中国药学杂志

No.	Pinelliae Rhizoma (in Chinese)	Gastrodiae Rhizoma (in Chinese)	Macrocephalae Rhizoma (in Chinese)	Citri Exocarpium Rubrum(in Chinese)	Poria cocos (in Chinese)	Glycyrrhizae Radix et Rhizoma(in Chinese)	Jujubae Fructus (in Chinese)
S1-S5	Sichuan Xichang (四川西昌)	Yunnan Zhaotong (云南昭通)	Anhui Bozhou (安徽亳州)	Sichuan Chengdu (四川成都)	Yunnan Qujing (云南曲靖)	Gansu Longxi (甘肃陇西)	Henan Anyang (河南安阳)
S6-S10	Gansu Qingshui (甘肃清水)	Anhui Yuexi (安徽岳西)	Hebei Lixian (河北蠡县)	Hubei Xiangyang (湖北襄阳)	Shaanxi Shangluo (陕西商洛)	Xinjiang Aletai (新疆阿勒泰)	Hebei Cangzhou (河北沧州)
S11-S15	Gansu Xihe (甘肃西河)	Shaanxi Shangluo (陕西商洛)	Hebei Anguo (河北安国)	Zhejiang Jinhua (浙江金华)	Anhui Yuexi (安徽岳西)	Neimenggu Eerduosi (内蒙古鄂尔多斯)	Hebei Anguo (河北安国)
S16-S20	Hubei Zhongxiang (湖北钟祥)	Yunnan (云南)	Zhejiang Panan (浙江磐安)	Zhejiang Jiangshan (浙江江山)	Yunnan (云南)	Gansu (甘肃)	Shaanxi Wenxi (山西闻喜)

No.	Pinelliae Rhizoma (in Chinese)	Gastrodiae Rhizoma (in Chinese)	Macrocephalae Rhizoma (in Chinese)	Citri Exocarpium Rubrum(in Chinese)	Poria cocos (in Chinese)	Glycyrrhizae Radix et Rhizoma(in Chinese)	Jujubae Fructus (in Chinese)
S1-S5	Sichuan Xichang (四川西昌)	Yunnan Zhaotong (云南昭通)	Anhui Bozhou (安徽亳州)	Sichuan Chengdu (四川成都)	Yunnan Qujing (云南曲靖)	Gansu Longxi (甘肃陇西)	Henan Anyang (河南安阳)
S6-S10	Gansu Qingshui (甘肃清水)	Anhui Yuexi (安徽岳西)	Hebei Lixian (河北蠡县)	Hubei Xiangyang (湖北襄阳)	Shaanxi Shangluo (陕西商洛)	Xinjiang Aletai (新疆阿勒泰)	Hebei Cangzhou (河北沧州)
S11-S15	Gansu Xihe (甘肃西河)	Shaanxi Shangluo (陕西商洛)	Hebei Anguo (河北安国)	Zhejiang Jinhua (浙江金华)	Anhui Yuexi (安徽岳西)	Neimenggu Eerduosi (内蒙古鄂尔多斯)	Hebei Anguo (河北安国)
S16-S20	Hubei Zhongxiang (湖北钟祥)	Yunnan (云南)	Zhejiang Panan (浙江磐安)	Zhejiang Jiangshan (浙江江山)	Yunnan (云南)	Gansu (甘肃)	Shaanxi Wenxi (山西闻喜)

t/min	A/%	B/%
0~1	4	96
1~6	4→15	96→85
6~15	15→30	85→70
15~20	30→45	70→55
20~25	45→65	55→35
25~27	65→90	35→10

t/min	A/%	B/%
0~1	4	96
1~6	4→15	96→85
6~15	15→30	85→70
15~20	30→45	70→55
20~25	45→65	55→35
25~27	65→90	35→10

Analysts	Formula	Q₁ (m/z)	Q₃ (m/z)	DP /V	CE /eV
Adenosine	267.10	268.2[M+H]⁺	136.0	63	22
Guanosine	283.09	284.2[M+H]⁺	151.8	35	25
Succinic acid	118.03	116.6[M-H]^-	72.9	-47	-21
Trigonelline	137.05	138.0[M+H]⁺	92.0	71	29
Gastrodin	286.11	284.9[M-H]^-	104.8	-44	-37
Parishin A	996.31	995.3[M-H]^-	727.3	-164	-34
Parishin B	728.22	727.4[M-H]^-	423.2	-81	-41
Parishin C	728.22	727.3[M-H]^-	422.9	-79	-39
Parishin E	460.12	459.2[M-H]^-	110.4	-86	-30
Atractylenolide Ⅱ	232.15	233.3[M+H]⁺	187.1	94	26
Atractylenolide Ⅲ	248.14	249.2[M+H]⁺	231.1	76	14
Chlorogenic acid	354.10	353.2[M-H]^-	190.7	-62	-23
Neochlorogenic acid	354.10	353.3[M-H]^-	190.6	-62	-23
Narirutin	580.18	579.1[M-H]^-	271.0	-167	-34
Hesperidin	610.19	609.1[M-H]^-	300.9	-162	-37
Rutin	610.15	609.1[M-H]^-	299.8	-184	-43
Naringin	402.13	403.0[M+H]⁺	373.1	102	36
Tangeretin	372.12	373.2[M+H]⁺	343.0	84	36
Poricoic acid A	498.69	497.2[M-H]^-	423.3	-214	-44
Liquiritin	418.13	417.2[M-H]^-	255.0	-134	-29
Glycyrrhizic acid	822.40	821.4[M-H]^-	350.8	-206	-55
Liquiritigenin	256.07	255.0[M-H]^-	134.7	-118	-25
Isoliquiritin	418.13	417.2[M-H]^-	254.7	-152	-33
Isoliquiritin apioside	550.17	549.1[M-H]^-	254.8	-169	-40
Cyclic AMP	329.05	327.8[M-H]^-	133.5	-147	-30

Analysts	Formula	Q₁ (m/z)	Q₃ (m/z)	DP /V	CE /eV
Adenosine	267.10	268.2[M+H]⁺	136.0	63	22
Guanosine	283.09	284.2[M+H]⁺	151.8	35	25
Succinic acid	118.03	116.6[M-H]^-	72.9	-47	-21
Trigonelline	137.05	138.0[M+H]⁺	92.0	71	29
Gastrodin	286.11	284.9[M-H]^-	104.8	-44	-37
Parishin A	996.31	995.3[M-H]^-	727.3	-164	-34
Parishin B	728.22	727.4[M-H]^-	423.2	-81	-41
Parishin C	728.22	727.3[M-H]^-	422.9	-79	-39
Parishin E	460.12	459.2[M-H]^-	110.4	-86	-30
Atractylenolide Ⅱ	232.15	233.3[M+H]⁺	187.1	94	26
Atractylenolide Ⅲ	248.14	249.2[M+H]⁺	231.1	76	14
Chlorogenic acid	354.10	353.2[M-H]^-	190.7	-62	-23
Neochlorogenic acid	354.10	353.3[M-H]^-	190.6	-62	-23
Narirutin	580.18	579.1[M-H]^-	271.0	-167	-34
Hesperidin	610.19	609.1[M-H]^-	300.9	-162	-37
Rutin	610.15	609.1[M-H]^-	299.8	-184	-43
Naringin	402.13	403.0[M+H]⁺	373.1	102	36
Tangeretin	372.12	373.2[M+H]⁺	343.0	84	36
Poricoic acid A	498.69	497.2[M-H]^-	423.3	-214	-44
Liquiritin	418.13	417.2[M-H]^-	255.0	-134	-29
Glycyrrhizic acid	822.40	821.4[M-H]^-	350.8	-206	-55
Liquiritigenin	256.07	255.0[M-H]^-	134.7	-118	-25
Isoliquiritin	418.13	417.2[M-H]^-	254.7	-152	-33
Isoliquiritin apioside	550.17	549.1[M-H]^-	254.8	-169	-40
Cyclic AMP	329.05	327.8[M-H]^-	133.5	-147	-30

Compounds	Regress equation	r	Liner range /μg·mL^-1	LOD /ng·mL^-1	LOQ / ng·mL^-1
Adenosine	Y=2.42×10⁹X+4.95×10⁵	0.998 3	0.04	~1.43	11.31	37.67
Guanosine	Y=1.16×10⁹X+1.83×10⁵	0.999 6	0.08	~3.2	22.21	73.97
Succinic acid	Y=6.35×10⁸X+1.63×10⁴	0.999 9	0.05	~1.83	12.18	40.56
Trigonelline	Y=9.6×10⁸X+4.58×10⁴	0.997 0	7.5×10^-3	~0.31	0.77	2.55
Gastrodin	Y=5.54×10⁶X+1.54×10⁴	0.995 5	0.36	~14.27	27.56	91.79
Parishin A	Y=1.12×10⁸X-9.28×10⁴	0.999 5	0.37	~14.85	3.39	11.39
Parishin B	Y=1.17×10⁸X-3.21×10⁴	0.999 7	0.28	~11.30	2.94	9.79
Parishin C	Y=1.35×10⁸X+7.03×10³	0.999 8	0.15	~5.92	4.41	14.67
Parishin E	Y=3.21×10⁸X-1.13×10⁵	0.999 8	0.3	~11.93	3.68	12.27
Atractylenolide Ⅱ	Y=1.49×10⁸X+4.8×10³	0.999 6	5×10^-3	~0.21	9.87	32.88
Atractylenolide Ⅲ	Y=9.81×10⁷X+5.64×10³	0.999 3	0.03	~1.25	0.35	1.16
Chlorogenic acid	Y=1.69×10⁹X+1.35×10⁵	0.999 9	0.03	~1.14	0.79	2.63
Neochlorogenic acid	Y=8.25×10⁸X+1.22×10⁴	0.999 9	0.05	~1.88	2.42	8.05
Narirutin	Y=7.52×10⁶X+1.39×10⁴	0.999 5	0.06	~2.52	1.21	4.04
Hesperidin	Y=3.33×10⁹X+1.43×10⁶	0.998 0	0.44	~17.46	1.01	3.37
Rutin	Y=4.23×10⁸X+1.79×10⁴	0.999 6	0.03	~1.33	1.9	6.56
Naringin	Y=2.43×10¹⁰X+2.66×10⁶	0.997 6	0.01	~0.51	1.24	5.59
Tangeretin	Y=1.74×10¹⁰X+1.3×10⁶	0.999 5	5×10^-3	~0.19	0.98	4.07
Poricoic acid A	Y=2.2×10¹⁰X+4.96×10⁴	0.998 9	2.62×10^-3	~0.11	1.96	6.54
Liquiritin	Y=1.06×10⁹X+3.22×10⁵	0.999 5	0.12	~4.74	3.23	10.75
Glycyrrhizic acid	Y=1.36×10⁸X-7.12×10⁵	0.991 6	0.17	~6.82	17.29	57.59
Liquiritigenin	Y=2.74×10⁸X+1.02×10⁴	0.999 8	0.02	~0.82	1.54	5.39
Isoliquiritin	Y=1.67×10⁹X+5.83×10⁴	0.999 5	0.05	~1.95	0.56	1.85
Isoliquiritin apioside	Y=7.77×10⁸X-2.18×10³	0.999 7	0.04	~1.47	10.23	34.09
Cyclic AMP	Y=1.66×10⁸X+5.67×10²	0.999 8	0.11	~4.32	4.01	13.34

Compounds	Regress equation	r	Liner range /μg·mL^-1	LOD /ng·mL^-1	LOQ / ng·mL^-1
Adenosine	Y=2.42×10⁹X+4.95×10⁵	0.998 3	0.04	~1.43	11.31	37.67
Guanosine	Y=1.16×10⁹X+1.83×10⁵	0.999 6	0.08	~3.2	22.21	73.97
Succinic acid	Y=6.35×10⁸X+1.63×10⁴	0.999 9	0.05	~1.83	12.18	40.56
Trigonelline	Y=9.6×10⁸X+4.58×10⁴	0.997 0	7.5×10^-3	~0.31	0.77	2.55
Gastrodin	Y=5.54×10⁶X+1.54×10⁴	0.995 5	0.36	~14.27	27.56	91.79
Parishin A	Y=1.12×10⁸X-9.28×10⁴	0.999 5	0.37	~14.85	3.39	11.39
Parishin B	Y=1.17×10⁸X-3.21×10⁴	0.999 7	0.28	~11.30	2.94	9.79
Parishin C	Y=1.35×10⁸X+7.03×10³	0.999 8	0.15	~5.92	4.41	14.67
Parishin E	Y=3.21×10⁸X-1.13×10⁵	0.999 8	0.3	~11.93	3.68	12.27
Atractylenolide Ⅱ	Y=1.49×10⁸X+4.8×10³	0.999 6	5×10^-3	~0.21	9.87	32.88
Atractylenolide Ⅲ	Y=9.81×10⁷X+5.64×10³	0.999 3	0.03	~1.25	0.35	1.16
Chlorogenic acid	Y=1.69×10⁹X+1.35×10⁵	0.999 9	0.03	~1.14	0.79	2.63
Neochlorogenic acid	Y=8.25×10⁸X+1.22×10⁴	0.999 9	0.05	~1.88	2.42	8.05
Narirutin	Y=7.52×10⁶X+1.39×10⁴	0.999 5	0.06	~2.52	1.21	4.04
Hesperidin	Y=3.33×10⁹X+1.43×10⁶	0.998 0	0.44	~17.46	1.01	3.37
Rutin	Y=4.23×10⁸X+1.79×10⁴	0.999 6	0.03	~1.33	1.9	6.56
Naringin	Y=2.43×10¹⁰X+2.66×10⁶	0.997 6	0.01	~0.51	1.24	5.59
Tangeretin	Y=1.74×10¹⁰X+1.3×10⁶	0.999 5	5×10^-3	~0.19	0.98	4.07
Poricoic acid A	Y=2.2×10¹⁰X+4.96×10⁴	0.998 9	2.62×10^-3	~0.11	1.96	6.54
Liquiritin	Y=1.06×10⁹X+3.22×10⁵	0.999 5	0.12	~4.74	3.23	10.75
Glycyrrhizic acid	Y=1.36×10⁸X-7.12×10⁵	0.991 6	0.17	~6.82	17.29	57.59
Liquiritigenin	Y=2.74×10⁸X+1.02×10⁴	0.999 8	0.02	~0.82	1.54	5.39
Isoliquiritin	Y=1.67×10⁹X+5.83×10⁴	0.999 5	0.05	~1.95	0.56	1.85
Isoliquiritin apioside	Y=7.77×10⁸X-2.18×10³	0.999 7	0.04	~1.47	10.23	34.09
Cyclic AMP	Y=1.66×10⁸X+5.67×10²	0.999 8	0.11	~4.32	4.01	13.34

Component	Recovery text	Average /%	RSD /%
Adenosine	97.36	101.59	103.50	101.98	104.59	100.95	99.55	100.77	98.20	100.94	2.32
Guanosine	99.93	96.86	101.39	95.13	91.15	93.86	95.09	98.53	100.26	96.91	3.50
Succinic acid	101.51	98.20	101.17	101.22	102.56	104.33	101.71	100.85	103.22	101.64	1.68
Trigonelline	101.28	99.49	96.89	90.14	101.15	97.03	98.38	96.82	95.88	97.45	3.45
Gastrodin	96.99	96.69	98.12	95.94	99.53	99.38	99.93	100.13	98.11	98.31	1.55
Parishin A	103.80	99.98	104.04	95.23	94.47	95.36	103.77	103.67	103.63	100.44	4.23
Parishin B	102.55	97.72	99.18	101.11	102.60	101.41	103.95	102.38	101.20	101.34	1.87
Parishin C	94.22	98.15	96.27	93.91	97.04	97.52	95.71	95.12	95.15	95.90	1.53
Parishin E	102.54	105.62	97.92	103.35	105.21	103.73	106.08	105.39	107.62	104.16	2.69
Atractylenolide Ⅱ	96.79	95.53	92.95	97.83	96.49	93.36	95.97	95.29	96.55	95.64	1.67
Atractylenolide Ⅲ	92.85	95.88	98.20	94.46	96.47	92.40	100.16	101.55	96.33	96.48	3.20
Chlorogenic acid	104.02	100.82	103.82	103.43	102.13	103.11	104.04	103.27	103.32	103.11	1.00
Neochlorogenic acid	100.74	96.38	91.93	95.84	96.46	91.92	92.44	103.23	95.55	96.05	4.05
Narirutin	107.73	102.47	106.26	105.16	104.79	105.93	106.80	100.38	105.31	104.98	2.16
Hesperidin	103.66	97.72	103.63	101.28	102.59	103.13	100.16	99.00	95.47	100.74	2.86
Rutin	97.61	106.45	104.09	105.42	106.42	104.55	105.72	105.38	104.91	104.50	2.59
Naringin	102.68	98.25	103.61	101.59	100.98	100.50	99.93	99.27	101.99	100.98	1.67
Tangeretin	99.89	100.95	100.48	100.54	100.78	101.73	99.95	100.47	100.29	100.56	0.55
Poricoic acid A	97.76	96.49	95.86	97.66	96.16	96.17	96.79	95.98	95.45	96.48	0.82
Liquiritin	95.30	96.66	94.30	96.68	97.72	96.43	93.76	95.12	94.16	95.57	1.43
Glycyrrhizic acid	104.96	104.50	103.62	104.87	105.72	105.76	104.28	105.47	103.07	104.69	0.89
Liquiritigenin	96.39	94.91	95.35	96.91	97.46	96.38	105.38	105.69	105.12	99.29	4.68
Isoliquiritin	95.35	95.36	94.61	95.12	95.00	96.74	98.34	95.32	101.88	96.41	2.44
Isoliquiritin apioside	100.86	100.80	98.49	99.53	100.67	102.11	102.51	102.29	103.17	101.16	1.50
Cyclic AMP	92.26	100.76	94.64	95.34	93.91	93.93	96.41	94.50	101.68	95.94	3.34

Component	Recovery text	Average /%	RSD /%
Adenosine	97.36	101.59	103.50	101.98	104.59	100.95	99.55	100.77	98.20	100.94	2.32
Guanosine	99.93	96.86	101.39	95.13	91.15	93.86	95.09	98.53	100.26	96.91	3.50
Succinic acid	101.51	98.20	101.17	101.22	102.56	104.33	101.71	100.85	103.22	101.64	1.68
Trigonelline	101.28	99.49	96.89	90.14	101.15	97.03	98.38	96.82	95.88	97.45	3.45
Gastrodin	96.99	96.69	98.12	95.94	99.53	99.38	99.93	100.13	98.11	98.31	1.55
Parishin A	103.80	99.98	104.04	95.23	94.47	95.36	103.77	103.67	103.63	100.44	4.23
Parishin B	102.55	97.72	99.18	101.11	102.60	101.41	103.95	102.38	101.20	101.34	1.87
Parishin C	94.22	98.15	96.27	93.91	97.04	97.52	95.71	95.12	95.15	95.90	1.53
Parishin E	102.54	105.62	97.92	103.35	105.21	103.73	106.08	105.39	107.62	104.16	2.69
Atractylenolide Ⅱ	96.79	95.53	92.95	97.83	96.49	93.36	95.97	95.29	96.55	95.64	1.67
Atractylenolide Ⅲ	92.85	95.88	98.20	94.46	96.47	92.40	100.16	101.55	96.33	96.48	3.20
Chlorogenic acid	104.02	100.82	103.82	103.43	102.13	103.11	104.04	103.27	103.32	103.11	1.00
Neochlorogenic acid	100.74	96.38	91.93	95.84	96.46	91.92	92.44	103.23	95.55	96.05	4.05
Narirutin	107.73	102.47	106.26	105.16	104.79	105.93	106.80	100.38	105.31	104.98	2.16
Hesperidin	103.66	97.72	103.63	101.28	102.59	103.13	100.16	99.00	95.47	100.74	2.86
Rutin	97.61	106.45	104.09	105.42	106.42	104.55	105.72	105.38	104.91	104.50	2.59
Naringin	102.68	98.25	103.61	101.59	100.98	100.50	99.93	99.27	101.99	100.98	1.67
Tangeretin	99.89	100.95	100.48	100.54	100.78	101.73	99.95	100.47	100.29	100.56	0.55
Poricoic acid A	97.76	96.49	95.86	97.66	96.16	96.17	96.79	95.98	95.45	96.48	0.82
Liquiritin	95.30	96.66	94.30	96.68	97.72	96.43	93.76	95.12	94.16	95.57	1.43
Glycyrrhizic acid	104.96	104.50	103.62	104.87	105.72	105.76	104.28	105.47	103.07	104.69	0.89
Liquiritigenin	96.39	94.91	95.35	96.91	97.46	96.38	105.38	105.69	105.12	99.29	4.68
Isoliquiritin	95.35	95.36	94.61	95.12	95.00	96.74	98.34	95.32	101.88	96.41	2.44
Isoliquiritin apioside	100.86	100.80	98.49	99.53	100.67	102.11	102.51	102.29	103.17	101.16	1.50
Cyclic AMP	92.26	100.76	94.64	95.34	93.91	93.93	96.41	94.50	101.68	95.94	3.34

Compounds	Content/mg·g^-1
Adenosine	0.141 7	0.069 0	0.070 0	0.065 5	0.086 2	0.080 9	0.109 7	0.074 8	0.099 7	0.085 5
Guanosine	0.342 3	0.252 8	0.213 1	0.236 7	0.236 0	0.231 7	0.253 4	0.307 3	0.260 2	0.333 3
Succinic acid	0.262 3	0.233 7	0.224 0	0.284 7	0.275 1	0.332 5	0.295 3	0.346 3	0.314 9	0.376 1
Trigonelline	0.034 4	0.037 2	0.029 6	0.041 7	0.035 5	0.030 4	0.033 0	0.026 2	0.038 9	0.027 4
Gastrodin	1.180 0	1.138 2	1.099 9	1.332 0	1.017 2	1.020 9	1.034 5	0.891 3	1.170 2	1.036 9
Parishin A	2.394 1	1.870 9	2.654 9	4.417 1	4.052 2	2.693 7	2.755 8	2.127 0	4.448 1	2.274 5
Parishin B	1.229 5	1.318 5	1.802 2	1.759 9	1.893 7	2.316 1	2.351 3	1.436 1	1.802 2	1.296 0
Parishin C	0.553 3	0.426 2	0.650 4	0.850 0	0.851 2	0.599 3	0.614 4	0.430 0	0.795 7	0.479 3
Parishin E	1.551 2	1.381 9	1.423 3	1.771 8	1.330 7	1.479 4	1.620 7	1.106 5	1.654 8	1.235 6
Atractylenolide Ⅱ	0.032 2	0.038 9	0.033 6	0.022 7	0.035 1	0.073 3	0.071 9	0.080 0	0.071 1	0.076 7
Atractylenolide Ⅲ	0.093 2	0.288 3	0.056 9	0.056 1	0.078 3	0.057 9	0.068 5	0.245 4	0.293 8	0.224 8
Chlorogenic acid	0.211 9	0.127 8	0.047 1	0.132 3	0.028 8	0.045 9	0.152 2	0.122 8	0.141 8	0.127 8
Neochlorogenic acid	0.055 6	0.013 9	0.010 3	0.043 6	0.029 6	0.013 7	0.021 8	0.020 1	0.016 6	0.022 5
Narirutin	0.404 1	0.525 2	0.312 2	0.285 3	0.688 3	0.301 1	0.616 0	0.444 6	0.526 2	0.459 5
Hesperidin	2.563 0	2.267 6	2.139 4	2.135 3	2.425 1	2.073 9	2.738 7	2.151 6	2.711 4	2.203 5
Rutin	0.188 8	0.140 7	0.184 9	0.169 1	0.229 6	0.183 1	0.100 3	0.191 0	0.153 1	0.197 2
Naringin	0.066 5	0.075 7	0.085 8	0.086 4	0.073 4	0.087 8	0.079 5	0.066 9	0.079 2	0.066 5
Tangeretin	0.025 7	0.026 8	0.029 0	0.029 1	0.025 0	0.029 6	0.029 6	0.021 8	0.030 1	0.021 9
Poricoic acid A	0.003 3	0.007 9	0.004 1	0.005 0	0.007 8	0.003 9	0.006 0	0.004 4	0.004 2	0.004 2
Liquiritin	0.671 2	1.891 7	0.740 5	1.471 3	1.561 4	0.738 7	0.715 8	0.777 7	1.963 8	0.831 1
Glycyrrhizic acid	1.776 0	1.471 0	1.714 3	1.283 1	1.628 9	1.705 8	2.137 0	1.833 9	1.330 1	1.827 5
Liquiritigenin	0.067 3	0.105 1	0.025 8	0.037 4	0.096 1	0.028 0	0.049 2	0.049 2	0.083 5	0.049 9
Isoliquiritin	0.077 0	0.230 3	0.089 6	0.161 1	0.189 2	0.088 0	0.083 0	0.101 9	0.220 7	0.107 6
Isoliquiritin apioside	0.226 7	0.254 1	0.362 7	0.238 6	0.222 3	0.357 5	0.350 6	0.304 1	0.258 4	0.331 7
Cyclic AMP	0.168 9	0.465 4	0.412 7	0.311 6	0.334	0.452 7	0.263 3	0.144 2	0.403 4	0.150 7
Compounds	Content /mg·g^-1
S11	S12	S13	S14	S15	S16	S17	S18	S19	S20
Adenosine	0.098 5	0.109 3	0.142 2	0.098 5	0.093 9	0.097 9	0.070 2	0.144 0	0.098 5	0.130 0
Guanosine	0.206 3	0.203 4	0.269 5	0.238 8	0.253 3	0.234 1	0.242 8	0.271 8	0.165 7	0.275 3
Succinic acid	0.242 6	0.197 1	0.162 3	0.227 3	0.229 3	0.357 3	0.299 9	0.220 1	0.199 4	0.167 1
Trigonelline	0.032 3	0.034 9	0.043 3	0.040 6	0.043 7	0.035 2	0.046 9	0.044 3	0.036 4	0.046 5
Gastrodin	1.258 7	1.067 0	1.073 4	1.065 5	1.317 8	1.463 2	1.210 8	1.054 3	1.126 2	1.183 7
Parishin A	1.528 7	1.438 5	2.257 8	1.477 2	1.799 8	2.567 4	4.064 0	1.419 2	1.522 4	2.322 3
Parishin B	0.988 1	1.010 1	1.318 9	0.926 3	1.041 0	1.526 2	1.636 5	1.010 1	1.014 5	1.093 9
Parishin C	0.671 3	0.501 4	0.680 7	0.468 6	0.481 2	0.687 0	0.851 2	0.419 9	0.528 5	0.693 4
Parishin E	1.492 6	1.011 8	1.772 8	1.121 1	1.433 3	1.638 4	1.927 8	1.740 9	0.865 9	1.893 6
Atractylenolide Ⅱ	0.034 1	0.016 6	0.020 2	0.020 1	0.103 6	0.031 1	0.022 7	0.093 3	0.019 5	0.020 1
Atractylenolide Ⅲ	0.106 9	0.037 2	0.046 3	0.046 8	0.337 0	0.072 0	0.070 5	0.296 7	0.048 5	0.055 5
Chlorogenic acid	0.102 7	0.069 3	0.257 5	0.073 2	0.103 5	0.037 4	0.108 4	0.056 6	0.057 7	0.257 9
Neochlorogenic acid	0.023 4	0.011 2	0.059 8	0.018 8	0.016 4	0.014 0	0.029 8	0.008 2	0.012 1	0.043 7
Narirutin	0.421 5	0.501 7	0.720 6	0.667 1	0.511 4	0.288 6	0.259 4	0.325 8	0.526 0	0.742 5
Hesperidin	2.121 4	2.120 8	2.291 5	2.379 7	2.249 9	2.155 4	2.118 3	2.166 8	2.174 3	2.323 0
Rutin	0.156 9	0.188 2	0.197 9	0.224 5	0.139 1	0.181 1	0.166 7	0.156 8	0.185 2	0.203 7
Naringin	0.075 7	0.078 7	0.085 8	0.075 1	0.076 8	0.093 3	0.089 7	0.079 8	0.079 8	0.085 6
Tangeretin	0.026 9	0.027 8	0.030 0	0.027 5	0.027 5	0.030 5	0.029 1	0.028 0	0.026 7	0.029 8
Poricoic acid A	0.004 7	0.004 6	0.007 3	0.003 4	0.004 8	0.003 9	0.005 0	0.006 2	0.004 2	0.007 8
Liquiritin	1.087 6	0.254 0	0.788 4	0.579 7	1.826 6	0.738 4	1.436 3	0.893 5	0.261 8	0.818 6
Glycyrrhizic acid	1.635 3	0.740 8	1.189 1	1.103 8	1.547 8	1.731 4	1.289 5	2.147 7	0.781 4	1.223 3
Liquiritigenin	0.041 8	0.055 8	0.057 8	0.038 7	0.111 3	0.027 9	0.037 2	0.029 9	0.056 2	0.063 1
Isoliquiritin	0.132 2	0.035 5	0.089 3	0.073 5	0.236 3	0.095 6	0.157 5	0.117 1	0.036 5	0.098 4
Isoliquiritin apioside	0.268 3	0.184 7	0.267 6	0.288 1	0.246 3	0.377 0	0.228 0	0.340 5	0.190 0	0.291 9
Cyclic AMP	0.607 6	0.397 5	0.420 7	0.429 5	0.454 8	0.508 5	0.386 6	0.499 2	0.325 2	0.522 9

Compounds	Content/mg·g^-1
Adenosine	0.141 7	0.069 0	0.070 0	0.065 5	0.086 2	0.080 9	0.109 7	0.074 8	0.099 7	0.085 5
Guanosine	0.342 3	0.252 8	0.213 1	0.236 7	0.236 0	0.231 7	0.253 4	0.307 3	0.260 2	0.333 3
Succinic acid	0.262 3	0.233 7	0.224 0	0.284 7	0.275 1	0.332 5	0.295 3	0.346 3	0.314 9	0.376 1
Trigonelline	0.034 4	0.037 2	0.029 6	0.041 7	0.035 5	0.030 4	0.033 0	0.026 2	0.038 9	0.027 4
Gastrodin	1.180 0	1.138 2	1.099 9	1.332 0	1.017 2	1.020 9	1.034 5	0.891 3	1.170 2	1.036 9
Parishin A	2.394 1	1.870 9	2.654 9	4.417 1	4.052 2	2.693 7	2.755 8	2.127 0	4.448 1	2.274 5
Parishin B	1.229 5	1.318 5	1.802 2	1.759 9	1.893 7	2.316 1	2.351 3	1.436 1	1.802 2	1.296 0
Parishin C	0.553 3	0.426 2	0.650 4	0.850 0	0.851 2	0.599 3	0.614 4	0.430 0	0.795 7	0.479 3
Parishin E	1.551 2	1.381 9	1.423 3	1.771 8	1.330 7	1.479 4	1.620 7	1.106 5	1.654 8	1.235 6
Atractylenolide Ⅱ	0.032 2	0.038 9	0.033 6	0.022 7	0.035 1	0.073 3	0.071 9	0.080 0	0.071 1	0.076 7
Atractylenolide Ⅲ	0.093 2	0.288 3	0.056 9	0.056 1	0.078 3	0.057 9	0.068 5	0.245 4	0.293 8	0.224 8
Chlorogenic acid	0.211 9	0.127 8	0.047 1	0.132 3	0.028 8	0.045 9	0.152 2	0.122 8	0.141 8	0.127 8
Neochlorogenic acid	0.055 6	0.013 9	0.010 3	0.043 6	0.029 6	0.013 7	0.021 8	0.020 1	0.016 6	0.022 5
Narirutin	0.404 1	0.525 2	0.312 2	0.285 3	0.688 3	0.301 1	0.616 0	0.444 6	0.526 2	0.459 5
Hesperidin	2.563 0	2.267 6	2.139 4	2.135 3	2.425 1	2.073 9	2.738 7	2.151 6	2.711 4	2.203 5
Rutin	0.188 8	0.140 7	0.184 9	0.169 1	0.229 6	0.183 1	0.100 3	0.191 0	0.153 1	0.197 2
Naringin	0.066 5	0.075 7	0.085 8	0.086 4	0.073 4	0.087 8	0.079 5	0.066 9	0.079 2	0.066 5
Tangeretin	0.025 7	0.026 8	0.029 0	0.029 1	0.025 0	0.029 6	0.029 6	0.021 8	0.030 1	0.021 9
Poricoic acid A	0.003 3	0.007 9	0.004 1	0.005 0	0.007 8	0.003 9	0.006 0	0.004 4	0.004 2	0.004 2
Liquiritin	0.671 2	1.891 7	0.740 5	1.471 3	1.561 4	0.738 7	0.715 8	0.777 7	1.963 8	0.831 1
Glycyrrhizic acid	1.776 0	1.471 0	1.714 3	1.283 1	1.628 9	1.705 8	2.137 0	1.833 9	1.330 1	1.827 5
Liquiritigenin	0.067 3	0.105 1	0.025 8	0.037 4	0.096 1	0.028 0	0.049 2	0.049 2	0.083 5	0.049 9
Isoliquiritin	0.077 0	0.230 3	0.089 6	0.161 1	0.189 2	0.088 0	0.083 0	0.101 9	0.220 7	0.107 6
Isoliquiritin apioside	0.226 7	0.254 1	0.362 7	0.238 6	0.222 3	0.357 5	0.350 6	0.304 1	0.258 4	0.331 7
Cyclic AMP	0.168 9	0.465 4	0.412 7	0.311 6	0.334	0.452 7	0.263 3	0.144 2	0.403 4	0.150 7
Compounds	Content /mg·g^-1
S11	S12	S13	S14	S15	S16	S17	S18	S19	S20
Adenosine	0.098 5	0.109 3	0.142 2	0.098 5	0.093 9	0.097 9	0.070 2	0.144 0	0.098 5	0.130 0
Guanosine	0.206 3	0.203 4	0.269 5	0.238 8	0.253 3	0.234 1	0.242 8	0.271 8	0.165 7	0.275 3
Succinic acid	0.242 6	0.197 1	0.162 3	0.227 3	0.229 3	0.357 3	0.299 9	0.220 1	0.199 4	0.167 1
Trigonelline	0.032 3	0.034 9	0.043 3	0.040 6	0.043 7	0.035 2	0.046 9	0.044 3	0.036 4	0.046 5
Gastrodin	1.258 7	1.067 0	1.073 4	1.065 5	1.317 8	1.463 2	1.210 8	1.054 3	1.126 2	1.183 7
Parishin A	1.528 7	1.438 5	2.257 8	1.477 2	1.799 8	2.567 4	4.064 0	1.419 2	1.522 4	2.322 3
Parishin B	0.988 1	1.010 1	1.318 9	0.926 3	1.041 0	1.526 2	1.636 5	1.010 1	1.014 5	1.093 9
Parishin C	0.671 3	0.501 4	0.680 7	0.468 6	0.481 2	0.687 0	0.851 2	0.419 9	0.528 5	0.693 4
Parishin E	1.492 6	1.011 8	1.772 8	1.121 1	1.433 3	1.638 4	1.927 8	1.740 9	0.865 9	1.893 6
Atractylenolide Ⅱ	0.034 1	0.016 6	0.020 2	0.020 1	0.103 6	0.031 1	0.022 7	0.093 3	0.019 5	0.020 1
Atractylenolide Ⅲ	0.106 9	0.037 2	0.046 3	0.046 8	0.337 0	0.072 0	0.070 5	0.296 7	0.048 5	0.055 5
Chlorogenic acid	0.102 7	0.069 3	0.257 5	0.073 2	0.103 5	0.037 4	0.108 4	0.056 6	0.057 7	0.257 9
Neochlorogenic acid	0.023 4	0.011 2	0.059 8	0.018 8	0.016 4	0.014 0	0.029 8	0.008 2	0.012 1	0.043 7
Narirutin	0.421 5	0.501 7	0.720 6	0.667 1	0.511 4	0.288 6	0.259 4	0.325 8	0.526 0	0.742 5
Hesperidin	2.121 4	2.120 8	2.291 5	2.379 7	2.249 9	2.155 4	2.118 3	2.166 8	2.174 3	2.323 0
Rutin	0.156 9	0.188 2	0.197 9	0.224 5	0.139 1	0.181 1	0.166 7	0.156 8	0.185 2	0.203 7
Naringin	0.075 7	0.078 7	0.085 8	0.075 1	0.076 8	0.093 3	0.089 7	0.079 8	0.079 8	0.085 6
Tangeretin	0.026 9	0.027 8	0.030 0	0.027 5	0.027 5	0.030 5	0.029 1	0.028 0	0.026 7	0.029 8
Poricoic acid A	0.004 7	0.004 6	0.007 3	0.003 4	0.004 8	0.003 9	0.005 0	0.006 2	0.004 2	0.007 8
Liquiritin	1.087 6	0.254 0	0.788 4	0.579 7	1.826 6	0.738 4	1.436 3	0.893 5	0.261 8	0.818 6
Glycyrrhizic acid	1.635 3	0.740 8	1.189 1	1.103 8	1.547 8	1.731 4	1.289 5	2.147 7	0.781 4	1.223 3
Liquiritigenin	0.041 8	0.055 8	0.057 8	0.038 7	0.111 3	0.027 9	0.037 2	0.029 9	0.056 2	0.063 1
Isoliquiritin	0.132 2	0.035 5	0.089 3	0.073 5	0.236 3	0.095 6	0.157 5	0.117 1	0.036 5	0.098 4
Isoliquiritin apioside	0.268 3	0.184 7	0.267 6	0.288 1	0.246 3	0.377 0	0.228 0	0.340 5	0.190 0	0.291 9
Cyclic AMP	0.607 6	0.397 5	0.420 7	0.429 5	0.454 8	0.508 5	0.386 6	0.499 2	0.325 2	0.522 9

UHPLC-MS/MS同时测定半夏白术天麻汤基准样品中25个成分的含量

PDF下载

蔡于罗 ¹ , 果佳慧 ¹ , 甄亚钦 ¹^,²^,³ , 姜国志 ²^,⁴ , 田伟 ¹^,²^,³^,^* , 牛丽颖 ¹^,²^,³^,^*

中国药学杂志 | 论著 2024,59(1): 88-96

收起

中国药学杂志 | 论著 2024, 59(1): 88-96

UHPLC-MS/MS同时测定半夏白术天麻汤基准样品中25个成分的含量

全屏

蔡于罗¹, 果佳慧¹, 甄亚钦¹^,²^,³, 姜国志²^,⁴, 田伟¹^,²^,³^,^*, 牛丽颖¹^,²^,³^,^*

作者信息

¹ 河北中医药大学,石家庄 050091

² 河北省中药配方颗粒技术创新中心,石家庄 050091

³ 中药材品质评价与标准化河北省工程研究中心,石家庄 050091

⁴ 神威药业集团有限公司, 石家庄 051430

蔡于罗,女,硕士研究生研究方向:中药分析及药效物质基础研究

通讯作者:

*田伟,男,硕士,高级实验师研究方向:中药分析及质量控制研究 Tel:(0311)89926890;

牛丽颖,女,教授,博士生导师研究方向:中药分析及药效物质基础研究 Tel:(0311)89926548

Simultaneous Determination of Twenty five Components in the Reference Sample of Banxiabaizhutianma Decoction by UHPLC-MS/MS

CAI Yuluo¹, GUO Jiahui¹, ZHEN Yaqin¹^,²^,³, JIANG Guozhi²^,⁴, TIAN Wei¹^,²^,³^,^*, NIU Liying¹^,²^,³^,^*

Affiliations

¹ Hebei University of Chinese Medicine, Shijiazhuang 050091, China

² Hebei TCM Formula Granule Innovation Center, Shijiazhuang 050091, China

³ Hebei TCM Quality Evaluation Standardization Engineering Research Center, Shijiazhuang 050091, China

⁴ Shineway Pharmaceutical Group Company Limited, Shijiazhuang 051430, China

出版时间: 2024-01-08 doi: 10.11669/cpj.2024.01.011

文章导航

摘要

收起

目的建立超高效液相色谱串联质谱法(UHPLC-MS/MS)同时测定半夏白术天麻汤基准样品(冻干粉)中腺苷、鸟苷、琥珀酸、葫芦巴碱、天麻素、巴利森苷A、巴利森苷B、巴利森苷C、巴利森苷E、白术内酯Ⅱ、白术内酯Ⅲ、绿原酸、新绿原酸、芸香柚皮苷、橙皮苷、芦丁、川陈皮素、桔皮素、茯苓酸 A、甘草苷、甘草酸、甘草素、异甘草苷、芹糖异甘草苷、环磷酸腺苷的含量。方法采用Shim-pack GIST C₁₈ (2.1 mm×100 mm, 2 μm)色谱柱进行分离,流动相为乙腈-0.1%甲酸,梯度洗脱,流速0.3 mL·min^-1;进样量1 μL。质谱条件采用电喷雾 (ESI)离子源正、负离子模式进行检测,多重反应监测(MRM)模式用于定量测定。结果所测25种化学成分在测定浓度范围内线性关系良好,相关系数均大于0.991;精密度、重复性和稳定性良好;平均加样回收率为95.57%~104.98%,RSD为0.55%~4.68%。结论本方法专属性强,灵敏度高,可为半夏白术天麻汤的质量控制研究提供实验依据。

关键词

半夏白术天麻汤 / 基准样品 / 超高效液相色谱串联质谱法 / 含量测定 / 质量控制

Abstract

收起

OBJECTIVE To establish a UHPLC-MS/MS method for the simultaneous content determination of Adenosine, guanosine, succinic acid, trigonelline, gastrodin, parishin A, parishin B, parishin C, parishin E, atractylenolide Ⅱ, atractylenolide Ⅲ, chlorogenic acid, neochlorogenic acid, narirutin, hesperidin, rutin, naringin, tangeretin, poricoic acid A, liquiritin, glycyrrhizic acid, liquiritigenin, isoliquiritin, isoliquiritin apioside, cyclic AMP. METHODS The Shim-pack GIST C₁₈ (2.1 mm×100 mm, 2 μm) column was used, the mobile phase was acetonitrile -0.1% formic acid, gradient elution, flow rate 0.3 mL·min^-1; injection volume 1 μL. ESI ion source for positive and negative ion scanning analysis using multiple reaction monitoring (MRM) mode. RESULTS All of the analytes showed good linearity (r≥0.991) in the tested ranges. The precision, repeatability and stability of the method were good for the twenty five components. The average recoveries were 95.57%-104.98% with the RSDs of 0.55%-4.68%. CONCLUSION This method is strong exclusivity and high sensitivity, which can provide experimental basis for the quality control research of Banxiabaizhutianma Decoction.

Key words

Banxiabaizhutianma decoction / benchmark sample / UHPLC-MS/MS / content determination / quality control

引用本文

蔡于罗, 果佳慧, 甄亚钦, 姜国志, 田伟, 牛丽颖. UHPLC-MS/MS同时测定半夏白术天麻汤基准样品中25个成分的含量. 中国药学杂志, 2024 , 59 (1) : 88 -96 . DOI: 10.11669/cpj.2024.01.011

CAI Yuluo, GUO Jiahui, ZHEN Yaqin, JIANG Guozhi, TIAN Wei, NIU Liying. Simultaneous Determination of Twenty five Components in the Reference Sample of Banxiabaizhutianma Decoction by UHPLC-MS/MS[J]. Chinese Pharmaceutical Journal, 2024 , 59 (1) : 88 -96 . DOI: 10.11669/cpj.2024.01.011

正文

收起

半夏白术天麻汤出自清代程国彭所著的《医学心悟》^[1],收录于国家中医药管理局发布的《古代经典名方目录(第一批)》,处方为半夏一钱五分,天麻、茯苓、橘红各一钱,白术三钱,甘草五分,煎煮时加入生姜一片,大枣两枚。半夏白术天麻汤具有化痰息风,健脾祛湿的功效,处方原文记载“眩,谓眼黑,晕者,头旋也,故称头旋眼花是也;有湿痰壅遏者,书云,头旋眼花,非天麻、半夏不除是也,半夏白术天麻汤主之。”半夏白术天麻汤主治因风痰上扰所致各类以眩晕为主症的疾病,临床常用于治疗高血压、椎-基底动脉供血不足、颈性眩晕、耳源性眩晕、神经性癫痫等症^[2-3],疗效显著,安全性高,故研发半夏白术天麻汤相关制剂具有十分重要的临床意义。

作为临床上治疗眩晕的经典方剂,迄今为止关于半夏白术天麻汤的文献报道多集中于药理作用和临床研究^[4-9],关于其基准样品及质量研究的报道较少。基准样品作为后续复方制剂生产及质量控制的参照,对于经典名方药物的开发至关重要^[10]。有学者采用高效液相色谱法(HPLC)同时测定了半夏白术天麻汤基准样品中7种活性成分的含量^[11],但中药化学成分复杂,其治疗作用的发挥往往是多种化学成分的协同效应,也是中药发挥药效的基础,仅以其中一两个或几个成分的含量作为评价指标来评价半夏白术天麻汤的质量较为片面。与单味中药饮片相比,中药复方的化学成分更为复杂,传统的HPLC分析时间长,杂质干扰大,因此本研究采用超高效液相色谱串联质谱法(UHPLC-MS/MS)同时测定半夏白术天麻汤基准样品中25种活性较强的化合物,方法快速、准确、灵敏度高,为进一步阐明半夏白术天麻汤的药效物质基础、完善其质量控制体系提供数据支撑和方法参考。

1 仪器与材料

收起

Shimadzu LC-30A型超高效液相色谱仪(日本岛津公司);4500 QTRAP三重四极杆线性离子阱质谱仪(美国AB公司,配有ESI离子源);Analyst^© TF 1.6.3数据采集软件(美国AB公司);色谱柱Shim-pack GIST C₁₈(100 mm × 2.1 mm, 2 μm);BSA224S-CW、CPA225D型电子分析天平(赛多利斯科学仪器北京有限公司);KQ-250 型超声波清洗器(功率 250 W,频率 40 kHz,昆山市超声仪器有限公司);BJH-W200F型陶瓷自动中药煲(广东天际电器股份有限公司);FD-1C-50冷冻干燥机(北京博医康实验仪器有限公司); HYCD-282A型医用冷藏冷冻箱(青岛海尔生物医疗股份有限公司);乙腈、甲醇、甲酸均为色谱纯,其他试剂均为分析纯,实验用水为屈臣氏蒸馏水。

对照品腺苷(批号为110879-200202,含量 98.3%)、琥珀酸(批号为110896-201602,含量 98%)、天麻素(批号为110807-201809,含量96.7%)、白术内酯Ⅱ(批号为111976-201501,含量99.9%)、橙皮苷(批号为110721-201818,含量96.2%)、甘草苷(批号为111610-201607,含量 93.1%)、绿原酸(批号为110753-201716,含量99.3%)均购自中国食品药品检定研究院;鸟苷(批号为160607,含量98%)、巴利森苷A(批号为18122907,含量 97%)、巴利森苷B(批号为18011805,含量98%)、巴利森苷C(批号为190321,含量 98%)、巴利森苷E(批号为190320,含量98%)、白术内酯Ⅲ(批号为18082201,含量98%)均购自成都普菲德生物技术有限公司;芹糖异甘草苷(批号B20987,含量98%);芸香柚皮苷(批号MUST-18101010,含量98.37%)、桔皮素 (批号MUST-18012910,含量 98%)、甘草酸(批号MUST-18060805,含量99.65%)、芦丁(批号MUST-16031813,含量99.65%)、川陈皮素(批号MUST-18042205,含量98.86%)、甘草素(批号MUST-18101611,含量99.66%)均购自成都曼斯特生物技术有限公司;新绿原酸(批号为PS974,含量98%)、环磷酸腺苷(批号为PS20437,含量98%)、葫芦巴碱(批号为PS426,含量98%)、异甘草苷(批号为PS12517,含量98%)均购自成都普思生物科技股份有限公司。

中药饮片半夏、天麻、白术、橘红、茯苓、甘草、生姜、大枣均由神威药业集团有限公司提供,具体信息见表1。经河北省药品检验院主任中药师孙宝惠鉴定,本研究所用半夏为天南星科植物半夏[Pinellia ternata(Thunb.)Breit.]的干燥块茎;天麻为兰科植物天麻(Gastrodia elata Bl.)的干燥块茎;白术为菊科植物白术(Atractylodes macrocephala Koidz.)的干燥根茎;橘红为芸香科植物橘(Citrus reticulata Blanco)及其栽培变种的干燥外层果皮;茯苓为多孔菌科真菌茯苓[Poria cocos(Schw.)Wolf]的干燥菌核;甘草为豆科植物甘草(Glycyrrhiza uralensis Fisch.)的干燥根和根茎;生姜为姜科植物姜(Zingiber officinale Rosc.)的新鲜根茎;大枣为鼠李科植物枣(Ziziphus jujube Mill.)的干燥成熟果实。

2 方法

收起

2.1 基准样品(冻干粉)的制备

半夏白术天麻汤基准样品按古籍记载结合文献考证折合为现代剂量进行制备,采用随机数字表法将不同批次饮片进行组合,取清半夏5.6 g,天麻、茯苓、橘红各3.73 g,白术11.19 g,甘草1.87 g置于煎药壶中,加生姜一片大枣两枚,煎煮两次,第一煎加8倍量水浸泡30 min,加热煮沸30 min,200目筛网过滤,药渣再加6倍量水加热煮沸20 min,200目筛网过滤,合并两次滤液,55 ℃低温浓缩,-40 ℃预冻12 h,冷冻干燥,即得半夏白术天麻汤基准样品(冻干粉)。

2.2 供试品溶液的制备

取半夏白术天麻汤基准样品(冻干粉)约0.1 g,精密称定,置具塞锥形瓶中,精密加入体积分数75%甲醇50 mL,称定重量,超声处理(功率250 W,频率40 kHz)20 min,放冷,再称定重量,用体积分数75%甲醇补足减失的重量,用0.22 μm微孔滤膜滤过,取续滤液,即得供试品溶液。

2.3 对照品溶液的制备

分别取25个对照品适量,精密称定,加体积分数75%甲醇溶解并稀释,摇匀,即得单一对照品储备液;分别精密吸取各对照品储备液适量置同一量瓶中,加体积分数75%甲醇溶液定容至刻度,摇匀,制成每1 mL含腺苷1.43 μg、鸟苷3.2 μg、琥珀酸1.83 μg、葫芦巴碱0.31 μg、天麻素14.27 μg、巴利森苷A 14.85 μg、巴利森苷B 11.3 μg、巴利森苷C 5.92 μg、巴利森苷E 11.93 μg、白术内酯Ⅱ 0.21 μg、白术内酯Ⅲ 1.25 μg、绿原酸1.14 μg、新绿原酸1.88 μg、芸香柚皮苷2.52 μg、橙皮苷17.46 μg、芦丁1.33 μg、川陈皮素0.51 μg、桔皮素0.19 μg、茯苓酸 A 0.11 μg、甘草苷4.74 μg、甘草酸6.82 μg、甘草素0.82μg、异甘草苷1.95 μg、芹糖异甘草苷1.47μg、环磷酸腺苷4.32 μg的混合对照品溶液,冷藏保存,备用。进样时过0.22 μm微孔滤膜。

2.4 液质条件

2.4.1 色谱条件

采用Shim-pack GIST C₁₈色谱柱 (2.1 mm×100 mm, 2.0 μm),柱温30 ℃,流动相A为乙腈,B为0.1%甲酸,梯度洗脱,每次进样前预平衡5 min,再进行洗脱程序。体积流量0.3 mL·min^-1;进样量1 μL。流动相梯度表见表2。

2.4.2 质谱条件

采用多重反应监测(MRM)的扫描方式下正负离子同时监测,离子源为电喷雾离子源(ESI),离子化电压(IS)为5 500和-4 500 V,离子源温度(TEM)为550 ℃,喷雾气(GS1,N₂)为345 kPa,辅助气(GS2,N₂)为345 kPa,接口持续加热,全程通入氮气,气帘气(CUR,N₂)为207 kPa,碰撞气(CAD)压力为medium,每个离子对的滞留时间(dwell time)为50 ms。每个待测化合物的监测离子对、解簇电压(DP)及碰撞能量(CE)见表3。混合对照品和被测成分的提取多重监测模式(MRM)见图1。

2.5 方法学考察

2.5.1 线性及范围

取“2.3”项下混合对照品溶液,精密量取0.25、0.5、1、2、4、8、10 mL,分别置10mL量瓶中,用体积分数75%甲醇稀释至刻度,得到25个成分系列质量浓度的标准曲线工作溶液,分别按“2.4”项下液质条件进样分析,以对照品的峰面积为(Y),其质量浓度为横坐标(X)进行线性回归,绘制标准曲线,得到回归方程,相关系数(r)及其线性范围。将混合对照品溶液逐步稀释并进样测定,以信噪比S/N=3和S/N=10时各对照品进样质量浓度分别作为检测限(LOD)和定量限(LOQ),结果见表4。

2.5.2 精密度考察

取混合对照品溶液,按“2.4”项下液质条件连续进样6针,进样量为 1 μL,测定各成分的峰面积,分别计算峰面积的相对标准差(RSD),结果显示腺苷、鸟苷、琥珀酸、葫芦巴碱、天麻素、巴利森苷A、巴利森苷B、巴利森苷C、巴利森苷E、白术内酯Ⅱ、白术内酯Ⅲ、绿原酸、新绿原酸、芸香柚皮苷、橙皮苷、芦丁、川陈皮素、桔皮素、茯苓酸 A、甘草苷、甘草酸、甘草素、异甘草苷、芹糖异甘草苷、环磷酸腺苷峰面积的RSD值分别为2.92%, 2.75%, 2.1%, 2.71%, 3.97%, 1.69%, 3.23%, 1.8%, 3.73%, 2.44%, 2.97%, 1.99%, 3.02%, 3.73%, 1.7%, 3.07%, 1.89%, 3.62%, 4.87%, 3.06%, 2.82%, 1.86%, 3.44%, 3.53%, 3.84%,表明仪器精密度良好。

2.5.3 稳定性考察

取半夏白术天麻汤基准样品(冻干粉),按“2.2”项下供试品制备方法制备供试品溶液,分别于0、4、8、12、18、24 h按“2.4”项下液质条件进样分析,测定峰面积并计算峰面积的RSD值,结果显示腺苷、鸟苷、琥珀酸、葫芦巴碱、天麻素、巴利森苷A、巴利森苷B、巴利森苷C、巴利森苷E、白术内酯Ⅱ、白术内酯Ⅲ、绿原酸、新绿原酸、芸香柚皮苷、橙皮苷、芦丁、川陈皮素、桔皮素、茯苓酸A、甘草苷、甘草酸、甘草素、异甘草苷、芹糖异甘草苷、环磷酸腺苷峰面积的RSD值分别为3.74%, 3.84%, 4.06%, 1.76%, 2.72%, 3.91%, 4.03%, 3.22%, 4.02%, 3.82%, 2.96%, 4.17%, 2.58%, 3.54%, 4.27%, 4.15%, 2.75%, 3.69%, 3.56%, 2.92%, 1.67%, 3.98%, 3.19%, 3.76%, 3.54%, 表明供试品溶液在24 h内稳定。

2.5.4 重复性考察

取同一批次半夏白术天麻汤基准样品(冻干粉),按“2.2”项下方法平行制备6份供试品溶液,按“2.4”项下液质条件进样分析,测定峰面积,根据标准曲线计算含量,求出含量的RSD,结果显示腺苷、鸟苷、琥珀酸、葫芦巴碱、天麻素、巴利森苷A、巴利森苷B、巴利森苷C、巴利森苷E、白术内酯Ⅱ、白术内酯Ⅲ、绿原酸、新绿原酸、芸香柚皮苷、橙皮苷、芦丁、川陈皮素、桔皮素、茯苓酸 A、甘草苷、甘草酸、甘草素、异甘草苷、芹糖异甘草苷、环磷酸腺苷的含量分别为0.141 7, 0.342 3, 0.262 3, 0.034 4, 1.180 0, 2.394 1, 1.229 5, 0.553 3, 1.551 2, 0.032 2, 0.093 2, 0.211 9, 0.055 6, 0.404 1, 2.563, 0.188 8, 0.066 5, 0.025 7, 0.003 3, 0.671 2, 1.776, 0.067 3, 0.077, 0.226 7, 0.168 9 mg·g^-1。含量的RSD值分别为3.54%, 3.2%, 2.44%, 3.01%, 4.42%, 3.56%, 3.97%, 2.06%, 3.15%, 2.24%, 3.08%, 2.84%, 2.24%, 2.73%, 3.01%, 2.02%, 1.58%, 0.71%, 0.89%, 3.87%, 1.65%, 4.33%, 2.26%, 2.92%, 2.35% (n=6), 表明方法的重复性良好。

2.5.5 准确度考察

取同一批次已测知含量的半夏白术天麻汤基准样品(冻干粉)9份,每份约0.05 g,精密称定,分别精密加入相当于样品含有量50%、100%、150%的混合对照品,每个水平平行3份,按“2.2”项下方法制备即得供试品。按“2.4”项下液质条件进样分析,记录峰面积,结果表明,25种成分的平均加样回收率在95%~105%之间,RSD值均小于5%,表明该方法准确度良好。结果见表5。

2.6 样品含量测定

分别取20批随机组合的半夏白术天麻汤基准样品(冻干粉)约0.1 g,精密称定,按“2.2”项下方法制备供试品溶液,按“2.4”项下液质条件进样测定峰面积,根据标准曲线计算其含量,结果见表6。

3 讨论

收起

本实验首先通过针泵进样的方法寻找25个待测成分的母离子与子离子,确定每个成分的DP和CE值, 并通过实验考察不同流动相系统最终选择乙腈-0.1%甲酸作为流动相体系,优化梯度条件使同分异构体互不干扰,各成分峰形、分离效果较好。接着考察了提取溶媒(水,体积分数50%甲醇,体积分数75%甲醇,甲醇),提取时间(10,20,30 min)以及提取方式(超声,回流),最终选择体积分数75%甲醇超声20 min制备供试品溶液。

除全方的基准样品(冻干粉)外,本实验还对缺味基准样品(冻干粉)和单味饮片水煎液进行进样分析,通过比对,归属相关色谱峰,腺苷,鸟苷,琥珀酸,葫芦巴碱来源于半夏;天麻素,巴利森苷A,巴利森苷B,巴利森苷C,巴利森苷E来源于天麻;绿原酸,新绿原酸,白术内酯Ⅱ,白术内酯Ⅲ来源于白术;橙皮苷、川陈皮素、桔皮素、芸香柚皮苷、芦丁来源于橘红;茯苓酸A来源于茯苓;甘草苷、甘草酸、甘草素、异甘草苷、芹糖异甘草苷来源于甘草;环磷酸腺苷来源于大枣。

中药复方“多成分”的本质决定其功效的发挥是“多靶点”作用于机体的综合效应, 因此全面评价复方整体质量,阐明复方药效物质不可或缺的前提是化学物质基础研究。UHPLC-MS/MS由于其多个特有的靶向扫描模式,已经成为中药复杂体系定量分析的主要手段之一^[12];网络药理学是在“疾病表型-基因-靶点-药物”的基础上, 采用网络分析的方法预测药物发挥药效的活性成分^[13],已广泛应用于中药潜在活性成分和作用靶点的预测研究中^[14]。笔者前期采用UPLC-Q-TOF-MS/MS法分析鉴定了91种成分,全面表征了半夏白术天麻汤基准样品(冻干粉)的化学成分组,主要包含22种含氮化合物,6种酚类化合物,5种内酯类化合物,10种三萜类化合物,28种黄酮类化合物,10种有机酸类等,在此基础上采用网络药理学和分子对接技术筛选得到其治疗眩晕的主要药效物质,包括葫芦巴碱、巴利森苷E、桔皮素、甘草酸、甘草素、环磷酸腺苷等。根据文献报道,腺苷,鸟苷,天麻素,巴利森苷,白术内酯Ⅲ,川陈皮素等有降压、抗癫痫、保护神经性损伤细胞以及抗痴呆的作用^[15-20],综合以上信息,最终选择天麻素等25种可测可控具有较强活性的化合物为指标成分进行含量测定。以25种化合物作为横坐标,以其各批次含量值为纵坐标绘制箱图,显示 20批半夏白术天麻汤基准样品(冻干粉)中25种化合物含量的数据分散情况,由图2可直观地看出检测的20批次样品含量均无异常值,其中天麻素,巴利森苷A,巴利森苷B,巴利森苷E,橙皮苷,甘草苷和甘草酸这7种成分在各批次中含量较高且波动较为稳定,可作为半夏白术天麻汤质量标志物的选择参考。不同批次基准样品(冻干粉)各活性成分的含量存在一定差异,可能与药材产地、采收加工以及饮片炮制有关。

本研究依据UPLC-Q-TOF-MS/MS 和“化学成分-疾病靶点”网络分析结果,从质量控制指标的选择原则和实际操作出发, 选取了半夏白术天麻汤基准样品(冻干粉)中25个药效物质进行含量测定,尽可能全面地表现出该复方制剂的内在质量。所建立的UHPLC-MS/MS方法快速准确,简便高效,重复性好, 为基于药效的复方半夏白术天麻汤的质量评价提供了依据。

基金

收起

河北省自然科学基金项目资助(H20222423335)
河北中医学院科技能力提升项目资助(KTY2019070)

参考文献

收起

文献

收起

参考文献引证文献

排序方式：

[1]

CHENG

G P

. Yixue Xinwu(医学心悟)[M]. Beijing: People's Medical Publishing House, 2006:154,202-203.

[2]

YAN

M H

, LI

, JIANG

Y H

. Clinical application and pharmacological research progress of Banxia Baizhu Tianma Decoction[J]. Chin J Integr Med Cardia Cerebro Vasc Dis(中西医结合心脑血管病杂志), 2020, 18(14):2265-2268.

[3]

DONG

M H

. Clinical application progress of Banxia Baizhu Tianma Decoction[J]. Chin J Ethnomed Ethnopharm(中国民族民间医药), 2012, 21(3):44-46.

[4]

YING

Z M

, SUI

G Y

, JIA

L Q

. Study on metabolites of BanxiaBaizhu Tianma Decoction in rat heart[J]. Chin Arch Tradit Chin Med(中华中医药学刊), 2023, 41(2):53-62.

[5]

WANG

Q G

, SUI

G Y

, DING

X Y

, et al. Effects of Banxia Baizhu Tianma Decoction on DsbA-L/adiponectin in rats with dyslipidemia and hypertension through FOXO1 pathway[J]. China J Tradit Chin Med Pharm(中华中医药杂志), 2022, 37(5):2898-2902.

[6]

, HU

Y Q

, L

, et al. Mechanism of Banxia Baizhu Tianma decoction in treating epilepsy:based on network pharmacology[J]. Mod Chin Med(中国现代中药), 2021, 23(8):1406-1415.

[7]

KANG

X L

. Clinical application experience of Banxia Baizhu Tianma decoction[J]. Inn Mong J Tradit Chin Med(内蒙古中医药), 2017, 36(19):50.

[8]

WANG

. Analysis of the efficacy of half-summer white gastrodia soup in the treatment of new hypertension[J]. China J Pharm Econ(中国药物经济学), 2017, 12(9):65-67.

[9]

LIU

Y C

, ZHANG

W G

, et al. Research progress of Banxiabai-zhutianma decoction in the treatment of phlegm-dampness obstructed hypertension[J]. Chin J Integr Med Cardia Cerebro Vasc Dis(中西医结合心脑血管病杂志), 2017, 15(11):1334-1336.

[10]

FENG

, TIAN

Y R

, et al. Multi-index determination and characteristic spectrum of reference substances of Danggui Jianzhong decoction[J]. Chin Pharm J(中国药学杂志), 2022, 57(10):799-807.

[11]

WANG

S L

, YANG

H M

, LI

H M

, et al. Fingerprint and multicomponent quantitative analysis of Banxia Baizhu Tianma decoction by HPLC[J]. Chin J Mod Med(中国当代医药), 2021, 28(8): 4-8, 17, 241.

[12]

YAN

, JIA

S L

, L

, et al. Strategy for the identification and quantitative analysis of the phytochemicals of traditional Chinese medicine by LC-MS/MS[J]. Acta Pharm Sin(药学学报), 2020, 55(7):1494-1503.

[13]

ZHANG

W N

, LI

A P

, LI

, et al. Progress on pharmacodynamic material basic of traditional Chinese medicin[J]. Chin Pharm J(中国药学杂志), 2018, 53(10):761-764.

[14]

XUE

J T

, HUANG

, KONG

W Y

, et al. Hypoglycemic bioactive components and mechanism of puerariae lobatae radix by network pharmacology[J]. Chin Pharm J(中国药学杂志), 2018, 53(20):1748-1754.

[15]

GUO

J C

. Experiences in diagnosis and treatment of vertigo by xin'an physicians in the Ming-Qing period and research on data mining as well as network pharmacology of Banxia Baizhu Tianma Decoction in treating vertigo[D]. Hefei: Anhui University of Chinese Medicine, 2021.

[16]

DING

X J

, XIONG

, YE

, et al. Advances in studies on chemical structure and pharmacological activities of natural nucleosides[J]. J Chengdu Univ Tradit Chin Med(成都中医药大学学报), 2018, 41(2):102-108.

[17]

HUANG

X F

, ZHENG

X R

, HUANG

C Y

. Based on network pharmacology, the mechanism of action of gastrodia in the treatment of cerebrovascular vertigo was discussed[J]. Shanxi J Tradit Chin Med(山西中医), 2022, 38(2):64-67.

[18]

QUAN

Y H

, SHANGGUAN

C H

, Research progress on pharmacological effects of phenols in Gastrodia elata on cardio-cerebralvascular diseases[J]. Chin Tradit Herb Drus(中草药), 2022, 53(14):4582-4592.

[19]

YAO

Z M

, CHEN

W D

, YANG

Z H

, et al. Research progress in Atractylodes macrocephala and predictive analysis on Q-marker[J]. Chin Tradit Herb Drus(中草药), 2019, 50(19):4796-4807.

[20]

CHEN

, WANG

, MA

J F

, et al. Clinical and experimental research progress of Banxia Baizhu Tianma Decoction in brain diseases[J]. J Liaoning Univ Tradit Chin Med(辽宁中医药大学学报), 2022, 24(11):67-72.

2024年第59卷第1期

PDF下载

115

引用本文

BibTeX

文章信息

doi: 10.11669/cpj.2024.01.011

接收时间：2022-10-08
首发时间：2025-11-12
出版时间：2024-01-08

补充材料

相关文章

文章信息

作者

出版历史

收稿日期：2022-10-08

基金

河北省自然科学基金项目资助(H20222423335)

河北中医学院科技能力提升项目资助(KTY2019070)

作者信息

¹ 河北中医药大学,石家庄 050091

² 河北省中药配方颗粒技术创新中心,石家庄 050091

³ 中药材品质评价与标准化河北省工程研究中心,石家庄 050091

⁴ 神威药业集团有限公司, 石家庄 051430

通讯作者:

*田伟,男,硕士,高级实验师研究方向:中药分析及质量控制研究 Tel:(0311)89926890;

牛丽颖,女,教授,博士生导师研究方向:中药分析及药效物质基础研究 Tel:(0311)89926548

参考文献

分享链接

https://castjournals.cast.org.cn/joweb/zgyxzz/CN/10.11669/cpj.2024.01.011

分享至

全文二维码

扫描看全文

引用本文

BibTeX

本文的引用情况

2种不同金属材料的力学参数

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

关闭全屏

BibTeX
EndNote
RefWorks
TxT

No.	Pinelliae Rhizoma (in Chinese)	Gastrodiae Rhizoma (in Chinese)	Macrocephalae Rhizoma (in Chinese)	Citri Exocarpium Rubrum(in Chinese)	Poria cocos (in Chinese)	Glycyrrhizae Radix et Rhizoma(in Chinese)	Jujubae Fructus (in Chinese)
S1-S5	Sichuan Xichang (四川西昌)	Yunnan Zhaotong (云南昭通)	Anhui Bozhou (安徽亳州)	Sichuan Chengdu (四川成都)	Yunnan Qujing (云南曲靖)	Gansu Longxi (甘肃陇西)	Henan Anyang (河南安阳)
S6-S10	Gansu Qingshui (甘肃清水)	Anhui Yuexi (安徽岳西)	Hebei Lixian (河北蠡县)	Hubei Xiangyang (湖北襄阳)	Shaanxi Shangluo (陕西商洛)	Xinjiang Aletai (新疆阿勒泰)	Hebei Cangzhou (河北沧州)
S11-S15	Gansu Xihe (甘肃西河)	Shaanxi Shangluo (陕西商洛)	Hebei Anguo (河北安国)	Zhejiang Jinhua (浙江金华)	Anhui Yuexi (安徽岳西)	Neimenggu Eerduosi (内蒙古鄂尔多斯)	Hebei Anguo (河北安国)
S16-S20	Hubei Zhongxiang (湖北钟祥)	Yunnan (云南)	Zhejiang Panan (浙江磐安)	Zhejiang Jiangshan (浙江江山)	Yunnan (云南)	Gansu (甘肃)	Shaanxi Wenxi (山西闻喜)

No.

Pinelliae Rhizoma
(in Chinese)

Gastrodiae Rhizoma
(in Chinese)

Macrocephalae Rhizoma
(in Chinese)

Citri Exocarpium
Rubrum(in Chinese)

Poria cocos
(in Chinese)

Glycyrrhizae Radix et
Rhizoma(in Chinese)

Jujubae Fructus
(in Chinese)

S1-S5

Sichuan Xichang
(四川西昌)

Yunnan Zhaotong
(云南昭通)

Anhui Bozhou
(安徽亳州)

Sichuan Chengdu
(四川成都)

Yunnan Qujing
(云南曲靖)

Gansu Longxi
(甘肃陇西)

Henan Anyang
(河南安阳)

S6-S10

Gansu Qingshui
(甘肃清水)

Anhui Yuexi
(安徽岳西)

Hebei Lixian
(河北蠡县)

Hubei Xiangyang
(湖北襄阳)

Shaanxi Shangluo
(陕西商洛)

Xinjiang Aletai
(新疆阿勒泰)

Hebei Cangzhou
(河北沧州)

S11-S15

Gansu Xihe
(甘肃西河)

Shaanxi Shangluo
(陕西商洛)

Hebei Anguo
(河北安国)

Zhejiang Jinhua
(浙江金华)

Anhui Yuexi
(安徽岳西)

Neimenggu Eerduosi
(内蒙古鄂尔多斯)

Hebei Anguo
(河北安国)

S16-S20

Hubei Zhongxiang
(湖北钟祥)

Yunnan
(云南)

Zhejiang Panan
(浙江磐安)

Zhejiang Jiangshan
(浙江江山)

Yunnan
(云南)

Gansu
(甘肃)

Shaanxi Wenxi
(山西闻喜)

t/min	A/%	B/%
0~1	4	96
1~6	4→15	96→85
6~15	15→30	85→70
15~20	30→45	70→55
20~25	45→65	55→35
25~27	65→90	35→10

t/min

A/%

B/%

0~1

1~6

4→15

96→85

6~15

15→30

85→70

15~20

30→45

70→55

20~25

45→65

55→35

25~27

65→90

35→10

Analysts	Formula	Q₁ (m/z)	Q₃ (m/z)	DP /V	CE /eV
Adenosine	267.10	268.2[M+H]⁺	136.0	63	22
Guanosine	283.09	284.2[M+H]⁺	151.8	35	25
Succinic acid	118.03	116.6[M-H]^-	72.9	-47	-21
Trigonelline	137.05	138.0[M+H]⁺	92.0	71	29
Gastrodin	286.11	284.9[M-H]^-	104.8	-44	-37
Parishin A	996.31	995.3[M-H]^-	727.3	-164	-34
Parishin B	728.22	727.4[M-H]^-	423.2	-81	-41
Parishin C	728.22	727.3[M-H]^-	422.9	-79	-39
Parishin E	460.12	459.2[M-H]^-	110.4	-86	-30
Atractylenolide Ⅱ	232.15	233.3[M+H]⁺	187.1	94	26
Atractylenolide Ⅲ	248.14	249.2[M+H]⁺	231.1	76	14
Chlorogenic acid	354.10	353.2[M-H]^-	190.7	-62	-23
Neochlorogenic acid	354.10	353.3[M-H]^-	190.6	-62	-23
Narirutin	580.18	579.1[M-H]^-	271.0	-167	-34
Hesperidin	610.19	609.1[M-H]^-	300.9	-162	-37
Rutin	610.15	609.1[M-H]^-	299.8	-184	-43
Naringin	402.13	403.0[M+H]⁺	373.1	102	36
Tangeretin	372.12	373.2[M+H]⁺	343.0	84	36
Poricoic acid A	498.69	497.2[M-H]^-	423.3	-214	-44
Liquiritin	418.13	417.2[M-H]^-	255.0	-134	-29
Glycyrrhizic acid	822.40	821.4[M-H]^-	350.8	-206	-55
Liquiritigenin	256.07	255.0[M-H]^-	134.7	-118	-25
Isoliquiritin	418.13	417.2[M-H]^-	254.7	-152	-33
Isoliquiritin apioside	550.17	549.1[M-H]^-	254.8	-169	-40
Cyclic AMP	329.05	327.8[M-H]^-	133.5	-147	-30

Analysts

Formula

Q₁
(m/z)

Q₃
(m/z)

DP
/V

CE
/eV

Adenosine

267.10

268.2[M+H]⁺

136.0

Guanosine

283.09

284.2[M+H]⁺

151.8

Succinic acid

118.03

116.6[M-H]^-

72.9

-47

-21

Trigonelline

137.05

138.0[M+H]⁺

92.0

Gastrodin

286.11

284.9[M-H]^-

104.8

-44

-37

Parishin A

996.31

995.3[M-H]^-

727.3

-164

-34

Parishin B

728.22

727.4[M-H]^-

423.2

-81

-41

Parishin C

728.22

727.3[M-H]^-

422.9

-79

-39

Parishin E

460.12

459.2[M-H]^-

110.4

-86

-30

Atractylenolide Ⅱ

232.15

233.3[M+H]⁺

187.1

Atractylenolide Ⅲ

248.14

249.2[M+H]⁺

231.1

Chlorogenic acid

354.10

353.2[M-H]^-

190.7

-62

-23

Neochlorogenic acid

354.10

353.3[M-H]^-

190.6

-62

-23

Narirutin

580.18

579.1[M-H]^-

271.0

-167

-34

Hesperidin

610.19

609.1[M-H]^-

300.9

-162

-37

Rutin

610.15

609.1[M-H]^-

299.8

-184

-43

Naringin

402.13

403.0[M+H]⁺

373.1

102

Tangeretin

372.12

373.2[M+H]⁺

343.0

Poricoic acid A

498.69

497.2[M-H]^-

423.3

-214

-44

Liquiritin

418.13

417.2[M-H]^-

255.0

-134

-29

Glycyrrhizic acid

822.40

821.4[M-H]^-

350.8

-206

-55

Liquiritigenin

256.07

255.0[M-H]^-

134.7

-118

-25

Isoliquiritin

418.13

417.2[M-H]^-

254.7

-152

-33

Isoliquiritin apioside

550.17

549.1[M-H]^-

254.8

-169

-40

Cyclic AMP

329.05

327.8[M-H]^-

133.5

-147

-30

Compounds	Regress equation	r	Liner range /μg·mL^-1	LOD /ng·mL^-1	LOQ / ng·mL^-1
Adenosine	Y=2.42×10⁹X+4.95×10⁵	0.998 3	0.04	~1.43	11.31	37.67
Guanosine	Y=1.16×10⁹X+1.83×10⁵	0.999 6	0.08	~3.2	22.21	73.97
Succinic acid	Y=6.35×10⁸X+1.63×10⁴	0.999 9	0.05	~1.83	12.18	40.56
Trigonelline	Y=9.6×10⁸X+4.58×10⁴	0.997 0	7.5×10^-3	~0.31	0.77	2.55
Gastrodin	Y=5.54×10⁶X+1.54×10⁴	0.995 5	0.36	~14.27	27.56	91.79
Parishin A	Y=1.12×10⁸X-9.28×10⁴	0.999 5	0.37	~14.85	3.39	11.39
Parishin B	Y=1.17×10⁸X-3.21×10⁴	0.999 7	0.28	~11.30	2.94	9.79
Parishin C	Y=1.35×10⁸X+7.03×10³	0.999 8	0.15	~5.92	4.41	14.67
Parishin E	Y=3.21×10⁸X-1.13×10⁵	0.999 8	0.3	~11.93	3.68	12.27
Atractylenolide Ⅱ	Y=1.49×10⁸X+4.8×10³	0.999 6	5×10^-3	~0.21	9.87	32.88
Atractylenolide Ⅲ	Y=9.81×10⁷X+5.64×10³	0.999 3	0.03	~1.25	0.35	1.16
Chlorogenic acid	Y=1.69×10⁹X+1.35×10⁵	0.999 9	0.03	~1.14	0.79	2.63
Neochlorogenic acid	Y=8.25×10⁸X+1.22×10⁴	0.999 9	0.05	~1.88	2.42	8.05
Narirutin	Y=7.52×10⁶X+1.39×10⁴	0.999 5	0.06	~2.52	1.21	4.04
Hesperidin	Y=3.33×10⁹X+1.43×10⁶	0.998 0	0.44	~17.46	1.01	3.37
Rutin	Y=4.23×10⁸X+1.79×10⁴	0.999 6	0.03	~1.33	1.9	6.56
Naringin	Y=2.43×10¹⁰X+2.66×10⁶	0.997 6	0.01	~0.51	1.24	5.59
Tangeretin	Y=1.74×10¹⁰X+1.3×10⁶	0.999 5	5×10^-3	~0.19	0.98	4.07
Poricoic acid A	Y=2.2×10¹⁰X+4.96×10⁴	0.998 9	2.62×10^-3	~0.11	1.96	6.54
Liquiritin	Y=1.06×10⁹X+3.22×10⁵	0.999 5	0.12	~4.74	3.23	10.75
Glycyrrhizic acid	Y=1.36×10⁸X-7.12×10⁵	0.991 6	0.17	~6.82	17.29	57.59
Liquiritigenin	Y=2.74×10⁸X+1.02×10⁴	0.999 8	0.02	~0.82	1.54	5.39
Isoliquiritin	Y=1.67×10⁹X+5.83×10⁴	0.999 5	0.05	~1.95	0.56	1.85
Isoliquiritin apioside	Y=7.77×10⁸X-2.18×10³	0.999 7	0.04	~1.47	10.23	34.09
Cyclic AMP	Y=1.66×10⁸X+5.67×10²	0.999 8	0.11	~4.32	4.01	13.34

Compounds

Regress equation

Liner range
/μg·mL^-1

LOD
/ng·mL^-1

LOQ
/ ng·mL^-1

Adenosine

Y=2.42×10⁹X+4.95×10⁵

0.998 3

0.04

~1.43

11.31

37.67

Guanosine

Y=1.16×10⁹X+1.83×10⁵

0.999 6

0.08

~3.2

22.21

73.97

Succinic acid

Y=6.35×10⁸X+1.63×10⁴

0.999 9

0.05

~1.83

12.18

40.56

Trigonelline

Y=9.6×10⁸X+4.58×10⁴

0.997 0

7.5×10^-3

~0.31

0.77

2.55

Gastrodin

Y=5.54×10⁶X+1.54×10⁴

0.995 5

0.36

~14.27

27.56

91.79

Parishin A

Y=1.12×10⁸X-9.28×10⁴

0.999 5

0.37

~14.85

3.39

11.39

Parishin B

Y=1.17×10⁸X-3.21×10⁴

0.999 7

0.28

~11.30

2.94

9.79

Parishin C

Y=1.35×10⁸X+7.03×10³

0.999 8

0.15

~5.92

4.41

14.67

Parishin E

Y=3.21×10⁸X-1.13×10⁵

0.999 8

0.3

~11.93

3.68

12.27

Atractylenolide Ⅱ

Y=1.49×10⁸X+4.8×10³

0.999 6

5×10^-3

~0.21

9.87

32.88

Atractylenolide Ⅲ

Y=9.81×10⁷X+5.64×10³

0.999 3

0.03

~1.25

0.35

1.16

Chlorogenic acid

Y=1.69×10⁹X+1.35×10⁵

0.999 9

0.03

~1.14

0.79

2.63

Neochlorogenic acid

Y=8.25×10⁸X+1.22×10⁴

0.999 9

0.05

~1.88

2.42

8.05

Narirutin

Y=7.52×10⁶X+1.39×10⁴

0.999 5

0.06

~2.52

1.21

4.04

Hesperidin

Y=3.33×10⁹X+1.43×10⁶

0.998 0

0.44

~17.46

1.01

3.37

Rutin

Y=4.23×10⁸X+1.79×10⁴

0.999 6

0.03

~1.33

1.9

6.56

Naringin

Y=2.43×10¹⁰X+2.66×10⁶

0.997 6

0.01

~0.51

1.24

5.59

Tangeretin

Y=1.74×10¹⁰X+1.3×10⁶

0.999 5

5×10^-3

~0.19

0.98

4.07

Poricoic acid A

Y=2.2×10¹⁰X+4.96×10⁴

0.998 9

2.62×10^-3

~0.11

1.96

6.54

Liquiritin

Y=1.06×10⁹X+3.22×10⁵

0.999 5

0.12

~4.74

3.23

10.75

Glycyrrhizic acid

Y=1.36×10⁸X-7.12×10⁵

0.991 6

0.17

~6.82

17.29

57.59

Liquiritigenin

Y=2.74×10⁸X+1.02×10⁴

0.999 8

0.02

~0.82

1.54

5.39

Isoliquiritin

Y=1.67×10⁹X+5.83×10⁴

0.999 5

0.05

~1.95

0.56

1.85

Isoliquiritin apioside

Y=7.77×10⁸X-2.18×10³

0.999 7

0.04

~1.47

10.23

34.09

Cyclic AMP

Y=1.66×10⁸X+5.67×10²

0.999 8

0.11

~4.32

4.01

13.34

Component	Recovery text	Average /%	RSD /%
Adenosine	97.36	101.59	103.50	101.98	104.59	100.95	99.55	100.77	98.20	100.94	2.32
Guanosine	99.93	96.86	101.39	95.13	91.15	93.86	95.09	98.53	100.26	96.91	3.50
Succinic acid	101.51	98.20	101.17	101.22	102.56	104.33	101.71	100.85	103.22	101.64	1.68
Trigonelline	101.28	99.49	96.89	90.14	101.15	97.03	98.38	96.82	95.88	97.45	3.45
Gastrodin	96.99	96.69	98.12	95.94	99.53	99.38	99.93	100.13	98.11	98.31	1.55
Parishin A	103.80	99.98	104.04	95.23	94.47	95.36	103.77	103.67	103.63	100.44	4.23
Parishin B	102.55	97.72	99.18	101.11	102.60	101.41	103.95	102.38	101.20	101.34	1.87
Parishin C	94.22	98.15	96.27	93.91	97.04	97.52	95.71	95.12	95.15	95.90	1.53
Parishin E	102.54	105.62	97.92	103.35	105.21	103.73	106.08	105.39	107.62	104.16	2.69
Atractylenolide Ⅱ	96.79	95.53	92.95	97.83	96.49	93.36	95.97	95.29	96.55	95.64	1.67
Atractylenolide Ⅲ	92.85	95.88	98.20	94.46	96.47	92.40	100.16	101.55	96.33	96.48	3.20
Chlorogenic acid	104.02	100.82	103.82	103.43	102.13	103.11	104.04	103.27	103.32	103.11	1.00
Neochlorogenic acid	100.74	96.38	91.93	95.84	96.46	91.92	92.44	103.23	95.55	96.05	4.05
Narirutin	107.73	102.47	106.26	105.16	104.79	105.93	106.80	100.38	105.31	104.98	2.16
Hesperidin	103.66	97.72	103.63	101.28	102.59	103.13	100.16	99.00	95.47	100.74	2.86
Rutin	97.61	106.45	104.09	105.42	106.42	104.55	105.72	105.38	104.91	104.50	2.59
Naringin	102.68	98.25	103.61	101.59	100.98	100.50	99.93	99.27	101.99	100.98	1.67
Tangeretin	99.89	100.95	100.48	100.54	100.78	101.73	99.95	100.47	100.29	100.56	0.55
Poricoic acid A	97.76	96.49	95.86	97.66	96.16	96.17	96.79	95.98	95.45	96.48	0.82
Liquiritin	95.30	96.66	94.30	96.68	97.72	96.43	93.76	95.12	94.16	95.57	1.43
Glycyrrhizic acid	104.96	104.50	103.62	104.87	105.72	105.76	104.28	105.47	103.07	104.69	0.89
Liquiritigenin	96.39	94.91	95.35	96.91	97.46	96.38	105.38	105.69	105.12	99.29	4.68
Isoliquiritin	95.35	95.36	94.61	95.12	95.00	96.74	98.34	95.32	101.88	96.41	2.44
Isoliquiritin apioside	100.86	100.80	98.49	99.53	100.67	102.11	102.51	102.29	103.17	101.16	1.50
Cyclic AMP	92.26	100.76	94.64	95.34	93.91	93.93	96.41	94.50	101.68	95.94	3.34

Component

Recovery text

Average
/%

RSD
/%

50%

100%

150%

Adenosine

97.36

101.59

103.50

101.98

104.59

100.95

99.55

100.77

98.20

100.94

2.32

Guanosine

99.93

96.86

101.39

95.13

91.15

93.86

95.09

98.53

100.26

96.91

3.50

Succinic acid

101.51

98.20

101.17

101.22

102.56

104.33

101.71

100.85

103.22

101.64

1.68

Trigonelline

101.28

99.49

96.89

90.14

101.15

97.03

98.38

96.82

95.88

97.45

3.45

Gastrodin

96.99

96.69

98.12

95.94

99.53

99.38

99.93

100.13

98.11

98.31

1.55

Parishin A

103.80

99.98

104.04

95.23

94.47

95.36

103.77

103.67

103.63

100.44

4.23

Parishin B

102.55

97.72

99.18

101.11

102.60

101.41

103.95

102.38

101.20

101.34

1.87

Parishin C

94.22

98.15

96.27

93.91

97.04

97.52

95.71

95.12

95.15

95.90

1.53

Parishin E

102.54

105.62

97.92

103.35

105.21

103.73

106.08

105.39

107.62

104.16

2.69

Atractylenolide Ⅱ

96.79

95.53

92.95

97.83

96.49

93.36

95.97

95.29

96.55

95.64

1.67

Atractylenolide Ⅲ

92.85

95.88

98.20

94.46

96.47

92.40

100.16

101.55

96.33

96.48

3.20

Chlorogenic acid

104.02

100.82

103.82

103.43

102.13

103.11

104.04

103.27

103.32

103.11

1.00

Neochlorogenic acid

100.74

96.38

91.93

95.84

96.46

91.92

92.44

103.23

95.55

96.05

4.05

Narirutin

107.73

102.47

106.26

105.16

104.79

105.93

106.80

100.38

105.31

104.98

2.16

Hesperidin

103.66

97.72

103.63

101.28

102.59

103.13

100.16

99.00

95.47

100.74

2.86

Rutin

97.61

106.45

104.09

105.42

106.42

104.55

105.72

105.38

104.91

104.50

2.59

Naringin

102.68

98.25

103.61

101.59

100.98

100.50

99.93

99.27

101.99

100.98

1.67

Tangeretin

99.89

100.95

100.48

100.54

100.78

101.73

99.95

100.47

100.29

100.56

0.55

Poricoic acid A

97.76

96.49

95.86

97.66

96.16

96.17

96.79

95.98

95.45

96.48

0.82

Liquiritin

95.30

96.66

94.30

96.68

97.72

96.43

93.76

95.12

94.16

95.57

1.43

Glycyrrhizic acid

104.96

104.50

103.62

104.87

105.72

105.76

104.28

105.47

103.07

104.69

0.89

Liquiritigenin

96.39

94.91

95.35

96.91

97.46

96.38

105.38

105.69

105.12

99.29

4.68

Isoliquiritin

95.35

95.36

94.61

95.12

95.00

96.74

98.34

95.32

101.88

96.41

2.44

Isoliquiritin apioside

100.86

100.80

98.49

99.53

100.67

102.11

102.51

102.29

103.17

101.16

1.50

Cyclic AMP

92.26

100.76

94.64

95.34

93.91

93.93

96.41

94.50

101.68

95.94

3.34

Compounds	Content/mg·g^-1
Adenosine	0.141 7	0.069 0	0.070 0	0.065 5	0.086 2	0.080 9	0.109 7	0.074 8	0.099 7	0.085 5
Guanosine	0.342 3	0.252 8	0.213 1	0.236 7	0.236 0	0.231 7	0.253 4	0.307 3	0.260 2	0.333 3
Succinic acid	0.262 3	0.233 7	0.224 0	0.284 7	0.275 1	0.332 5	0.295 3	0.346 3	0.314 9	0.376 1
Trigonelline	0.034 4	0.037 2	0.029 6	0.041 7	0.035 5	0.030 4	0.033 0	0.026 2	0.038 9	0.027 4
Gastrodin	1.180 0	1.138 2	1.099 9	1.332 0	1.017 2	1.020 9	1.034 5	0.891 3	1.170 2	1.036 9
Parishin A	2.394 1	1.870 9	2.654 9	4.417 1	4.052 2	2.693 7	2.755 8	2.127 0	4.448 1	2.274 5
Parishin B	1.229 5	1.318 5	1.802 2	1.759 9	1.893 7	2.316 1	2.351 3	1.436 1	1.802 2	1.296 0
Parishin C	0.553 3	0.426 2	0.650 4	0.850 0	0.851 2	0.599 3	0.614 4	0.430 0	0.795 7	0.479 3
Parishin E	1.551 2	1.381 9	1.423 3	1.771 8	1.330 7	1.479 4	1.620 7	1.106 5	1.654 8	1.235 6
Atractylenolide Ⅱ	0.032 2	0.038 9	0.033 6	0.022 7	0.035 1	0.073 3	0.071 9	0.080 0	0.071 1	0.076 7
Atractylenolide Ⅲ	0.093 2	0.288 3	0.056 9	0.056 1	0.078 3	0.057 9	0.068 5	0.245 4	0.293 8	0.224 8
Chlorogenic acid	0.211 9	0.127 8	0.047 1	0.132 3	0.028 8	0.045 9	0.152 2	0.122 8	0.141 8	0.127 8
Neochlorogenic acid	0.055 6	0.013 9	0.010 3	0.043 6	0.029 6	0.013 7	0.021 8	0.020 1	0.016 6	0.022 5
Narirutin	0.404 1	0.525 2	0.312 2	0.285 3	0.688 3	0.301 1	0.616 0	0.444 6	0.526 2	0.459 5
Hesperidin	2.563 0	2.267 6	2.139 4	2.135 3	2.425 1	2.073 9	2.738 7	2.151 6	2.711 4	2.203 5
Rutin	0.188 8	0.140 7	0.184 9	0.169 1	0.229 6	0.183 1	0.100 3	0.191 0	0.153 1	0.197 2
Naringin	0.066 5	0.075 7	0.085 8	0.086 4	0.073 4	0.087 8	0.079 5	0.066 9	0.079 2	0.066 5
Tangeretin	0.025 7	0.026 8	0.029 0	0.029 1	0.025 0	0.029 6	0.029 6	0.021 8	0.030 1	0.021 9
Poricoic acid A	0.003 3	0.007 9	0.004 1	0.005 0	0.007 8	0.003 9	0.006 0	0.004 4	0.004 2	0.004 2
Liquiritin	0.671 2	1.891 7	0.740 5	1.471 3	1.561 4	0.738 7	0.715 8	0.777 7	1.963 8	0.831 1
Glycyrrhizic acid	1.776 0	1.471 0	1.714 3	1.283 1	1.628 9	1.705 8	2.137 0	1.833 9	1.330 1	1.827 5
Liquiritigenin	0.067 3	0.105 1	0.025 8	0.037 4	0.096 1	0.028 0	0.049 2	0.049 2	0.083 5	0.049 9
Isoliquiritin	0.077 0	0.230 3	0.089 6	0.161 1	0.189 2	0.088 0	0.083 0	0.101 9	0.220 7	0.107 6
Isoliquiritin apioside	0.226 7	0.254 1	0.362 7	0.238 6	0.222 3	0.357 5	0.350 6	0.304 1	0.258 4	0.331 7
Cyclic AMP	0.168 9	0.465 4	0.412 7	0.311 6	0.334	0.452 7	0.263 3	0.144 2	0.403 4	0.150 7
Compounds	Content /mg·g^-1
S11	S12	S13	S14	S15	S16	S17	S18	S19	S20
Adenosine	0.098 5	0.109 3	0.142 2	0.098 5	0.093 9	0.097 9	0.070 2	0.144 0	0.098 5	0.130 0
Guanosine	0.206 3	0.203 4	0.269 5	0.238 8	0.253 3	0.234 1	0.242 8	0.271 8	0.165 7	0.275 3
Succinic acid	0.242 6	0.197 1	0.162 3	0.227 3	0.229 3	0.357 3	0.299 9	0.220 1	0.199 4	0.167 1
Trigonelline	0.032 3	0.034 9	0.043 3	0.040 6	0.043 7	0.035 2	0.046 9	0.044 3	0.036 4	0.046 5
Gastrodin	1.258 7	1.067 0	1.073 4	1.065 5	1.317 8	1.463 2	1.210 8	1.054 3	1.126 2	1.183 7
Parishin A	1.528 7	1.438 5	2.257 8	1.477 2	1.799 8	2.567 4	4.064 0	1.419 2	1.522 4	2.322 3
Parishin B	0.988 1	1.010 1	1.318 9	0.926 3	1.041 0	1.526 2	1.636 5	1.010 1	1.014 5	1.093 9
Parishin C	0.671 3	0.501 4	0.680 7	0.468 6	0.481 2	0.687 0	0.851 2	0.419 9	0.528 5	0.693 4
Parishin E	1.492 6	1.011 8	1.772 8	1.121 1	1.433 3	1.638 4	1.927 8	1.740 9	0.865 9	1.893 6
Atractylenolide Ⅱ	0.034 1	0.016 6	0.020 2	0.020 1	0.103 6	0.031 1	0.022 7	0.093 3	0.019 5	0.020 1
Atractylenolide Ⅲ	0.106 9	0.037 2	0.046 3	0.046 8	0.337 0	0.072 0	0.070 5	0.296 7	0.048 5	0.055 5
Chlorogenic acid	0.102 7	0.069 3	0.257 5	0.073 2	0.103 5	0.037 4	0.108 4	0.056 6	0.057 7	0.257 9
Neochlorogenic acid	0.023 4	0.011 2	0.059 8	0.018 8	0.016 4	0.014 0	0.029 8	0.008 2	0.012 1	0.043 7
Narirutin	0.421 5	0.501 7	0.720 6	0.667 1	0.511 4	0.288 6	0.259 4	0.325 8	0.526 0	0.742 5
Hesperidin	2.121 4	2.120 8	2.291 5	2.379 7	2.249 9	2.155 4	2.118 3	2.166 8	2.174 3	2.323 0
Rutin	0.156 9	0.188 2	0.197 9	0.224 5	0.139 1	0.181 1	0.166 7	0.156 8	0.185 2	0.203 7
Naringin	0.075 7	0.078 7	0.085 8	0.075 1	0.076 8	0.093 3	0.089 7	0.079 8	0.079 8	0.085 6
Tangeretin	0.026 9	0.027 8	0.030 0	0.027 5	0.027 5	0.030 5	0.029 1	0.028 0	0.026 7	0.029 8
Poricoic acid A	0.004 7	0.004 6	0.007 3	0.003 4	0.004 8	0.003 9	0.005 0	0.006 2	0.004 2	0.007 8
Liquiritin	1.087 6	0.254 0	0.788 4	0.579 7	1.826 6	0.738 4	1.436 3	0.893 5	0.261 8	0.818 6
Glycyrrhizic acid	1.635 3	0.740 8	1.189 1	1.103 8	1.547 8	1.731 4	1.289 5	2.147 7	0.781 4	1.223 3
Liquiritigenin	0.041 8	0.055 8	0.057 8	0.038 7	0.111 3	0.027 9	0.037 2	0.029 9	0.056 2	0.063 1
Isoliquiritin	0.132 2	0.035 5	0.089 3	0.073 5	0.236 3	0.095 6	0.157 5	0.117 1	0.036 5	0.098 4
Isoliquiritin apioside	0.268 3	0.184 7	0.267 6	0.288 1	0.246 3	0.377 0	0.228 0	0.340 5	0.190 0	0.291 9
Cyclic AMP	0.607 6	0.397 5	0.420 7	0.429 5	0.454 8	0.508 5	0.386 6	0.499 2	0.325 2	0.522 9

Compounds

Content/mg·g^-1

S10

Adenosine

0.141 7

0.069 0

0.070 0

0.065 5

0.086 2

0.080 9

0.109 7

0.074 8

0.099 7

0.085 5

Guanosine

0.342 3

0.252 8

0.213 1

0.236 7

0.236 0

0.231 7

0.253 4

0.307 3

0.260 2

0.333 3

Succinic acid

0.262 3

0.233 7

0.224 0

0.284 7

0.275 1

0.332 5

0.295 3

0.346 3

0.314 9

0.376 1

Trigonelline

0.034 4

0.037 2

0.029 6

0.041 7

0.035 5

0.030 4

0.033 0

0.026 2

0.038 9

0.027 4

Gastrodin

1.180 0

1.138 2

1.099 9

1.332 0

1.017 2

1.020 9

1.034 5

0.891 3

1.170 2

1.036 9

Parishin A

2.394 1

1.870 9

2.654 9

4.417 1

4.052 2

2.693 7

2.755 8

2.127 0

4.448 1

2.274 5

Parishin B

1.229 5

1.318 5

1.802 2

1.759 9

1.893 7

2.316 1

2.351 3

1.436 1

1.802 2

1.296 0

Parishin C

0.553 3

0.426 2

0.650 4

0.850 0

0.851 2

0.599 3

0.614 4

0.430 0

0.795 7

0.479 3

Parishin E

1.551 2

1.381 9

1.423 3

1.771 8

1.330 7

1.479 4

1.620 7

1.106 5

1.654 8

1.235 6

Atractylenolide Ⅱ

0.032 2

0.038 9

0.033 6

0.022 7

0.035 1

0.073 3

0.071 9

0.080 0

0.071 1

0.076 7

Atractylenolide Ⅲ

0.093 2

0.288 3

0.056 9

0.056 1

0.078 3

0.057 9

0.068 5

0.245 4

0.293 8

0.224 8

Chlorogenic acid

0.211 9

0.127 8

0.047 1

0.132 3

0.028 8

0.045 9

0.152 2

0.122 8

0.141 8

0.127 8

Neochlorogenic acid

0.055 6

0.013 9

0.010 3

0.043 6

0.029 6

0.013 7

0.021 8

0.020 1

0.016 6

0.022 5

Narirutin

0.404 1

0.525 2

0.312 2

0.285 3

0.688 3

0.301 1

0.616 0

0.444 6

0.526 2

0.459 5

Hesperidin

2.563 0

2.267 6

2.139 4

2.135 3

2.425 1

2.073 9

2.738 7

2.151 6

2.711 4

2.203 5

Rutin

0.188 8

0.140 7

0.184 9

0.169 1

0.229 6

0.183 1

0.100 3

0.191 0

0.153 1

0.197 2

Naringin

0.066 5

0.075 7

0.085 8

0.086 4

0.073 4

0.087 8

0.079 5

0.066 9

0.079 2

0.066 5

Tangeretin

0.025 7

0.026 8

0.029 0

0.029 1

0.025 0

0.029 6

0.021 8

0.030 1

0.021 9

Poricoic acid A

0.003 3

0.007 9

0.004 1

0.005 0

0.007 8

0.003 9

0.006 0

0.004 4

0.004 2

Liquiritin

0.671 2

1.891 7

0.740 5

1.471 3

1.561 4

0.738 7

0.715 8

0.777 7

1.963 8

0.831 1

Glycyrrhizic acid

1.776 0

1.471 0

1.714 3

1.283 1

1.628 9

1.705 8

2.137 0

1.833 9

1.330 1

1.827 5

Liquiritigenin

0.067 3

0.105 1

0.025 8

0.037 4

0.096 1

0.028 0

0.049 2

0.083 5

0.049 9

Isoliquiritin

0.077 0

0.230 3

0.089 6

0.161 1

0.189 2

0.088 0

0.083 0

0.101 9

0.220 7

0.107 6

Isoliquiritin apioside

0.226 7

0.254 1

0.362 7

0.238 6

0.222 3

0.357 5

0.350 6

0.304 1

0.258 4

0.331 7

Cyclic AMP

0.168 9

0.465 4

0.412 7

0.311 6

0.334

0.452 7

0.263 3

0.144 2

0.403 4

0.150 7

Compounds

Content /mg·g^-1

S11

S12

S13

S14

S15

S16

S17

S18

S19

S20

Adenosine

0.098 5

0.109 3

0.142 2

0.098 5

0.093 9

0.097 9

0.070 2

0.144 0

0.098 5

0.130 0

Guanosine

0.206 3

0.203 4

0.269 5

0.238 8

0.253 3

0.234 1

0.242 8

0.271 8

0.165 7

0.275 3

Succinic acid

0.242 6

0.197 1

0.162 3

0.227 3

0.229 3

0.357 3

0.299 9

0.220 1

0.199 4

0.167 1

Trigonelline

0.032 3

0.034 9

0.043 3

0.040 6

0.043 7

0.035 2

0.046 9

0.044 3

0.036 4

0.046 5

Gastrodin

1.258 7

1.067 0

1.073 4

1.065 5

1.317 8

1.463 2

1.210 8

1.054 3

1.126 2

1.183 7

Parishin A

1.528 7

1.438 5

2.257 8

1.477 2

1.799 8

2.567 4

4.064 0

1.419 2

1.522 4

2.322 3

Parishin B

0.988 1

1.010 1

1.318 9

0.926 3

1.041 0

1.526 2

1.636 5

1.010 1

1.014 5

1.093 9

Parishin C

0.671 3

0.501 4

0.680 7

0.468 6

0.481 2

0.687 0

0.851 2

0.419 9

0.528 5

0.693 4

Parishin E

1.492 6

1.011 8

1.772 8

1.121 1

1.433 3

1.638 4

1.927 8

1.740 9

0.865 9

1.893 6

Atractylenolide Ⅱ

0.034 1

0.016 6

0.020 2

0.020 1

0.103 6

0.031 1

0.022 7

0.093 3

0.019 5

0.020 1

Atractylenolide Ⅲ

0.106 9

0.037 2

0.046 3

0.046 8

0.337 0

0.072 0

0.070 5

0.296 7

0.048 5

0.055 5

Chlorogenic acid

0.102 7

0.069 3

0.257 5

0.073 2

0.103 5

0.037 4

0.108 4

0.056 6

0.057 7

0.257 9

Neochlorogenic acid

0.023 4

0.011 2

0.059 8

0.018 8

0.016 4

0.014 0

0.029 8

0.008 2

0.012 1

0.043 7

Narirutin

0.421 5

0.501 7

0.720 6

0.667 1

0.511 4

0.288 6

0.259 4

0.325 8

0.526 0

0.742 5

Hesperidin

2.121 4

2.120 8

2.291 5

2.379 7

2.249 9

2.155 4

2.118 3

2.166 8

2.174 3

2.323 0

Rutin

0.156 9

0.188 2

0.197 9

0.224 5

0.139 1

0.181 1

0.166 7

0.156 8

0.185 2

0.203 7

Naringin

0.075 7

0.078 7

0.085 8

0.075 1

0.076 8

0.093 3

0.089 7

0.079 8

0.085 6

Tangeretin

0.026 9

0.027 8

0.030 0

0.027 5

0.030 5

0.029 1

0.028 0

0.026 7

0.029 8

Poricoic acid A

0.004 7

0.004 6

0.007 3

0.003 4

0.004 8

0.003 9

0.005 0

0.006 2

0.004 2

0.007 8

Liquiritin

1.087 6

0.254 0

0.788 4

0.579 7

1.826 6

0.738 4

1.436 3

0.893 5

0.261 8

0.818 6

Glycyrrhizic acid

1.635 3

0.740 8

1.189 1

1.103 8

1.547 8

1.731 4

1.289 5

2.147 7

0.781 4

1.223 3

Liquiritigenin

0.041 8

0.055 8

0.057 8

0.038 7

0.111 3

0.027 9

0.037 2

0.029 9

0.056 2

0.063 1

Isoliquiritin

0.132 2

0.035 5

0.089 3

0.073 5

0.236 3

0.095 6

0.157 5

0.117 1

0.036 5

0.098 4

Isoliquiritin apioside

0.268 3

0.184 7

0.267 6

0.288 1

0.246 3

0.377 0

0.228 0

0.340 5

0.190 0

0.291 9

Cyclic AMP

0.607 6

0.397 5

0.420 7

0.429 5

0.454 8

0.508 5

0.386 6

0.499 2

0.325 2

0.522 9