C₂₁H₂₉NO₃	343.214 7	3.418	[M+H]⁺	Alkaloids	[21]
34	Crepidine isomer 1	C₂₁H₂₉NO₃	343.214 7	3.469	[M+H]⁺	Alkaloids	[21]
35	Crepidine isomer 5	C₂₁H₂₉NO₃	343.214 7	3.526	[M+H]⁺	Alkaloids	[21]
36	N-Isopentenyl-dendrobinium	C₂₁H₃₃NO₂	332.258 9	3.824	[M]⁺	Alkaloids	[21]
37	Mubironine B	C₁₅H₂₃O₂N	249.172 8	12.065	[M+H]⁺	Alkaloids	[15]
38	Dendrine	C₁₉H₂₉NO₄	335.209 6	5.981	[M]⁺	Alkaloids	[25]
39	6-Hydroxynobiline	C₁₇H₂₇O₄N	309.194 0	3.045	[M+H]⁺	Alkaloids	[26]
40	Dendrobine	C₁₆H₂₅O₂N	263.188 5	9.075	[M]⁺	Alkaloids	[27]
41	Dendroamine	C₁₆H₂₅O₃N	279.183 4	9.053	[M]⁺	Alkaloids	[28]
42	Gigantol isomer 1	C₁₆H₁₈O₄	274.120 5	3.891	[M+H]⁺	Bibenzyls	[29]
43	Gigantol	C₁₆H₁₈O₄	274.120 5	3.533	[M+H]⁺	Bibenzyls	[29]
44	Dendrocandin K	C₃₁H₃₀O₇	514.199 1	4.492	[M+H]⁺	Bibenzyls	[30]
45	Chrysotoxine	C₁₈H₂₂O₅	318.146 7	5.423	[M+H]⁺	Bibenzyls	[31]
46	Crepidatin	C₁₈H₂₂O₅	318.146 7	5.222	[M+H]⁺	Bibenzyls	[21]
47	Isoschaftoside isomer 1	C₂₆H₂₈O₁₄	564.147 9	2.659	[M+H]⁺	Flavonoids	[32]
48	Isoschaftoside	C₂₆H₂₈O₁₄	564.147 9	2.716	[M+H]⁺	Flavonoids	[32]
49	Kaempferol	C₁₅H₁₀O₆	286.047 7	2.747	[M+H]⁺	Flavonoids	[29]
50	Rutin	C₂₇H₃₀O₁₆	610.153 3	2.865	[M+H]⁺	Flavonoids	[29]
51	Quercetin	C₁₅H₁₀O₇	302.042 6	2.872	[M+H]⁺	Flavonoids	[29]
52	Dihydropinosylvin methyl ether	C₁₅H₁₆O₂	228.115 0	3.281	[M+H]⁺	Flavonoids	[29]
53	Violanthin	C₂₇H₃₀O₁₄	578.163 5	7.923	[M+H]⁺	Flavonoids	[33]
54	Schaftoside	C₂₆H₂₈O₁₄	564.147 9	2.609	[M+H]⁺	Flavonoids	[32]
55	Apigenin-6-C-α-L-arabinoside-8-C-β-D-xyloside	C₂₅H₂₆O₁₃	534.137 3	2.838	[M+H]⁺	Flavonoids	[34]
56	Glucosylvitexin	C₂₇H₃₀O₁₅	594.158 4	2.749	[M+H]⁺	Flavonoids	[35]
57	Confusarin	C₁₇H₁₆O₅	300.099 7	7.912	[M+H]⁺	Phenanthrenes	[36]
58	Denobilone B	C₁₅H₁₆O₄	260.104 8	7.682	[M+H]⁺	Phenanthrenes	[37]

No.	Compound	Leaf of D. crepidatum	Stem of D. crepidatum	Leaf of D. officinale	Stem of D. officinale
1	Dendronobilin K	0.22	0.41	0.00	0.00
2	Dendronobilin N	0.13	0.19	0.00	0.00
3	Aduncin	0.00	0.04	0.11	13.97
4	Flakinin B	0.08	0.04	0.00	0.00
5	Dendronobiloside C/D	0.10	0.31	1.14	8.19
6	Dendroside D isomer 1	0.97	0.45	7.96	2.75
7	Dendroside D	9.47	7.03	55.63	45.65
8	Shihunidine	0.08	0.01	0.00	0.00
9	Mubironine B	0.04	0.04	0.13	1.16
10	Dendrobine	0.08	0.04	0.63	0.00
11	Inosine	0.07	0.00	0.59	0.00
12	Inosine isomer 1	0.04	0.00	0.33	0.00
13	Dendrocrepidine D	0.52	0.52	0.00	0.00
14	N-Methyl-dendrobine isomer 1	0.31	0.33	0.00	0.00
15	N-Methyl-dendrobine	1.07	1.96	0.00	0.00
16	N-Methyl-dendrobine isomer 2	0.99	1.50	0.00	0.00
17	2-Hydroxydendrobine	0.57	1.21	0.00	0.00
18	Dendroamine	0.06	0.02	0.58	0.00
19	Crepidamine	6.16	6.43	0.00	0.00
20	Dendrocrepidine C	9.34	9.82	0.00	0.00
21	Crepidatumines C	7.53	14.23	0.00	0.00
22	Homocrepidine B	4.14	3.91	0.00	0.00
23	Homocrepidine B isomer 1	6.42	5.38	0.00	0.00
24	Nobilonine	0.69	0.32	0.00	0.00
25	6-Hydroxynobiline	0.82	0.09	0.00	0.00
26	Dendrocrepidine E isomer 1	7.19	0.82	0.00	0.00
27	Dendrocrepidine E	10.64	13.52	0.00	0.00
28	N-Isopentenyl-dendrobinium	1.10	1.35	0.00	0.00
29	Dendrine	0.13	0.06	0.00	0.00
30	Crepidine isomer 1	0.55	0.21	0.00	0.00
31	Crepidine isomer 2	1.12	0.33	0.00	0.00
32	Crepidine isomer 3	1.43	0.09	0.00	0.00
33	Crepidine	9.05	8.94	0.00	0.00
34	Crepidine isomer 3	0.61	0.40	0.00	0.00
35	Crepidine isomer 5	2.39	1.49	0.00	0.00
36	Dendrocrepidine B	8.23	13.16	0.00	0.00
37	N-Isopentenyl-dendroxinium	0.21	0.06	0.00	0.00
38	Dendrocrepine isomer 1	0.11	0.07	0.00	0.00
39	Dendrocrepine isomer 2	0.45	0.28	0.00	0.00
40	Dendrocrepine	0.69	1.54	0.00	0.00
41	Ddendrocrepine isomer 3	0.08	0.16	0.00	0.00
42	Gigantol isomer 1	0.17	0.11	0.00	0.00
43	Gigantol	1.25	0.87	0.00	0.00
44	Crepidatin	0.46	0.57	0.00	0.00
45	Chrysotoxine	0.04	0.03	0.12	0.00
46	Dendrocandin K	0.06	0.12	0.00	0.00
47	Dihydropinosylvin methyl ether	0.07	0.17	0.00	0.00
48	Kaempferol	2.91	0.90	0.00	0.00
49	Quercetin	0.07	0.00	9.33	2.32
50	Apigenin-6-C-α-L-arabinoside-8-C-β-D-xyloside	0.00	0.00	0.93	0.63
51	Isoschaftoside	0.00	0.00	1.04	1.66
52	Isoschaftoside isomer 1	0.00	0.00	1.26	1.80
53	Schaftoside	0.00	0.00	1.13	1.81
54	Violanthin	0.01	0.01	0.03	0.00
55	Glucosylvitexin	0.78	0.22	0.21	8.03
56	Rutin	0.11	0.00	17.41	6.65
57	Denobilone B	0.07	0.00	0.65	0.00
58	Confusarin	0.14	0.23	0.80	5.37

No.	Compound	Leaf of D. crepidatum	Stem of D. crepidatum	Leaf of D. officinale	Stem of D. officinale
1	Dendronobilin K	0.22	0.41	0.00	0.00
2	Dendronobilin N	0.13	0.19	0.00	0.00
3	Aduncin	0.00	0.04	0.11	13.97
4	Flakinin B	0.08	0.04	0.00	0.00
5	Dendronobiloside C/D	0.10	0.31	1.14	8.19
6	Dendroside D isomer 1	0.97	0.45	7.96	2.75
7	Dendroside D	9.47	7.03	55.63	45.65
8	Shihunidine	0.08	0.01	0.00	0.00
9	Mubironine B	0.04	0.04	0.13	1.16
10	Dendrobine	0.08	0.04	0.63	0.00
11	Inosine	0.07	0.00	0.59	0.00
12	Inosine isomer 1	0.04	0.00	0.33	0.00
13	Dendrocrepidine D	0.52	0.52	0.00	0.00
14	N-Methyl-dendrobine isomer 1	0.31	0.33	0.00	0.00
15	N-Methyl-dendrobine	1.07	1.96	0.00	0.00
16	N-Methyl-dendrobine isomer 2	0.99	1.50	0.00	0.00
17	2-Hydroxydendrobine	0.57	1.21	0.00	0.00
18	Dendroamine	0.06	0.02	0.58	0.00
19	Crepidamine	6.16	6.43	0.00	0.00
20	Dendrocrepidine C	9.34	9.82	0.00	0.00
21	Crepidatumines C	7.53	14.23	0.00	0.00
22	Homocrepidine B	4.14	3.91	0.00	0.00
23	Homocrepidine B isomer 1	6.42	5.38	0.00	0.00
24	Nobilonine	0.69	0.32	0.00	0.00
25	6-Hydroxynobiline	0.82	0.09	0.00	0.00
26	Dendrocrepidine E isomer 1	7.19	0.82	0.00	0.00
27	Dendrocrepidine E	10.64	13.52	0.00	0.00
28	N-Isopentenyl-dendrobinium	1.10	1.35	0.00	0.00
29	Dendrine	0.13	0.06	0.00	0.00
30	Crepidine isomer 1	0.55	0.21	0.00	0.00
31	Crepidine isomer 2	1.12	0.33	0.00	0.00
32	Crepidine isomer 3	1.43	0.09	0.00	0.00
33	Crepidine	9.05	8.94	0.00	0.00
34	Crepidine isomer 3	0.61	0.40	0.00	0.00
35	Crepidine isomer 5	2.39	1.49	0.00	0.00
36	Dendrocrepidine B	8.23	13.16	0.00	0.00
37	N-Isopentenyl-dendroxinium	0.21	0.06	0.00	0.00
38	Dendrocrepine isomer 1	0.11	0.07	0.00	0.00
39	Dendrocrepine isomer 2	0.45	0.28	0.00	0.00
40	Dendrocrepine	0.69	1.54	0.00	0.00
41	Ddendrocrepine isomer 3	0.08	0.16	0.00	0.00
42	Gigantol isomer 1	0.17	0.11	0.00	0.00
43	Gigantol	1.25	0.87	0.00	0.00
44	Crepidatin	0.46	0.57	0.00	0.00
45	Chrysotoxine	0.04	0.03	0.12	0.00
46	Dendrocandin K	0.06	0.12	0.00	0.00
47	Dihydropinosylvin methyl ether	0.07	0.17	0.00	0.00
48	Kaempferol	2.91	0.90	0.00	0.00
49	Quercetin	0.07	0.00	9.33	2.32
50	Apigenin-6-C-α-L-arabinoside-8-C-β-D-xyloside	0.00	0.00	0.93	0.63
51	Isoschaftoside	0.00	0.00	1.04	1.66
52	Isoschaftoside isomer 1	0.00	0.00	1.26	1.80
53	Schaftoside	0.00	0.00	1.13	1.81
54	Violanthin	0.01	0.01	0.03	0.00
55	Glucosylvitexin	0.78	0.22	0.21	8.03
56	Rutin	0.11	0.00	17.41	6.65
57	Denobilone B	0.07	0.00	0.65	0.00
58	Confusarin	0.14	0.23	0.80	5.37

Compound	P	VIP
Crepidamine	0.003 155	1.173 56
Crepidine isomer 3	0.001 799	2.158 45
Crepidatumines C	0.032 592	1.774 13
Kaempferol	0.000 187	2.837 34
Crepidine	0.021 959	3.392 17
Dendrocrepidine C	0.000 007	3.297 02
Crepidine isomer 3	0.038 898	1.747 11
Dendrocrepidine D	0.018 880	1.037 13
Crepidine isomer 4	0.000 112	1.092 13
Crepidine isomer 1	0.000 000	1.180 16
Gigantol	0.002 447	1.517 39
Nobilonine	0.016 435	3.290 58
Dendrocrepidine E	0.001 015	3.315 20
Glucosylvitexin	0.000 725	2.748 92

Compound	P	VIP
Crepidamine	0.003 155	1.173 56
Crepidine isomer 3	0.001 799	2.158 45
Crepidatumines C	0.032 592	1.774 13
Kaempferol	0.000 187	2.837 34
Crepidine	0.021 959	3.392 17
Dendrocrepidine C	0.000 007	3.297 02
Crepidine isomer 3	0.038 898	1.747 11
Dendrocrepidine D	0.018 880	1.037 13
Crepidine isomer 4	0.000 112	1.092 13
Crepidine isomer 1	0.000 000	1.180 16
Gigantol	0.002 447	1.517 39
Nobilonine	0.016 435	3.290 58
Dendrocrepidine E	0.001 015	3.315 20
Glucosylvitexin	0.000 725	2.748 92

Compound	P	VIP
Quercetin	0.000 000	2.779 12
Rutin	0.000 000	3.781 34
Dendroside D	0.000 000	6.513 22

Compound	P	VIP
Quercetin	0.000 000	2.779 12
Rutin	0.000 000	3.781 34
Dendroside D	0.000 000	6.513 22

Compound	P	VIP
Crepidatumines C	0.000 007	4.597 49
Kaempferol	0.000 001	1.172 98
Crepidine	0.000 016	3.684 33
Dendrocrepidine C	0.000 006	3.874 26
Dendrocrepine	0.000 005	1.530 33
N-Methyl-dendrobine isomer 1	0.000 005	1.509 95
Dendrocrepine isomer 3	0.000 112	1.016 92
Dendrocrepidine B	0.000 004	4.463 95
N-Methyl-dendrobine	0.000 003	1.727 57
Dendrocrepidine D	0.000 006	2.090 09
Homocrepidine B	0.000 002	2.457 86
Crepidine isomer 5	0.000 512	1.495 60
2-Hydroxydendrobine	0.000 050	1.362 89
Gigantol	0.002 428	1.101 12
Dendroside D	0.011 910	2.631 75
Dendrocrepidine E	0.000 007	4.516 34

Compound	P	VIP
Crepidatumines C	0.000 007	4.597 49
Kaempferol	0.000 001	1.172 98
Crepidine	0.000 016	3.684 33
Dendrocrepidine C	0.000 006	3.874 26
Dendrocrepine	0.000 005	1.530 33
N-Methyl-dendrobine isomer 1	0.000 005	1.509 95
Dendrocrepine isomer 3	0.000 112	1.016 92
Dendrocrepidine B	0.000 004	4.463 95
N-Methyl-dendrobine	0.000 003	1.727 57
Dendrocrepidine D	0.000 006	2.090 09
Homocrepidine B	0.000 002	2.457 86
Crepidine isomer 5	0.000 512	1.495 60
2-Hydroxydendrobine	0.000 050	1.362 89
Gigantol	0.002 428	1.101 12
Dendroside D	0.011 910	2.631 75
Dendrocrepidine E	0.000 007	4.516 34

Compound	P	VIP
Crepidamine	0.000 000	1.021 75
Crepidine isomer 3	0.000 000	1.670 81
Crepidatumines C	0.000 000	3.839 51
Kaempferol	0.000 000	2.389 89
Crepidine	0.000 000	4.204 14
Dendrocrepidine C	0.000 000	4.276 13
Quercetin	0.000 000	1.774 34
Rutin	0.000 000	3.781 34
Dendrocrepine	0.000 000	1.163 09
N-Methyl-dendrobine isomer 1	0.000 000	1.394 59
Crepidine isomer 2	0.000 000	1.477 62
6-Hydroxynobiline	0.000 000	1.269 23
Dendrocrepidine B	0.000 000	3.536 80
N-Methyl-dendrobine	0.000 000	1.446 07
Dendrocrepidine D	0.000 000	1.626 84
Homocrepidine B	0.000 000	2.843 94
2-Hydroxydendrobine	0.000 050	1.362 89
Crepidine isomer 4	0.000 000	1.089 44
Crepidine isomer 1	0.000 001	1.034 84
Crepidine isomer 5	0.000 000	2.162 56
Gigantol	0.000 000	1.564 25
Dendrocrepidine E	0.000 001	4.550 24

Compound	P	VIP
Crepidamine	0.000 000	1.021 75
Crepidine isomer 3	0.000 000	1.670 81
Crepidatumines C	0.000 000	3.839 51
Kaempferol	0.000 000	2.389 89
Crepidine	0.000 000	4.204 14
Dendrocrepidine C	0.000 000	4.276 13
Quercetin	0.000 000	1.774 34
Rutin	0.000 000	3.781 34
Dendrocrepine	0.000 000	1.163 09
N-Methyl-dendrobine isomer 1	0.000 000	1.394 59
Crepidine isomer 2	0.000 000	1.477 62
6-Hydroxynobiline	0.000 000	1.269 23
Dendrocrepidine B	0.000 000	3.536 80
N-Methyl-dendrobine	0.000 000	1.446 07
Dendrocrepidine D	0.000 000	1.626 84
Homocrepidine B	0.000 000	2.843 94
2-Hydroxydendrobine	0.000 050	1.362 89
Crepidine isomer 4	0.000 000	1.089 44
Crepidine isomer 1	0.000 001	1.034 84
Crepidine isomer 5	0.000 000	2.162 56
Gigantol	0.000 000	1.564 25
Dendrocrepidine E	0.000 001	4.550 24

基于UPLC-Q-TOF-MS/MS代谢组学的铁皮石斛和玫瑰石斛化学成分差异研究

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娄港归 ¹^,^# , 夏杰 ¹^,^# , 杨健 ² , 王宏鹏 ³ , 梁宗锁 ¹ , 肖艺 ⁴ , 李振达 ⁴ , 张煜 ⁵ , 刘志超 ⁶ , 施宛丽 ³ , 张晓丹 ¹^,^* , 杨东风 ¹^,^*

药学学报 | 专题报道Ⅱ：植物天然产物生物合成及合成生物学 2021,56(12): 3331-3344

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药学学报 | 专题报道Ⅱ：植物天然产物生物合成及合成生物学 2021, 56(12): 3331-3344

基于UPLC-Q-TOF-MS/MS代谢组学的铁皮石斛和玫瑰石斛化学成分差异研究

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娄港归¹^,^#, 夏杰¹^,^#, 杨健², 王宏鹏³, 梁宗锁¹, 肖艺⁴, 李振达⁴, 张煜⁵, 刘志超⁶, 施宛丽³, 张晓丹¹^,^*, 杨东风¹^,^*

作者信息

1.浙江理工大学生命科学与医药学院, 浙江省植物次生代谢调控重点实验室, 浙江杭州 310018

2.中国中医科学院中药资源中心, 道地药材国家重点实验室培育基地, 北京 100700

3.浙江科技学院生物与化学工程学院, 浙江杭州 310023

4.宁波易中禾药用植物研究院有限公司, 浙江宁波 315010

5.云南野兰堂生物科技有限公司, 云南昆明 650114

6.六安市农业科学研究院中药材研究室, 安徽六安 237000

通讯作者:

*张晓丹, E-mail: zxd211@zstu.edu.cn;

杨东风, E-mail: ydf807@sina.com

Differences in the chemical composition of Dendrobium officinale Kimura et Migo and Dendrobium crepidatum Lindl based on UPLC-Q-TOF-MS/MS and metabolomics

Gang-gui LOU¹, Jie XIA¹, Jian YANG², Hong-peng WANG³, Zong-suo LIANG¹, Yi XIAO⁴, Zhen-da LI⁴, Yu ZHANG⁵, Zhi-chao LIU⁶, Wan-li SHI³, Xiao-dan ZHANG¹^,^*, Dong-feng YANG¹^,^*

Affiliations

1. College of Life Sciences and Medicine, Zhejiang Sci-Tech University, Key Laboratory of Plant Secondary Metabolism and Regulation of Zhejiang Province, Hangzhou 310018, China

2. State Key Laboratory Breeding Base of Dao-di Herbs, National Resource Center for Chinese Materia Medica, China Academy of Chinese Medical Sciences, Beijing 100700, China

3. School of Biological and Chemical Engineering, Zhejiang University of Science and Technology, Hangzhou 310023, China

4. Ningbo Yizhonghe Medical Plant Research Institute Co., Ltd., Ningbo 315010, China

5. Yunnan Yelantang Biological Technology Co., Ltd., Kunming 650114, China

6. Laboratory of Traditional Chinese Medicine, Lu'an Academy of Agricultural Sciences, Lu'an 237000, China

出版时间: 2021-12-12 doi: 10.16438/j.0513-4870.2021-0939

文章导航

摘要

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铁皮石斛和玫瑰石斛均为石斛属植物, 前者为我国名贵中药材, 后者为云南地方用药, 都有滋阴养胃的作用。为揭示两种石斛及其不同部位间化学成分差异, 本研究采用超高效液相色谱-串联四级杆-飞行时间质谱(UPLC-Q-TOF-MS/MS) 技术分别对铁皮石斛和玫瑰石斛的茎和叶进行化学成分分析, 并通过主成分分析(PCA) 和偏最小二乘判别分析(OPLS-DA) 等多元变量分析方法研究石斛种间和部位间代谢产物差异, 结果在两种石斛物种中共鉴定到58种化学成分。通过质谱规律的解析发现生物碱类成分的物质在质谱中与氮连接的侧环更容易断裂。PCA分析结果表明铁皮石斛茎叶与玫瑰石斛茎叶可以明显分离, 说明铁皮石斛和玫瑰石斛化学成分差异显著。通过OPLS-DA分析发现玫瑰石斛与铁皮石斛茎间有16种差异代谢物, 叶间有22种差异代谢物, 两种石斛间的差异成分主要为玫瑰石斛碱B、玫瑰石斛碱C、玫瑰石斛啶碱等, 玫瑰石斛茎叶之间存在14种差异代谢物, 铁皮石斛茎叶间代谢产物差异不大。综上, 本研究发现两种石斛化学成分差异较大, 铁皮石斛小分子化合物以萜类和黄酮类成分为主, 生物碱含量较低, 茎叶间成分差异不大。玫瑰石斛则以生物碱和萜类成分为主, 玫瑰石斛碱、玫瑰石斛胺等为其特有成分, 茎叶间成分差异较大。该研究为石斛资源的开发利用提供了理论依据。

关键词

铁皮石斛 / 玫瑰石斛 / 不同部位 / UPLC-Q-TOF-MS/MS / 差异代谢物

Abstract

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Dendrobium officinale Kimura et Migo is a rare Chinese herbal medicine, while Dendrobium crepidatum Lindl is a local medicine in Yunnan, both of which have the function of nourishing yin and stomach. To reveal the differences in chemical composition between the two species, ultra-performance liquid chromatography-quadrupole-time of flight mass spectrometry (UPLC-Q-TOF-MS/MS) was used to analyze the chemical composition of stems and leaves of D. officinale and D. crepidatum. Principal component analysis (PCA) and partial least squares discriminant analysis (OPLS-DA) were used to determine the differences in metabolites between species and parts of Dendrobium. Fifty-eight chemical compounds were identified in the two species. Analysis indicated that the side ring of alkaloids connected with nitrogen was readily cleaved during analysis. The results of PCA analysis showed that the stems and leaves of D. officinale and D. crepidatum could be easily differentiated, and the chemical constituents of D. officinale and D. crepidatum were significantly different. OPLS-DA analysis showed that there were 16 metabolite differences between the stems and 22 differences in metabolites between the leaves of D. officinale and D. crepidatum. The main metabolite differences in components between the two Dendrobium species were dendrocrepidine B, dendrocrepidine C and dendrocrepine. There were 14 differences in metabolites between the stems and leaves of D. crepidatum. In conclusion, the chemical compositions of D. officinale and D. crepidatum are quite different; the small molecular compounds of D. officinale are mainly terpenoids and flavonoids, and the content of alkaloids is low. There is no significant difference between stem and leaf. In contrast, D. crepidatum is mainly composed of alkaloids and terpenoids, with crepidamine and dendrocrepine as its unique components, and there are great differences in the components between stems and leaves. This study provides a theoretical basis for the development and utilization of Dendrobium resources.

Key words

Dendrobium officinale Kimura et Migo / Dendrobium crepidatum Lindl / different parts / UPLC-Q-TOF-MS/MS / differential metabolites

引用本文

娄港归, 夏杰, 杨健, 王宏鹏, 梁宗锁, 肖艺, 李振达, 张煜, 刘志超, 施宛丽, 张晓丹, 杨东风. 基于UPLC-Q-TOF-MS/MS代谢组学的铁皮石斛和玫瑰石斛化学成分差异研究. 药学学报, 2021 , 56 (12) : 3331 -3344 . DOI: 10.16438/j.0513-4870.2021-0939

Gang-gui LOU, Jie XIA, Jian YANG, Hong-peng WANG, Zong-suo LIANG, Yi XIAO, Zhen-da LI, Yu ZHANG, Zhi-chao LIU, Wan-li SHI, Xiao-dan ZHANG, Dong-feng YANG. Differences in the chemical composition of Dendrobium officinale Kimura et Migo and Dendrobium crepidatum Lindl based on UPLC-Q-TOF-MS/MS and metabolomics[J]. Acta Pharmaceutica Sinica, 2021 , 56 (12) : 3331 -3344 . DOI: 10.16438/j.0513-4870.2021-0939

正文

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铁皮石斛(Dendrobium officinale Kimura et Migo), 为兰科石斛属珍稀名贵草本植物, 分布于浙江、安徽、广西、云南、福建等地。铁皮石斛的药用历史悠久, 是我国传统的道地药材, 为中华九大仙草之首, 在我国民间应用广泛^[1]。《中国药学大词典》称铁皮石斛“专滋肺胃之气液, 气液冲旺, 肾水自生”, 用于养阴生津, 治疗阴虚津亏诸症。现代科学研究表明, 铁皮石斛中的石斛多糖等多种有效成分可以增加体内T细胞和B细胞的代谢, 从而提高机体免疫能力^[2]。同时, 铁皮石斛在抗氧化、抗肿瘤、抗疲劳、改善糖尿病等方面具有显著效果^[3-6]。另外, 铁皮石斛也具有改善肝病变、抗高血压中风、抗炎、抗肿瘤、减少辐射、改善肠道微环境、促进心肌收缩等作用^[7-13]。玫瑰石斛(Dendrobium crepidatum Lindl) 同属兰科石斛属, 主要分布于云南、贵州及东南亚等地。据中国植物物种信息数据库记载, 玫瑰石斛具有滋阴益胃、生津除烦、润肺止咳的功效, 用于口干烦渴、阴伤津亏、病后虚热、目暗不明、肺痨、食欲不振等症状。近年来, 随着石斛的广泛使用, 石斛属多种植物在民间被作为代替石斛的民间习用药材, 其中玫瑰石斛在云南南部地区被当作石斛来使用, 是一种地方用药^[14]。因此, 研究铁皮石斛和玫瑰石斛茎叶间的化学成分差异, 对于玫瑰石斛资源的开发利用非常重要。

本研究主要采用超高效液相色谱-串联四级杆-飞行时间质谱(UPLC-Q-TOF-MS) 技术分别对铁皮石斛和玫瑰石斛的茎和叶进行化学成分分析, 进而利用主成分分析和偏最小二乘法分析法, 寻找两者之间的差异代谢物, 为石斛物种鉴别和资源开发等提供科学依据。

仪器与材料

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仪器 ACQUITY^TM UPLC/Q-TOF/MS超高效液相色谱四极杆飞行时间高分辨质谱联用仪、MassLynx V4.1质谱工作站(美国Waters公司); 色谱柱: Waters ACQUITY UPLC HSS T3液相色谱柱(2.1 mm × 100 mm, 1.7 μm); Xevo G2-XS Q-Tof质谱检测器; SIMCA-P 14.1数据处理软件(瑞士Umetrics公司); GZX-9070ME电热鼓风干燥箱(上海博讯实业有限公司公司); Sartorius BT25S电子天平(德国Sartoriu公司); LG-01高速中药粉碎机(浙江瑞安市百信制药机械有限公司); KQ-400KDE型高功率数控超声波清洗器(昆山市超声仪器有限公司); Thermo Micro 21R台式高速冷冻离心机(美国Thermo公司); CR-SP412超纯水仪(上海力康生物医疗科技控股有限公司)。乙腈、甲酸、乙醇(色谱纯, Fisher Scientific, Fairlawn, NJ, 美国), 甲醇为质谱纯(美国Tedia公司)。

材料铁皮石斛全草于2020年10月采自浙江宁波, 生长年限为2年, 玫瑰石斛全草于2020年10月采自云南昆明, 生长年限为2年, 所有样品均经浙江理工大学生命科学与医药学院张晓丹、杨东风教授鉴定为石斛属铁皮石斛(Dend-robium officinale Kimura et Migo) 和玫瑰石斛(Dendrobium crepidatum Lindl)。留样凭证保存于浙江省植物次生代谢重点实验室。取收集的铁皮石斛、玫瑰石斛鲜样, 分离茎和叶, 除去根和泥沙, 除净叶鞘, 将其剪碎后, 在55 ℃下烘干至恒重备用。

色谱条件 采用Waters ACQUITY UPLC HSS T3液相色谱柱(2.1 mm × 100 mm, 1.7 μm); 柱温40 ℃; 流速0.4 mL·min^-1; 进样量1.0 μL; 检测波长254 nm; 流动相为水(A)-乙腈溶液(B), 梯度洗脱: 0~1 min为96%→96% A, 1~2 min为96%→50% A, 2~8 min为50%→30% A, 8~12 min为30%→5% A, 12~15 min为5%→5% A, 15~15 min为5%→96% A, 15~18 min为96%→96% A。

质谱条件 质谱检测以正离子电喷雾模式操作, 用四极杆飞行时间质谱仪Xevo G2-XS Q-Tof质谱检测器检测。氮气和氩气分别用作去溶剂化气体和碰撞气体。全扫描数据来自50至1 200 Da, 源温度为100 ℃, 去溶剂化温度为400 ℃, 扫描频率10.000 s, 锥电压为40.000 V。锁定喷雾标准为400 mg·mL^-1, 低碰撞能量扫描的碰撞能量为6.000 V, 高碰撞能量扫描的碰撞能量为30至70 V质谱仪, UPLC系统由MassLynx4.1软件(Waters, MA, USA) 控制。采用MS^E模式进行continue数据采集。

供试品溶液制备 将烘干的两种石斛茎、叶样品粉碎机粉碎, 过60目筛。精密称量0.02 g供试样品粉末, 加入体积分数70%的甲醇提取液1 mL, 振荡混匀2 min, 超声萃取45 min, 取出, 放冷, 然后8 000 r·min^-1离心10 min, 取上清, 经0.22 μm的微孔滤膜过滤, 即得供试品溶液, 每组设置4个重复, 放置4 ℃冰箱备用。

数据处理与统计方法 质谱数据处理采用Waters公司QI软件进行色谱峰自动识别、峰匹配、峰对齐、峰提取、峰积分和归一化处理, 得到的二级质谱结合在线数据库[SciFinder、MassBank of North America (MoNA)] 及已报道的文献对代谢物进行鉴定, 推测可能的化合物裂解规律。得到的数据输入SIMCA-P 14.1软件进行无监督的主成分分析(PCA), 从总体上得到各组样本之间的总体代谢差异和组内样本之间的变异度大小。有监督的正交偏最小二乘判别分析(OPLS-DA), 获得导致两组之间显著差异的相关代谢物信息。

结果与分析

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1 两种石斛茎叶化学成分定性分析

采用UPLC-Q-TOF-MS/MS的方法分别对两种石斛的茎和叶进行分析, 通过比较两种石斛不同部位的总离子流图(图 1), 发现同种石斛的不同部位间成分差异较小, 而在同一部位中两种石斛的成分差异较大。从两种石斛总离子流图中分离出759个质量峰, 结合石斛文献和公共数据库MassBank of North America (MoNA), 根据UPLC-MS/MS矩阵中的保留时间、质荷比及碎片离子等信息对两种石斛茎叶中的代谢产物进行指认, 两种石斛中共鉴定58个代谢产物, 如表 1^[15-37]所示, 其中生物碱34种, 黄酮类10种, 萜类7种, 联苄类5种, 菲类2种。

用峰面积分别计算两种石斛不同部位已经鉴定出的成分占58种物质总峰面积的百分比, 如表 2所示, 发现玫瑰石斛叶中生物碱峰面积比例为82.89%, 黄酮为3.95%, 萜类为10.96%, 联苄类为1.98%, 菲类为0.21%; 玫瑰石斛茎中生物碱峰面积比例为88.31%, 黄酮为1.30%, 萜类为8.46%, 联苄类为1.70%, 菲类为0.22%。玫瑰石斛中小分子成分以生物碱和萜类为主, 主要包括玫瑰石斛胺、玫瑰石斛碱B、C、E等生物碱, 以及萜类成分石斛苷D等。铁皮石斛茎中萜类成分占比最高, 达到70.56%, 主要为石斛苷D及其结构类似物; 黄酮类成分占比也较大, 达到22.90%, 主要包括芦丁、槲皮素等成分; 其生物碱、联苄类和菲类成分较少。铁皮石斛叶和茎成分组成差异不大。

2 化学成分的质谱解析

利用MasslynxV4.1软件进行质谱数据处理, 得到一级质谱精确相对分子质量, 其中选择碎片响应强度高的主要质谱峰进行鉴定, 再通过匹配二级质谱中的主要碎片离子, 结合在线数据库及已报道的文献对代谢物进行表征, 推测可能的化合物裂解规律。将文献中有关石斛成分的化合物数据进行收集整理, 共收录两百多种石斛化学成分信息, 通过比对, 初步鉴定出58种成分, 包括化合物名称、化学式、分子质量、保留时间、质谱类型等。

2.1 黄酮类

通过质谱图可以看到, 在保留时间(t_R) 为2.87 min时, 低能量通道下得到的精确质荷比m/z 303.051 9 [M+H]⁺, 其中m/z 304.053 7是m/z 303.051 9 [M+H]⁺的同位素峰。在高能量通道下得到二级质谱出现的275.059 4、257.049 5、229.053 3、201.057 4、153.056 5、125.080 0、109.396 4质谱峰特征碎片能进一步确认该化合物结构, 通过数据库匹配出分子式为C₁₅H₁₀O₇, 推测该化合物为槲皮素(quercetin)。其中m/z 275.059 4为槲皮素去CO产生的碎片, m/z 257.049 5为m/z 275.059 4继续脱去一分子H₂O后产生的碎片, m/z 229.053 3为m/z 257.059 4继续脱去CO后产生的碎片, m/z 201.057 4为m/z 229.053 3继续脱去CO后产生的碎片, 另一条裂解途径中m/z 153.056 5为槲皮素中间环发生逆Diels-Alder反应(RDA) 产生的碎片, m/z 125.080 0为m/z 153.056 5失去CO得到的碎片, m/z 109.396 4为m/z 153.056 5继续丢失CO₂得到的碎片, 这符合黄酮类化合物一般裂解规律, 结合文献^[38], 鉴定该化合物为槲皮素(quercetin), 裂解途径如图 2。

2.2 生物碱类

通过质谱图可以看到, 在保留时间为6.34 min时, 低能量通道下给出的精确质荷比获得m/z 279.102 3 [M]⁺, m/z 302.087 4 [M+Na]⁺, m/z 580.103 5 [2M+Na]⁺的质谱信号, 其中m/z 301.085 3是m/z 302.087 4 [M+Na]⁺的同位素峰, m/z 579.173 6是m/z 580.103 5 [2M+Na]⁺的同位素峰。在高能量通道下产生二级质谱出现的261.097 1、233.096 8、219.084 3、190.079 1质谱峰特征碎片能进一步确认该化合物结构, 通过数据库匹配出分子式为C₁₆H₂₅O₃N, 推测该化合物为2-羟基石斛碱(2-hydroxydendrobine)。其中m/z 261.097 1为2-羟基石斛碱脱去一分子H₂O产生的碎片, m/z 233.096 8为m/z 261.097 1继续脱去两分子CH₃后产生的碎片, m/z 219.084 3为m/z 233.096 8继续脱去CH₃后产生的碎片, 另一条裂解途径中m/z 219.084 3为m/z 261.097 1继续脱去CO₂后产生的碎片, m/z 190.079 1为m/z 219.084 3失去NH (CH₃) 的碎片, 这符合生物碱类化合物一般裂解规律, 结合文献和数据库^[39], 鉴定该化合物为2-羟基石斛碱(2-hydroxydendrobine), 裂解途径如图 3。

通过质谱图可以看到, 在保留时间为2.74 min时, 低能量通道下给出的精确质荷比获得m/z 288.196 2 [M+H]⁺的质谱信号, 其中m/z 289.201 0是m/z 288.196 2 [M+H]⁺的同位素峰。在高能量通道下产生二级质谱出现的271.187 6、270.184 4、253.176 8、252.175 0、226.157 8、228.137 6、184.112 3等质谱峰特征碎片能进一步确认该化合物结构, 其中271.187 6是270.184 4的同位素峰, 253.176 8是252.175 0的同位素峰, 226.157 8是228.137 6的同位素峰, 通过数据库匹配出分子式为C₁₈H₂₅NO₂, 推测该化合物为玫瑰石斛胺(crepidamine)。其中m/z 270.184 4为玫瑰石斛胺脱去一分子H₂O后产生的碎片, m/z 252.175 0为m/z 270.184 4继续失去一分子H₂O后产生的碎片, m/z 228.137 6为m/z 270.184 4脱去C₂H₂O后产生的碎片, m/z 184.112 3为m/z 228.137 6脱去C₃H₈后产生的碎片, 这与生物碱类中间环N原子比较活跃, 质谱碰撞与N连接的侧环容易断裂有关, 经过文献对比^[21], 鉴定该化合物为玫瑰石斛胺(crepidamine), 裂解途径如图 4。

2.3 萜类

通过质谱图可以看到, 在保留时间为8.29 min时, 低能量通道下获得精确质荷比m/z 295.132 6 [M+H]⁺, m/z 317.113 9 [M+Na]⁺, m/z 611.239 0 [2M+Na]⁺的质谱信号, 其中m/z 296.135 3为m/z 295.132 6 [M+H]⁺同位素峰, m/z 318.120 3为m/z 317.113 9 [M+Na]⁺的同位素峰, m/z 612.241 0为m/z 611.239 0 [2M+Na]⁺的同位素峰。在高能量通道下产生二级质谱出现的280.111 6、277.123 2、262.099 9等质谱特征碎片峰能进一步确认该化合物结构, 通过数据库匹配出分子式为C₁₅H₁₈O₆, 推测该化合物为钩状石斛素(aduncin)。其中m/z 277.119 8为m/z 295.132 6脱去一分子H₂O产生的碎片, m/z 233.096 8为m/z 277.119 8脱去一分子CO₂产生的碎片, m/z 189.070 5为m/z 233.096 8继续脱去一分子CO₂产生的碎片, m/z 249.126 7为m/z 277.123 2脱去一分子C₂H₄产生的碎片。经过文献对比^[30], 鉴定该化合物为钩状石斛素(aduncin), 裂解途径如图 5。

3 基于UPLC-Q-TOF-MS/MS代谢组学的两种石斛茎、叶差异代谢物分析

利用SIMCA-P 14.1软件对预处理后的数据进行PCA和OPLS-DA分析, 并通过载荷图, 以变量投影重要性(VIP值) > 1、统计学t检验P < 0.05为阈值, 筛选差异代谢物。PCA分析的得分散点图能从整体上观察各组的分离情况, 直观地显示不同样品之间的整体差异。结果显示(图 6), 不同物种不同部位之间明显分离, 这表明两个物种不同部位之间存在明显差异。横坐标为描述多维数据矩阵中最显著的特性; 纵坐标为除横坐标以外的所能描述多维数据矩阵中最显著的特性。在横坐标上, 玫瑰石斛和铁皮石斛明显分离, 这说明物种间的差异是分离玫瑰石斛和铁皮石斛的最显著的特性。在纵坐标上, 两种石斛的茎与叶明显分离, 且茎、叶分别分布在同侧, 这说明部位之间的差异是第二显著的特性。铁皮石斛茎叶两组相距较近, 组间差异可能较小; 而玫瑰石斛茎叶两组相距较远, 组间差异可能较大。

PCA作为一种反映原始数据状态的无监督方法, 环境等其他因素以及系统错误都会影响实验结果。为排除由与实验无关的某些因素引起的代谢变化, 并获得更准确的结果, 本研究使用有监督的OPLS-DA分析对数据进行进一步处理, 确定潜在的差异成分。建立OPLS-DA模型分别分析同种石斛不同部位和不同石斛同种部位的差异。OPLS-DA分析着重强调组间的差异, 通过拟合度(R²Y) 和预测度(Q²) 对模型准确性进行评价, 一般R²Y值较大, Q² > 0.5表明该模型较好。其中叶组R²Y = 1, Q² = 1; 茎组R²Y = 0.999, Q² = 0.990; 玫瑰组R²Y = 1, Q² = 0.997; 铁皮组R²Y = 1, Q² = 0.999。对以下四个模型进行置换检验, 用于验证OPLS-DA模型的拟合程度, Q²截距值小于0, 表明模型有效, 可以进行后续的差异成分寻找。

3.1 玫瑰石斛茎叶之间差异代谢物分析

根据S-plot图结合VIP值和t检验P值筛选差异代谢物(VIP值> 1, P值< 0.05) (图 7), 得到14种差异代谢物(表 3)。玫瑰石斛茎叶组间差异较大, 与PCA指示结果一致。玫瑰石斛胺、crepidatumines C、玫瑰石斛碱D、玫瑰石斛碱E等物质峰是造成玫瑰石斛茎叶差异的主要成分。其中crepidatumines C在茎叶中的比例分别为14.23%和7.53%; 玫瑰石斛碱E比例分别为13.52%和10.64%。

3.2 铁皮石斛茎叶之间差异代谢物分析

根据S-plot图结合VIP值和t检验P值筛选差异代谢物(VIP值> 1, P值< 0.05) (图 8), 得到3种差异代谢物(表 4)。铁皮石斛茎叶之间仅存在3个差异代谢物, 说明组间差异较小, 与PCA指示结果一致。对筛选到的差异代谢物的峰面积进行比较发现, 槲皮素、芦丁、石斛苷D在铁皮石斛叶中的占比明显高于茎。铁皮石斛茎中槲皮素、芦丁、石斛苷D的比例分别为2.32%、6.65%和45.65%; 在叶中的比例分别为9.33%、17.41%和55.63%。石斛苷D占铁皮石斛中已鉴定成分比例的一半左右。

3.3 铁皮石斛茎与玫瑰石斛茎之间差异代谢物分析

根据S-plot图结合VIP值和t检验P值筛选差异代谢物(VIP值> 1, P值< 0.05) (图 9), 得到16种差异代谢物(表 5)。对筛选到的差异代谢物在铁皮石斛茎和玫瑰石斛茎中的峰面积进行比较, 发现crepidatumines C、玫瑰石斛碱C、玫瑰石斛碱、N-甲基石斛碱、玫瑰石斛碱D、玫瑰啶碱B、2-羟基石斛碱、玫瑰石斛啶碱、玫瑰石斛碱B、石斛酚和山柰酚等成分只在玫瑰石斛茎中检测到, 在铁皮石茎中未检测到, 其中crepidatumines C、玫瑰石斛碱B、玫瑰石斛碱E、玫瑰石斛啶碱, 比例分别达到14.23%、13.16%、13.52%和8.94%。可以作为鉴别铁皮石斛和玫瑰石斛的关键差异代谢物。石斛苷D在玫瑰石斛茎和铁皮石斛茎中均能检测到, 且在玫瑰石斛中峰面积比例为7.03%, 明显低于铁皮石斛的45.65%。

3.4 铁皮石斛叶与玫瑰石斛叶之间差异代谢物分析

根据S-plot图结合VIP值和t检验P值筛选差异代谢物(VIP值> 1, P值< 0.05) (图 10), 得到22种差异代谢物(表 6)。对筛选到的差异代谢物在铁皮石斛叶和玫瑰石斛叶中的峰面积进行比较, 结果显示, 玫瑰石斛胺、crepidatumines C、山柰酚、玫瑰石斛啶碱、玫瑰石斛碱C、玫瑰石斛碱、N-甲基石斛季铵碱、玫瑰石斛碱B、玫瑰石斛碱D、玫瑰啶碱B、2-羟基石斛碱和石斛酚仅在玫瑰石斛叶中检测到, 在铁皮石斛叶中未检测到, 其中玫瑰石斛碱C比例达9.34%, 玫瑰石斛碱E比例达10.64%, 玫瑰石斛啶碱比例达9.05%, 槲皮素和芦丁在玫瑰石斛叶和铁皮石斛叶中均存在, 且铁皮石斛叶中峰面积明显高于玫瑰石斛, 其中铁皮石斛叶中槲皮素比例为9.33%, 芦丁比例为17.41%, 在玫瑰石斛中二者分别为0.07%和0.11%。

讨论

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石斛属植物种类繁多, 其中铁皮石斛、金钗石斛、霍山石斛、流苏石斛和鼓槌石斛被《中华人民共和国药典》收录^[40]。药用石斛化学成分复杂, 主要包括多糖类、生物碱类、黄酮类、菲类、联苄类、挥发油类等多种活性物质^[41], 具有抗血管生成、免疫调节、抗糖尿病、抑制白内障、神经保护、保肝、抗炎、抗血小板聚集等作用^[42]。不同化学成分在不同石斛间的含量分布也存在较大差异。如生物碱在金钗石斛中的含量明显高于铁皮石斛, 尤其石斛碱成分含量是同属其他植物中最高的^[43], 是金钗石斛的特征性成分。铁皮石斛中活性成分主要为黄酮和石斛多糖^{[44, 45]}, 生物碱成分与金钗石斛相比含量很低^[46]。王再花等^[47]采用热水浸提法和酸性染料比色法比较研究了26种野生石斛, 发现玫瑰石斛的生物碱含量为0.500%, 高于金钗石斛的0.415%, 而铁皮石斛中仅为0.068%。说明玫瑰石斛的生物碱含量极高, 可能是玫瑰石斛的主要药用成分, 具有极大的开发价值。本研究采用基于UPLC-Q-TOF-MS/MS技术分别对铁皮石斛和玫瑰石斛的茎和叶进行化学成分分析, 共鉴定或推断出58个代谢物, 其中生物碱34种, 黄酮类10种, 萜类7种, 联苄类5种和菲类2种。计算不同物质峰面积的相对比例, 发现玫瑰石斛叶中生物碱峰面积比例为82.89%, 黄酮为3.95%, 萜类为10.96%; 茎中生物碱比例为88.31%, 黄酮为1.30%, 萜类为8.46%。铁皮石斛叶生物碱比例为2.25%, 黄酮为31.33%, 萜类为64.84%; 茎生物碱比例为1.72%, 黄酮为22.90%, 萜类为70.56%。结合PCA和OPLS-DA多变量统计分析, 发现玫瑰石斛和铁皮石斛之间存在的种间差异较大。铁皮石斛中黄酮类和萜类成分显著高于玫瑰石斛, 主要包括槲皮素、芦丁和石斛苷D。其中石斛苷D及其异构体的面积比例在铁皮石斛叶中达到了63.59%, 茎中达到48.40%。这些成分具有抗氧化、抗肿瘤、抗炎症、抗菌、降血糖、保护心血管和免疫调节等药理作用^[48-50]。玫瑰石斛碱、玫瑰石斛碱B、玫瑰石斛碱C、玫瑰石斛碱D、玫瑰石斛啶碱、玫瑰石斛胺、玫瑰啶碱B等玫瑰石斛特有的生物碱是造成玫瑰石斛和铁皮石斛差异的主要成分。同时, 这些化合物可以作为鉴别铁皮石斛和玫瑰石斛的标志性代谢物。李振坚等^[21]的研究表明玫瑰石斛中的玫瑰石斛碱、玫瑰石斛啶碱、玫瑰石斛胺等生物碱为中氮茚生物碱, 与金钗石斛中倍半萜生物碱不同。目前分离到的中氮茚生物碱主要分布于石斛属、娃儿藤属和杜英属的植物中。现有的研究表明中氮茚及其衍生物具有抗结核、抗氧化、抗菌、抗癌、抗炎等药理活性^[51]。结合对玫瑰石斛的抗炎^[52]、抗氧化^[53]、细胞毒性^[53]、缓解急性肺损伤^[54]、神经保护^[55]等研究, 推测生物碱可能是玫瑰石斛中的主要药效成分。Hu等^[54]提取了玫瑰石斛的总生物碱成分, 并发现玫瑰石斛总生物碱可通过下调tlr4介导的MyD88/MAPK信号通路, 抑制脂多糖(LPS) 激活的巨噬细胞中一氧化氮(NO) 的生成, 并对LPS诱导的小鼠急性肺损伤具有保护作用。虽然玫瑰石斛在云南地区被当作石斛来使用, 但其药效的物质基础并不明确, 由于玫瑰石斛的生物碱含量甚至高于《中国药典》中记载的金钗石斛, 因此, 玫瑰石斛具有极大的资源开发价值。目前玫瑰石斛已实现人工栽培, 对玫瑰石斛生物碱的药理活性仍需做进一步的研究。若能阐明玫瑰石斛中生物碱的药理活性, 将极大提升玫瑰石斛的药用价值。

综上, 本研究通过UPLC-Q-TOF-MS/MS技术, 对玫瑰石斛和铁皮石斛茎、叶的成分进行了鉴定与对比, 发现铁皮石斛中主要的小分子成分为萜类和黄酮, 玫瑰石斛中主要的小分子成分为生物碱和萜类。其中玫瑰石斛碱、玫瑰石斛碱B、玫瑰石斛碱C、玫瑰石斛碱D、玫瑰石斛碱E、玫瑰石斛啶碱、玫瑰石斛胺、玫瑰啶碱B等多种生物碱成分只存在于玫瑰石斛。对石斛属内多种药材的鉴别与资源利用具有指导意义, 同时为开发玫瑰石斛资源提供了新思路。

作者贡献: 娄港归、夏杰负责实验研究、数据分析及文稿撰写, 王宏鹏、施宛丽、杨健负责成分检测, 梁宗锁、肖艺、李振达、张煜、刘志超负责石斛样本采集和数据分析, 通讯作者张晓丹、杨东风负责项目总体设计、规划以及稿件修改。

利益冲突: 本文作者声明该论文没有涉及任何利益冲突。

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中央本级重大增减支项目子课题(2060302)
浙江省自然科学基金杰出青年基金资助项目(LR21H280002)
中央级公益性科研院所基本科研业务费专项(ZZXT201906)
宁波市3315系列计划项目(2019B-24-C)
国家级大学生创新创业训练计划项目(202011057025)

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2021年第56卷第12期

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doi: 10.16438/j.0513-4870.2021-0939

接收时间：2021-06-28
首发时间：2025-12-18
出版时间：2021-12-12

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收稿日期：2021-06-28
修回日期：2021-09-13

基金

中央本级重大增减支项目子课题(2060302)

浙江省自然科学基金杰出青年基金资助项目(LR21H280002)

中央级公益性科研院所基本科研业务费专项(ZZXT201906)

宁波市3315系列计划项目(2019B-24-C)

国家级大学生创新创业训练计划项目(202011057025)

作者信息

1.浙江理工大学生命科学与医药学院, 浙江省植物次生代谢调控重点实验室, 浙江杭州 310018

2.中国中医科学院中药资源中心, 道地药材国家重点实验室培育基地, 北京 100700

3.浙江科技学院生物与化学工程学院, 浙江杭州 310023

4.宁波易中禾药用植物研究院有限公司, 浙江宁波 315010

5.云南野兰堂生物科技有限公司, 云南昆明 650114

6.六安市农业科学研究院中药材研究室, 安徽六安 237000

通讯作者:

*张晓丹, E-mail: zxd211@zstu.edu.cn;

杨东风, E-mail: ydf807@sina.com

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2种不同金属材料的力学参数

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

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TxT

No.	Compound	Formula	MW	R_t/min	Ion type	Classification	Ref.
1	Flakinin B	C₁₆H₂₄O₅	296.162 3	2.941	[M+H]⁺	Terpenoids	[15]
2	Dendronobilin N	C₁₅H₂₄O₄	268.167 4	2.987	[M+H]⁺	Terpenoids	[16]
3	Dendronobilin K	C₁₅H₂₄O₄	268.167 4	3.102	[M+H]⁺	Terpenoids	[16]
4	Aduncin	C₁₅H₁₈O₆	294.110 3	8.286	[M+H]⁺	Terpenoids	[17]
5	Dendroside D isomer 1	C₂₇H₄₄O₁₄	592.273 1	10.639	[M+H]⁺	Terpenoids	[18]
6	Dendroside D	C₂₇H₄₄O₁₄	592.273 1	10.287	[M+H]⁺	Terpenoids	[18]
7	Dendronobiloside C/D	C₂₇H₄₄O₁₂	560.283 2	10.363	[M+H]⁺	Terpenoids	[19]
8	Inosine isomer 1	C₁₀H₁₂N₄O₅	268.080 7	0.661	[M+H]⁺	Alkaloids	[20]
9	Inosine	C₁₀H₁₂N₄O₅	268.080 7	0.941	[M+H]⁺	Alkaloids	[20]
10	Dendrocrepine isomer 2	C₃₃H₄₄O₃N₂	516.335 1	2.457	[M+H]⁺	Alkaloids	[21]
11	Drepidamine	C₁₈H₂₅NO₂	287.188 5	3.125	[M+H]⁺	Alkaloids	[21]
12	Nobilonine	C₁₇H₂₇NO₃	293.199 0	2.609	[M+H]⁺	Alkaloids	[21]
13	Crepidine isomer 3	C₂₁H₂₉NO₃	343.214 7	2.682	[M+H]⁺	Alkaloids	[21]
14	Crepidatumines C	C₁₈H₂₅NO₂	287.188 5	2.722	[M+H]⁺	Alkaloids	[21]
15	Dendrocrepine isomer 1	C₃₃H₄₄O₃N₂	516.335 1	2.732	[M+H]⁺	Alkaloids	[21]
16	Crepidine	C₂₁H₂₉NO₃	343.214 7	2.777	[M+H]⁺	Alkaloids	[21]
17	Dendrocrepidine C	C₁₈H₂₅O₂N	287.188 5	2.823	[M+H]⁺	Alkaloids	[21]
18	N-Methyldendrobinium isomer 1	C₁₇H₂₈O₂N	278.212 0	2.858	[M]⁺	Alkaloids	[22]
19	Dendrocrepidine E	C₃₃H₄₅O₄N₂	533.337 9	3.417	[M+H]⁺	Alkaloids	[21]
20	Dendrocrepidine E isomer 1	C₃₃H₄₅O₄N₂	533.337 9	3.365	[M+H]⁺	Alkaloids	[21]
21	Dendrocrepine	C₃₃H₄₄O₃N₂	516.335 1	2.987	[M+H]⁺	Alkaloids	[21]
22	N-Methyldendrobinium isomer 2	C₁₇H₂₈O₂N	278.212 0	2.987	[M]⁺	Alkaloids	[22]
23	Crepidine isomer 2	C₂₁H₂₉NO₃	343.214 7	3.021	[M+H]⁺	Alkaloids	[21]
24	Shihunidine	C₁₂H₁₃NO₂	203.094 6	3.041	[M+H]⁺	Alkaloids	[23]
25	Ddendrocrepine isomer 3	C₃₃H₄₄O₃N₂	516.335 1	3.057	[M+H]⁺	Alkaloids	[21]
26	Dendrocrepidine B	C₂₀H₂₇NO₄	345.194 0	3.083	[M+H]⁺	Alkaloids	[21]
27	Homocrepidine B isomer 1	C₂₀H₂₇NO₄	345.194 0	3.323	[M+H]⁺	Alkaloids	[21]
28	N-Methyldendrobinium	C₁₇H₂₈O₂N	278.212 0	3.106	[M]⁺	Alkaloids	[22]
29	Dendrocrepidine D	C₁₇H₂₂NO₂	272.165 0	3.151	[M+H]⁺	Alkaloids	[21]
30	Homocrepidine B	C₁₈H₂₇NO₂	289.204 1	3.201	[M+H]⁺	Alkaloids	[21]
31	N-Isopentenyl-dendroxinium	C₂₂H₃₃NO₃	360.253 8	3.281	[M]⁺	Alkaloids	[21]
32	2-Hydroxydendrobine	C₁₆H₂₅NO₃	279.183 4	3.289	[M]⁺	Alkaloids	[24]
33	Crepidine isomer 3	C₂₁H₂₉NO₃	343.214 7	3.418	[M+H]⁺	Alkaloids	[21]
34	Crepidine isomer 1	C₂₁H₂₉NO₃	343.214 7	3.469	[M+H]⁺	Alkaloids	[21]
35	Crepidine isomer 5	C₂₁H₂₉NO₃	343.214 7	3.526	[M+H]⁺	Alkaloids	[21]
36	N-Isopentenyl-dendrobinium	C₂₁H₃₃NO₂	332.258 9	3.824	[M]⁺	Alkaloids	[21]
37	Mubironine B	C₁₅H₂₃O₂N	249.172 8	12.065	[M+H]⁺	Alkaloids	[15]
38	Dendrine	C₁₉H₂₉NO₄	335.209 6	5.981	[M]⁺	Alkaloids	[25]
39	6-Hydroxynobiline	C₁₇H₂₇O₄N	309.194 0	3.045	[M+H]⁺	Alkaloids	[26]
40	Dendrobine	C₁₆H₂₅O₂N	263.188 5	9.075	[M]⁺	Alkaloids	[27]
41	Dendroamine	C₁₆H₂₅O₃N	279.183 4	9.053	[M]⁺	Alkaloids	[28]
42	Gigantol isomer 1	C₁₆H₁₈O₄	274.120 5	3.891	[M+H]⁺	Bibenzyls	[29]
43	Gigantol	C₁₆H₁₈O₄	274.120 5	3.533	[M+H]⁺	Bibenzyls	[29]
44	Dendrocandin K	C₃₁H₃₀O₇	514.199 1	4.492	[M+H]⁺	Bibenzyls	[30]
45	Chrysotoxine	C₁₈H₂₂O₅	318.146 7	5.423	[M+H]⁺	Bibenzyls	[31]
46	Crepidatin	C₁₈H₂₂O₅	318.146 7	5.222	[M+H]⁺	Bibenzyls	[21]
47	Isoschaftoside isomer 1	C₂₆H₂₈O₁₄	564.147 9	2.659	[M+H]⁺	Flavonoids	[32]
48	Isoschaftoside	C₂₆H₂₈O₁₄	564.147 9	2.716	[M+H]⁺	Flavonoids	[32]
49	Kaempferol	C₁₅H₁₀O₆	286.047 7	2.747	[M+H]⁺	Flavonoids	[29]
50	Rutin	C₂₇H₃₀O₁₆	610.153 3	2.865	[M+H]⁺	Flavonoids	[29]
51	Quercetin	C₁₅H₁₀O₇	302.042 6	2.872	[M+H]⁺	Flavonoids	[29]
52	Dihydropinosylvin methyl ether	C₁₅H₁₆O₂	228.115 0	3.281	[M+H]⁺	Flavonoids	[29]
53	Violanthin	C₂₇H₃₀O₁₄	578.163 5	7.923	[M+H]⁺	Flavonoids	[33]
54	Schaftoside	C₂₆H₂₈O₁₄	564.147 9	2.609	[M+H]⁺	Flavonoids	[32]
55	Apigenin-6-C-α-L-arabinoside-8-C-β-D-xyloside	C₂₅H₂₆O₁₃	534.137 3	2.838	[M+H]⁺	Flavonoids	[34]
56	Glucosylvitexin	C₂₇H₃₀O₁₅	594.158 4	2.749	[M+H]⁺	Flavonoids	[35]
57	Confusarin	C₁₇H₁₆O₅	300.099 7	7.912	[M+H]⁺	Phenanthrenes	[36]
58	Denobilone B	C₁₅H₁₆O₄	260.104 8	7.682	[M+H]⁺	Phenanthrenes	[37]

No.

Compound

Formula

R_t/min

Ion type

Classification

Ref.

Flakinin B

C₁₆H₂₄O₅

296.162 3

2.941

[M+H]⁺

Terpenoids

[15]

Dendronobilin N

C₁₅H₂₄O₄

268.167 4

2.987

[M+H]⁺

Terpenoids

[16]

Dendronobilin K

C₁₅H₂₄O₄

268.167 4

3.102

[M+H]⁺

Terpenoids

[16]

Aduncin

C₁₅H₁₈O₆

294.110 3

8.286

[M+H]⁺

Terpenoids

[17]

Dendroside D isomer 1

C₂₇H₄₄O₁₄

592.273 1

10.639

[M+H]⁺

Terpenoids

[18]

Dendroside D

C₂₇H₄₄O₁₄

592.273 1

10.287

[M+H]⁺

Terpenoids

[18]

Dendronobiloside C/D

C₂₇H₄₄O₁₂

560.283 2

10.363

[M+H]⁺

Terpenoids

[19]

Inosine isomer 1

C₁₀H₁₂N₄O₅

268.080 7

0.661

[M+H]⁺

Alkaloids

[20]

Inosine

C₁₀H₁₂N₄O₅

268.080 7

0.941

[M+H]⁺

Alkaloids

[20]

Dendrocrepine isomer 2

C₃₃H₄₄O₃N₂

516.335 1

2.457

[M+H]⁺

Alkaloids

[21]

Drepidamine

C₁₈H₂₅NO₂

287.188 5

3.125

[M+H]⁺

Alkaloids

[21]

Nobilonine

C₁₇H₂₇NO₃

293.199 0

2.609

[M+H]⁺

Alkaloids

[21]

Crepidine isomer 3

C₂₁H₂₉NO₃

343.214 7

2.682

[M+H]⁺

Alkaloids

[21]

Crepidatumines C

C₁₈H₂₅NO₂

287.188 5

2.722

[M+H]⁺

Alkaloids

[21]

Dendrocrepine isomer 1

C₃₃H₄₄O₃N₂

516.335 1

2.732

[M+H]⁺

Alkaloids

[21]

Crepidine

C₂₁H₂₉NO₃

343.214 7

2.777

[M+H]⁺

Alkaloids

[21]

Dendrocrepidine C

C₁₈H₂₅O₂N

287.188 5

2.823

[M+H]⁺

Alkaloids

[21]

N-Methyldendrobinium isomer 1

C₁₇H₂₈O₂N

278.212 0

2.858

[M]⁺

Alkaloids

[22]

Dendrocrepidine E

C₃₃H₄₅O₄N₂

533.337 9

3.417

[M+H]⁺

Alkaloids

[21]

Dendrocrepidine E isomer 1

C₃₃H₄₅O₄N₂

533.337 9

3.365

[M+H]⁺

Alkaloids

[21]

Dendrocrepine

C₃₃H₄₄O₃N₂

516.335 1

2.987

[M+H]⁺

Alkaloids

[21]

N-Methyldendrobinium isomer 2

C₁₇H₂₈O₂N

278.212 0

2.987

[M]⁺

Alkaloids

[22]

Crepidine isomer 2

C₂₁H₂₉NO₃

343.214 7

3.021

[M+H]⁺

Alkaloids

[21]

Shihunidine

C₁₂H₁₃NO₂

203.094 6

3.041

[M+H]⁺

Alkaloids

[23]

Ddendrocrepine isomer 3

C₃₃H₄₄O₃N₂

516.335 1

3.057

[M+H]⁺

Alkaloids

[21]

Dendrocrepidine B

C₂₀H₂₇NO₄

345.194 0

3.083

[M+H]⁺

Alkaloids

[21]

Homocrepidine B isomer 1

C₂₀H₂₇NO₄

345.194 0

3.323

[M+H]⁺

Alkaloids

[21]

N-Methyldendrobinium

C₁₇H₂₈O₂N

278.212 0

3.106

[M]⁺

Alkaloids

[22]

Dendrocrepidine D

C₁₇H₂₂NO₂

272.165 0

3.151

[M+H]⁺

Alkaloids

[21]

Homocrepidine B

C₁₈H₂₇NO₂

289.204 1

3.201

[M+H]⁺

Alkaloids

[21]

N-Isopentenyl-dendroxinium

C₂₂H₃₃NO₃

360.253 8

3.281

[M]⁺

Alkaloids

[21]

2-Hydroxydendrobine

C₁₆H₂₅NO₃

279.183 4

3.289

[M]⁺

Alkaloids

[24]

Crepidine isomer 3

C₂₁H₂₉NO₃

343.214 7

3.418

[M+H]⁺

Alkaloids

[21]

Crepidine isomer 1

C₂₁H₂₉NO₃

343.214 7

3.469

[M+H]⁺

Alkaloids

[21]

Crepidine isomer 5

C₂₁H₂₉NO₃

343.214 7

3.526

[M+H]⁺

Alkaloids

[21]

N-Isopentenyl-dendrobinium

C₂₁H₃₃NO₂

332.258 9

3.824

[M]⁺

Alkaloids

[21]

Mubironine B

C₁₅H₂₃O₂N

249.172 8

12.065

[M+H]⁺

Alkaloids

[15]

Dendrine

C₁₉H₂₉NO₄

335.209 6

5.981

[M]⁺

Alkaloids

[25]

6-Hydroxynobiline

C₁₇H₂₇O₄N

309.194 0

3.045

[M+H]⁺

Alkaloids

[26]

Dendrobine

C₁₆H₂₅O₂N

263.188 5

9.075

[M]⁺

Alkaloids

[27]

Dendroamine

C₁₆H₂₅O₃N

279.183 4

9.053

[M]⁺

Alkaloids

[28]

Gigantol isomer 1

C₁₆H₁₈O₄

274.120 5

3.891

[M+H]⁺

Bibenzyls

[29]

Gigantol

C₁₆H₁₈O₄

274.120 5

3.533

[M+H]⁺

Bibenzyls

[29]

Dendrocandin K

C₃₁H₃₀O₇

514.199 1

4.492

[M+H]⁺

Bibenzyls

[30]

Chrysotoxine

C₁₈H₂₂O₅

318.146 7

5.423

[M+H]⁺

Bibenzyls

[31]

Crepidatin

C₁₈H₂₂O₅

318.146 7

5.222

[M+H]⁺

Bibenzyls

[21]

Isoschaftoside isomer 1

C₂₆H₂₈O₁₄

564.147 9

2.659

[M+H]⁺

Flavonoids

[32]

Isoschaftoside

C₂₆H₂₈O₁₄

564.147 9

2.716

[M+H]⁺

Flavonoids

[32]

Kaempferol

C₁₅H₁₀O₆

286.047 7

2.747

[M+H]⁺

Flavonoids

[29]

Rutin

C₂₇H₃₀O₁₆

610.153 3

2.865

[M+H]⁺

Flavonoids

[29]

Quercetin

C₁₅H₁₀O₇

302.042 6

2.872

[M+H]⁺

Flavonoids

[29]

Dihydropinosylvin methyl ether

C₁₅H₁₆O₂

228.115 0

3.281

[M+H]⁺

Flavonoids

[29]

Violanthin

C₂₇H₃₀O₁₄

578.163 5

7.923

[M+H]⁺

Flavonoids

[33]

Schaftoside

C₂₆H₂₈O₁₄

564.147 9

2.609

[M+H]⁺

Flavonoids

[32]

Apigenin-6-C-α-L-arabinoside-8-C-β-D-xyloside

C₂₅H₂₆O₁₃

534.137 3

2.838

[M+H]⁺

Flavonoids

[34]

Glucosylvitexin

C₂₇H₃₀O₁₅

594.158 4

2.749

[M+H]⁺

Flavonoids

[35]

Confusarin

C₁₇H₁₆O₅

300.099 7

7.912

[M+H]⁺

Phenanthrenes

[36]

Denobilone B

C₁₅H₁₆O₄

260.104 8

7.682

[M+H]⁺

Phenanthrenes

[37]

No.	Compound	Leaf of D. crepidatum	Stem of D. crepidatum	Leaf of D. officinale	Stem of D. officinale
1	Dendronobilin K	0.22	0.41	0.00	0.00
2	Dendronobilin N	0.13	0.19	0.00	0.00
3	Aduncin	0.00	0.04	0.11	13.97
4	Flakinin B	0.08	0.04	0.00	0.00
5	Dendronobiloside C/D	0.10	0.31	1.14	8.19
6	Dendroside D isomer 1	0.97	0.45	7.96	2.75
7	Dendroside D	9.47	7.03	55.63	45.65
8	Shihunidine	0.08	0.01	0.00	0.00
9	Mubironine B	0.04	0.04	0.13	1.16
10	Dendrobine	0.08	0.04	0.63	0.00
11	Inosine	0.07	0.00	0.59	0.00
12	Inosine isomer 1	0.04	0.00	0.33	0.00
13	Dendrocrepidine D	0.52	0.52	0.00	0.00
14	N-Methyl-dendrobine isomer 1	0.31	0.33	0.00	0.00
15	N-Methyl-dendrobine	1.07	1.96	0.00	0.00
16	N-Methyl-dendrobine isomer 2	0.99	1.50	0.00	0.00
17	2-Hydroxydendrobine	0.57	1.21	0.00	0.00
18	Dendroamine	0.06	0.02	0.58	0.00
19	Crepidamine	6.16	6.43	0.00	0.00
20	Dendrocrepidine C	9.34	9.82	0.00	0.00
21	Crepidatumines C	7.53	14.23	0.00	0.00
22	Homocrepidine B	4.14	3.91	0.00	0.00
23	Homocrepidine B isomer 1	6.42	5.38	0.00	0.00
24	Nobilonine	0.69	0.32	0.00	0.00
25	6-Hydroxynobiline	0.82	0.09	0.00	0.00
26	Dendrocrepidine E isomer 1	7.19	0.82	0.00	0.00
27	Dendrocrepidine E	10.64	13.52	0.00	0.00
28	N-Isopentenyl-dendrobinium	1.10	1.35	0.00	0.00
29	Dendrine	0.13	0.06	0.00	0.00
30	Crepidine isomer 1	0.55	0.21	0.00	0.00
31	Crepidine isomer 2	1.12	0.33	0.00	0.00
32	Crepidine isomer 3	1.43	0.09	0.00	0.00
33	Crepidine	9.05	8.94	0.00	0.00
34	Crepidine isomer 3	0.61	0.40	0.00	0.00
35	Crepidine isomer 5	2.39	1.49	0.00	0.00
36	Dendrocrepidine B	8.23	13.16	0.00	0.00
37	N-Isopentenyl-dendroxinium	0.21	0.06	0.00	0.00
38	Dendrocrepine isomer 1	0.11	0.07	0.00	0.00
39	Dendrocrepine isomer 2	0.45	0.28	0.00	0.00
40	Dendrocrepine	0.69	1.54	0.00	0.00
41	Ddendrocrepine isomer 3	0.08	0.16	0.00	0.00
42	Gigantol isomer 1	0.17	0.11	0.00	0.00
43	Gigantol	1.25	0.87	0.00	0.00
44	Crepidatin	0.46	0.57	0.00	0.00
45	Chrysotoxine	0.04	0.03	0.12	0.00
46	Dendrocandin K	0.06	0.12	0.00	0.00
47	Dihydropinosylvin methyl ether	0.07	0.17	0.00	0.00
48	Kaempferol	2.91	0.90	0.00	0.00
49	Quercetin	0.07	0.00	9.33	2.32
50	Apigenin-6-C-α-L-arabinoside-8-C-β-D-xyloside	0.00	0.00	0.93	0.63
51	Isoschaftoside	0.00	0.00	1.04	1.66
52	Isoschaftoside isomer 1	0.00	0.00	1.26	1.80
53	Schaftoside	0.00	0.00	1.13	1.81
54	Violanthin	0.01	0.01	0.03	0.00
55	Glucosylvitexin	0.78	0.22	0.21	8.03
56	Rutin	0.11	0.00	17.41	6.65
57	Denobilone B	0.07	0.00	0.65	0.00
58	Confusarin	0.14	0.23	0.80	5.37

No.

Compound

Leaf of D. crepidatum

Stem of D. crepidatum

Leaf of D. officinale

Stem of D. officinale

Dendronobilin K

0.22

0.41

0.00

Dendronobilin N

0.13

0.19

0.00

Aduncin

0.00

0.04

0.11

13.97

Flakinin B

0.08

0.04

0.00

Dendronobiloside C/D

0.10

0.31

1.14

8.19

Dendroside D isomer 1

0.97

0.45

7.96

2.75

Dendroside D

9.47

7.03

55.63

45.65

Shihunidine

0.08

0.01

0.00

Mubironine B

0.04

0.13

1.16

Dendrobine

0.08

0.04

0.63

0.00

Inosine

0.07

0.00

0.59

0.00

Inosine isomer 1

0.04

0.00

0.33

0.00

Dendrocrepidine D

0.52

0.00

N-Methyl-dendrobine isomer 1

0.31

0.33

0.00

N-Methyl-dendrobine

1.07

1.96

0.00

N-Methyl-dendrobine isomer 2

0.99

1.50

0.00

2-Hydroxydendrobine

0.57

1.21

0.00

Dendroamine

0.06

0.02

0.58

0.00

Crepidamine

6.16

6.43

0.00

Dendrocrepidine C

9.34

9.82

0.00

Crepidatumines C

7.53

14.23

0.00

Homocrepidine B

4.14

3.91

0.00

Homocrepidine B isomer 1

6.42

5.38

0.00

Nobilonine

0.69

0.32

0.00

6-Hydroxynobiline

0.82

0.09

0.00

Dendrocrepidine E isomer 1

7.19

0.82

0.00

Dendrocrepidine E

10.64

13.52

0.00

N-Isopentenyl-dendrobinium

1.10

1.35

0.00

Dendrine

0.13

0.06

0.00

Crepidine isomer 1

0.55

0.21

0.00

Crepidine isomer 2

1.12

0.33

0.00

Crepidine isomer 3

1.43

0.09

0.00

Crepidine

9.05

8.94

0.00

Crepidine isomer 3

0.61

0.40

0.00

Crepidine isomer 5

2.39

1.49

0.00

Dendrocrepidine B

8.23

13.16

0.00

N-Isopentenyl-dendroxinium

0.21

0.06

0.00

Dendrocrepine isomer 1

0.11

0.07

0.00

Dendrocrepine isomer 2

0.45

0.28

0.00

Dendrocrepine

0.69

1.54

0.00

Ddendrocrepine isomer 3

0.08

0.16

0.00

Gigantol isomer 1

0.17

0.11

0.00

Gigantol

1.25

0.87

0.00

Crepidatin

0.46

0.57

0.00

Chrysotoxine

0.04

0.03

0.12

0.00

Dendrocandin K

0.06

0.12

0.00

Dihydropinosylvin methyl ether

0.07

0.17

0.00

Kaempferol

2.91

0.90

0.00

Quercetin

0.07

0.00

9.33

2.32

Apigenin-6-C-α-L-arabinoside-8-C-β-D-xyloside

0.00

0.93

0.63

Isoschaftoside

0.00

1.04

1.66

Isoschaftoside isomer 1

0.00

1.26

1.80

Schaftoside

0.00

1.13

1.81

Violanthin

0.01

0.03

0.00

Glucosylvitexin

0.78

0.22

0.21

8.03

Rutin

0.11

0.00

17.41

6.65

Denobilone B

0.07

0.00

0.65

0.00

Confusarin

0.14

0.23

0.80

5.37

Compound	P	VIP
Crepidamine	0.003 155	1.173 56
Crepidine isomer 3	0.001 799	2.158 45
Crepidatumines C	0.032 592	1.774 13
Kaempferol	0.000 187	2.837 34
Crepidine	0.021 959	3.392 17
Dendrocrepidine C	0.000 007	3.297 02
Crepidine isomer 3	0.038 898	1.747 11
Dendrocrepidine D	0.018 880	1.037 13
Crepidine isomer 4	0.000 112	1.092 13
Crepidine isomer 1	0.000 000	1.180 16
Gigantol	0.002 447	1.517 39
Nobilonine	0.016 435	3.290 58
Dendrocrepidine E	0.001 015	3.315 20
Glucosylvitexin	0.000 725	2.748 92

Compound

VIP

Crepidamine

0.003 155

1.173 56

Crepidine isomer 3

0.001 799

2.158 45

Crepidatumines C

0.032 592

1.774 13

Kaempferol

0.000 187

2.837 34

Crepidine

0.021 959

3.392 17

Dendrocrepidine C

0.000 007

3.297 02

Crepidine isomer 3

0.038 898

1.747 11

Dendrocrepidine D

0.018 880

1.037 13

Crepidine isomer 4

0.000 112

1.092 13

Crepidine isomer 1

0.000 000

1.180 16

Gigantol

0.002 447

1.517 39

Nobilonine

0.016 435

3.290 58

Dendrocrepidine E

0.001 015

3.315 20

Glucosylvitexin

0.000 725

2.748 92

Compound	P	VIP
Quercetin	0.000 000	2.779 12
Rutin	0.000 000	3.781 34
Dendroside D	0.000 000	6.513 22

Compound

VIP

Quercetin

0.000 000

2.779 12

Rutin

0.000 000

3.781 34

Dendroside D

0.000 000

6.513 22

Compound	P	VIP
Crepidatumines C	0.000 007	4.597 49
Kaempferol	0.000 001	1.172 98
Crepidine	0.000 016	3.684 33
Dendrocrepidine C	0.000 006	3.874 26
Dendrocrepine	0.000 005	1.530 33
N-Methyl-dendrobine isomer 1	0.000 005	1.509 95
Dendrocrepine isomer 3	0.000 112	1.016 92
Dendrocrepidine B	0.000 004	4.463 95
N-Methyl-dendrobine	0.000 003	1.727 57
Dendrocrepidine D	0.000 006	2.090 09
Homocrepidine B	0.000 002	2.457 86
Crepidine isomer 5	0.000 512	1.495 60
2-Hydroxydendrobine	0.000 050	1.362 89
Gigantol	0.002 428	1.101 12
Dendroside D	0.011 910	2.631 75
Dendrocrepidine E	0.000 007	4.516 34

Compound

VIP

Crepidatumines C

0.000 007

4.597 49

Kaempferol

0.000 001

1.172 98

Crepidine

0.000 016

3.684 33

Dendrocrepidine C

0.000 006

3.874 26

Dendrocrepine

0.000 005

1.530 33

N-Methyl-dendrobine isomer 1

0.000 005

1.509 95

Dendrocrepine isomer 3

0.000 112

1.016 92

Dendrocrepidine B

0.000 004

4.463 95

N-Methyl-dendrobine

0.000 003

1.727 57

Dendrocrepidine D

0.000 006

2.090 09

Homocrepidine B

0.000 002

2.457 86

Crepidine isomer 5

0.000 512

1.495 60

2-Hydroxydendrobine

0.000 050

1.362 89

Gigantol

0.002 428

1.101 12

Dendroside D

0.011 910

2.631 75

Dendrocrepidine E

0.000 007

4.516 34

Compound	P	VIP
Crepidamine	0.000 000	1.021 75
Crepidine isomer 3	0.000 000	1.670 81
Crepidatumines C	0.000 000	3.839 51
Kaempferol	0.000 000	2.389 89
Crepidine	0.000 000	4.204 14
Dendrocrepidine C	0.000 000	4.276 13
Quercetin	0.000 000	1.774 34
Rutin	0.000 000	3.781 34
Dendrocrepine	0.000 000	1.163 09
N-Methyl-dendrobine isomer 1	0.000 000	1.394 59
Crepidine isomer 2	0.000 000	1.477 62
6-Hydroxynobiline	0.000 000	1.269 23
Dendrocrepidine B	0.000 000	3.536 80
N-Methyl-dendrobine	0.000 000	1.446 07
Dendrocrepidine D	0.000 000	1.626 84
Homocrepidine B	0.000 000	2.843 94
2-Hydroxydendrobine	0.000 050	1.362 89
Crepidine isomer 4	0.000 000	1.089 44
Crepidine isomer 1	0.000 001	1.034 84
Crepidine isomer 5	0.000 000	2.162 56
Gigantol	0.000 000	1.564 25
Dendrocrepidine E	0.000 001	4.550 24

Compound

VIP

Crepidamine

0.000 000

1.021 75

Crepidine isomer 3

0.000 000

1.670 81

Crepidatumines C

0.000 000

3.839 51

Kaempferol

0.000 000

2.389 89

Crepidine

0.000 000

4.204 14

Dendrocrepidine C

0.000 000

4.276 13

Quercetin

0.000 000

1.774 34

Rutin

0.000 000

3.781 34

Dendrocrepine

0.000 000

1.163 09

N-Methyl-dendrobine isomer 1

0.000 000

1.394 59

Crepidine isomer 2

0.000 000

1.477 62

6-Hydroxynobiline

0.000 000

1.269 23

Dendrocrepidine B

0.000 000

3.536 80

N-Methyl-dendrobine

0.000 000

1.446 07

Dendrocrepidine D

0.000 000

1.626 84

Homocrepidine B

0.000 000

2.843 94

2-Hydroxydendrobine

0.000 050

1.362 89

Crepidine isomer 4

0.000 000

1.089 44

Crepidine isomer 1

0.000 001

1.034 84

Crepidine isomer 5

0.000 000

2.162 56

Gigantol

0.000 000

1.564 25

Dendrocrepidine E

0.000 001

4.550 24