药学学报

No.	Origin	Location	Collection time
QL-01	J. przewalskii	Shuangqiaogou, Dawei Township, Xiaojin County, Aba Tibetan and Qiang Autonomous Prefecture, SC	2019.07.03
QL-02	J. przewalskii	Zeku County, Huangnan Tibet Aut. Pre., QH	2020.07.17
QL-03	J. Przewalskii	Xiongrang Village, Zeku County, Huangnan Tibet Aut. Pre., QH	2020.07.17
QL-04	J. przewalskii	Tibetan Medical Hospital of Golog Tibet Aut. Pre., QH	2020.07.31
QL-05	J. przewalskii	Lajia Town, Maqin County, Golog Tibet Aut. Pre., QH	2020.07.30
QL-06	J. przewalskii	Xiangda Town, Nangqian County, Yushu Tibet Aut. Pre., QH	2020.08.03
QL-07	J. przewalskii	Maixiu Town, Zeku County, Huangnan Tibet Aut. Pre., QH	2020.08.22
QL-08	J. przewalskii	Maixiu Town Longcanggou, Zeku County, Huangnan Tibet Aut. Pre., QH	2020.08.22
XB-01	J. pingii var. wilsonii	Dege County, Ganzi Tibet Aut. Pre., SC	2019.07.24
XB-02	J. pingii var. wilsonii	Jiaduo Village, Ganzi County, Ganzi Tibet Aut. Pre., SC	2019.06.27
XB-03	J. pingii var. wilsonii	China Tibet Hospital, Derong County, Ganzi Tibet Aut. Pre., SC	2019.06.27
XB-04	J. pingii var. wilsonii	Tibetan Hospital of Ganzi Tibet Aut. Pre., SC	2019.07.22
XB-05	J. pingii var. wilsonii	TCM Market of Chengdu International Trade City, SC (No. 6-1-1158)	2020.06.25
XB-06	J. pingii var. wilsonii	TCM Market of Chengdu International Trade City, SC (No. 6-1-0725)	2020.07.22
XB-07	J. pingii var. wilsonii	TCM Market of Chengdu International Trade City, SC (No. 6-1-1158)	2020.07.22
XB-08	J. pingii var. wilsonii	Lhasa Agricultural Product Quality Supervision, Inspection and Testing Center, Tibet Aut. Reg.	2020.07.12
XB-09	J. pingii var. wilsonii	Affiliated Hospital of Tibet Medical University, Tibet Aut. Reg.	2020.07.22
XB-10	J. pingii var. wilsonii	International Tibetan TCM Trading City, Tibet Aut. Reg.	2020.07.22
XB-11	J. pingii var. wilsonii	Tibetan Medical Hospital of Golog Tibet Aut. Pre., QH	2020.07.31
XB-12	J. pingii var. wilsonii	Tibetan Hospital of Chengduo County, Yushu Tibet Aut. Pre., QH	2020.08.02
XB-13	J. pingii var. wilsonii	Kangding Airport, Ganzi Tibet Aut. Pre., SC	2020.08.08
XB-14	J. pingii var. wilsonii	Kangding Airport, Ganzi Tibet Aut. Pre., SC	2020.08.08
XB-15	J. pingii var. wilsonii	Baima Snow Mountain, Deqin County, YN	2020.08.13
XB-16	J. pingii var. wilsonii	The Second Pass of Baima Snow Mountain, Deqin County, YN	2020.08.14
XB-17	J. pingii var. wilsonii	Sangri County, Lashannan City, Tibet Aut. Reg.	2020.08.15
XB-18	J. pingii var. wilsonii	Near Gabila, Kangding City, Ganzi Tibet Aut. Pre., SC	2020.08.18
XB-19	J. pingii var. wilsonii	Mangkang County, Changdu, Tibet Aut. Reg.	2020.08.16
DZ-01	J. indica	Dege County, Ganzi Tibet Aut. Pre., SC	2019.07.23
DZ-02	J. indica	Tu'er Mountain Foot, Litang County, Ganzi Tibet Aut. Pre., SC	2019.09.28
DZ-03	J. indica	International Tibetan TCM Trading City, Tibet Aut. Reg.	2019.08.01
DZ-04	J. indica	International Tibetan TCM Trading City, Tibet Aut. Reg.	2020.06.21
DZ-05	J. indica	Northern Grassland Medicinal Materials Development Co., Ltd of Tibet Aut. Reg.	2020.06.26
DZ-06	J. indica	Rui Junfang Biotechnology Development Co., Ltd of Tibet Aut. Reg.	2020.06.25
DZ-07	J. indica	Tibetan Hospital of Lingzhi City, Tibet Aut. Reg.	2020.07.16
DZ-08	J. indica	Zheduoshan, Kangding City, Ganzi Tibet Aut. Pre., SC	2020.07.01
DZ-09	J. indica	Sejila Mountain, Linzhi City, Tibet Aut. Reg.	2020.07.01
DZ-10	J. indica	Shannan City, Tibet Aut. Reg.	2020.08.05
DZ-11	J. indica	Kongse Township, Daofu County, Ganzi Tibet Aut. Pre., SC	2020.08.06
DZ-12	J. indica	Yangxi Road, Heqing County, Dali City, YN	2020.08.06
DZ-13	J. indica	Derong Sino Tibetan Hospital, Ganzi Tibet Aut. Pre., SC	2020.08.07
DZ-14	J. indica	Baima Snow Mountain, Deqin County, Diqing Tibet Aut. Pre., YN	2020.08.11
DZ-15	J. indica	Dalanggu Village, Xiangcheng County, Ganzi Tibet Aut. Pre., SC	2020.08.15
DZ-16	J. indica	Tiegohe, Litang County, Ganzi Tibet Aut. Pre., SC	2020.08.13
DZ-17	J. indica	Shengping Town, Deqin County, Diqing Tibet Aut. Pre., YN	2020.08.17
DZ-18	J. indica	Rui Junfang Biotechnology Development Co., Ltd of Tibet Aut. Reg.	2020.08.16
DZ-19	J. indica	Lulang Town, Linzhi County, Linzhi City, Tibet Aut. Reg.	2020.08.25
GS-01	J. squamata	Guinan County, Hainan Tibet Aut. Pre., QH	2019.09.28
GS-02	J. squamata	Tibetan Hospital, Dege County, Ganzi Tibet Aut. Pre., SC	2019.07.24
GS-03	J. squamata	Huzhu Tu Autonomous County, Haidong City, QH	2019.09.28
GS-04	J. squamata	Tibetan Hospital, Huangzhong District, Xining City, QH	2019.09.27
GS-05	J. squamata	TCM Market of Chengdu International Trade City, SC (No. 6-1-1158)	2020.07.16
GS-06	J. squamata	Tibetan Hospital, Qinghai Province	2020.07.17
GS-07	J. squamata	Tibetan Hospital of Hainan Tibet Aut. Pre., QH	2020.07.17
GS-08	J. squamata	Tibetan Hospital of Zeku County, Qinghai Province	2020.07.17
GS-09	J. squamata	Medicinal Materials Market of Qinghai Sanzhi Trading Co., Ltd, QH	2020.07.17
GS-10	J. squamata	Zheduoshan, Kangding City, SC	2020.07.16
GS-11	J. squamata	Shannan City, Tibet Aut. Reg.	2020.08.05
GS-12	J. squamata	Tibetan Hospital of Nangqian County, Yushu Tibet Aut. Pre., QH	2020.08.03
GS-13	J. squamata	Xiazha Town, Shiqu County, Ganzi Tibet Aut. Pre., SC	2020.08.06
GS-14	J. squamata	Baima Snow Mountain, Deqin County, YN	2020.08.13
GS-15	J. squamata	Litang County, Ganzi Tibet Aut. Pre., SC	2020.08.17
DG-01	J. tibetica	Tibetan Medicine Factory of Naqu City, Tibet Aut. Reg.	2019.08.01
DG-02	J. tibetica	TCM Market of Chengdu International Trade City, SC (No. 6-1-0725)	2020.06.27
DG-03	J. tibetica	Tibetan Hospital of Chengduo County, Yushu Tibet Aut. Pre., QH	2020.08.02
DG-04	J. tibetica	Shannan Xueyuan Medicinal Materials Co., Ltd, Tibet Aut. Reg.	2020.08.05
DG-05	J. tibetica	Tibetan Medicine Co., Ltd. of Tibet Tibetan Medical College, Tibet Aut. Reg.	2020.08.17

No.	Origin	Location	Collection time
QL-01	J. przewalskii	Shuangqiaogou, Dawei Township, Xiaojin County, Aba Tibetan and Qiang Autonomous Prefecture, SC	2019.07.03
QL-02	J. przewalskii	Zeku County, Huangnan Tibet Aut. Pre., QH	2020.07.17
QL-03	J. Przewalskii	Xiongrang Village, Zeku County, Huangnan Tibet Aut. Pre., QH	2020.07.17
QL-04	J. przewalskii	Tibetan Medical Hospital of Golog Tibet Aut. Pre., QH	2020.07.31
QL-05	J. przewalskii	Lajia Town, Maqin County, Golog Tibet Aut. Pre., QH	2020.07.30
QL-06	J. przewalskii	Xiangda Town, Nangqian County, Yushu Tibet Aut. Pre., QH	2020.08.03
QL-07	J. przewalskii	Maixiu Town, Zeku County, Huangnan Tibet Aut. Pre., QH	2020.08.22
QL-08	J. przewalskii	Maixiu Town Longcanggou, Zeku County, Huangnan Tibet Aut. Pre., QH	2020.08.22
XB-01	J. pingii var. wilsonii	Dege County, Ganzi Tibet Aut. Pre., SC	2019.07.24
XB-02	J. pingii var. wilsonii	Jiaduo Village, Ganzi County, Ganzi Tibet Aut. Pre., SC	2019.06.27
XB-03	J. pingii var. wilsonii	China Tibet Hospital, Derong County, Ganzi Tibet Aut. Pre., SC	2019.06.27
XB-04	J. pingii var. wilsonii	Tibetan Hospital of Ganzi Tibet Aut. Pre., SC	2019.07.22
XB-05	J. pingii var. wilsonii	TCM Market of Chengdu International Trade City, SC (No. 6-1-1158)	2020.06.25
XB-06	J. pingii var. wilsonii	TCM Market of Chengdu International Trade City, SC (No. 6-1-0725)	2020.07.22
XB-07	J. pingii var. wilsonii	TCM Market of Chengdu International Trade City, SC (No. 6-1-1158)	2020.07.22
XB-08	J. pingii var. wilsonii	Lhasa Agricultural Product Quality Supervision, Inspection and Testing Center, Tibet Aut. Reg.	2020.07.12
XB-09	J. pingii var. wilsonii	Affiliated Hospital of Tibet Medical University, Tibet Aut. Reg.	2020.07.22
XB-10	J. pingii var. wilsonii	International Tibetan TCM Trading City, Tibet Aut. Reg.	2020.07.22
XB-11	J. pingii var. wilsonii	Tibetan Medical Hospital of Golog Tibet Aut. Pre., QH	2020.07.31
XB-12	J. pingii var. wilsonii	Tibetan Hospital of Chengduo County, Yushu Tibet Aut. Pre., QH	2020.08.02
XB-13	J. pingii var. wilsonii	Kangding Airport, Ganzi Tibet Aut. Pre., SC	2020.08.08
XB-14	J. pingii var. wilsonii	Kangding Airport, Ganzi Tibet Aut. Pre., SC	2020.08.08
XB-15	J. pingii var. wilsonii	Baima Snow Mountain, Deqin County, YN	2020.08.13
XB-16	J. pingii var. wilsonii	The Second Pass of Baima Snow Mountain, Deqin County, YN	2020.08.14
XB-17	J. pingii var. wilsonii	Sangri County, Lashannan City, Tibet Aut. Reg.	2020.08.15
XB-18	J. pingii var. wilsonii	Near Gabila, Kangding City, Ganzi Tibet Aut. Pre., SC	2020.08.18
XB-19	J. pingii var. wilsonii	Mangkang County, Changdu, Tibet Aut. Reg.	2020.08.16
DZ-01	J. indica	Dege County, Ganzi Tibet Aut. Pre., SC	2019.07.23
DZ-02	J. indica	Tu'er Mountain Foot, Litang County, Ganzi Tibet Aut. Pre., SC	2019.09.28
DZ-03	J. indica	International Tibetan TCM Trading City, Tibet Aut. Reg.	2019.08.01
DZ-04	J. indica	International Tibetan TCM Trading City, Tibet Aut. Reg.	2020.06.21
DZ-05	J. indica	Northern Grassland Medicinal Materials Development Co., Ltd of Tibet Aut. Reg.	2020.06.26
DZ-06	J. indica	Rui Junfang Biotechnology Development Co., Ltd of Tibet Aut. Reg.	2020.06.25
DZ-07	J. indica	Tibetan Hospital of Lingzhi City, Tibet Aut. Reg.	2020.07.16
DZ-08	J. indica	Zheduoshan, Kangding City, Ganzi Tibet Aut. Pre., SC	2020.07.01
DZ-09	J. indica	Sejila Mountain, Linzhi City, Tibet Aut. Reg.	2020.07.01
DZ-10	J. indica	Shannan City, Tibet Aut. Reg.	2020.08.05
DZ-11	J. indica	Kongse Township, Daofu County, Ganzi Tibet Aut. Pre., SC	2020.08.06
DZ-12	J. indica	Yangxi Road, Heqing County, Dali City, YN	2020.08.06
DZ-13	J. indica	Derong Sino Tibetan Hospital, Ganzi Tibet Aut. Pre., SC	2020.08.07
DZ-14	J. indica	Baima Snow Mountain, Deqin County, Diqing Tibet Aut. Pre., YN	2020.08.11
DZ-15	J. indica	Dalanggu Village, Xiangcheng County, Ganzi Tibet Aut. Pre., SC	2020.08.15
DZ-16	J. indica	Tiegohe, Litang County, Ganzi Tibet Aut. Pre., SC	2020.08.13
DZ-17	J. indica	Shengping Town, Deqin County, Diqing Tibet Aut. Pre., YN	2020.08.17
DZ-18	J. indica	Rui Junfang Biotechnology Development Co., Ltd of Tibet Aut. Reg.	2020.08.16
DZ-19	J. indica	Lulang Town, Linzhi County, Linzhi City, Tibet Aut. Reg.	2020.08.25
GS-01	J. squamata	Guinan County, Hainan Tibet Aut. Pre., QH	2019.09.28
GS-02	J. squamata	Tibetan Hospital, Dege County, Ganzi Tibet Aut. Pre., SC	2019.07.24
GS-03	J. squamata	Huzhu Tu Autonomous County, Haidong City, QH	2019.09.28
GS-04	J. squamata	Tibetan Hospital, Huangzhong District, Xining City, QH	2019.09.27
GS-05	J. squamata	TCM Market of Chengdu International Trade City, SC (No. 6-1-1158)	2020.07.16
GS-06	J. squamata	Tibetan Hospital, Qinghai Province	2020.07.17
GS-07	J. squamata	Tibetan Hospital of Hainan Tibet Aut. Pre., QH	2020.07.17
GS-08	J. squamata	Tibetan Hospital of Zeku County, Qinghai Province	2020.07.17
GS-09	J. squamata	Medicinal Materials Market of Qinghai Sanzhi Trading Co., Ltd, QH	2020.07.17
GS-10	J. squamata	Zheduoshan, Kangding City, SC	2020.07.16
GS-11	J. squamata	Shannan City, Tibet Aut. Reg.	2020.08.05
GS-12	J. squamata	Tibetan Hospital of Nangqian County, Yushu Tibet Aut. Pre., QH	2020.08.03
GS-13	J. squamata	Xiazha Town, Shiqu County, Ganzi Tibet Aut. Pre., SC	2020.08.06
GS-14	J. squamata	Baima Snow Mountain, Deqin County, YN	2020.08.13
GS-15	J. squamata	Litang County, Ganzi Tibet Aut. Pre., SC	2020.08.17
DG-01	J. tibetica	Tibetan Medicine Factory of Naqu City, Tibet Aut. Reg.	2019.08.01
DG-02	J. tibetica	TCM Market of Chengdu International Trade City, SC (No. 6-1-0725)	2020.06.27
DG-03	J. tibetica	Tibetan Hospital of Chengduo County, Yushu Tibet Aut. Pre., QH	2020.08.02
DG-04	J. tibetica	Shannan Xueyuan Medicinal Materials Co., Ltd, Tibet Aut. Reg.	2020.08.05
DG-05	J. tibetica	Tibetan Medicine Co., Ltd. of Tibet Tibetan Medical College, Tibet Aut. Reg.	2020.08.17

No.	t_R /min	Molecular formula	Theoretical mass (m/z)	Measured mass [M+H]⁺/ [M+Na]⁺ (ppm)	Measured mass [M-H]^- (ppm)	MS/MS (m/z)	Compound	Ref.
1	0.62	C₇H₁₂O₆	192.063 4	/	191.055 4 (-1.0)	173.044 9 [M-H₂O]^- (-0.6); 127.039 5 [M-H₂O-CO₂]^- (1.6)	Auinic acid
2	0.68	C₆H₁₂O₆	180.063 4	/	179.055 4 (-1.1)	161.044 6 [M-H-H₂O]^- (-2.5)	Fructose
3	0.93	C₉H₁₁NO₃	181.073 9	182.081 7 (0.5)	180.066 1 (-3.3)	163.044 6 [M-NO₃]^- (-2.5); 136.076 3 [M+H-H₂O-CO]⁺ (0.7)	L-Tyrosine
4	0.95	C₁₀H₁₃N₅O₄	267.096 8	268.104 9 (1.1)	/	136.072 2 [M+H-C₅H₈O₄]⁺ (0.0); 119.049 7 [M+H-NH₃-C₅H₈O₄]⁺ (0.8); 94.040 7 [M+H-C₅H₈O₄-NH₂CN]⁺ (2.1)	Adenosine	[9]
5	1.21	C₇H₆O₅	170.021 5	171.029 6 (1.8)	169.013 2 (-3.0)	125.023 6 [M-COOH]^- (-2.4); 127.039 7 [M+H-COO]⁺ (1.6); 79.018 0 [C₅H₃O]^- (2.5)	Gallic acid
6	1.31	C₁₂H₂₂O₁₁	342.116 2	/	341.108 4 (-3.6)	179.049 7 [M-H-glc]^- (-1.1); 161.044 6 [M-H-glc-H₂O]^- (-2.5); 119.034 4 [C₄H₇O₄]^- (-1.7)	Sucrose
7	1.36	C₁₁H₁₆O₈	276.084 5	299.074 8 (1.7)	275.076 8 (0.4)	/	Unknown
8	1.51	C₇H₆O₃	138.031 7	/	137.023 6 (-2.2)	93.033 7 [M-H-CO₂]^- (-3.2)	Salicylic acid
9	1.93	C₃₀H₂₆O₁₃	594.137 3	595.145 7 (0.8)	593.128 4 (-1.9)	441.080 8 [M-glc]^- (0.5); 423.070 8 [M-glc-H₂O]^- (0.7); 305.065 3 [C₁₅H₁₃O₇]^- (-0.3); 283.024 3 [C₁₅H₇O₆]^- (0.7); 255.028 7 [C₁₄H₇O₅]^- (1.2)	Gallocatechin-(4α→8)-catechin or catechin-(4α→8)-gallocatechin	[10]
10	2.33	C₇H₆O₄	154.026 0	/	153.018 9 (0.7)	109.028 7 [M-COOH]^- (-2.8)	Protocatechuic acid	[11]
11	2.48	C₁₆H₁₈O₉	354.095 1	377.084 9 (2.2)	353.087 9 (0.6)	191.055 8 [M-H-C₉H₆O₃]^- (1.0); 173.044 9 [M-H-C₉H₆O₃-H₂O]^- (-0.6); 161.023 2 [M-H-C₇H₁₂O₆]^- (-4.3); 135.044 4 [M-H-C₇H₁₀O₆-CO]^- (-1.5); 109.028 5 [M-H-C₇H₁₀O₆-CO-C₂H₂]^- (-4.6)	Chlorogenic acid	[12]
12	2.52	C₃₀H₂₆O₁₃	594.137 3	595.145 1 (-0.2)	593.130 2 (1.2)	441.082 4 [M-H-glc]^- (0.5); 423.071 9 [M-glc-H₂O]^- (0.7); 305.066 0 [C₁₅H₁₃O₇]^- (-0.3); 283.024 5 [C₁₅H₇O₆]^- (0.7); 255.029 6 [C₁₄H₇O₅]^- (1.2)	Gallocatechin-(4α→8)-catechin or catechin-(4α→8)-gallocatechin
13	2.97	C₁₅H₁₄O₆	290.079 0	291.087 5 (2.1)	289.070 8 (-1.4)	579.149 8 [2M+H]⁺ (-0.9); 577.133 7 [2M-H]^- (-1.6); 245.080 7 [M-H-CO₂]^- (-2.9); 229.050 1 [M-H-H₂O-C₂H₂O]^- (3.4); 203.070 0 [M-H-H₂O-C₃O₂]^- (-3.9); 187.038 8 [M-H-CO₂-C₃H₆O]^- (-3.7); 179.033 8 [M-H-C₆H₆O₂]^- (-3.4); 161.023 1 [M-H-CO₂-2C₂H₂O]^- (5.0); 137.024 0 [M-H-C₈H₈O₃]^- (-1.4); 123.044 6 [M-H-C₉H₈O₃]^- (0.0)	Epicatechin	[13]
14	4.63	C₃₀H₂₆O₁₂	578.520 0	579.151 4 (1.9)	577.134 4 (-0.3)	427.103 7 [M+H-C₈H₇O₃]⁺ (1.9); 409.093 0 [M+H-C₈H₇O₃-H₂O]⁺ (1.7); 407.076 4 [M-H-C₈H₇O₃-H₂O]^- (-0.7); 291.087 1 [M+H-C₈H₇O₃-C₇H₄O₃]⁺ (0.7); 289.072 0 [M+H-C₁₅H₁₄O₆]⁺ (2.8)	Proanthocyanidin B1	[14]
15	4.93	C₉H₈O₃	164.047 3	/	163.038 9 (-3.7)	147.044 1 [M-H-H₂O]^- (-3.4); 119.049 7 [M-H-CH₂O₂]^- (0.0)	p-Hydroxycinnamic acid
16	5.31	C₁₅H₁₄O₆	290.079 0	291.087 6 (2.1)	289.071 0 (-0.7)	245.044 8 [M-H₂O-C₂H₂]^- (-0.8); 227.070 9 [M-H-CO₂-H₂O]^- (0.4); 203.070 8 [M-H-C₃H₂O₃]^- (0.0); 205.049 9 [M-H-C₄H₄O₂]^- (-1.0); 179.034 2 [M-H-C₆H₆O₂]^- (-1.1); 151.039 3 [C₈H₇O₃]⁺ (-1.3); 139.039 3 [C₇H₇O₃]⁺ (-1.4); 137.032 6 [C₇H₅O₃]^- (-2.2); 125.023 7 [C₆H₅O₃]^- (-1.6); 109.028 7 [C₆H₅O₂]^- (-2.8)	Catechin	[15]
17	6.55	C₃₀H₂₆O₁₂	578.520 0	579.159 1 (-0.3)	577.134 2 (-0.7)	427.1029 [M+H-C₈H₇O₃]⁺ (0.5); 409.091 9 [M+H-C₈H₇O₃-H₂O]⁺ (-1.0); 407.1414 [M-H-C₈H₇O₃-H₂O]^- (0.7); 291.087 1 [M+H-C₈H₇O₃-C₇H₄O₃]⁺ (0.7); 289.071 4 [M+H-C₁₅H₁₄O₆]⁺ (0.7)	Proanthocyanidin B	[16]
18	8.44	C₂₁H₂₂O₁₁	450.116 2	451.124 4 (0.9)	449.108 5 (0.2)	287.054 6 [M-H-glc]^- (-3.5); 289.071 1 [M+H-glc]⁺ (-0.3); 259.059 7 [M-H-glc-H₂O]^- (-3.5); 151.002 7 [M-H-glc-C₈H₈O₂]^- (-2.6); 107.013 3 [M-H-glc-C₈H₇O₂-CO-OH]^- (1.9); 125.023 7 [M-H-glc-C₇H₄O₄]^- (-1.6)	Eriodictyol-7-O-glucoside	[17]
19	9.75	C₂₀H₁₈O₁₁	434.084 9	/	433.077 1 (-1.4)	867.161 8 [2M-H]^- (-0.2); 301.034 8 [C₁₅H₉O₇]^- (0.0)	Quercetin-3-O-β-D-glucopyranoside	[18]
20	10.07	C₉H₈O₄	180.042 6	/	179.034 7 (1.7)	161.023 8 [M-H-H₂O]^- (-0.6)	Caffeic acid
21	10.11	C₉H₆O₃	162.031 7	163.039 7 (1.2)	161.023 4 (-3.1)	/	Unknown
22	11.6	C₁₆H₂₆O₈	346.162 8	369.152 9 (1.1)	345.154 8 (-0.3)	/	Unknown
23	12.13	C₂₄H₃₂O₁₁	496.194 5	519.184 0 (-0.4)	495.184 2 (-3.6)	/	Unknown
24	13.83	C₂₅H₃₄O₁₂	526.205 0	549.194 5 (-0.5)	525.198 2 (1.9)	/	Unknown
25	15.61	C₂₅H₃₂O₁₀	492.199 5	515.188 5 (-1.6)	491.192 5 (1.6)	/	Unknown
26	15.78	C₂₁H₂₀O₁₂	464.095 5	465.104 2 (1.9)	463.087 4 (-0.6)	303.050 5 [M+H-glc]⁺ (-4.0); 301.034 8 [M-H-glc]^- (3.2); 271.023 6 [C₁₄H₇O₆]^- (-2.6); 257.094 6 [M+H-glc-CH₂O₂]⁺ (1.6); 255.065 1 [M+H-glc-CH₂O₂]^- (-2.4)	Hyperoside
27	16.98	C₂₁H₂₀O₁₂	464.095 5	465.104 3 (2.2)	463.087 6 (-0.2)	929.194 6 [2M+H]⁺ (0.0); 927.183 2 [2M-H]^- (0.1); 301.034 3 [M-H-glc]^- (1.7); 303.050 7 [M+H-glc]^- (0.7); 151.003 0 [C₇H₃O₄]⁺ (3.3)	Hypolaetin-7-O-β-D-glucopyranoside^*
28	17.05	C₂₇H₃₀O₁₆	610.517 5	611.162 0 (1.2)	609.145 3 (-0.5)	465.104 1 [M+H-C₆H₁₀O₄]⁺ (1.7); 463.087 8 [M-H-C₆H₁₀O₄]^- (0.2); 301.034 1 [M-H-rutinose]^- (-2.3); 303.051 2 [M+H-rutinose]⁺ (2.3); 271.024 3 [M-H-rutinose-CO]^--(0.0); 257.044 9 [M+H-rutinose-CO₂]⁺ (-0.4); 255.029 0 [M-H-rutinose-CO₂]^- (-1.2); 151.039 2 [M-H-rutinose-C₈H₄O₅-CO]^- (-2.0)	Rutinum	[19]
29	17.10	C₂₀H₁₈O₁₂	450.079 8	451.087 9 (0.4)	449.072 5 (1.1)	/	Unknown
30	17.67	C₂₆H₃₄O₁₁	522.210 1	545.199 6 (-0.6)	521.202 8 (1.0)	545.199 6 [M+Na]⁺ (-0.6); 521.202 8 [M-H]^- (1.0)	Isolarisiresinol-2α- O-β-D-glucoside or isolarisiresinol-3α- O-β-D-glucoside, isomer 1	[20]
31	17.86	C₂₆H₃₄O₁₁	522.210 1	545.200 6 (1.3)	521.201 7 (-1.2)	545.199 6 [M+Na]⁺ (-0.6); 521.202 8 [M-H]^- (1.0)	Isolarisiresinol-2α- O-β-D-glucoside or isolarisiresinol-3α- O-β-D-glucoside, isomer 2
32	17.98	C₁₈H₂₆O₉	386.157 7	409.147 5 (0.0)	385.150 9 (2.6)	207.101 7 [M+H-glc-H₂O]⁺ (-1.9)	Methylsyringin^*	[21, 22]
33	19.01	C₂₁H₂₀O₁₂	464.095 5	465.103 7 (0.9)	463.088 7 (2.2)	303.050 4 [M+H-glc]⁺ [-0.3]; 301.034 2 [M-H-glc]^- (2.0); 25 7.0450 [M+H-glc-CH₂O₂]⁺ (0.0)	Quercetin-3-O-β-D-lucopyranoside	[23]
34	20.80	C₂₁H₂₀O₁₁	448.100 6	449.109 3 (2.0)	447.096 5 (1.8)	895.193 8 [2M-H]^- (0.6); 303.051 2 [M+H-rha]⁺ (2.3); 301.033 8 [M-H-rha]^- (-3.3); 271.023 9 [M-H-rha-H-CO]^- (-1.5); 255.029 1 [M-H-rha-CO-OH]^- (-0.8); 229.052 7 [C₁₄H₁₃O₃]⁺ (0.9); 151.002 2 [M-H-rha-C₇HO₄]^- (-2.6); 109.029 4 [C₆H₅O₂]⁺ (0.9)	Quercitrin^*	[24]
35	21.04	C₂₀H₁₈O₁₁	434.084 9	435.092 8 (0.2)	433.077 6 (1.2)	867.160 9 [2M-H]^- (1.0); 303.051 1 [M+H-Xyl]⁺ (2.0); 301.034 1 [M-H-Xyl]^- (-1.7); 135.044 3 [C₈H₇O₂]^- (-2.2); 316.947 6 [M-H-glc]^- (0.0); 261.133 8 [M-H-glc-2CO]^- (0.0)	Hypolaetin-7-O-β-D-xylopyranoside^*	[25]
36	22.77	C₂₀H₂₆O₆	362.172 9	385.162 7 (0.0)	361.163 3 (-5.0)	/	Unknown
37	23.02	C₂₁H₂₀O₁₁	448.100 6	449.108 7 (0.7)	447.092 7 (0.0)	287.055 7 [M+H-glc]⁺ (0.3); 285.039 9 [M-H-glc]^- (0.0); 151.003 1 [C₇H₃O₄]^- (0.0); 153.018 8 [C₇H₅O₄]⁺ (0.0)	Cynaroside	[26]
38	24.26	C₁₅H₁₀O₆	286.047 7	287.056 0 (1.4)	285.039 7 (-0.7)	241.050 6 [M-CO₂]^- (2.1); 153.018 8 [M+H-C₈H₆O₂]⁺ (0.0); 151.039 0 [M-H-C₈H₆O₂]^- (-3.3); 133.028 4 [M-H-C₇H₄O₄]^- (-4.5)	Luteolin	[26]
39	24.73	C₃₃H₄₀O₁₉	740.216 4	/	739.205 0 (-4.9)	593.145 7 [M-H-C₆H₁₂O₄]^- (1.5); 431.092 4 [M-H-C₁₂H₂₂O₉]^- (1.2); 285.040 1 [M-H-C₆H₁₂O₄-C₁₂H₂₂O₉]^- (0.7)	Robinin	[27]
40	26.64	C₃₆H₂₈O₁₅	700.142 8	701.150 9 (0.4)	699.135 2 (0.3)	539.098 2 [M+H-162 (hexose unit)]⁺ (0.7); 537.083 0 [M-H-162 (hexose unit)]^- (1.5)	Cupressuflavone 4'-O-β-D-glucopyranosides	[28]
41	29.01	C₁₅H₁₀O₅	270.052 8	271.060 5 (-0.4)	269.044 7 (-1.1)	225.056 0 [M-H-CO₂]^- (3.6); 183.044 8 [M-H-H₂O-C₃O₂]^- (1.1); 201.163 8 [M-H-C₃O₂]^- (-2.5); 213.055 0 [M-H-CO-CO]^- (-0.9); 241.048 9 [M-H-CO]^- (-5.0)	Apigenin	[29]
42	29.37	C₃₆H₂₈O₁₅	700.142 8	701.150 6 (0.0)	699.133 4 (-2.3)	/	Unknown
43	29.99	C₁₁H₁₀O₃	190.063 0	213.052 8 (0.0); 191.070 7 (-0.5)	/	213.052 8 [M+Na]⁺ (0.0); 191.070 7 [M+H]⁺ (-0.5)	Ekersenin^*	[30]
44	31.36	C₃₀H₁₈O₁₀	538.090 0	539.097 4 (-0.7)	537.083 6 (2.6)	1 075.172 2 [2M-H]^- (3.1); 377.066 3 [M+H-C₉H₆0₃]⁺ (0.5); 375.050 5 [M-H-C₉H₆O₃]^- (0.0); 121.029 0 [C₇H₅O₂]⁺ (0.0)	Cupressuflavone^*	[31]
45	32.83	C₃₀H₁₈O₁₀	538.090 0	539.098 3 (0.9)	537.082 9 (1.3)	1 075.176 5 [2M-H]^- (0.8); 1 077.190 2 [2M+H]⁺ (0.0); 521.087 7 [M+H-H₂O]⁺ (0.8); 497.087 8 [M+H-C₂H₂O]⁺ (1.0); 403.045 8 [M+H-C₈H₆O-H₂O]⁺ (1.0); 379.045 8 [M+H-C₈H₆O-C₂H₂O]⁺ (1.1); 377.066 5 [M+H-C₉H₆O₃]⁺ (1.1); 311.055 9 [M+H-C₈H₆O-C₃O₂]⁺ (1.0); 283.060 6 [M+H-C₈H₆O-C₃O₂-CO]⁺ (0.0); 121.029 0 [C₇H₅O₂]⁺ (0.0)	Amentoflavone^*	[32]
46	34.33	C₃₀H₁₈O₁₀	538.090 0	539.097 6 (-0.4)	537.082 2 (0.0)	521.087 4 [M+H-H₂O]⁺ (0.2); 413.068 8 [M+H-C₆H₄O₃]⁺ (-1.9); 403.045 7 [M+H-C₈H₆O-H₂O]⁺ (0.7); 387.087 0 [M+H-C₇H₄O₄]⁺ (0.3); 375.050 2 [M+H-C₈H₆O-H₂O-CO]⁺ (-0.8); 283.060 7 [M+H-C₁₄H₉O₅]⁺ (0.4); 153.018 7 [C₇H₅O₄]⁺ (-0.7); 121.028 9 [C₇H₅O₂]⁺ (-0.8)	Robustaflavone	[32]
47	35.72	C₃₀H₂₀O₁₀	540.105 6	541.113 5 (0.0)	539.095 8 (2.8)	/	Unknown
48	39.61	C₃₁H₂₀O₁₀	552.484 5	553.114 1 (1.1)	551.098 6 (1.5)	421.055 9 [M+H-C₉H₈O]⁺ (-0.2); 403.045 7 [M+H-C₉H₈O-H₂O]⁺ (0.7); 377.069 2 [M+H-C₁₀H₈O₃]⁺ (-1.1); 375.054 0 [M-H-C₁₀H₈O₃]^- (0.3); 135.044 1 [C₈H₈O₂]⁺ (-3.7)	Podocarpusflavone A^*	[32]
49	41.95	C₃₁H₂₀O₁₀	552.105 6	553.114 1 (1.1)	551.097 4 (-0.7)	1 105.222 2 [2M+H]⁺ (2.8); 1 103.205 7 [2M-H]^- (2.0); 403.046 0 [M+H-C₈H₆O-CH₃OH]⁺ (1.5); 390.978 5 [M+H-C₉H₆O₃]⁺ (2.6); 153.018 4 [C₇H₅O₄]⁺ (-2.6)	4′-Methoxy robustaflavone	[31, 32]
50	43.17	C₃₀H₁₈O₁₀	538.090 0	539.097 6 (-0.6)	537.081 8 (-0.7)	387.087 0 [M+H-C₇H₄O₄]⁺ (0.3); 287.237 4 [M+H-C₁₅H₉O₄]⁺ (-0.3); 285.221 3 [M-H-C₁₅H₉O₄]^- (-1.8); 269.191 1 [M+H-C₁₅H₉O₅]⁺ (2.2); 257.047 9 [M+H-C₁₅H₉O₄-CO]⁺ (-2.3); 243.065 5 [M+H-C₁₅H₉O₅-CO]⁺ (-0.8); 153.018 7 [C₇H₅O₄]⁺ (-0.7); 121.028 9 [C₇H₅O₂]⁺ (-0.8)	Hinokiflavone^*	[32]
51	44.20	C₂₂H₃₄O₅	378.240 6	401.230 4(0.0)	377.231 7(-2.9)	/	Unknown
52	46.67	C₃₅H₆₀O₆	576.439 0	577.446 8 (0.0)	/	577.446 8 [M+H]⁺ (0.0)	β-Daucosterol	[33]
53	47.47	C₃₂H₂₂O₁₀	566.121 3	567.130 1 (1.8)	565.114 7 (2.1)	435.071 1 [M+H-C₉H₈O]⁺ (-1.1); 417.061 2 [M+H-C₉H₈O-H₂O]⁺ (0.5); 391.081 6 [M+H-C₁₀H₈O₃]⁺ (-0.5); 389.066 1 [M-H-C₁₀H₈O₃]^- (0.0); 167.128 6 [C₈H₆O₄]⁺ (-1.8); 135.044 3 [C₈H₈O₂]⁺ (-2.2)	Putraflavone B	[34]
54	52.99	C₂₀H₂₈O₂	300.208 9	301.218 0 (4.0)	299.200 3 (-3.0)	241.159 3 [M+H-C₂H₆-C₂H₆]⁺ (0.4); 213.127 8 [M+H-C₂H₆-C₂H₆-CO]⁺ (-0.5)	Sugiol	[35]
55	55.68	C₂₀H₂₆O₄	330.183 1	331.190 3 (-1.8)	329.172 9 (0.0)	331.190 3 [M+H]⁺ (-1.8); 329.172 9 [M-H]^- (0.0)	Carnosol	[36]
56	59.85	C₂₀H₃₀O₂	302.224 6	303.232 6 (0.7)	301.217 1 (1.0)	257.226 6 [M-COOH]⁺ (1.2); 149.132 8 [M-COOH-C₆H₆(CH₃)₂]⁺ (-1.3); 123.117 2 [M+H-COOH-C₆H₆CH₂CH(CH₃)₂]⁺ (1.6)	Abietic acid	[37]
57	62.38	C₂₉H₅₀O	414.386 2	415.394 0 (0.0)	/	397.383 4 [M-OH]⁺ (3.5); 161.133 0 [M-OH-C₁₇H₃₃]⁺ (2.1); 109.181 7 [M-OH-C₁₇H₃₃-C₄H₅]⁺ (1.2); 81.070 4 [C₆H₉]⁺ (1.5)	β-Sitosterol	[38]
58	63.19	C₂₀H₂₈O₂	300.208 9	323.198 6 (-0.3)	299.200 8 (-1.0)	/	Unknown

No.	t_R /min	Molecular formula	Theoretical mass (m/z)	Measured mass [M+H]⁺/ [M+Na]⁺ (ppm)	Measured mass [M-H]^- (ppm)	MS/MS (m/z)	Compound	Ref.
1	0.62	C₇H₁₂O₆	192.063 4	/	191.055 4 (-1.0)	173.044 9 [M-H₂O]^- (-0.6); 127.039 5 [M-H₂O-CO₂]^- (1.6)	Auinic acid
2	0.68	C₆H₁₂O₆	180.063 4	/	179.055 4 (-1.1)	161.044 6 [M-H-H₂O]^- (-2.5)	Fructose
3	0.93	C₉H₁₁NO₃	181.073 9	182.081 7 (0.5)	180.066 1 (-3.3)	163.044 6 [M-NO₃]^- (-2.5); 136.076 3 [M+H-H₂O-CO]⁺ (0.7)	L-Tyrosine
4	0.95	C₁₀H₁₃N₅O₄	267.096 8	268.104 9 (1.1)	/	136.072 2 [M+H-C₅H₈O₄]⁺ (0.0); 119.049 7 [M+H-NH₃-C₅H₈O₄]⁺ (0.8); 94.040 7 [M+H-C₅H₈O₄-NH₂CN]⁺ (2.1)	Adenosine	[9]
5	1.21	C₇H₆O₅	170.021 5	171.029 6 (1.8)	169.013 2 (-3.0)	125.023 6 [M-COOH]^- (-2.4); 127.039 7 [M+H-COO]⁺ (1.6); 79.018 0 [C₅H₃O]^- (2.5)	Gallic acid
6	1.31	C₁₂H₂₂O₁₁	342.116 2	/	341.108 4 (-3.6)	179.049 7 [M-H-glc]^- (-1.1); 161.044 6 [M-H-glc-H₂O]^- (-2.5); 119.034 4 [C₄H₇O₄]^- (-1.7)	Sucrose
7	1.36	C₁₁H₁₆O₈	276.084 5	299.074 8 (1.7)	275.076 8 (0.4)	/	Unknown
8	1.51	C₇H₆O₃	138.031 7	/	137.023 6 (-2.2)	93.033 7 [M-H-CO₂]^- (-3.2)	Salicylic acid
9	1.93	C₃₀H₂₆O₁₃	594.137 3	595.145 7 (0.8)	593.128 4 (-1.9)	441.080 8 [M-glc]^- (0.5); 423.070 8 [M-glc-H₂O]^- (0.7); 305.065 3 [C₁₅H₁₃O₇]^- (-0.3); 283.024 3 [C₁₅H₇O₆]^- (0.7); 255.028 7 [C₁₄H₇O₅]^- (1.2)	Gallocatechin-(4α→8)-catechin or catechin-(4α→8)-gallocatechin	[10]
10	2.33	C₇H₆O₄	154.026 0	/	153.018 9 (0.7)	109.028 7 [M-COOH]^- (-2.8)	Protocatechuic acid	[11]
11	2.48	C₁₆H₁₈O₉	354.095 1	377.084 9 (2.2)	353.087 9 (0.6)	191.055 8 [M-H-C₉H₆O₃]^- (1.0); 173.044 9 [M-H-C₉H₆O₃-H₂O]^- (-0.6); 161.023 2 [M-H-C₇H₁₂O₆]^- (-4.3); 135.044 4 [M-H-C₇H₁₀O₆-CO]^- (-1.5); 109.028 5 [M-H-C₇H₁₀O₆-CO-C₂H₂]^- (-4.6)	Chlorogenic acid	[12]
12	2.52	C₃₀H₂₆O₁₃	594.137 3	595.145 1 (-0.2)	593.130 2 (1.2)	441.082 4 [M-H-glc]^- (0.5); 423.071 9 [M-glc-H₂O]^- (0.7); 305.066 0 [C₁₅H₁₃O₇]^- (-0.3); 283.024 5 [C₁₅H₇O₆]^- (0.7); 255.029 6 [C₁₄H₇O₅]^- (1.2)	Gallocatechin-(4α→8)-catechin or catechin-(4α→8)-gallocatechin
13	2.97	C₁₅H₁₄O₆	290.079 0	291.087 5 (2.1)	289.070 8 (-1.4)	579.149 8 [2M+H]⁺ (-0.9); 577.133 7 [2M-H]^- (-1.6); 245.080 7 [M-H-CO₂]^- (-2.9); 229.050 1 [M-H-H₂O-C₂H₂O]^- (3.4); 203.070 0 [M-H-H₂O-C₃O₂]^- (-3.9); 187.038 8 [M-H-CO₂-C₃H₆O]^- (-3.7); 179.033 8 [M-H-C₆H₆O₂]^- (-3.4); 161.023 1 [M-H-CO₂-2C₂H₂O]^- (5.0); 137.024 0 [M-H-C₈H₈O₃]^- (-1.4); 123.044 6 [M-H-C₉H₈O₃]^- (0.0)	Epicatechin	[13]
14	4.63	C₃₀H₂₆O₁₂	578.520 0	579.151 4 (1.9)	577.134 4 (-0.3)	427.103 7 [M+H-C₈H₇O₃]⁺ (1.9); 409.093 0 [M+H-C₈H₇O₃-H₂O]⁺ (1.7); 407.076 4 [M-H-C₈H₇O₃-H₂O]^- (-0.7); 291.087 1 [M+H-C₈H₇O₃-C₇H₄O₃]⁺ (0.7); 289.072 0 [M+H-C₁₅H₁₄O₆]⁺ (2.8)	Proanthocyanidin B1	[14]
15	4.93	C₉H₈O₃	164.047 3	/	163.038 9 (-3.7)	147.044 1 [M-H-H₂O]^- (-3.4); 119.049 7 [M-H-CH₂O₂]^- (0.0)	p-Hydroxycinnamic acid
16	5.31	C₁₅H₁₄O₆	290.079 0	291.087 6 (2.1)	289.071 0 (-0.7)	245.044 8 [M-H₂O-C₂H₂]^- (-0.8); 227.070 9 [M-H-CO₂-H₂O]^- (0.4); 203.070 8 [M-H-C₃H₂O₃]^- (0.0); 205.049 9 [M-H-C₄H₄O₂]^- (-1.0); 179.034 2 [M-H-C₆H₆O₂]^- (-1.1); 151.039 3 [C₈H₇O₃]⁺ (-1.3); 139.039 3 [C₇H₇O₃]⁺ (-1.4); 137.032 6 [C₇H₅O₃]^- (-2.2); 125.023 7 [C₆H₅O₃]^- (-1.6); 109.028 7 [C₆H₅O₂]^- (-2.8)	Catechin	[15]
17	6.55	C₃₀H₂₆O₁₂	578.520 0	579.159 1 (-0.3)	577.134 2 (-0.7)	427.1029 [M+H-C₈H₇O₃]⁺ (0.5); 409.091 9 [M+H-C₈H₇O₃-H₂O]⁺ (-1.0); 407.1414 [M-H-C₈H₇O₃-H₂O]^- (0.7); 291.087 1 [M+H-C₈H₇O₃-C₇H₄O₃]⁺ (0.7); 289.071 4 [M+H-C₁₅H₁₄O₆]⁺ (0.7)	Proanthocyanidin B	[16]
18	8.44	C₂₁H₂₂O₁₁	450.116 2	451.124 4 (0.9)	449.108 5 (0.2)	287.054 6 [M-H-glc]^- (-3.5); 289.071 1 [M+H-glc]⁺ (-0.3); 259.059 7 [M-H-glc-H₂O]^- (-3.5); 151.002 7 [M-H-glc-C₈H₈O₂]^- (-2.6); 107.013 3 [M-H-glc-C₈H₇O₂-CO-OH]^- (1.9); 125.023 7 [M-H-glc-C₇H₄O₄]^- (-1.6)	Eriodictyol-7-O-glucoside	[17]
19	9.75	C₂₀H₁₈O₁₁	434.084 9	/	433.077 1 (-1.4)	867.161 8 [2M-H]^- (-0.2); 301.034 8 [C₁₅H₉O₇]^- (0.0)	Quercetin-3-O-β-D-glucopyranoside	[18]
20	10.07	C₉H₈O₄	180.042 6	/	179.034 7 (1.7)	161.023 8 [M-H-H₂O]^- (-0.6)	Caffeic acid
21	10.11	C₉H₆O₃	162.031 7	163.039 7 (1.2)	161.023 4 (-3.1)	/	Unknown
22	11.6	C₁₆H₂₆O₈	346.162 8	369.152 9 (1.1)	345.154 8 (-0.3)	/	Unknown
23	12.13	C₂₄H₃₂O₁₁	496.194 5	519.184 0 (-0.4)	495.184 2 (-3.6)	/	Unknown
24	13.83	C₂₅H₃₄O₁₂	526.205 0	549.194 5 (-0.5)	525.198 2 (1.9)	/	Unknown
25	15.61	C₂₅H₃₂O₁₀	492.199 5	515.188 5 (-1.6)	491.192 5 (1.6)	/	Unknown
26	15.78	C₂₁H₂₀O₁₂	464.095 5	465.104 2 (1.9)	463.087 4 (-0.6)	303.050 5 [M+H-glc]⁺ (-4.0); 301.034 8 [M-H-glc]^- (3.2); 271.023 6 [C₁₄H₇O₆]^- (-2.6); 257.094 6 [M+H-glc-CH₂O₂]⁺ (1.6); 255.065 1 [M+H-glc-CH₂O₂]^- (-2.4)	Hyperoside
27	16.98	C₂₁H₂₀O₁₂	464.095 5	465.104 3 (2.2)	463.087 6 (-0.2)	929.194 6 [2M+H]⁺ (0.0); 927.183 2 [2M-H]^- (0.1); 301.034 3 [M-H-glc]^- (1.7); 303.050 7 [M+H-glc]^- (0.7); 151.003 0 [C₇H₃O₄]⁺ (3.3)	Hypolaetin-7-O-β-D-glucopyranoside^*
28	17.05	C₂₇H₃₀O₁₆	610.517 5	611.162 0 (1.2)	609.145 3 (-0.5)	465.104 1 [M+H-C₆H₁₀O₄]⁺ (1.7); 463.087 8 [M-H-C₆H₁₀O₄]^- (0.2); 301.034 1 [M-H-rutinose]^- (-2.3); 303.051 2 [M+H-rutinose]⁺ (2.3); 271.024 3 [M-H-rutinose-CO]^--(0.0); 257.044 9 [M+H-rutinose-CO₂]⁺ (-0.4); 255.029 0 [M-H-rutinose-CO₂]^- (-1.2); 151.039 2 [M-H-rutinose-C₈H₄O₅-CO]^- (-2.0)	Rutinum	[19]
29	17.10	C₂₀H₁₈O₁₂	450.079 8	451.087 9 (0.4)	449.072 5 (1.1)	/	Unknown
30	17.67	C₂₆H₃₄O₁₁	522.210 1	545.199 6 (-0.6)	521.202 8 (1.0)	545.199 6 [M+Na]⁺ (-0.6); 521.202 8 [M-H]^- (1.0)	Isolarisiresinol-2α- O-β-D-glucoside or isolarisiresinol-3α- O-β-D-glucoside, isomer 1	[20]
31	17.86	C₂₆H₃₄O₁₁	522.210 1	545.200 6 (1.3)	521.201 7 (-1.2)	545.199 6 [M+Na]⁺ (-0.6); 521.202 8 [M-H]^- (1.0)	Isolarisiresinol-2α- O-β-D-glucoside or isolarisiresinol-3α- O-β-D-glucoside, isomer 2
32	17.98	C₁₈H₂₆O₉	386.157 7	409.147 5 (0.0)	385.150 9 (2.6)	207.101 7 [M+H-glc-H₂O]⁺ (-1.9)	Methylsyringin^*	[21, 22]
33	19.01	C₂₁H₂₀O₁₂	464.095 5	465.103 7 (0.9)	463.088 7 (2.2)	303.050 4 [M+H-glc]⁺ [-0.3]; 301.034 2 [M-H-glc]^- (2.0); 25 7.0450 [M+H-glc-CH₂O₂]⁺ (0.0)	Quercetin-3-O-β-D-lucopyranoside	[23]
34	20.80	C₂₁H₂₀O₁₁	448.100 6	449.109 3 (2.0)	447.096 5 (1.8)	895.193 8 [2M-H]^- (0.6); 303.051 2 [M+H-rha]⁺ (2.3); 301.033 8 [M-H-rha]^- (-3.3); 271.023 9 [M-H-rha-H-CO]^- (-1.5); 255.029 1 [M-H-rha-CO-OH]^- (-0.8); 229.052 7 [C₁₄H₁₃O₃]⁺ (0.9); 151.002 2 [M-H-rha-C₇HO₄]^- (-2.6); 109.029 4 [C₆H₅O₂]⁺ (0.9)	Quercitrin^*	[24]
35	21.04	C₂₀H₁₈O₁₁	434.084 9	435.092 8 (0.2)	433.077 6 (1.2)	867.160 9 [2M-H]^- (1.0); 303.051 1 [M+H-Xyl]⁺ (2.0); 301.034 1 [M-H-Xyl]^- (-1.7); 135.044 3 [C₈H₇O₂]^- (-2.2); 316.947 6 [M-H-glc]^- (0.0); 261.133 8 [M-H-glc-2CO]^- (0.0)	Hypolaetin-7-O-β-D-xylopyranoside^*	[25]
36	22.77	C₂₀H₂₆O₆	362.172 9	385.162 7 (0.0)	361.163 3 (-5.0)	/	Unknown
37	23.02	C₂₁H₂₀O₁₁	448.100 6	449.108 7 (0.7)	447.092 7 (0.0)	287.055 7 [M+H-glc]⁺ (0.3); 285.039 9 [M-H-glc]^- (0.0); 151.003 1 [C₇H₃O₄]^- (0.0); 153.018 8 [C₇H₅O₄]⁺ (0.0)	Cynaroside	[26]
38	24.26	C₁₅H₁₀O₆	286.047 7	287.056 0 (1.4)	285.039 7 (-0.7)	241.050 6 [M-CO₂]^- (2.1); 153.018 8 [M+H-C₈H₆O₂]⁺ (0.0); 151.039 0 [M-H-C₈H₆O₂]^- (-3.3); 133.028 4 [M-H-C₇H₄O₄]^- (-4.5)	Luteolin	[26]
39	24.73	C₃₃H₄₀O₁₉	740.216 4	/	739.205 0 (-4.9)	593.145 7 [M-H-C₆H₁₂O₄]^- (1.5); 431.092 4 [M-H-C₁₂H₂₂O₉]^- (1.2); 285.040 1 [M-H-C₆H₁₂O₄-C₁₂H₂₂O₉]^- (0.7)	Robinin	[27]
40	26.64	C₃₆H₂₈O₁₅	700.142 8	701.150 9 (0.4)	699.135 2 (0.3)	539.098 2 [M+H-162 (hexose unit)]⁺ (0.7); 537.083 0 [M-H-162 (hexose unit)]^- (1.5)	Cupressuflavone 4'-O-β-D-glucopyranosides	[28]
41	29.01	C₁₅H₁₀O₅	270.052 8	271.060 5 (-0.4)	269.044 7 (-1.1)	225.056 0 [M-H-CO₂]^- (3.6); 183.044 8 [M-H-H₂O-C₃O₂]^- (1.1); 201.163 8 [M-H-C₃O₂]^- (-2.5); 213.055 0 [M-H-CO-CO]^- (-0.9); 241.048 9 [M-H-CO]^- (-5.0)	Apigenin	[29]
42	29.37	C₃₆H₂₈O₁₅	700.142 8	701.150 6 (0.0)	699.133 4 (-2.3)	/	Unknown
43	29.99	C₁₁H₁₀O₃	190.063 0	213.052 8 (0.0); 191.070 7 (-0.5)	/	213.052 8 [M+Na]⁺ (0.0); 191.070 7 [M+H]⁺ (-0.5)	Ekersenin^*	[30]
44	31.36	C₃₀H₁₈O₁₀	538.090 0	539.097 4 (-0.7)	537.083 6 (2.6)	1 075.172 2 [2M-H]^- (3.1); 377.066 3 [M+H-C₉H₆0₃]⁺ (0.5); 375.050 5 [M-H-C₉H₆O₃]^- (0.0); 121.029 0 [C₇H₅O₂]⁺ (0.0)	Cupressuflavone^*	[31]
45	32.83	C₃₀H₁₈O₁₀	538.090 0	539.098 3 (0.9)	537.082 9 (1.3)	1 075.176 5 [2M-H]^- (0.8); 1 077.190 2 [2M+H]⁺ (0.0); 521.087 7 [M+H-H₂O]⁺ (0.8); 497.087 8 [M+H-C₂H₂O]⁺ (1.0); 403.045 8 [M+H-C₈H₆O-H₂O]⁺ (1.0); 379.045 8 [M+H-C₈H₆O-C₂H₂O]⁺ (1.1); 377.066 5 [M+H-C₉H₆O₃]⁺ (1.1); 311.055 9 [M+H-C₈H₆O-C₃O₂]⁺ (1.0); 283.060 6 [M+H-C₈H₆O-C₃O₂-CO]⁺ (0.0); 121.029 0 [C₇H₅O₂]⁺ (0.0)	Amentoflavone^*	[32]
46	34.33	C₃₀H₁₈O₁₀	538.090 0	539.097 6 (-0.4)	537.082 2 (0.0)	521.087 4 [M+H-H₂O]⁺ (0.2); 413.068 8 [M+H-C₆H₄O₃]⁺ (-1.9); 403.045 7 [M+H-C₈H₆O-H₂O]⁺ (0.7); 387.087 0 [M+H-C₇H₄O₄]⁺ (0.3); 375.050 2 [M+H-C₈H₆O-H₂O-CO]⁺ (-0.8); 283.060 7 [M+H-C₁₄H₉O₅]⁺ (0.4); 153.018 7 [C₇H₅O₄]⁺ (-0.7); 121.028 9 [C₇H₅O₂]⁺ (-0.8)	Robustaflavone	[32]
47	35.72	C₃₀H₂₀O₁₀	540.105 6	541.113 5 (0.0)	539.095 8 (2.8)	/	Unknown
48	39.61	C₃₁H₂₀O₁₀	552.484 5	553.114 1 (1.1)	551.098 6 (1.5)	421.055 9 [M+H-C₉H₈O]⁺ (-0.2); 403.045 7 [M+H-C₉H₈O-H₂O]⁺ (0.7); 377.069 2 [M+H-C₁₀H₈O₃]⁺ (-1.1); 375.054 0 [M-H-C₁₀H₈O₃]^- (0.3); 135.044 1 [C₈H₈O₂]⁺ (-3.7)	Podocarpusflavone A^*	[32]
49	41.95	C₃₁H₂₀O₁₀	552.105 6	553.114 1 (1.1)	551.097 4 (-0.7)	1 105.222 2 [2M+H]⁺ (2.8); 1 103.205 7 [2M-H]^- (2.0); 403.046 0 [M+H-C₈H₆O-CH₃OH]⁺ (1.5); 390.978 5 [M+H-C₉H₆O₃]⁺ (2.6); 153.018 4 [C₇H₅O₄]⁺ (-2.6)	4′-Methoxy robustaflavone	[31, 32]
50	43.17	C₃₀H₁₈O₁₀	538.090 0	539.097 6 (-0.6)	537.081 8 (-0.7)	387.087 0 [M+H-C₇H₄O₄]⁺ (0.3); 287.237 4 [M+H-C₁₅H₉O₄]⁺ (-0.3); 285.221 3 [M-H-C₁₅H₉O₄]^- (-1.8); 269.191 1 [M+H-C₁₅H₉O₅]⁺ (2.2); 257.047 9 [M+H-C₁₅H₉O₄-CO]⁺ (-2.3); 243.065 5 [M+H-C₁₅H₉O₅-CO]⁺ (-0.8); 153.018 7 [C₇H₅O₄]⁺ (-0.7); 121.028 9 [C₇H₅O₂]⁺ (-0.8)	Hinokiflavone^*	[32]
51	44.20	C₂₂H₃₄O₅	378.240 6	401.230 4(0.0)	377.231 7(-2.9)	/	Unknown
52	46.67	C₃₅H₆₀O₆	576.439 0	577.446 8 (0.0)	/	577.446 8 [M+H]⁺ (0.0)	β-Daucosterol	[33]
53	47.47	C₃₂H₂₂O₁₀	566.121 3	567.130 1 (1.8)	565.114 7 (2.1)	435.071 1 [M+H-C₉H₈O]⁺ (-1.1); 417.061 2 [M+H-C₉H₈O-H₂O]⁺ (0.5); 391.081 6 [M+H-C₁₀H₈O₃]⁺ (-0.5); 389.066 1 [M-H-C₁₀H₈O₃]^- (0.0); 167.128 6 [C₈H₆O₄]⁺ (-1.8); 135.044 3 [C₈H₈O₂]⁺ (-2.2)	Putraflavone B	[34]
54	52.99	C₂₀H₂₈O₂	300.208 9	301.218 0 (4.0)	299.200 3 (-3.0)	241.159 3 [M+H-C₂H₆-C₂H₆]⁺ (0.4); 213.127 8 [M+H-C₂H₆-C₂H₆-CO]⁺ (-0.5)	Sugiol	[35]
55	55.68	C₂₀H₂₆O₄	330.183 1	331.190 3 (-1.8)	329.172 9 (0.0)	331.190 3 [M+H]⁺ (-1.8); 329.172 9 [M-H]^- (0.0)	Carnosol	[36]
56	59.85	C₂₀H₃₀O₂	302.224 6	303.232 6 (0.7)	301.217 1 (1.0)	257.226 6 [M-COOH]⁺ (1.2); 149.132 8 [M-COOH-C₆H₆(CH₃)₂]⁺ (-1.3); 123.117 2 [M+H-COOH-C₆H₆CH₂CH(CH₃)₂]⁺ (1.6)	Abietic acid	[37]
57	62.38	C₂₉H₅₀O	414.386 2	415.394 0 (0.0)	/	397.383 4 [M-OH]⁺ (3.5); 161.133 0 [M-OH-C₁₇H₃₃]⁺ (2.1); 109.181 7 [M-OH-C₁₇H₃₃-C₄H₅]⁺ (1.2); 81.070 4 [C₆H₉]⁺ (1.5)	β-Sitosterol	[38]
58	63.19	C₂₀H₂₈O₂	300.208 9	323.198 6 (-0.3)	299.200 8 (-1.0)	/	Unknown

Compound	Peak	VIP (ESI⁺)	VIP (ESI^－)
Abietic acid	56	18.434 12	/
C₂₅H₃₄O₁₂	24	/	14.512 43
C₂₄H₃₂O₁₁	23	/	11.461 65
4'-Methoxy robustaflavone	49	10.240 51	10.806 80
C₂₂H₃₄O₅	51	/	10.211 32
Hinokiflavone	50	/	9.621 84
C₁₆H₂₆O₈	22	/	8.971 32
Hypolaetin-7-O-β-D-xylopyranoside	35	8.728 47	/
C₂₀H₂₈O₂	58	7.348 05	/
C₃₀H₂₀O₁₀	47	6.942 69	/
Podocarpusflavone A	48	/	6.908 60
C₃₆H₂₈O₁₅	42	6.447 10	/
Quercitrin	34	6.178 06	/
Amentoflavone	45	5.646 62	6.544 26
Proanthocyanidin B1	14	4.943 33	4.584 01
Sugiol	54	4.564 51	/
C₂₀H₂₆O₆	36	/	4.268 83
Catechin	16	3.996 22	3.509 34
C₉H₆O₃	21	3.627 38	/
Auinic acid	1	/	3.303 37
C₂₅H₃₂O₁₀	25	/	3.203 47

Compound	Peak	VIP (ESI⁺)	VIP (ESI^－)
Abietic acid	56	18.434 12	/
C₂₅H₃₄O₁₂	24	/	14.512 43
C₂₄H₃₂O₁₁	23	/	11.461 65
4'-Methoxy robustaflavone	49	10.240 51	10.806 80
C₂₂H₃₄O₅	51	/	10.211 32
Hinokiflavone	50	/	9.621 84
C₁₆H₂₆O₈	22	/	8.971 32
Hypolaetin-7-O-β-D-xylopyranoside	35	8.728 47	/
C₂₀H₂₈O₂	58	7.348 05	/
C₃₀H₂₀O₁₀	47	6.942 69	/
Podocarpusflavone A	48	/	6.908 60
C₃₆H₂₈O₁₅	42	6.447 10	/
Quercitrin	34	6.178 06	/
Amentoflavone	45	5.646 62	6.544 26
Proanthocyanidin B1	14	4.943 33	4.584 01
Sugiol	54	4.564 51	/
C₂₀H₂₆O₆	36	/	4.268 83
Catechin	16	3.996 22	3.509 34
C₉H₆O₃	21	3.627 38	/
Auinic acid	1	/	3.303 37
C₂₅H₃₂O₁₀	25	/	3.203 47

基于UPLC-Q-TOF-MS/MS代谢组学技术筛选不同基原圆柏品种鉴别的化学标志物

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赵紫薇 ¹ , 彭芳 ² , 张琨 ¹ , 罗玉婷 ² , 曾宇骄 ² , 武鑫玥 ² , 唐策 ¹^,^* , 范刚 ¹^,^*

药学学报 | 研究论文 2023,58(7): 1880-1893

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药学学报 | 研究论文 2023, 58(7): 1880-1893

基于UPLC-Q-TOF-MS/MS代谢组学技术筛选不同基原圆柏品种鉴别的化学标志物

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赵紫薇¹, 彭芳², 张琨¹, 罗玉婷², 曾宇骄², 武鑫玥², 唐策¹^,^*, 范刚¹^,^*

作者信息

1.成都中医药大学民族医药学院, 四川成都 611137

2.成都中医药大学药学院, 四川成都 611137

通讯作者:

*范刚, E-mail: fangang1111@163.com;

唐策, E-mail:tangce@cdutcm.edu.cn

Selection of chemical markers for identification of different species of Juniperri Caulis et Folium based on UPLC-Q-TOF-MS/MS metabonomics technology

Zi-wei ZHAO¹, Fang PENG², Kun ZHANG¹, Yu-ting LUO², Yu-jiao ZENG², Xin-yue WU², Ce TANG¹^,^*, Gang FAN¹^,^*

Affiliations

1. School of Ethnic Medicine of Chengdu University of Traditional Chinese Medicine, Chengdu 611137, China

2. School of Medicine of Chengdu University of Traditional Chinese Medicine, Chengdu 611137, China

出版时间: 2023-07-12 doi: 10.16438/j.0513-4870.2022-1285

文章导航

摘要

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本研究采用超高效液相色谱-四极杆-飞行时间质谱(UPLC-Q-TOF-MS/MS) 非靶向代谢组学技术, 分析鉴定圆柏药材的整体化学成分, 并结合主成分分析和偏最小二乘判别分析筛选不同基原圆柏品种鉴别的化学标志物。结果共检测出58个化学成分, 鉴定了其中46个化学成分, 包括26个黄酮类、8个有机酸类及其衍生物、4个苯丙素类、3个萜类、5个其他类成分, 其中methylsyringin和ekersenin为首次在圆柏中鉴定的成分。在正离子模式下筛选出12个品种鉴别的化学标志物, 在负离子模式下筛选出13个品种鉴别的化学标志物。结果表明, UPLC-Q-TOF-MS/MS代谢组学技术结合化学计量学方法, 可有效揭示不同基原圆柏药材的化学成分差异, 为其品种鉴别和质量控制提供参考。

关键词

圆柏 / UPLC-Q-TOF-MS/MS / 代谢组学 / 品种鉴定

Abstract

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In this study, untargeted metabolomics technology based on ultra-high-performance liquid chromatography-quadrupole/time of flight mass spectrometry (UPLC-Q-TOF-MS/MS) was used to analyze and identify the overall chemical components of Juniperri Caulis et Folium. Chemical markers for the identification of different Juniperri Caulis et Folium species were screened by integrated principal component analysis and partial least squares discriminant analysis. A total of 58 chemical components were detected and 46 of them were identified, including 26 flavonoids, 8 organic acids and their derivatives, 4 phenylpropanoids, 3 terpenoids, and 5 other components. Among them, methylsyringin and ekersenin were identified for the first time. In the positive ion mode, 12 markers were screened, and in the negative ion mode, 13 markers were screened for species identification. In summary, UPLC-Q-TOF-MS/MS metabonomics technology combined with chemometrics method can effectively reveal the chemical composition differences of different Juniperri Caulis et Folium species, and provide reference for its species identification and quality control.

Key words

Juniperri Caulis et Folium / UPLC-Q-TOF-MS/MS / Metabonomics / Species identification

引用本文

赵紫薇, 彭芳, 张琨, 罗玉婷, 曾宇骄, 武鑫玥, 唐策, 范刚. 基于UPLC-Q-TOF-MS/MS代谢组学技术筛选不同基原圆柏品种鉴别的化学标志物. 药学学报, 2023 , 58 (7) : 1880 -1893 . DOI: 10.16438/j.0513-4870.2022-1285

Zi-wei ZHAO, Fang PENG, Kun ZHANG, Yu-ting LUO, Yu-jiao ZENG, Xin-yue WU, Ce TANG, Gang FAN. Selection of chemical markers for identification of different species of Juniperri Caulis et Folium based on UPLC-Q-TOF-MS/MS metabonomics technology[J]. Acta Pharmaceutica Sinica, 2023 , 58 (7) : 1880 -1893 . DOI: 10.16438/j.0513-4870.2022-1285

正文

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圆柏为常用藏药材, 味苦性凉, 能清热、消炎、干黄水, 常用于治疗肾病, 尿涩, 膀胱病, 关节炎, 月经不调等^[1]。圆柏是典型的多基原药材, 同属多种植物均能入药。课题组前期对西藏、青海、四川、云南等藏区藏医院、藏药制药企业及药材市场的圆柏药材使用情况进行了调查, 发现使用的品种主要为滇藏方枝柏Juniperus indica、香柏J. pingii var. wilsonii、高山柏J. squamata、大果圆柏J. tibetica和祁连圆柏J. przewalskii^[2]。圆柏的基原多样性和混淆使用不利于市场监管, 也影响其质量稳定性和可控性。因此, 采用现代科学技术筛选可鉴别圆柏不同基原品种的化学标志物, 对于其质量控制具有重要的意义。

近年来, 代谢组学技术已广泛运用于植物药材的整体成分分析、品种鉴别和质量评价等研究中^[3]。超高效液相色谱-四极杆-飞行时间串联质谱法(ultra-high-performance liquid chromatography-quadrupole/time of flight mass spectrometry, UPLC-Q-TOF-MS/MS) 技术是代谢组学研究的主要工具^[4], 具有高灵敏度、高分辨率、高质量精度及扫描范围广等优点^{[5, 6]}。目前, 张娇等^[7]、马明芳等^[8]对圆柏单一基原品种进行了化学成分研究, 但不同基原圆柏药材之间的化学成分是否有差异仍然未知。本研究采用基于高分辨质谱的植物代谢组学技术对圆柏药材中的小分子代谢物进行全面分析表征, 同时结合主成分分析(principal components analysis, PCA)、偏最小二乘法判别分析(partial least squares discriminant analysis, PLS-DA)等多元统计学方法对不同品种间的代谢物进行比较分析, 以期找出化学标志物, 为圆柏的品种鉴别和质量评价提供新方法。

材料与方法

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仪器 Waters Acquity UPLC^TM超高效液相色谱仪(美国Waters公司), 配有四元高压泵, 自动进样器, PDA检测器, Empower色谱工作站, 连接Q-TOF analyzer in a SYNAPT G2 HDMS system高分辨质谱仪, 配备电喷雾离子源和MassLynx v4.1质谱工作站; Sorvall Legend Micro 17高速离心机(美国Thermo Fisher Scientific公司); BT125D十万分之一电子天平(德国Sartorius公司); SB-4200DTD超声波清洗器(宁波新芝生物科技股份有限公司)。

试剂海波拉亭-7-O-β-D-吡喃葡萄糖苷(批号: DST202019-053)、methylsyringin (批号: DST202020-044)、槲皮苷(批号: DST202007-001)、海波拉亭-7-O-β-D-吡喃木糖苷(批号: DST202019-029)、ekersenin (批号: DST202004-009)、柏木双黄酮(批号: DST202010-002)、穗花衫双黄酮(批号: DTS201025-046)、扁柏双黄酮(批号: DST200619-009) 和罗汉松双黄酮A (批号: DST200919-053) 均购于成都乐美天医药公司, 纯度 > 98%。色谱级乙腈, 色谱级甲酸(美国Sigma公司)、亮氨酸脑啡肽(美国Waters公司), 蒸馏水(广州屈臣氏食品饮料有限公司)。甲醇(成都市科隆化学品有限公司) 等试剂均为分析纯。

样品本研究共收集66批圆柏药材, 经重庆市中药研究院秦松云副研究员鉴定为滇藏方枝柏J. indica、香柏J. pingii var. wilsonii、高山柏J. squamata、大果圆柏J. tibetica和祁连圆柏J. przewalskii, 样品信息详见表 1。

色谱条件 色谱柱为Acquity UPLC^® BEH C18 (100 mm × 2.1 mm, 1.7 μm); 流动相为0.1%甲酸水(A)- 0.1%甲酸乙腈(B), 梯度洗脱程序为: 0~3 min, 4%~5% B; 3~7 min, 5%~7% B; 7~9 min, 7%~9% B; 9~13 min, 9%~10% B; 13~24 min, 10%~18% B; 24~30 min, 18%~28% B; 30~35 min, 28%~30% B; 35~55 min, 30%~50% B; 55~58 min, 50%~52% B; 58~60 min, 52%~65% B; 60~65 min, 65%~65% B。流速为0.4 mL·min^-1, 柱温为40℃, 进样量为1 μL。

质谱条件 采用Waters SYNAPT G2 HDMS系统。以氮气作为雾化、锥孔气, 源温度: 150 ℃, 反向锥孔气流: 50 L·h^-1, 脱溶剂气温度: 450 ℃, 脱溶剂气流: 800 L·h^-1, 隔: 0.02 s, 质荷比: m/z 100~1 500 Da, 锁定质量数(亮氨酸脑啡肽): 正离子模式: m/z 556.277 1 [M+H]⁺, 负离子模式m/z 554.261 5 [M-H]^-。

供试品溶液制备 取圆柏药材粉末(过三号筛) 约1 g, 精密称定, 置具塞锥形瓶中, 精密加入甲醇30 mL, 称定重量, 超声处理(功率250 W, 频率40 kHz) 30 min, 放冷, 再次称定重量, 用甲醇补足减少的重量, 摇匀, 滤过, 取滤液, 13 000 r·min^-1离心15 min, 取上清液过0.22 μm的微孔滤膜, 即得。

数据处理与统计分析 查阅国内外圆柏及其同属柏科植物化学成分研究相关文献, 收集圆柏中各类化学成分, 建立圆柏质谱数据库, 将数据库导入UNIFI 1.8 (Waters, 美国) 在线软件进行化学成分鉴定。通过人工校验和核实精确分子量、出峰时间、裂解碎片、加合离子峰, 筛选质量误差在±5 ppm内, 确认和指证化合物。将UPLC-Q-TOF-MS/MS获得的原始数据导入Progenesis QI软件进行峰提取、峰匹配及归一化前处理后, 筛选并导出鉴别化合物数据。利用SIMCA-P 14.1软件对预处理后的数据进行PCA、PLS-DA分析, 根据变量重要性投影值(variable importance in projection, VIP) > 3、P < 0.05筛选潜在差异代谢物。潜在差异代谢物采用Metaboanalyst 5.0进行热图分析。

结果

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1 圆柏化学成分的质谱鉴定

对不同基原的66批圆柏样品进行UPLC-Q-TOF-MS/MS分析, 结果发现各基原圆柏样品的总离子流图基本相似。结合UNIFI自动匹配化合物与人工校验化合物, 共检测出58个化学成分, 鉴定了其中46个化学成分, 其中在正离子模式下鉴定了37个成分, 在负离子模式下鉴定了42个成分, 包括26个黄酮类成分、8个有机酸类成分及其衍生物、4个苯丙素类成分、3个萜类成分、5个其他类成分, 以及12个未知成分。总离子流图见图 1, 各化合物的质谱信息见表 2^[9-38]。

1.1 黄酮类成分

本研究从圆柏药材中鉴定了26个黄酮类化合物。黄酮类成分易发生典型的逆狄尔斯-阿德尔反应(Retro Diels-Alder reaction, RDA), 易失去H₂O、CO和C₂H₂O等。其中双黄酮类的裂解方式可根据C环断裂位置的不同分为三种类型: 穗花衫双黄酮裂解类型(在Ⅱ环1/3、0/4位更易发生裂解)、罗波斯塔双黄酮类型(在Ⅰ环1/3、1/4位更易发生裂解)、扁柏双黄酮类型(C-O键易发生裂解)^[34]。因此, 根据不同的碎片离子可推测黄酮类化合物及其同分异构体。以C₃₀H₁₈O₁₀同分异构体穗花衫双黄酮(化合物45)、罗波斯塔双黄酮(化合物46)、扁柏双黄酮(化合物50) 为例, 其裂解途径如下。

化合物45, 其准分子离子峰为m/z 539.098 3 [M+H]⁺, 537.082 9 [M-H]^-。MS²中Ⅱ环中1/3 C环断裂生成特征碎片离子m/z 419.076 6 [M+H-C₈H₆O]⁺、再失去H₂O生成特征碎片离子m/z 403.045 8 [M+H-C₈H₆O-H₂O]⁺, 后失去CO, 生成特征碎片离子m/z 377.066 5 [M+H-C₉H₆O₃]⁺; Ⅱ环中0/4 C环断裂生成特征碎片离子377.066 5 [M+H-C₉H₆O₃]⁺, 结合文献^{[7, 8, 32, 34]}并通过MassLynx v 4.1 Elemental Composition拟合化学式为C₃₀H₁₈O₁₀, 经对照品比对鉴定该化合物为穗花杉双黄酮(amentoflavone), 裂解途径如图 2。

化合物46, 其准分子离子峰为m/z 539.097 6 [M+H]⁺, 537.082 2 [M-H]^-。MS²中Ⅰ环中1/3 C环断裂生成特征碎片离子m/z 387.087 2 [M+H-C₇H₄O₄]⁺; Ⅰ环中1/4 C环断裂生成特征碎片离子413.068 8 [M+H-C₆H₄O₃]⁺, 结合文献^{[7, 8, 32, 34]}并通过MassLynx v 4.1 Elemental Composition拟合化学式为C₃₀H₁₈O₁₀, 推测该化合物为罗波斯塔双黄酮(robustaflavone)。

化合物50, 其准分子离子峰为m/z 539.097 6 [M+H]⁺, 537.081 8 [M-H]^-。MS²中C-O键断裂生成特征碎片离子m/z 287.237 4 [M+H-C₁₅H₉O₄]⁺, 269.191 1 [M+H-C₁₅H₉O₅]⁺, 243.065 5 [M+H-C₁₅H₉O₅-CO]⁺。结合文献^{[7, 8, 32, 34]}并通过、MassLynx v 4.1 Elemental Composition拟合化学式为C₃₀H₁₈O₁₀, 经对照品比对鉴定该化合物为扁柏双黄酮(hinokiflavone)。

1.2 有机酸类成分

有机酸类是分子结构中含有羧基(-COOH) 的化合物, 其具有很强的抗氧化、抗菌消炎和调血脂等药理作用^[12]。有机酸类化合物裂解规律一般是容易丢失CO、H₂O、C₂H₂等一系列中性基团, 从圆柏中初步推定8个有机酸类化合物, 以绿原酸(化合物11) 为例, 其准分子离子峰为m/z 353.087 9 [M-H]^-, MS²显示其组成部分咖啡酸m/z 161.023 2 [M-H-C₇H₁₂O₆]^-及奎宁酸m/z 191.055 8 [M-H-C₉H₆O₃]^-碎片离子峰, 后丢失CO、H₂O、C₂H₂等一系列中性基团生成特征碎片离子m/z 173.044 9 [M-H-C₉H₆O₃-H₂O]^-、135.044 4 [M-H-C₇H₁₀O₆-CO]^-、109.028 5 [M-H-C₇H₁₀O₆-CO-C₂H₂]^-等。结合文献^{[12, 37]}并通过UNIFI 1.8 (Waters, 美国) 数据库匹配以及MassLynx v 4.1 Elemental Composition拟合化学式为C₁₆H₁₈O₉, 推测该化合物为绿原酸, 裂解途径如图 3。

1.3 苯丙素类成分

苯丙素是一类由C₆-C₃结构单元构成的一类化合物, 从圆柏中初步推定4个苯丙素类成分: 异落叶松脂素-3α-O-β-D-葡萄糖苷或其同分异构体(化合物30、31) 以及2个首次鉴定在圆柏中鉴定出的苯丙素类成分methylsyringin (化合物32)、ekersenin (化合物43), 以methylsyringin (化合物32) 为例, 其准分子离子峰为m/z 385.150 9 [M-H]^-, MS²中脱去葡萄糖及一分子的水生成特征碎片离子m/z 207.101 7 [M+H-glc-H₂O]⁺, 结合文献^{[21, 22]}并通过MassLynx v 4.1 Elemental Composition拟合化学式为C₁₈H₂₆O₉, 经对照品比对鉴定该化合物为methylsyringin。

1.4 萜类成分

萜类化合物是指存在自然中, 分子式为异戊二烯倍数的化合物及其衍生物的总称^[38], 在植物生命活动中, 萜类化合物具有重要的作用。目前, 从圆柏中初步推定3个萜类成分: β-谷甾醇(化合物52)、柳杉酚(化合物54)、鼠尾草酚(化合物55)。以β-谷甾醇(化合物52) 为例, 其准分子离子峰为m/z 415.394 0 [M+H]⁺, MS²中C₃-OH羟基易脱水生成m/z 397.383 4 [M-H₂O+H]⁺的特征碎片离子, 进一步C环易发生裂解, 生成m/z 148.124 1、161.133 0等特征碎片离子。结合文献^{[9, 38]}并通过MassLynx v 4.1 Elemental Composition拟合化学式为C₂₉H₅₀O, 推测该化合物为β-谷甾醇。

1.5 其他成分

除了黄酮类、有机酸类及其衍生物、苯丙素类和萜类化合物, 本研究还鉴定出果糖(化合物2)、蔗糖(化合物6)、L-络氨酸(化合物3)、腺苷(化合物4) 和β-胡萝卜苷(化合物57)。以腺苷(化合物4) 为例, 推导其裂解过程, 其准分子离子峰为m/z 268.104 9 [M+H]⁺, MS²中N-糖苷键易裂解, 中性丢失1分子核糖(C₅H₁₀O₅, m/z 132), 生成m/z 136.072 2 [M+H-C₅H₈O₄]⁺的腺嘌呤碱基离子, 继续开环, 中性丢失NH₃、HCN等, 生成m/z 119.049 7、94.040 7的特征碎片离子。结合文献^[9]并通过UNIFI 1.8 (Waters, 美国) 数据库匹配以及MassLynx v 4.1 Elemental Composition拟合化学式为C₁₀H₁₃N₅O₄, 推测该化合物为腺苷。

2 基于模式识别研究不同基原圆柏药材的化学成分差异

以预处理的所有化合物的峰面积(正离子16 384个化合物、负离子16 842个化合物) 为指标, 利用SIMCA-P 14.1软件进行PCA和PLS-DA非靶向代谢组学分析。数据采用Par法进行预处理, 用PCA观察样品的自然聚集, 所有样品的PCA三维得分图如图 4所示。在正离子(ESI⁺)、负离子(ESI^-) 模式下, PCA模型的R²X分别为0.859和0.842, Q²分别为0.582和0.624, 表明该模型稳定性良好。PCA分析结果表明, 圆柏5个基原品种无法得到有效分离, 还需进一步采用有监督的识别模式分析。

为了减少组内差异的干扰, 更好地揭示圆柏不同品种之间的化学成分差异, 本研究进一步采用有监督的模式识别方法偏最小二乘判别分析(PLS-DA) 对66批样品进行分析, 所有样品的PLS-DA三维得分图如图 4所示。正、负离子数据的PLS-DA模型置换检验参数R²X分别为0.836和0.801, 表明该模型稳定性良好。PLS-DA分析结果表明, 5个品种(祁连圆柏、滇藏方枝柏、香柏、高山柏、大果圆柏) 在三维图谱中得到了较好的分离, 说明圆柏5个品种之间的化学成分存在一定的差异。

3 筛选圆柏品种鉴别的化学标志物

为筛选可鉴别圆柏不同品种的化学标志物, 本研究VIP > 3、P < 0.05为阈值, 筛选差异代谢物(表 3)。本研究在ESI⁺模式下筛选出12个潜在的种间差异成分, 在ESI^-模式下筛选出13个潜在的种间差异成分。其中4′-甲基-罗斯塔特双黄酮、穗花衫双黄酮、原花青素B1、儿茶素4个化学成分为正负离子共有的潜在种间差异成分。

分别以正负离子模式下21个潜在标志物的峰面积为指标, 采用SIMCA-P 14.1软件对所有圆柏样品再进行PCA和PLS-DA分析。正离子和负离子PCA模型的R²X分别为0.999和0.999, Q²分别为0.762和0.865。正离子和负离子PLS-DA模型的R²X分别为0.755和0.893, Q²分别为0.772和0.875。结果圆柏5个品种(祁连圆柏、滇藏方枝柏、香柏、高山柏、大果圆柏) 在PCA和PLS-DA中均得到了明显的分离(图 5), 表明这21个差异化学成分可作为化学标志物, 用于圆柏药材的品种鉴别。

4 圆柏品种鉴别化学标志物的热图分析

为进一步观察化学标志物在不同品种中的分布情况, 采用Metaboanalyst 5.0对66批圆柏进行相关性分析, 以正离子12个和负离子13个标志物的峰面积为指标, 计算其Pearson相关系数, 并作聚类热图分析。因样本量较大, 以组间差异结果展示更为直观, 见图 6。图中深红棕色到深蓝色的颜色变化反映了代谢物在圆柏不同基原药材中的分布情况, 其中红棕色颜色越深代表其相对含量较高, 反之蓝色越深则代表其相对含量较低。从图 6可以看出4'-甲基-罗斯塔特双黄酮、穗花衫双黄酮在高山柏和香柏药材中含量较高, 儿茶素在高山柏药材中的含量明显低于其他4个品种, 原花青素B1在滇藏方枝柏药材中含量较高。热图分析结果进一步说明了这21个化学标志物在圆柏5个品种中具有明显的差异。

讨论

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本实验采用UPLC-Q-TOF-MS/MS分析技术检测出圆柏58个化学成分, 鉴定了其中46个化学成分。结果表明, 圆柏药材主要含有黄酮类、有机酸类、苯丙素类等化学成分。其中, 9个化学成分经对照品比对确定, 包括海波拉亭-7-O-β-D-吡喃葡萄糖苷(化合物27)、methylsyringin (化合物32)、槲皮苷(化合物34)、海波拉亭-7-O-β-D-吡喃木糖苷(化合物35)、ekersenin (化合物43)、柏木双黄酮(化合物44)、穗花杉双黄酮(化合物46)、罗汉松双黄酮A (化合物48)、扁柏双黄酮(化合物50)。此外, methylsyringin和ekersenin为首次在圆柏中鉴定的成分。结果表明, UPLC-Q-TOF-MS/MS技术可以快速、准确地对圆柏中的化学成分进行定性表征。

采用PCA、PLS-DA等模式识别方法, 发现高山柏、滇藏方枝柏、香柏、祁连圆柏和大果圆柏之间的化学成分存在差异, 结合VIP > 3和P < 0.05筛选出21个可用于圆柏品种鉴别的化学标志物, 这21个标志物多为黄酮类成分, 如穗花衫双黄酮、槲皮苷、扁柏双黄酮、原花青素B1等。现代研究表明, 黄酮类化合物具有较好的抗炎, 抗肿瘤等生物活性^[39], 如穗花杉双黄酮具有抗炎^[34]、抗肿瘤^[40]、抗心肌缺血^[41]等作用; 槲皮苷具有抗炎^[42]、抗氧化^[43]、抗肿瘤^[44]、抗病毒^[45]等药理作用, 这与圆柏药材的传统功效有较好的相关性。因此, 本研究结果也可为今后圆柏不同品种的质量评价提供参考。

尽管UPLC-Q-TOF-MS/MS技术具有分析速度快、分辨率高, 可以精确检测相对分子质量且二级质谱能提示特征离子碎片信息等^[46]优点, 但目前未知化学成分的鉴定仍具有挑战。目前, 藏药还存在基础研究薄弱, 大多化学成分不明确等问题, 且药材中存在许多同分异构体, 其二级碎片离子和裂解规律极为相近, 增加了化学成分精准定性的困难, 因此今后还需结合二维核磁共振、植物化学分离等技术和方法不断完善圆柏的化学成分数据库, 促进其质量控制和药效物质基础研究。

作者贡献: 赵紫薇、彭芳负责实验研究、数据分析及文稿撰写, 张琨、罗玉婷负责实验操作, 曾宇骄、武鑫玥负责圆柏样本采集, 通讯作者唐策、范刚负责项目总体设计、规划、指导写作以及稿件修改。

利益冲突: 所有作者均不存在任何利益冲突。

基金

收起

国家重点研发计划项目(2019YFC1712302)
四川省重点研发项目(2022YFS0434)

参考文献

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文献

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2023年第58卷第7期

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文章信息

doi: 10.16438/j.0513-4870.2022-1285

接收时间：2022-11-28
首发时间：2025-11-21
出版时间：2023-07-12

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收稿日期：2022-11-28
修回日期：2023-05-19

基金

国家重点研发计划项目(2019YFC1712302)

四川省重点研发项目(2022YFS0434)

作者信息

1.成都中医药大学民族医药学院, 四川成都 611137

2.成都中医药大学药学院, 四川成都 611137

通讯作者:

*范刚, E-mail: fangang1111@163.com;

唐策, E-mail:tangce@cdutcm.edu.cn

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2种不同金属材料的力学参数

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

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No.	Origin	Location	Collection time
QL-01	J. przewalskii	Shuangqiaogou, Dawei Township, Xiaojin County, Aba Tibetan and Qiang Autonomous Prefecture, SC	2019.07.03
QL-02	J. przewalskii	Zeku County, Huangnan Tibet Aut. Pre., QH	2020.07.17
QL-03	J. Przewalskii	Xiongrang Village, Zeku County, Huangnan Tibet Aut. Pre., QH	2020.07.17
QL-04	J. przewalskii	Tibetan Medical Hospital of Golog Tibet Aut. Pre., QH	2020.07.31
QL-05	J. przewalskii	Lajia Town, Maqin County, Golog Tibet Aut. Pre., QH	2020.07.30
QL-06	J. przewalskii	Xiangda Town, Nangqian County, Yushu Tibet Aut. Pre., QH	2020.08.03
QL-07	J. przewalskii	Maixiu Town, Zeku County, Huangnan Tibet Aut. Pre., QH	2020.08.22
QL-08	J. przewalskii	Maixiu Town Longcanggou, Zeku County, Huangnan Tibet Aut. Pre., QH	2020.08.22
XB-01	J. pingii var. wilsonii	Dege County, Ganzi Tibet Aut. Pre., SC	2019.07.24
XB-02	J. pingii var. wilsonii	Jiaduo Village, Ganzi County, Ganzi Tibet Aut. Pre., SC	2019.06.27
XB-03	J. pingii var. wilsonii	China Tibet Hospital, Derong County, Ganzi Tibet Aut. Pre., SC	2019.06.27
XB-04	J. pingii var. wilsonii	Tibetan Hospital of Ganzi Tibet Aut. Pre., SC	2019.07.22
XB-05	J. pingii var. wilsonii	TCM Market of Chengdu International Trade City, SC (No. 6-1-1158)	2020.06.25
XB-06	J. pingii var. wilsonii	TCM Market of Chengdu International Trade City, SC (No. 6-1-0725)	2020.07.22
XB-07	J. pingii var. wilsonii	TCM Market of Chengdu International Trade City, SC (No. 6-1-1158)	2020.07.22
XB-08	J. pingii var. wilsonii	Lhasa Agricultural Product Quality Supervision, Inspection and Testing Center, Tibet Aut. Reg.	2020.07.12
XB-09	J. pingii var. wilsonii	Affiliated Hospital of Tibet Medical University, Tibet Aut. Reg.	2020.07.22
XB-10	J. pingii var. wilsonii	International Tibetan TCM Trading City, Tibet Aut. Reg.	2020.07.22
XB-11	J. pingii var. wilsonii	Tibetan Medical Hospital of Golog Tibet Aut. Pre., QH	2020.07.31
XB-12	J. pingii var. wilsonii	Tibetan Hospital of Chengduo County, Yushu Tibet Aut. Pre., QH	2020.08.02
XB-13	J. pingii var. wilsonii	Kangding Airport, Ganzi Tibet Aut. Pre., SC	2020.08.08
XB-14	J. pingii var. wilsonii	Kangding Airport, Ganzi Tibet Aut. Pre., SC	2020.08.08
XB-15	J. pingii var. wilsonii	Baima Snow Mountain, Deqin County, YN	2020.08.13
XB-16	J. pingii var. wilsonii	The Second Pass of Baima Snow Mountain, Deqin County, YN	2020.08.14
XB-17	J. pingii var. wilsonii	Sangri County, Lashannan City, Tibet Aut. Reg.	2020.08.15
XB-18	J. pingii var. wilsonii	Near Gabila, Kangding City, Ganzi Tibet Aut. Pre., SC	2020.08.18
XB-19	J. pingii var. wilsonii	Mangkang County, Changdu, Tibet Aut. Reg.	2020.08.16
DZ-01	J. indica	Dege County, Ganzi Tibet Aut. Pre., SC	2019.07.23
DZ-02	J. indica	Tu'er Mountain Foot, Litang County, Ganzi Tibet Aut. Pre., SC	2019.09.28
DZ-03	J. indica	International Tibetan TCM Trading City, Tibet Aut. Reg.	2019.08.01
DZ-04	J. indica	International Tibetan TCM Trading City, Tibet Aut. Reg.	2020.06.21
DZ-05	J. indica	Northern Grassland Medicinal Materials Development Co., Ltd of Tibet Aut. Reg.	2020.06.26
DZ-06	J. indica	Rui Junfang Biotechnology Development Co., Ltd of Tibet Aut. Reg.	2020.06.25
DZ-07	J. indica	Tibetan Hospital of Lingzhi City, Tibet Aut. Reg.	2020.07.16
DZ-08	J. indica	Zheduoshan, Kangding City, Ganzi Tibet Aut. Pre., SC	2020.07.01
DZ-09	J. indica	Sejila Mountain, Linzhi City, Tibet Aut. Reg.	2020.07.01
DZ-10	J. indica	Shannan City, Tibet Aut. Reg.	2020.08.05
DZ-11	J. indica	Kongse Township, Daofu County, Ganzi Tibet Aut. Pre., SC	2020.08.06
DZ-12	J. indica	Yangxi Road, Heqing County, Dali City, YN	2020.08.06
DZ-13	J. indica	Derong Sino Tibetan Hospital, Ganzi Tibet Aut. Pre., SC	2020.08.07
DZ-14	J. indica	Baima Snow Mountain, Deqin County, Diqing Tibet Aut. Pre., YN	2020.08.11
DZ-15	J. indica	Dalanggu Village, Xiangcheng County, Ganzi Tibet Aut. Pre., SC	2020.08.15
DZ-16	J. indica	Tiegohe, Litang County, Ganzi Tibet Aut. Pre., SC	2020.08.13
DZ-17	J. indica	Shengping Town, Deqin County, Diqing Tibet Aut. Pre., YN	2020.08.17
DZ-18	J. indica	Rui Junfang Biotechnology Development Co., Ltd of Tibet Aut. Reg.	2020.08.16
DZ-19	J. indica	Lulang Town, Linzhi County, Linzhi City, Tibet Aut. Reg.	2020.08.25
GS-01	J. squamata	Guinan County, Hainan Tibet Aut. Pre., QH	2019.09.28
GS-02	J. squamata	Tibetan Hospital, Dege County, Ganzi Tibet Aut. Pre., SC	2019.07.24
GS-03	J. squamata	Huzhu Tu Autonomous County, Haidong City, QH	2019.09.28
GS-04	J. squamata	Tibetan Hospital, Huangzhong District, Xining City, QH	2019.09.27
GS-05	J. squamata	TCM Market of Chengdu International Trade City, SC (No. 6-1-1158)	2020.07.16
GS-06	J. squamata	Tibetan Hospital, Qinghai Province	2020.07.17
GS-07	J. squamata	Tibetan Hospital of Hainan Tibet Aut. Pre., QH	2020.07.17
GS-08	J. squamata	Tibetan Hospital of Zeku County, Qinghai Province	2020.07.17
GS-09	J. squamata	Medicinal Materials Market of Qinghai Sanzhi Trading Co., Ltd, QH	2020.07.17
GS-10	J. squamata	Zheduoshan, Kangding City, SC	2020.07.16
GS-11	J. squamata	Shannan City, Tibet Aut. Reg.	2020.08.05
GS-12	J. squamata	Tibetan Hospital of Nangqian County, Yushu Tibet Aut. Pre., QH	2020.08.03
GS-13	J. squamata	Xiazha Town, Shiqu County, Ganzi Tibet Aut. Pre., SC	2020.08.06
GS-14	J. squamata	Baima Snow Mountain, Deqin County, YN	2020.08.13
GS-15	J. squamata	Litang County, Ganzi Tibet Aut. Pre., SC	2020.08.17
DG-01	J. tibetica	Tibetan Medicine Factory of Naqu City, Tibet Aut. Reg.	2019.08.01
DG-02	J. tibetica	TCM Market of Chengdu International Trade City, SC (No. 6-1-0725)	2020.06.27
DG-03	J. tibetica	Tibetan Hospital of Chengduo County, Yushu Tibet Aut. Pre., QH	2020.08.02
DG-04	J. tibetica	Shannan Xueyuan Medicinal Materials Co., Ltd, Tibet Aut. Reg.	2020.08.05
DG-05	J. tibetica	Tibetan Medicine Co., Ltd. of Tibet Tibetan Medical College, Tibet Aut. Reg.	2020.08.17

No.

Origin

Location

Collection time

QL-01

J. przewalskii

Shuangqiaogou, Dawei Township, Xiaojin County, Aba Tibetan and Qiang Autonomous Prefecture, SC

2019.07.03

QL-02

J. przewalskii

Zeku County, Huangnan Tibet Aut. Pre., QH

2020.07.17

QL-03

J. Przewalskii

Xiongrang Village, Zeku County, Huangnan Tibet Aut. Pre., QH

2020.07.17

QL-04

J. przewalskii

Tibetan Medical Hospital of Golog Tibet Aut. Pre., QH

2020.07.31

QL-05

J. przewalskii

Lajia Town, Maqin County, Golog Tibet Aut. Pre., QH

2020.07.30

QL-06

J. przewalskii

Xiangda Town, Nangqian County, Yushu Tibet Aut. Pre., QH

2020.08.03

QL-07

J. przewalskii

Maixiu Town, Zeku County, Huangnan Tibet Aut. Pre., QH

2020.08.22

QL-08

J. przewalskii

Maixiu Town Longcanggou, Zeku County, Huangnan Tibet Aut. Pre., QH

2020.08.22

XB-01

J. pingii var. wilsonii

Dege County, Ganzi Tibet Aut. Pre., SC

2019.07.24

XB-02

J. pingii var. wilsonii

Jiaduo Village, Ganzi County, Ganzi Tibet Aut. Pre., SC

2019.06.27

XB-03

J. pingii var. wilsonii

China Tibet Hospital, Derong County, Ganzi Tibet Aut. Pre., SC

2019.06.27

XB-04

J. pingii var. wilsonii

Tibetan Hospital of Ganzi Tibet Aut. Pre., SC

2019.07.22

XB-05

J. pingii var. wilsonii

TCM Market of Chengdu International Trade City, SC (No. 6-1-1158)

2020.06.25

XB-06

J. pingii var. wilsonii

TCM Market of Chengdu International Trade City, SC (No. 6-1-0725)

2020.07.22

XB-07

J. pingii var. wilsonii

TCM Market of Chengdu International Trade City, SC (No. 6-1-1158)

2020.07.22

XB-08

J. pingii var. wilsonii

Lhasa Agricultural Product Quality Supervision, Inspection and Testing Center, Tibet Aut. Reg.

2020.07.12

XB-09

J. pingii var. wilsonii

Affiliated Hospital of Tibet Medical University, Tibet Aut. Reg.

2020.07.22

XB-10

J. pingii var. wilsonii

International Tibetan TCM Trading City, Tibet Aut. Reg.

2020.07.22

XB-11

J. pingii var. wilsonii

Tibetan Medical Hospital of Golog Tibet Aut. Pre., QH

2020.07.31

XB-12

J. pingii var. wilsonii

Tibetan Hospital of Chengduo County, Yushu Tibet Aut. Pre., QH

2020.08.02

XB-13

J. pingii var. wilsonii

Kangding Airport, Ganzi Tibet Aut. Pre., SC

2020.08.08

XB-14

J. pingii var. wilsonii

Kangding Airport, Ganzi Tibet Aut. Pre., SC

2020.08.08

XB-15

J. pingii var. wilsonii

Baima Snow Mountain, Deqin County, YN

2020.08.13

XB-16

J. pingii var. wilsonii

The Second Pass of Baima Snow Mountain, Deqin County, YN

2020.08.14

XB-17

J. pingii var. wilsonii

Sangri County, Lashannan City, Tibet Aut. Reg.

2020.08.15

XB-18

J. pingii var. wilsonii

Near Gabila, Kangding City, Ganzi Tibet Aut. Pre., SC

2020.08.18

XB-19

J. pingii var. wilsonii

Mangkang County, Changdu, Tibet Aut. Reg.

2020.08.16

DZ-01

J. indica

Dege County, Ganzi Tibet Aut. Pre., SC

2019.07.23

DZ-02

J. indica

Tu'er Mountain Foot, Litang County, Ganzi Tibet Aut. Pre., SC

2019.09.28

DZ-03

J. indica

International Tibetan TCM Trading City, Tibet Aut. Reg.

2019.08.01

DZ-04

J. indica

International Tibetan TCM Trading City, Tibet Aut. Reg.

2020.06.21

DZ-05

J. indica

Northern Grassland Medicinal Materials Development Co., Ltd of Tibet Aut. Reg.

2020.06.26

DZ-06

J. indica

Rui Junfang Biotechnology Development Co., Ltd of Tibet Aut. Reg.

2020.06.25

DZ-07

J. indica

Tibetan Hospital of Lingzhi City, Tibet Aut. Reg.

2020.07.16

DZ-08

J. indica

Zheduoshan, Kangding City, Ganzi Tibet Aut. Pre., SC

2020.07.01

DZ-09

J. indica

Sejila Mountain, Linzhi City, Tibet Aut. Reg.

2020.07.01

DZ-10

J. indica

Shannan City, Tibet Aut. Reg.

2020.08.05

DZ-11

J. indica

Kongse Township, Daofu County, Ganzi Tibet Aut. Pre., SC

2020.08.06

DZ-12

J. indica

Yangxi Road, Heqing County, Dali City, YN

2020.08.06

DZ-13

J. indica

Derong Sino Tibetan Hospital, Ganzi Tibet Aut. Pre., SC

2020.08.07

DZ-14

J. indica

Baima Snow Mountain, Deqin County, Diqing Tibet Aut. Pre., YN

2020.08.11

DZ-15

J. indica

Dalanggu Village, Xiangcheng County, Ganzi Tibet Aut. Pre., SC

2020.08.15

DZ-16

J. indica

Tiegohe, Litang County, Ganzi Tibet Aut. Pre., SC

2020.08.13

DZ-17

J. indica

Shengping Town, Deqin County, Diqing Tibet Aut. Pre., YN

2020.08.17

DZ-18

J. indica

Rui Junfang Biotechnology Development Co., Ltd of Tibet Aut. Reg.

2020.08.16

DZ-19

J. indica

Lulang Town, Linzhi County, Linzhi City, Tibet Aut. Reg.

2020.08.25

GS-01

J. squamata

Guinan County, Hainan Tibet Aut. Pre., QH

2019.09.28

GS-02

J. squamata

Tibetan Hospital, Dege County, Ganzi Tibet Aut. Pre., SC

2019.07.24

GS-03

J. squamata

Huzhu Tu Autonomous County, Haidong City, QH

2019.09.28

GS-04

J. squamata

Tibetan Hospital, Huangzhong District, Xining City, QH

2019.09.27

GS-05

J. squamata

TCM Market of Chengdu International Trade City, SC (No. 6-1-1158)

2020.07.16

GS-06

J. squamata

Tibetan Hospital, Qinghai Province

2020.07.17

GS-07

J. squamata

Tibetan Hospital of Hainan Tibet Aut. Pre., QH

2020.07.17

GS-08

J. squamata

Tibetan Hospital of Zeku County, Qinghai Province

2020.07.17

GS-09

J. squamata

Medicinal Materials Market of Qinghai Sanzhi Trading Co., Ltd, QH

2020.07.17

GS-10

J. squamata

Zheduoshan, Kangding City, SC

2020.07.16

GS-11

J. squamata

Shannan City, Tibet Aut. Reg.

2020.08.05

GS-12

J. squamata

Tibetan Hospital of Nangqian County, Yushu Tibet Aut. Pre., QH

2020.08.03

GS-13

J. squamata

Xiazha Town, Shiqu County, Ganzi Tibet Aut. Pre., SC

2020.08.06

GS-14

J. squamata

Baima Snow Mountain, Deqin County, YN

2020.08.13

GS-15

J. squamata

Litang County, Ganzi Tibet Aut. Pre., SC

2020.08.17

DG-01

J. tibetica

Tibetan Medicine Factory of Naqu City, Tibet Aut. Reg.

2019.08.01

DG-02

J. tibetica

TCM Market of Chengdu International Trade City, SC (No. 6-1-0725)

2020.06.27

DG-03

J. tibetica

Tibetan Hospital of Chengduo County, Yushu Tibet Aut. Pre., QH

2020.08.02

DG-04

J. tibetica

Shannan Xueyuan Medicinal Materials Co., Ltd, Tibet Aut. Reg.

2020.08.05

DG-05

J. tibetica

Tibetan Medicine Co., Ltd. of Tibet Tibetan Medical College, Tibet Aut. Reg.

2020.08.17

No.	t_R /min	Molecular formula	Theoretical mass (m/z)	Measured mass [M+H]⁺/ [M+Na]⁺ (ppm)	Measured mass [M-H]^- (ppm)	MS/MS (m/z)	Compound	Ref.
1	0.62	C₇H₁₂O₆	192.063 4	/	191.055 4 (-1.0)	173.044 9 [M-H₂O]^- (-0.6); 127.039 5 [M-H₂O-CO₂]^- (1.6)	Auinic acid
2	0.68	C₆H₁₂O₆	180.063 4	/	179.055 4 (-1.1)	161.044 6 [M-H-H₂O]^- (-2.5)	Fructose
3	0.93	C₉H₁₁NO₃	181.073 9	182.081 7 (0.5)	180.066 1 (-3.3)	163.044 6 [M-NO₃]^- (-2.5); 136.076 3 [M+H-H₂O-CO]⁺ (0.7)	L-Tyrosine
4	0.95	C₁₀H₁₃N₅O₄	267.096 8	268.104 9 (1.1)	/	136.072 2 [M+H-C₅H₈O₄]⁺ (0.0); 119.049 7 [M+H-NH₃-C₅H₈O₄]⁺ (0.8); 94.040 7 [M+H-C₅H₈O₄-NH₂CN]⁺ (2.1)	Adenosine	[9]
5	1.21	C₇H₆O₅	170.021 5	171.029 6 (1.8)	169.013 2 (-3.0)	125.023 6 [M-COOH]^- (-2.4); 127.039 7 [M+H-COO]⁺ (1.6); 79.018 0 [C₅H₃O]^- (2.5)	Gallic acid
6	1.31	C₁₂H₂₂O₁₁	342.116 2	/	341.108 4 (-3.6)	179.049 7 [M-H-glc]^- (-1.1); 161.044 6 [M-H-glc-H₂O]^- (-2.5); 119.034 4 [C₄H₇O₄]^- (-1.7)	Sucrose
7	1.36	C₁₁H₁₆O₈	276.084 5	299.074 8 (1.7)	275.076 8 (0.4)	/	Unknown
8	1.51	C₇H₆O₃	138.031 7	/	137.023 6 (-2.2)	93.033 7 [M-H-CO₂]^- (-3.2)	Salicylic acid
9	1.93	C₃₀H₂₆O₁₃	594.137 3	595.145 7 (0.8)	593.128 4 (-1.9)	441.080 8 [M-glc]^- (0.5); 423.070 8 [M-glc-H₂O]^- (0.7); 305.065 3 [C₁₅H₁₃O₇]^- (-0.3); 283.024 3 [C₁₅H₇O₆]^- (0.7); 255.028 7 [C₁₄H₇O₅]^- (1.2)	Gallocatechin-(4α→8)-catechin or catechin-(4α→8)-gallocatechin	[10]
10	2.33	C₇H₆O₄	154.026 0	/	153.018 9 (0.7)	109.028 7 [M-COOH]^- (-2.8)	Protocatechuic acid	[11]
11	2.48	C₁₆H₁₈O₉	354.095 1	377.084 9 (2.2)	353.087 9 (0.6)	191.055 8 [M-H-C₉H₆O₃]^- (1.0); 173.044 9 [M-H-C₉H₆O₃-H₂O]^- (-0.6); 161.023 2 [M-H-C₇H₁₂O₆]^- (-4.3); 135.044 4 [M-H-C₇H₁₀O₆-CO]^- (-1.5); 109.028 5 [M-H-C₇H₁₀O₆-CO-C₂H₂]^- (-4.6)	Chlorogenic acid	[12]
12	2.52	C₃₀H₂₆O₁₃	594.137 3	595.145 1 (-0.2)	593.130 2 (1.2)	441.082 4 [M-H-glc]^- (0.5); 423.071 9 [M-glc-H₂O]^- (0.7); 305.066 0 [C₁₅H₁₃O₇]^- (-0.3); 283.024 5 [C₁₅H₇O₆]^- (0.7); 255.029 6 [C₁₄H₇O₅]^- (1.2)	Gallocatechin-(4α→8)-catechin or catechin-(4α→8)-gallocatechin
13	2.97	C₁₅H₁₄O₆	290.079 0	291.087 5 (2.1)	289.070 8 (-1.4)	579.149 8 [2M+H]⁺ (-0.9); 577.133 7 [2M-H]^- (-1.6); 245.080 7 [M-H-CO₂]^- (-2.9); 229.050 1 [M-H-H₂O-C₂H₂O]^- (3.4); 203.070 0 [M-H-H₂O-C₃O₂]^- (-3.9); 187.038 8 [M-H-CO₂-C₃H₆O]^- (-3.7); 179.033 8 [M-H-C₆H₆O₂]^- (-3.4); 161.023 1 [M-H-CO₂-2C₂H₂O]^- (5.0); 137.024 0 [M-H-C₈H₈O₃]^- (-1.4); 123.044 6 [M-H-C₉H₈O₃]^- (0.0)	Epicatechin	[13]
14	4.63	C₃₀H₂₆O₁₂	578.520 0	579.151 4 (1.9)	577.134 4 (-0.3)	427.103 7 [M+H-C₈H₇O₃]⁺ (1.9); 409.093 0 [M+H-C₈H₇O₃-H₂O]⁺ (1.7); 407.076 4 [M-H-C₈H₇O₃-H₂O]^- (-0.7); 291.087 1 [M+H-C₈H₇O₃-C₇H₄O₃]⁺ (0.7); 289.072 0 [M+H-C₁₅H₁₄O₆]⁺ (2.8)	Proanthocyanidin B1	[14]
15	4.93	C₉H₈O₃	164.047 3	/	163.038 9 (-3.7)	147.044 1 [M-H-H₂O]^- (-3.4); 119.049 7 [M-H-CH₂O₂]^- (0.0)	p-Hydroxycinnamic acid
16	5.31	C₁₅H₁₄O₆	290.079 0	291.087 6 (2.1)	289.071 0 (-0.7)	245.044 8 [M-H₂O-C₂H₂]^- (-0.8); 227.070 9 [M-H-CO₂-H₂O]^- (0.4); 203.070 8 [M-H-C₃H₂O₃]^- (0.0); 205.049 9 [M-H-C₄H₄O₂]^- (-1.0); 179.034 2 [M-H-C₆H₆O₂]^- (-1.1); 151.039 3 [C₈H₇O₃]⁺ (-1.3); 139.039 3 [C₇H₇O₃]⁺ (-1.4); 137.032 6 [C₇H₅O₃]^- (-2.2); 125.023 7 [C₆H₅O₃]^- (-1.6); 109.028 7 [C₆H₅O₂]^- (-2.8)	Catechin	[15]
17	6.55	C₃₀H₂₆O₁₂	578.520 0	579.159 1 (-0.3)	577.134 2 (-0.7)	427.1029 [M+H-C₈H₇O₃]⁺ (0.5); 409.091 9 [M+H-C₈H₇O₃-H₂O]⁺ (-1.0); 407.1414 [M-H-C₈H₇O₃-H₂O]^- (0.7); 291.087 1 [M+H-C₈H₇O₃-C₇H₄O₃]⁺ (0.7); 289.071 4 [M+H-C₁₅H₁₄O₆]⁺ (0.7)	Proanthocyanidin B	[16]
18	8.44	C₂₁H₂₂O₁₁	450.116 2	451.124 4 (0.9)	449.108 5 (0.2)	287.054 6 [M-H-glc]^- (-3.5); 289.071 1 [M+H-glc]⁺ (-0.3); 259.059 7 [M-H-glc-H₂O]^- (-3.5); 151.002 7 [M-H-glc-C₈H₈O₂]^- (-2.6); 107.013 3 [M-H-glc-C₈H₇O₂-CO-OH]^- (1.9); 125.023 7 [M-H-glc-C₇H₄O₄]^- (-1.6)	Eriodictyol-7-O-glucoside	[17]
19	9.75	C₂₀H₁₈O₁₁	434.084 9	/	433.077 1 (-1.4)	867.161 8 [2M-H]^- (-0.2); 301.034 8 [C₁₅H₉O₇]^- (0.0)	Quercetin-3-O-β-D-glucopyranoside	[18]
20	10.07	C₉H₈O₄	180.042 6	/	179.034 7 (1.7)	161.023 8 [M-H-H₂O]^- (-0.6)	Caffeic acid
21	10.11	C₉H₆O₃	162.031 7	163.039 7 (1.2)	161.023 4 (-3.1)	/	Unknown
22	11.6	C₁₆H₂₆O₈	346.162 8	369.152 9 (1.1)	345.154 8 (-0.3)	/	Unknown
23	12.13	C₂₄H₃₂O₁₁	496.194 5	519.184 0 (-0.4)	495.184 2 (-3.6)	/	Unknown
24	13.83	C₂₅H₃₄O₁₂	526.205 0	549.194 5 (-0.5)	525.198 2 (1.9)	/	Unknown
25	15.61	C₂₅H₃₂O₁₀	492.199 5	515.188 5 (-1.6)	491.192 5 (1.6)	/	Unknown
26	15.78	C₂₁H₂₀O₁₂	464.095 5	465.104 2 (1.9)	463.087 4 (-0.6)	303.050 5 [M+H-glc]⁺ (-4.0); 301.034 8 [M-H-glc]^- (3.2); 271.023 6 [C₁₄H₇O₆]^- (-2.6); 257.094 6 [M+H-glc-CH₂O₂]⁺ (1.6); 255.065 1 [M+H-glc-CH₂O₂]^- (-2.4)	Hyperoside
27	16.98	C₂₁H₂₀O₁₂	464.095 5	465.104 3 (2.2)	463.087 6 (-0.2)	929.194 6 [2M+H]⁺ (0.0); 927.183 2 [2M-H]^- (0.1); 301.034 3 [M-H-glc]^- (1.7); 303.050 7 [M+H-glc]^- (0.7); 151.003 0 [C₇H₃O₄]⁺ (3.3)	Hypolaetin-7-O-β-D-glucopyranoside^*
28	17.05	C₂₇H₃₀O₁₆	610.517 5	611.162 0 (1.2)	609.145 3 (-0.5)	465.104 1 [M+H-C₆H₁₀O₄]⁺ (1.7); 463.087 8 [M-H-C₆H₁₀O₄]^- (0.2); 301.034 1 [M-H-rutinose]^- (-2.3); 303.051 2 [M+H-rutinose]⁺ (2.3); 271.024 3 [M-H-rutinose-CO]^--(0.0); 257.044 9 [M+H-rutinose-CO₂]⁺ (-0.4); 255.029 0 [M-H-rutinose-CO₂]^- (-1.2); 151.039 2 [M-H-rutinose-C₈H₄O₅-CO]^- (-2.0)	Rutinum	[19]
29	17.10	C₂₀H₁₈O₁₂	450.079 8	451.087 9 (0.4)	449.072 5 (1.1)	/	Unknown
30	17.67	C₂₆H₃₄O₁₁	522.210 1	545.199 6 (-0.6)	521.202 8 (1.0)	545.199 6 [M+Na]⁺ (-0.6); 521.202 8 [M-H]^- (1.0)	Isolarisiresinol-2α- O-β-D-glucoside or isolarisiresinol-3α- O-β-D-glucoside, isomer 1	[20]
31	17.86	C₂₆H₃₄O₁₁	522.210 1	545.200 6 (1.3)	521.201 7 (-1.2)	545.199 6 [M+Na]⁺ (-0.6); 521.202 8 [M-H]^- (1.0)	Isolarisiresinol-2α- O-β-D-glucoside or isolarisiresinol-3α- O-β-D-glucoside, isomer 2
32	17.98	C₁₈H₂₆O₉	386.157 7	409.147 5 (0.0)	385.150 9 (2.6)	207.101 7 [M+H-glc-H₂O]⁺ (-1.9)	Methylsyringin^*	[21, 22]
33	19.01	C₂₁H₂₀O₁₂	464.095 5	465.103 7 (0.9)	463.088 7 (2.2)	303.050 4 [M+H-glc]⁺ [-0.3]; 301.034 2 [M-H-glc]^- (2.0); 25 7.0450 [M+H-glc-CH₂O₂]⁺ (0.0)	Quercetin-3-O-β-D-lucopyranoside	[23]
34	20.80	C₂₁H₂₀O₁₁	448.100 6	449.109 3 (2.0)	447.096 5 (1.8)	895.193 8 [2M-H]^- (0.6); 303.051 2 [M+H-rha]⁺ (2.3); 301.033 8 [M-H-rha]^- (-3.3); 271.023 9 [M-H-rha-H-CO]^- (-1.5); 255.029 1 [M-H-rha-CO-OH]^- (-0.8); 229.052 7 [C₁₄H₁₃O₃]⁺ (0.9); 151.002 2 [M-H-rha-C₇HO₄]^- (-2.6); 109.029 4 [C₆H₅O₂]⁺ (0.9)	Quercitrin^*	[24]
35	21.04	C₂₀H₁₈O₁₁	434.084 9	435.092 8 (0.2)	433.077 6 (1.2)	867.160 9 [2M-H]^- (1.0); 303.051 1 [M+H-Xyl]⁺ (2.0); 301.034 1 [M-H-Xyl]^- (-1.7); 135.044 3 [C₈H₇O₂]^- (-2.2); 316.947 6 [M-H-glc]^- (0.0); 261.133 8 [M-H-glc-2CO]^- (0.0)	Hypolaetin-7-O-β-D-xylopyranoside^*	[25]
36	22.77	C₂₀H₂₆O₆	362.172 9	385.162 7 (0.0)	361.163 3 (-5.0)	/	Unknown
37	23.02	C₂₁H₂₀O₁₁	448.100 6	449.108 7 (0.7)	447.092 7 (0.0)	287.055 7 [M+H-glc]⁺ (0.3); 285.039 9 [M-H-glc]^- (0.0); 151.003 1 [C₇H₃O₄]^- (0.0); 153.018 8 [C₇H₅O₄]⁺ (0.0)	Cynaroside	[26]
38	24.26	C₁₅H₁₀O₆	286.047 7	287.056 0 (1.4)	285.039 7 (-0.7)	241.050 6 [M-CO₂]^- (2.1); 153.018 8 [M+H-C₈H₆O₂]⁺ (0.0); 151.039 0 [M-H-C₈H₆O₂]^- (-3.3); 133.028 4 [M-H-C₇H₄O₄]^- (-4.5)	Luteolin	[26]
39	24.73	C₃₃H₄₀O₁₉	740.216 4	/	739.205 0 (-4.9)	593.145 7 [M-H-C₆H₁₂O₄]^- (1.5); 431.092 4 [M-H-C₁₂H₂₂O₉]^- (1.2); 285.040 1 [M-H-C₆H₁₂O₄-C₁₂H₂₂O₉]^- (0.7)	Robinin	[27]
40	26.64	C₃₆H₂₈O₁₅	700.142 8	701.150 9 (0.4)	699.135 2 (0.3)	539.098 2 [M+H-162 (hexose unit)]⁺ (0.7); 537.083 0 [M-H-162 (hexose unit)]^- (1.5)	Cupressuflavone 4'-O-β-D-glucopyranosides	[28]
41	29.01	C₁₅H₁₀O₅	270.052 8	271.060 5 (-0.4)	269.044 7 (-1.1)	225.056 0 [M-H-CO₂]^- (3.6); 183.044 8 [M-H-H₂O-C₃O₂]^- (1.1); 201.163 8 [M-H-C₃O₂]^- (-2.5); 213.055 0 [M-H-CO-CO]^- (-0.9); 241.048 9 [M-H-CO]^- (-5.0)	Apigenin	[29]
42	29.37	C₃₆H₂₈O₁₅	700.142 8	701.150 6 (0.0)	699.133 4 (-2.3)	/	Unknown
43	29.99	C₁₁H₁₀O₃	190.063 0	213.052 8 (0.0); 191.070 7 (-0.5)	/	213.052 8 [M+Na]⁺ (0.0); 191.070 7 [M+H]⁺ (-0.5)	Ekersenin^*	[30]
44	31.36	C₃₀H₁₈O₁₀	538.090 0	539.097 4 (-0.7)	537.083 6 (2.6)	1 075.172 2 [2M-H]^- (3.1); 377.066 3 [M+H-C₉H₆0₃]⁺ (0.5); 375.050 5 [M-H-C₉H₆O₃]^- (0.0); 121.029 0 [C₇H₅O₂]⁺ (0.0)	Cupressuflavone^*	[31]
45	32.83	C₃₀H₁₈O₁₀	538.090 0	539.098 3 (0.9)	537.082 9 (1.3)	1 075.176 5 [2M-H]^- (0.8); 1 077.190 2 [2M+H]⁺ (0.0); 521.087 7 [M+H-H₂O]⁺ (0.8); 497.087 8 [M+H-C₂H₂O]⁺ (1.0); 403.045 8 [M+H-C₈H₆O-H₂O]⁺ (1.0); 379.045 8 [M+H-C₈H₆O-C₂H₂O]⁺ (1.1); 377.066 5 [M+H-C₉H₆O₃]⁺ (1.1); 311.055 9 [M+H-C₈H₆O-C₃O₂]⁺ (1.0); 283.060 6 [M+H-C₈H₆O-C₃O₂-CO]⁺ (0.0); 121.029 0 [C₇H₅O₂]⁺ (0.0)	Amentoflavone^*	[32]
46	34.33	C₃₀H₁₈O₁₀	538.090 0	539.097 6 (-0.4)	537.082 2 (0.0)	521.087 4 [M+H-H₂O]⁺ (0.2); 413.068 8 [M+H-C₆H₄O₃]⁺ (-1.9); 403.045 7 [M+H-C₈H₆O-H₂O]⁺ (0.7); 387.087 0 [M+H-C₇H₄O₄]⁺ (0.3); 375.050 2 [M+H-C₈H₆O-H₂O-CO]⁺ (-0.8); 283.060 7 [M+H-C₁₄H₉O₅]⁺ (0.4); 153.018 7 [C₇H₅O₄]⁺ (-0.7); 121.028 9 [C₇H₅O₂]⁺ (-0.8)	Robustaflavone	[32]
47	35.72	C₃₀H₂₀O₁₀	540.105 6	541.113 5 (0.0)	539.095 8 (2.8)	/	Unknown
48	39.61	C₃₁H₂₀O₁₀	552.484 5	553.114 1 (1.1)	551.098 6 (1.5)	421.055 9 [M+H-C₉H₈O]⁺ (-0.2); 403.045 7 [M+H-C₉H₈O-H₂O]⁺ (0.7); 377.069 2 [M+H-C₁₀H₈O₃]⁺ (-1.1); 375.054 0 [M-H-C₁₀H₈O₃]^- (0.3); 135.044 1 [C₈H₈O₂]⁺ (-3.7)	Podocarpusflavone A^*	[32]
49	41.95	C₃₁H₂₀O₁₀	552.105 6	553.114 1 (1.1)	551.097 4 (-0.7)	1 105.222 2 [2M+H]⁺ (2.8); 1 103.205 7 [2M-H]^- (2.0); 403.046 0 [M+H-C₈H₆O-CH₃OH]⁺ (1.5); 390.978 5 [M+H-C₉H₆O₃]⁺ (2.6); 153.018 4 [C₇H₅O₄]⁺ (-2.6)	4′-Methoxy robustaflavone	[31, 32]
50	43.17	C₃₀H₁₈O₁₀	538.090 0	539.097 6 (-0.6)	537.081 8 (-0.7)	387.087 0 [M+H-C₇H₄O₄]⁺ (0.3); 287.237 4 [M+H-C₁₅H₉O₄]⁺ (-0.3); 285.221 3 [M-H-C₁₅H₉O₄]^- (-1.8); 269.191 1 [M+H-C₁₅H₉O₅]⁺ (2.2); 257.047 9 [M+H-C₁₅H₉O₄-CO]⁺ (-2.3); 243.065 5 [M+H-C₁₅H₉O₅-CO]⁺ (-0.8); 153.018 7 [C₇H₅O₄]⁺ (-0.7); 121.028 9 [C₇H₅O₂]⁺ (-0.8)	Hinokiflavone^*	[32]
51	44.20	C₂₂H₃₄O₅	378.240 6	401.230 4(0.0)	377.231 7(-2.9)	/	Unknown
52	46.67	C₃₅H₆₀O₆	576.439 0	577.446 8 (0.0)	/	577.446 8 [M+H]⁺ (0.0)	β-Daucosterol	[33]
53	47.47	C₃₂H₂₂O₁₀	566.121 3	567.130 1 (1.8)	565.114 7 (2.1)	435.071 1 [M+H-C₉H₈O]⁺ (-1.1); 417.061 2 [M+H-C₉H₈O-H₂O]⁺ (0.5); 391.081 6 [M+H-C₁₀H₈O₃]⁺ (-0.5); 389.066 1 [M-H-C₁₀H₈O₃]^- (0.0); 167.128 6 [C₈H₆O₄]⁺ (-1.8); 135.044 3 [C₈H₈O₂]⁺ (-2.2)	Putraflavone B	[34]
54	52.99	C₂₀H₂₈O₂	300.208 9	301.218 0 (4.0)	299.200 3 (-3.0)	241.159 3 [M+H-C₂H₆-C₂H₆]⁺ (0.4); 213.127 8 [M+H-C₂H₆-C₂H₆-CO]⁺ (-0.5)	Sugiol	[35]
55	55.68	C₂₀H₂₆O₄	330.183 1	331.190 3 (-1.8)	329.172 9 (0.0)	331.190 3 [M+H]⁺ (-1.8); 329.172 9 [M-H]^- (0.0)	Carnosol	[36]
56	59.85	C₂₀H₃₀O₂	302.224 6	303.232 6 (0.7)	301.217 1 (1.0)	257.226 6 [M-COOH]⁺ (1.2); 149.132 8 [M-COOH-C₆H₆(CH₃)₂]⁺ (-1.3); 123.117 2 [M+H-COOH-C₆H₆CH₂CH(CH₃)₂]⁺ (1.6)	Abietic acid	[37]
57	62.38	C₂₉H₅₀O	414.386 2	415.394 0 (0.0)	/	397.383 4 [M-OH]⁺ (3.5); 161.133 0 [M-OH-C₁₇H₃₃]⁺ (2.1); 109.181 7 [M-OH-C₁₇H₃₃-C₄H₅]⁺ (1.2); 81.070 4 [C₆H₉]⁺ (1.5)	β-Sitosterol	[38]
58	63.19	C₂₀H₂₈O₂	300.208 9	323.198 6 (-0.3)	299.200 8 (-1.0)	/	Unknown

No.

t_R /min

Molecular formula

Theoretical mass (m/z)

Measured mass
[M+H]⁺/
[M+Na]⁺ (ppm)

Measured mass
[M-H]^- (ppm)

MS/MS (m/z)

Compound

Ref.

0.62

C₇H₁₂O₆

192.063 4

191.055 4 (-1.0)

173.044 9 [M-H₂O]^- (-0.6);
127.039 5 [M-H₂O-CO₂]^- (1.6)

Auinic acid

0.68

C₆H₁₂O₆

180.063 4

179.055 4 (-1.1)

161.044 6 [M-H-H₂O]^- (-2.5)

Fructose

0.93

C₉H₁₁NO₃

181.073 9

182.081 7 (0.5)

180.066 1 (-3.3)

163.044 6 [M-NO₃]^- (-2.5);
136.076 3 [M+H-H₂O-CO]⁺ (0.7)

L-Tyrosine

0.95

C₁₀H₁₃N₅O₄

267.096 8

268.104 9 (1.1)

136.072 2 [M+H-C₅H₈O₄]⁺ (0.0);
119.049 7 [M+H-NH₃-C₅H₈O₄]⁺ (0.8);
94.040 7 [M+H-C₅H₈O₄-NH₂CN]⁺ (2.1)

Adenosine

[9]

1.21

C₇H₆O₅

170.021 5

171.029 6 (1.8)

169.013 2 (-3.0)

125.023 6 [M-COOH]^- (-2.4);
127.039 7 [M+H-COO]⁺ (1.6);
79.018 0 [C₅H₃O]^- (2.5)

Gallic acid

1.31

C₁₂H₂₂O₁₁

342.116 2

341.108 4 (-3.6)

179.049 7 [M-H-glc]^- (-1.1);
161.044 6 [M-H-glc-H₂O]^- (-2.5);
119.034 4 [C₄H₇O₄]^- (-1.7)

Sucrose

1.36

C₁₁H₁₆O₈

276.084 5

299.074 8 (1.7)

275.076 8 (0.4)

Unknown

1.51

C₇H₆O₃

138.031 7

137.023 6 (-2.2)

93.033 7 [M-H-CO₂]^- (-3.2)

Salicylic acid

1.93

C₃₀H₂₆O₁₃

594.137 3

595.145 7 (0.8)

593.128 4 (-1.9)

441.080 8 [M-glc]^- (0.5);
423.070 8 [M-glc-H₂O]^- (0.7);
305.065 3 [C₁₅H₁₃O₇]^- (-0.3);
283.024 3 [C₁₅H₇O₆]^- (0.7);
255.028 7 [C₁₄H₇O₅]^- (1.2)

Gallocatechin-(4α→8)-catechin or catechin-(4α→8)-gallocatechin

[10]

2.33

C₇H₆O₄

154.026 0

153.018 9 (0.7)

109.028 7 [M-COOH]^- (-2.8)

Protocatechuic acid

[11]

2.48

C₁₆H₁₈O₉

354.095 1

377.084 9 (2.2)

353.087 9 (0.6)

191.055 8 [M-H-C₉H₆O₃]^- (1.0);
173.044 9 [M-H-C₉H₆O₃-H₂O]^- (-0.6);
161.023 2 [M-H-C₇H₁₂O₆]^- (-4.3);
135.044 4 [M-H-C₇H₁₀O₆-CO]^- (-1.5);
109.028 5 [M-H-C₇H₁₀O₆-CO-C₂H₂]^- (-4.6)

Chlorogenic acid

[12]

2.52

C₃₀H₂₆O₁₃

594.137 3

595.145 1 (-0.2)

593.130 2 (1.2)

441.082 4 [M-H-glc]^- (0.5);
423.071 9 [M-glc-H₂O]^- (0.7);
305.066 0 [C₁₅H₁₃O₇]^- (-0.3);
283.024 5 [C₁₅H₇O₆]^- (0.7);
255.029 6 [C₁₄H₇O₅]^- (1.2)

Gallocatechin-(4α→8)-catechin or catechin-(4α→8)-gallocatechin

2.97

C₁₅H₁₄O₆

290.079 0

291.087 5 (2.1)

289.070 8 (-1.4)

579.149 8 [2M+H]⁺ (-0.9);
577.133 7 [2M-H]^- (-1.6);
245.080 7 [M-H-CO₂]^- (-2.9);
229.050 1 [M-H-H₂O-C₂H₂O]^- (3.4); 203.070 0 [M-H-H₂O-C₃O₂]^- (-3.9); 187.038 8 [M-H-CO₂-C₃H₆O]^- (-3.7); 179.033 8 [M-H-C₆H₆O₂]^- (-3.4); 161.023 1 [M-H-CO₂-2C₂H₂O]^- (5.0); 137.024 0 [M-H-C₈H₈O₃]^- (-1.4); 123.044 6 [M-H-C₉H₈O₃]^- (0.0)

Epicatechin

[13]

4.63

C₃₀H₂₆O₁₂

578.520 0

579.151 4 (1.9)

577.134 4 (-0.3)

427.103 7 [M+H-C₈H₇O₃]⁺ (1.9);
409.093 0 [M+H-C₈H₇O₃-H₂O]⁺ (1.7); 407.076 4 [M-H-C₈H₇O₃-H₂O]^- (-0.7); 291.087 1 [M+H-C₈H₇O₃-C₇H₄O₃]⁺ (0.7);
289.072 0 [M+H-C₁₅H₁₄O₆]⁺ (2.8)

Proanthocyanidin B1

[14]

4.93

C₉H₈O₃

164.047 3

163.038 9 (-3.7)

147.044 1 [M-H-H₂O]^- (-3.4);
119.049 7 [M-H-CH₂O₂]^- (0.0)

p-Hydroxycinnamic acid

5.31

C₁₅H₁₄O₆

290.079 0

291.087 6 (2.1)

289.071 0 (-0.7)

245.044 8 [M-H₂O-C₂H₂]^- (-0.8);
227.070 9 [M-H-CO₂-H₂O]^- (0.4); 203.070 8 [M-H-C₃H₂O₃]^- (0.0);
205.049 9 [M-H-C₄H₄O₂]^- (-1.0); 179.034 2 [M-H-C₆H₆O₂]^- (-1.1);
151.039 3 [C₈H₇O₃]⁺ (-1.3);
139.039 3 [C₇H₇O₃]⁺ (-1.4);
137.032 6 [C₇H₅O₃]^- (-2.2);
125.023 7 [C₆H₅O₃]^- (-1.6);
109.028 7 [C₆H₅O₂]^- (-2.8)

Catechin

[15]

6.55

C₃₀H₂₆O₁₂

578.520 0

579.159 1 (-0.3)

577.134 2 (-0.7)

427.1029 [M+H-C₈H₇O₃]⁺ (0.5);
409.091 9 [M+H-C₈H₇O₃-H₂O]⁺ (-1.0); 407.1414 [M-H-C₈H₇O₃-H₂O]^- (0.7); 291.087 1 [M+H-C₈H₇O₃-C₇H₄O₃]⁺ (0.7); 289.071 4 [M+H-C₁₅H₁₄O₆]⁺ (0.7)

Proanthocyanidin B

[16]

8.44

C₂₁H₂₂O₁₁

450.116 2

451.124 4 (0.9)

449.108 5 (0.2)

287.054 6 [M-H-glc]^- (-3.5);
289.071 1 [M+H-glc]⁺ (-0.3);
259.059 7 [M-H-glc-H₂O]^- (-3.5); 151.002 7 [M-H-glc-C₈H₈O₂]^- (-2.6); 107.013 3 [M-H-glc-C₈H₇O₂-CO-OH]^- (1.9);
125.023 7 [M-H-glc-C₇H₄O₄]^- (-1.6)

Eriodictyol-7-O-glucoside

[17]

9.75

C₂₀H₁₈O₁₁

434.084 9

433.077 1 (-1.4)

867.161 8 [2M-H]^- (-0.2);
301.034 8 [C₁₅H₉O₇]^- (0.0)

Quercetin-3-O-β-D-glucopyranoside

[18]

10.07

C₉H₈O₄

180.042 6

179.034 7 (1.7)

161.023 8 [M-H-H₂O]^- (-0.6)

Caffeic acid

10.11

C₉H₆O₃

162.031 7

163.039 7 (1.2)

161.023 4 (-3.1)

Unknown

11.6

C₁₆H₂₆O₈

346.162 8

369.152 9 (1.1)

345.154 8 (-0.3)

Unknown

12.13

C₂₄H₃₂O₁₁

496.194 5

519.184 0 (-0.4)

495.184 2 (-3.6)

Unknown

13.83

C₂₅H₃₄O₁₂

526.205 0

549.194 5 (-0.5)

525.198 2 (1.9)

Unknown

15.61

C₂₅H₃₂O₁₀

492.199 5

515.188 5 (-1.6)

491.192 5 (1.6)

Unknown

15.78

C₂₁H₂₀O₁₂

464.095 5

465.104 2 (1.9)

463.087 4 (-0.6)

303.050 5 [M+H-glc]⁺ (-4.0);
301.034 8 [M-H-glc]^- (3.2);
271.023 6 [C₁₄H₇O₆]^- (-2.6);
257.094 6 [M+H-glc-CH₂O₂]⁺ (1.6);
255.065 1 [M+H-glc-CH₂O₂]^- (-2.4)

Hyperoside

16.98

C₂₁H₂₀O₁₂

464.095 5

465.104 3 (2.2)

463.087 6 (-0.2)

929.194 6 [2M+H]⁺ (0.0);
927.183 2 [2M-H]^- (0.1);
301.034 3 [M-H-glc]^- (1.7);
303.050 7 [M+H-glc]^- (0.7);
151.003 0 [C₇H₃O₄]⁺ (3.3)

Hypolaetin-7-O-β-D-glucopyranoside^*

17.05

C₂₇H₃₀O₁₆

610.517 5

611.162 0 (1.2)

609.145 3 (-0.5)

465.104 1 [M+H-C₆H₁₀O₄]⁺ (1.7);
463.087 8 [M-H-C₆H₁₀O₄]^- (0.2);
301.034 1 [M-H-rutinose]^- (-2.3); 303.051 2 [M+H-rutinose]⁺ (2.3);
271.024 3 [M-H-rutinose-CO]^--(0.0); 257.044 9 [M+H-rutinose-CO₂]⁺ (-0.4); 255.029 0 [M-H-rutinose-CO₂]^- (-1.2); 151.039 2 [M-H-rutinose-C₈H₄O₅-CO]^- (-2.0)

Rutinum

[19]

17.10

C₂₀H₁₈O₁₂

450.079 8

451.087 9 (0.4)

449.072 5 (1.1)

Unknown

17.67

C₂₆H₃₄O₁₁

522.210 1

545.199 6 (-0.6)

521.202 8 (1.0)

545.199 6 [M+Na]⁺ (-0.6);
521.202 8 [M-H]^- (1.0)

Isolarisiresinol-2α- O-β-D-glucoside or isolarisiresinol-3α- O-β-D-glucoside, isomer 1

[20]

17.86

C₂₆H₃₄O₁₁

522.210 1

545.200 6 (1.3)

521.201 7 (-1.2)

545.199 6 [M+Na]⁺ (-0.6);
521.202 8 [M-H]^- (1.0)

Isolarisiresinol-2α- O-β-D-glucoside or isolarisiresinol-3α- O-β-D-glucoside, isomer 2

17.98

C₁₈H₂₆O₉

386.157 7

409.147 5 (0.0)

385.150 9 (2.6)

207.101 7 [M+H-glc-H₂O]⁺ (-1.9)

Methylsyringin^*

[21, 22]

19.01

C₂₁H₂₀O₁₂

464.095 5

465.103 7 (0.9)

463.088 7 (2.2)

303.050 4 [M+H-glc]⁺ [-0.3];
301.034 2 [M-H-glc]^- (2.0);
25 7.0450 [M+H-glc-CH₂O₂]⁺ (0.0)

Quercetin-3-O-β-D-lucopyranoside

[23]

20.80

C₂₁H₂₀O₁₁

448.100 6

449.109 3 (2.0)

447.096 5 (1.8)

895.193 8 [2M-H]^- (0.6);
303.051 2 [M+H-rha]⁺ (2.3);
301.033 8 [M-H-rha]^- (-3.3);
271.023 9 [M-H-rha-H-CO]^- (-1.5); 255.029 1 [M-H-rha-CO-OH]^- (-0.8); 229.052 7 [C₁₄H₁₃O₃]⁺ (0.9);
151.002 2 [M-H-rha-C₇HO₄]^- (-2.6);
109.029 4 [C₆H₅O₂]⁺ (0.9)

Quercitrin^*

[24]

21.04

C₂₀H₁₈O₁₁

434.084 9

435.092 8 (0.2)

433.077 6 (1.2)

867.160 9 [2M-H]^- (1.0);
303.051 1 [M+H-Xyl]⁺ (2.0);
301.034 1 [M-H-Xyl]^- (-1.7);
135.044 3 [C₈H₇O₂]^- (-2.2);
316.947 6 [M-H-glc]^- (0.0);
261.133 8 [M-H-glc-2CO]^- (0.0)

Hypolaetin-7-O-β-D-xylopyranoside^*

[25]

22.77

C₂₀H₂₆O₆

362.172 9

385.162 7 (0.0)

361.163 3 (-5.0)

Unknown

23.02

C₂₁H₂₀O₁₁

448.100 6

449.108 7 (0.7)

447.092 7 (0.0)

287.055 7 [M+H-glc]⁺ (0.3);
285.039 9 [M-H-glc]^- (0.0);
151.003 1 [C₇H₃O₄]^- (0.0);
153.018 8 [C₇H₅O₄]⁺ (0.0)

Cynaroside

[26]

24.26

C₁₅H₁₀O₆

286.047 7

287.056 0 (1.4)

285.039 7 (-0.7)

241.050 6 [M-CO₂]^- (2.1);
153.018 8 [M+H-C₈H₆O₂]⁺ (0.0);
151.039 0 [M-H-C₈H₆O₂]^- (-3.3);
133.028 4 [M-H-C₇H₄O₄]^- (-4.5)

Luteolin

[26]

24.73

C₃₃H₄₀O₁₉

740.216 4

739.205 0 (-4.9)

593.145 7 [M-H-C₆H₁₂O₄]^- (1.5);
431.092 4 [M-H-C₁₂H₂₂O₉]^- (1.2);
285.040 1 [M-H-C₆H₁₂O₄-C₁₂H₂₂O₉]^- (0.7)

Robinin

[27]

26.64

C₃₆H₂₈O₁₅

700.142 8

701.150 9 (0.4)

699.135 2 (0.3)

539.098 2 [M+H-162 (hexose unit)]⁺ (0.7);
537.083 0 [M-H-162 (hexose unit)]^- (1.5)

Cupressuflavone 4'-O-β-D-glucopyranosides

[28]

29.01

C₁₅H₁₀O₅

270.052 8

271.060 5 (-0.4)

269.044 7 (-1.1)

225.056 0 [M-H-CO₂]^- (3.6);
183.044 8 [M-H-H₂O-C₃O₂]^- (1.1); 201.163 8 [M-H-C₃O₂]^- (-2.5);
213.055 0 [M-H-CO-CO]^- (-0.9);
241.048 9 [M-H-CO]^- (-5.0)

Apigenin

[29]

29.37

C₃₆H₂₈O₁₅

700.142 8

701.150 6 (0.0)

699.133 4 (-2.3)

Unknown

29.99

C₁₁H₁₀O₃

190.063 0

213.052 8 (0.0);
191.070 7 (-0.5)

213.052 8 [M+Na]⁺ (0.0);
191.070 7 [M+H]⁺ (-0.5)

Ekersenin^*

[30]

31.36

C₃₀H₁₈O₁₀

538.090 0

539.097 4 (-0.7)

537.083 6 (2.6)

1 075.172 2 [2M-H]^- (3.1);
377.066 3 [M+H-C₉H₆0₃]⁺ (0.5);
375.050 5 [M-H-C₉H₆O₃]^- (0.0);
121.029 0 [C₇H₅O₂]⁺ (0.0)

Cupressuflavone^*

[31]

32.83

C₃₀H₁₈O₁₀

538.090 0

539.098 3 (0.9)

537.082 9 (1.3)

1 075.176 5 [2M-H]^- (0.8);
1 077.190 2 [2M+H]⁺ (0.0);
521.087 7 [M+H-H₂O]⁺ (0.8);
497.087 8 [M+H-C₂H₂O]⁺ (1.0);
403.045 8 [M+H-C₈H₆O-H₂O]⁺ (1.0); 379.045 8 [M+H-C₈H₆O-C₂H₂O]⁺ (1.1); 377.066 5 [M+H-C₉H₆O₃]⁺ (1.1);
311.055 9 [M+H-C₈H₆O-C₃O₂]⁺ (1.0); 283.060 6 [M+H-C₈H₆O-C₃O₂-CO]⁺ (0.0);
121.029 0 [C₇H₅O₂]⁺ (0.0)

Amentoflavone^*

[32]

34.33

C₃₀H₁₈O₁₀

538.090 0

539.097 6 (-0.4)

537.082 2 (0.0)

521.087 4 [M+H-H₂O]⁺ (0.2);
413.068 8 [M+H-C₆H₄O₃]⁺ (-1.9);
403.045 7 [M+H-C₈H₆O-H₂O]⁺ (0.7); 387.087 0 [M+H-C₇H₄O₄]⁺ (0.3);
375.050 2 [M+H-C₈H₆O-H₂O-CO]⁺ (-0.8);
283.060 7 [M+H-C₁₄H₉O₅]⁺ (0.4);
153.018 7 [C₇H₅O₄]⁺ (-0.7);
121.028 9 [C₇H₅O₂]⁺ (-0.8)

Robustaflavone

[32]

35.72

C₃₀H₂₀O₁₀

540.105 6

541.113 5 (0.0)

539.095 8 (2.8)

Unknown

39.61

C₃₁H₂₀O₁₀

552.484 5

553.114 1 (1.1)

551.098 6 (1.5)

421.055 9 [M+H-C₉H₈O]⁺ (-0.2);
403.045 7 [M+H-C₉H₈O-H₂O]⁺ (0.7);
377.069 2 [M+H-C₁₀H₈O₃]⁺ (-1.1);
375.054 0 [M-H-C₁₀H₈O₃]^- (0.3);
135.044 1 [C₈H₈O₂]⁺ (-3.7)

Podocarpusflavone A^*

[32]

41.95

C₃₁H₂₀O₁₀

552.105 6

553.114 1 (1.1)

551.097 4 (-0.7)

1 105.222 2 [2M+H]⁺ (2.8);
1 103.205 7 [2M-H]^- (2.0);
403.046 0 [M+H-C₈H₆O-CH₃OH]⁺ (1.5); 390.978 5 [M+H-C₉H₆O₃]⁺ (2.6);
153.018 4 [C₇H₅O₄]⁺ (-2.6)

4′-Methoxy robustaflavone

[31, 32]

43.17

C₃₀H₁₈O₁₀

538.090 0

539.097 6 (-0.6)

537.081 8 (-0.7)

387.087 0 [M+H-C₇H₄O₄]⁺ (0.3);
287.237 4 [M+H-C₁₅H₉O₄]⁺ (-0.3); 285.221 3 [M-H-C₁₅H₉O₄]^- (-1.8); 269.191 1 [M+H-C₁₅H₉O₅]⁺ (2.2);
257.047 9 [M+H-C₁₅H₉O₄-CO]⁺ (-2.3); 243.065 5 [M+H-C₁₅H₉O₅-CO]⁺ (-0.8); 153.018 7 [C₇H₅O₄]⁺ (-0.7);
121.028 9 [C₇H₅O₂]⁺ (-0.8)

Hinokiflavone^*

[32]

44.20

C₂₂H₃₄O₅

378.240 6

401.230 4(0.0)

377.231 7(-2.9)

Unknown

46.67

C₃₅H₆₀O₆

576.439 0

577.446 8 (0.0)

577.446 8 [M+H]⁺ (0.0)

β-Daucosterol

[33]

47.47

C₃₂H₂₂O₁₀

566.121 3

567.130 1 (1.8)

565.114 7 (2.1)

435.071 1 [M+H-C₉H₈O]⁺ (-1.1);
417.061 2 [M+H-C₉H₈O-H₂O]⁺ (0.5); 391.081 6 [M+H-C₁₀H₈O₃]⁺ (-0.5); 389.066 1 [M-H-C₁₀H₈O₃]^- (0.0);
167.128 6 [C₈H₆O₄]⁺ (-1.8);
135.044 3 [C₈H₈O₂]⁺ (-2.2)

Putraflavone B

[34]

52.99

C₂₀H₂₈O₂

300.208 9

301.218 0 (4.0)

299.200 3 (-3.0)

241.159 3 [M+H-C₂H₆-C₂H₆]⁺ (0.4); 213.127 8 [M+H-C₂H₆-C₂H₆-CO]⁺ (-0.5)

Sugiol

[35]

55.68

C₂₀H₂₆O₄

330.183 1

331.190 3 (-1.8)

329.172 9 (0.0)

331.190 3 [M+H]⁺ (-1.8);
329.172 9 [M-H]^- (0.0)

Carnosol

[36]

59.85

C₂₀H₃₀O₂

302.224 6

303.232 6 (0.7)

301.217 1 (1.0)

257.226 6 [M-COOH]⁺ (1.2);
149.132 8 [M-COOH-C₆H₆(CH₃)₂]⁺ (-1.3);
123.117 2 [M+H-COOH-C₆H₆CH₂CH(CH₃)₂]⁺ (1.6)

Abietic acid

[37]

62.38

C₂₉H₅₀O

414.386 2

415.394 0 (0.0)

397.383 4 [M-OH]⁺ (3.5);
161.133 0 [M-OH-C₁₇H₃₃]⁺ (2.1);
109.181 7 [M-OH-C₁₇H₃₃-C₄H₅]⁺ (1.2);
81.070 4 [C₆H₉]⁺ (1.5)

β-Sitosterol

[38]

63.19

C₂₀H₂₈O₂

300.208 9

323.198 6 (-0.3)

299.200 8 (-1.0)

Unknown

Compound	Peak	VIP (ESI⁺)	VIP (ESI^－)
Abietic acid	56	18.434 12	/
C₂₅H₃₄O₁₂	24	/	14.512 43
C₂₄H₃₂O₁₁	23	/	11.461 65
4'-Methoxy robustaflavone	49	10.240 51	10.806 80
C₂₂H₃₄O₅	51	/	10.211 32
Hinokiflavone	50	/	9.621 84
C₁₆H₂₆O₈	22	/	8.971 32
Hypolaetin-7-O-β-D-xylopyranoside	35	8.728 47	/
C₂₀H₂₈O₂	58	7.348 05	/
C₃₀H₂₀O₁₀	47	6.942 69	/
Podocarpusflavone A	48	/	6.908 60
C₃₆H₂₈O₁₅	42	6.447 10	/
Quercitrin	34	6.178 06	/
Amentoflavone	45	5.646 62	6.544 26
Proanthocyanidin B1	14	4.943 33	4.584 01
Sugiol	54	4.564 51	/
C₂₀H₂₆O₆	36	/	4.268 83
Catechin	16	3.996 22	3.509 34
C₉H₆O₃	21	3.627 38	/
Auinic acid	1	/	3.303 37
C₂₅H₃₂O₁₀	25	/	3.203 47

Compound

Peak

VIP (ESI⁺)

VIP (ESI^－)

Abietic acid

18.434 12

C₂₅H₃₄O₁₂

14.512 43

C₂₄H₃₂O₁₁

11.461 65

4'-Methoxy robustaflavone

10.240 51

10.806 80

C₂₂H₃₄O₅

10.211 32

Hinokiflavone

9.621 84

C₁₆H₂₆O₈

8.971 32

Hypolaetin-7-O-β-D-xylopyranoside

8.728 47

C₂₀H₂₈O₂

7.348 05

C₃₀H₂₀O₁₀

6.942 69

Podocarpusflavone A

6.908 60

C₃₆H₂₈O₁₅

6.447 10

Quercitrin

6.178 06

Amentoflavone

5.646 62

6.544 26

Proanthocyanidin B1

4.943 33

4.584 01

Sugiol

4.564 51

C₂₀H₂₆O₆

4.268 83

Catechin

3.996 22

3.509 34

C₉H₆O₃

3.627 38

Auinic acid

3.303 37

C₂₅H₃₂O₁₀

3.203 47