中国药学杂志

No.	Origin(in Chinese)	Collection time	No.	Origin(in Chinese)	Collection time
S1	Shendu,Minxian,Gansu(甘肃省岷县申都乡)	2022.10	S9	Dacaotan,Zhangxian,Gansu(甘肃省漳县大草滩镇)	2023.10
S2	Zichuan,Minxian,Gansu(甘肃省岷县麻子川镇)	2022.10	S10	Sancha,Zhangxian,Gansu(甘肃省漳县三岔镇)	2023.10
S3	Qingshui,Minxian,Gansu(甘肃省岷县清水镇)	2022.10	S11	Nanfeng,Minle,Gansu(甘肃省民乐县南丰镇)	2022.09
S4	Shili,Minxian,Gansu(甘肃省岷县十里镇)	2022.10	S12	Fengle,Minle,Gansu(甘肃省民乐县丰乐镇)	2022.09
S5	Puma,Minxian,Gansu(甘肃省岷县蒲麻镇)	2022.10	S13	Xinzhuang,Datong,Qinghai(青海省大通县新庄镇)	2022.09
S6	Lyujing,Minxian,Gansu(甘肃省岷县闾井镇)	2022.10	S14	Gonghe,Huangzhong,Qinghai(青海省湟中区共和镇)	2022.09
S7	Huichuan,Weiyuan,Gansu(甘肃省渭源县会川镇)	2023.10	S15	Mapo,Yuzhong,Gansu(甘肃省榆中县马坡乡)	2022.09
S8	Tianjiahe,Weiyuan,Gansu(甘肃省渭源县田家河乡)	2023.10	S16	Heping,Yuzhong,Gansu(甘肃省榆中县和平镇)	2022.10

No.	Origin(in Chinese)	Collection time	No.	Origin(in Chinese)	Collection time
S1	Shendu,Minxian,Gansu(甘肃省岷县申都乡)	2022.10	S9	Dacaotan,Zhangxian,Gansu(甘肃省漳县大草滩镇)	2023.10
S2	Zichuan,Minxian,Gansu(甘肃省岷县麻子川镇)	2022.10	S10	Sancha,Zhangxian,Gansu(甘肃省漳县三岔镇)	2023.10
S3	Qingshui,Minxian,Gansu(甘肃省岷县清水镇)	2022.10	S11	Nanfeng,Minle,Gansu(甘肃省民乐县南丰镇)	2022.09
S4	Shili,Minxian,Gansu(甘肃省岷县十里镇)	2022.10	S12	Fengle,Minle,Gansu(甘肃省民乐县丰乐镇)	2022.09
S5	Puma,Minxian,Gansu(甘肃省岷县蒲麻镇)	2022.10	S13	Xinzhuang,Datong,Qinghai(青海省大通县新庄镇)	2022.09
S6	Lyujing,Minxian,Gansu(甘肃省岷县闾井镇)	2022.10	S14	Gonghe,Huangzhong,Qinghai(青海省湟中区共和镇)	2022.09
S7	Huichuan,Weiyuan,Gansu(甘肃省渭源县会川镇)	2023.10	S15	Mapo,Yuzhong,Gansu(甘肃省榆中县马坡乡)	2022.09
S8	Tianjiahe,Weiyuan,Gansu(甘肃省渭源县田家河乡)	2023.10	S16	Heping,Yuzhong,Gansu(甘肃省榆中县和平镇)	2022.10

No.	Similarity	No.	Similarity
S1	0.989	0.99	T1	0.99	0.991
S2	0.997	0.998	T2	0.996	0.997
S3	0.992	0.992	T3	0.995	0.995
S4	0.993	0.993	T4	0.99	0.990
S5	0.989	0.989	T5	0.991	0.992
S6	0.996	0.997	T6	0.998	0.998
S7	0.995	0.995	T7	0.992	0.992
S8	0.996	0.997	T8	0.997	0.997
S9	0.992	0.992	T9	0.994	0.995
S10	0.995	0.994	T10	0.996	0.997
S11	0.990	0.989	T11	0.995	0.995
S12	0.974	0.973	T12	0.997	0.997
S13	0.988	0.988	T13	0.992	0.992
S14	0.928	0.929	T14	0.996	0.996
S15	0.950	0.949	T15	0.993	0.992
S16	0.978	0.978	T16	0.999	0.999

No.	Similarity	No.	Similarity
S1	0.989	0.99	T1	0.99	0.991
S2	0.997	0.998	T2	0.996	0.997
S3	0.992	0.992	T3	0.995	0.995
S4	0.993	0.993	T4	0.99	0.990
S5	0.989	0.989	T5	0.991	0.992
S6	0.996	0.997	T6	0.998	0.998
S7	0.995	0.995	T7	0.992	0.992
S8	0.996	0.997	T8	0.997	0.997
S9	0.992	0.992	T9	0.994	0.995
S10	0.995	0.994	T10	0.996	0.997
S11	0.990	0.989	T11	0.995	0.995
S12	0.974	0.973	T12	0.997	0.997
S13	0.988	0.988	T13	0.992	0.992
S14	0.928	0.929	T14	0.996	0.996
S15	0.950	0.949	T15	0.993	0.992
S16	0.978	0.978	T16	0.999	0.999

Peak	Component	Paired-sample test	t value	df	P value	Effective dose
13	Ligustilide	RAS-SFAS	5.249	15	<0.001	1.35
8	Senkyunolide I	RAS-SFAS	6.907	15	<0.001	1.726
11	Coniferyl ferulate	RAS-SFAS	8.114	15	<0.001	2.028

Peak	Component	Paired-sample test	t value	df	P value	Effective dose
13	Ligustilide	RAS-SFAS	5.249	15	<0.001	1.35
8	Senkyunolide I	RAS-SFAS	6.907	15	<0.001	1.726
11	Coniferyl ferulate	RAS-SFAS	8.114	15	<0.001	2.028

Component	Regressione quation	r²	Linear range/μg·mL^-1
Tryptophan	Y=15.016X-4.610 9	0.999 7	2.80	-89.60
Chlorogenic acid	Y=4.956 1X-2.281 4	0.999 6	3.30	-105.50
Ferulic acid	Y=9.855X+0.695 5	0.999 8	2.48	-79.4
Senkyunolide I	Y=50.366X+5.471 6	0.999 8	1.35	-43.16
Senkyunolide H	Y=62.848X+2.554 7	0.999 8	0.52	-16.74
Coniferyl ferulate	Y=10.21X+6.472 8	0.999 8	3.10	-99.30
Ligustilide	Y=7.585X+22.72	0.999 8	14.78	-473.00
Butyliden phthalide	Y=1.256 1X+5.776 2	0.999 4	8.20	-262.33

Component	Regressione quation	r²	Linear range/μg·mL^-1
Tryptophan	Y=15.016X-4.610 9	0.999 7	2.80	-89.60
Chlorogenic acid	Y=4.956 1X-2.281 4	0.999 6	3.30	-105.50
Ferulic acid	Y=9.855X+0.695 5	0.999 8	2.48	-79.4
Senkyunolide I	Y=50.366X+5.471 6	0.999 8	1.35	-43.16
Senkyunolide H	Y=62.848X+2.554 7	0.999 8	0.52	-16.74
Coniferyl ferulate	Y=10.21X+6.472 8	0.999 8	3.10	-99.30
Ligustilide	Y=7.585X+22.72	0.999 8	14.78	-473.00
Butyliden phthalide	Y=1.256 1X+5.776 2	0.999 4	8.20	-262.33

Components	m(Sample)/g	m(Original)/μg	m(Added)/μg	m(Found)/μg	Recovery/%	Mean recovery/%	RSD/%
Tryptophan	0.501 5	244.49	122.15	364.71	98.42	98.98	1.82
	0.502 0	244.73	122.15	366.15	99.40
	0.500 1	243.80	122.15	365.21	99.39
	0.501 2	244.34	244.3	480.45	96.65
	0.500 9	244.19	244.3	481.26	97.04
	0.501 3	244.39	244.3	490.19	100.61
	0.501 8	244.63	366.45	618.56	102.04
	0.500 5	244.00	366.45	610.47	100.01
	0.500 2	243.85	366.45	600.26	97.26
Chlorogenic acid	0.501 5	115.28	57.6	173.88	101.74	99.28	2.31
	0.502 0	115.39	57.6	171.27	97.01
	0.500 1	114.96	57.6	170.59	96.58
	0.501 2	115.21	115.20	230.69	100.24
	0.500 9	115.14	115.2	232.86	102.19
	0.501 3	115.23	115.2	226.01	96.16
	0.501 8	115.35	172.8	288.10	99.97
	0.500 5	115.05	172.8	289.68	101.06
	0.500 2	114.98	172.8	285.3	98.56
Ferulic acid	0.501 5	209.87	104.85	314.85	100.12	99.25	2.04
	0.502 0	210.08	104.85	313.67	98.80
	0.500 1	209.29	104.85	312.19	98.14
	0.501 2	209.75	209.7	414.46	97.62
	0.500 9	209.62	209.7	415.70	98.27
	0.501 3	209.79	209.7	421.96	101.18
	0.501 8	210.00	314.55	525.15	100.19
	0.500 5	209.45	314.55	523.97	99.99
	0.500 2	209.33	314.55	520.55	98.94
Senkyunolide I	0.501 5	186.53	93.2	281.13	101.50	100.69	1.32
	0.502 0	186.71	93.2	279.67	99.74
	0.500 1	186.01	93.2	280.45	101.33
	0.501 2	186.42	186.4	372.89	100.04
	0.500 9	186.30	186.4	378.86	103.30
	0.501 3	186.45	186.4	375.16	101.24
	0.501 8	186.64	279.6	466.10	99.95
	0.500 5	186.16	279.6	462.23	98.74
	0.500 2	186.04	279.6	466.67	100.37
Senkyunolide H	0.501 5	30.63	15.3	45.80	99.17	98.59	1.55
	0.502 0	30.66	45.61	15.3	97.73
	0.500 1	30.54	45.35	15.3	96.79
	0.501 2	30.61	60.85	30.6	98.83
	0.500 9	30.59	60.74	30.6	98.53
	0.501 3	30.61	60.08	30.6	96.29
	0.501 8	30.64	75.87	45.9	98.53
	0.500 5	30.57	76.76	45.9	100.64
	0.500 2	30.55	76.80	45.9	100.77
Coniferyl ferulate	0.501 5	566.88	846.4	283.2	98.70	99.78	1.65
	0.502 0	567.45	850.2	283.2	99.84
	0.500 1	565.30	849.52	283.2	100.36
	0.501 2	566.54	1 132.6	566.4	99.94
	0.500 9	566.20	1 134.5	566.4	100.34
	0.501 3	566.65	1 124.9	566.4	98.56
	0.501 8	567.22	1 420.45	849.6	100.43
	0.500 5	565.75	1 389.42	849.6	96.95
	0.500 2	565.41	1 439.87	849.8	102.90
Ligustilide	0.501 5	3 849.03	5 835.19	1 920.3	103.43	101.06	1.32
	0.502 0	3 852.87	5 789.83	1 920.3	100.87
	0.500 1	3 838.29	5 794.59	1 920.3	101.87
	0.501 2	3 846.73	7 655.34	3 840.6	99.17
	0.500 9	3 844.43	7 689.59	3 840.6	100.12
	0.501 3	3 847.50	7 737.91	3 840.6	101.30
	0.501 8	3 851.34	9 581.32	5 760.9	99.46
	0.500 5	3 841.36	9 695.52	5 760.9	101.62
	0.500 2	3 839.06	9 699.85	5 760.9	101.73
Butyliden phthalide	0.501 5	719.03	1 088.67	359.2	102.91	100.52	1.93
	0.502 0	719.75	1 074.95	359.2	98.89
	0.500 1	717.02	1 075.69	359.2	99.85
	0.501 2	718.60	1 449.68	718.4	101.76
	0.500 9	718.17	1 460.93	718.4	103.39
	0.501 3	718.74	1 428.56	718.4	98.81
	0.501 8	719.46	1 796.88	1 077.6	99.98
	0.500 5	717.60	1 809.74	1 077.6	101.35
	0.500 2	717.17	1 770.75	1 077.6	97.77

Components	m(Sample)/g	m(Original)/μg	m(Added)/μg	m(Found)/μg	Recovery/%	Mean recovery/%	RSD/%
Tryptophan	0.501 5	244.49	122.15	364.71	98.42	98.98	1.82
	0.502 0	244.73	122.15	366.15	99.40
	0.500 1	243.80	122.15	365.21	99.39
	0.501 2	244.34	244.3	480.45	96.65
	0.500 9	244.19	244.3	481.26	97.04
	0.501 3	244.39	244.3	490.19	100.61
	0.501 8	244.63	366.45	618.56	102.04
	0.500 5	244.00	366.45	610.47	100.01
	0.500 2	243.85	366.45	600.26	97.26
Chlorogenic acid	0.501 5	115.28	57.6	173.88	101.74	99.28	2.31
	0.502 0	115.39	57.6	171.27	97.01
	0.500 1	114.96	57.6	170.59	96.58
	0.501 2	115.21	115.20	230.69	100.24
	0.500 9	115.14	115.2	232.86	102.19
	0.501 3	115.23	115.2	226.01	96.16
	0.501 8	115.35	172.8	288.10	99.97
	0.500 5	115.05	172.8	289.68	101.06
	0.500 2	114.98	172.8	285.3	98.56
Ferulic acid	0.501 5	209.87	104.85	314.85	100.12	99.25	2.04
	0.502 0	210.08	104.85	313.67	98.80
	0.500 1	209.29	104.85	312.19	98.14
	0.501 2	209.75	209.7	414.46	97.62
	0.500 9	209.62	209.7	415.70	98.27
	0.501 3	209.79	209.7	421.96	101.18
	0.501 8	210.00	314.55	525.15	100.19
	0.500 5	209.45	314.55	523.97	99.99
	0.500 2	209.33	314.55	520.55	98.94
Senkyunolide I	0.501 5	186.53	93.2	281.13	101.50	100.69	1.32
	0.502 0	186.71	93.2	279.67	99.74
	0.500 1	186.01	93.2	280.45	101.33
	0.501 2	186.42	186.4	372.89	100.04
	0.500 9	186.30	186.4	378.86	103.30
	0.501 3	186.45	186.4	375.16	101.24
	0.501 8	186.64	279.6	466.10	99.95
	0.500 5	186.16	279.6	462.23	98.74
	0.500 2	186.04	279.6	466.67	100.37
Senkyunolide H	0.501 5	30.63	15.3	45.80	99.17	98.59	1.55
	0.502 0	30.66	45.61	15.3	97.73
	0.500 1	30.54	45.35	15.3	96.79
	0.501 2	30.61	60.85	30.6	98.83
	0.500 9	30.59	60.74	30.6	98.53
	0.501 3	30.61	60.08	30.6	96.29
	0.501 8	30.64	75.87	45.9	98.53
	0.500 5	30.57	76.76	45.9	100.64
	0.500 2	30.55	76.80	45.9	100.77
Coniferyl ferulate	0.501 5	566.88	846.4	283.2	98.70	99.78	1.65
	0.502 0	567.45	850.2	283.2	99.84
	0.500 1	565.30	849.52	283.2	100.36
	0.501 2	566.54	1 132.6	566.4	99.94
	0.500 9	566.20	1 134.5	566.4	100.34
	0.501 3	566.65	1 124.9	566.4	98.56
	0.501 8	567.22	1 420.45	849.6	100.43
	0.500 5	565.75	1 389.42	849.6	96.95
	0.500 2	565.41	1 439.87	849.8	102.90
Ligustilide	0.501 5	3 849.03	5 835.19	1 920.3	103.43	101.06	1.32
	0.502 0	3 852.87	5 789.83	1 920.3	100.87
	0.500 1	3 838.29	5 794.59	1 920.3	101.87
	0.501 2	3 846.73	7 655.34	3 840.6	99.17
	0.500 9	3 844.43	7 689.59	3 840.6	100.12
	0.501 3	3 847.50	7 737.91	3 840.6	101.30
	0.501 8	3 851.34	9 581.32	5 760.9	99.46
	0.500 5	3 841.36	9 695.52	5 760.9	101.62
	0.500 2	3 839.06	9 699.85	5 760.9	101.73
Butyliden phthalide	0.501 5	719.03	1 088.67	359.2	102.91	100.52	1.93
	0.502 0	719.75	1 074.95	359.2	98.89
	0.500 1	717.02	1 075.69	359.2	99.85
	0.501 2	718.60	1 449.68	718.4	101.76
	0.500 9	718.17	1 460.93	718.4	103.39
	0.501 3	718.74	1 428.56	718.4	98.81
	0.501 8	719.46	1 796.88	1 077.6	99.98
	0.500 5	717.60	1 809.74	1 077.6	101.35
	0.500 2	717.17	1 770.75	1 077.6	97.77

No.	Tryptophan	Chlorogenic acid	Ferulic acid	Senkyunolide I	Senkyunolide H	Coniferyl ferulate	Ligustilide	Butyliden phthalide
S1	0.520 5	0.243 6	0.351 1	0.212 0	0.039 2	0.785 2	7.237 3	0.497 5
S2	0.579 4	0.198 4	0.430 3	0.218 3	0.038 7	0.970 1	7.718 3	0.962 5
S3	0.674 0	0.162 9	0.332 4	0.239 6	0.040 5	1.135 1	6.775 4	1.038 9
S4	0.487 5	0.229 9	0.418 5	0.371 9	0.061 1	1.130 4	7.675 0	1.433 8
S5	0.489 4	0.208 1	0.355 6	0.399 7	0.066 5	1.265 9	7.454 1	1.433 8
S6	0.631 6	0.599 5	0.336 9	0.268 5	0.048 0	1.082 2	7.142 4	0.994 3
S7	0.249 9	0.250 9	0.365 7	0.251 1	0.047 3	1.390 5	9.335 7	0.914 7
S8	0.531 5	0.204 0	0.326 4	0.217 5	0.041 3	0.933 7	7.029 0	0.914 7
S9	0.546 1	0.210 5	0.329 2	0.193 9	0.037 8	0.658 7	6.072 4	0.987 9
S10	0.455 5	0.295 2	0.443 2	0.335 3	0.060 9	1.235 0	10.852 4	0.793 7
S11	0.489 4	0.208 1	0.355 6	0.399 7	0.066 5	1.265 9	7.454 1	1.433 8
S12	0.337 5	0.253 3	0.458 7	0.235 4	0.024 3	1.558 6	10.447 4	0.497 5
S13	0.302 1	0.305 7	0.368 6	0.429 8	0.075 1	1.335 3	10.655 7	1.159 9
S14	0.502 7	0.516 4	0.443 2	0.460 6	0.073 7	0.899 6	7.694 6	1.682 2
S15	0.309 3	0.255 7	0.407 9	0.295 7	0.053 1	1.468 1	7.693 5	1.573 9
S16	0.388 7	0.157 2	0.420 5	0.409 5	0.069 2	0.620 3	6.165 2	1.720 4
T1	0.644 9	0.277 5	0.434 7	0.109 7	0.019 9	0.440 9	5.266 6	0.242 8
T2	0.543 2	0.168 5	0.488 7	0.143 4	0.025 6	0.390 3	5.795 0	0.605 8
T3	0.698 5	0.183 9	0.409 2	0.231 4	0.037 3	0.769 2	5.895 7	0.863 7
T4	0.723 0	0.234 7	0.360 0	0.189 7	0.031 9	0.511 0	4.653 8	0.809 6
T5	0.658 8	0.143 5	0.351 1	0.184 1	0.030 4	0.499 2	4.662 3	0.688 6
T6	0.732 6	0.688 3	0.496 4	0.222 5	0.039 0	0.789 9	6.762 7	0.927 4
T7	0.276 3	0.249 2	0.422 1	0.152 4	0.029 2	0.561 5	6.777 5	0.249 1
T8	0.523 7	0.199 2	0.422 1	0.139 4	0.025 0	0.547 8	6.013 9	0.293 7
T9	0.410 0	0.254 9	0.415 6	0.130 8	0.024 0	0.397 4	5.303 0	0.621 7
T10	0.586 6	0.158 0	0.442 0	0.170 9	0.031 8	0.323 7	4.992 4	0.777 8
T11	0.506 2	0.239 6	0.330 4	0.221 1	0.033 8	0.437 7	6.886 1	0.902 0
T12	0.585 5	0.192 7	0.397 4	0.091 3	0.040 6	0.565 0	5.532 4	0.914 7
T13	0.457 7	0.211 3	0.382 4	0.246 6	0.043 1	0.457 7	4.748 7	0.863 7
T14	0.440 6	0.531 7	0.405 1	0.317 1	0.054 6	0.460 0	4.506 7	0.959 3
T15	0.244 3	0.390 5	0.420 1	0.285 9	0.049 0	0.782 9	3.969 8	0.921 1
T16	0.471 3	0.258 1	0.425 8	0.185 9	0.030 6	0.606 6	6.038 7	0.835 1

No.	Tryptophan	Chlorogenic acid	Ferulic acid	Senkyunolide I	Senkyunolide H	Coniferyl ferulate	Ligustilide	Butyliden phthalide
S1	0.520 5	0.243 6	0.351 1	0.212 0	0.039 2	0.785 2	7.237 3	0.497 5
S2	0.579 4	0.198 4	0.430 3	0.218 3	0.038 7	0.970 1	7.718 3	0.962 5
S3	0.674 0	0.162 9	0.332 4	0.239 6	0.040 5	1.135 1	6.775 4	1.038 9
S4	0.487 5	0.229 9	0.418 5	0.371 9	0.061 1	1.130 4	7.675 0	1.433 8
S5	0.489 4	0.208 1	0.355 6	0.399 7	0.066 5	1.265 9	7.454 1	1.433 8
S6	0.631 6	0.599 5	0.336 9	0.268 5	0.048 0	1.082 2	7.142 4	0.994 3
S7	0.249 9	0.250 9	0.365 7	0.251 1	0.047 3	1.390 5	9.335 7	0.914 7
S8	0.531 5	0.204 0	0.326 4	0.217 5	0.041 3	0.933 7	7.029 0	0.914 7
S9	0.546 1	0.210 5	0.329 2	0.193 9	0.037 8	0.658 7	6.072 4	0.987 9
S10	0.455 5	0.295 2	0.443 2	0.335 3	0.060 9	1.235 0	10.852 4	0.793 7
S11	0.489 4	0.208 1	0.355 6	0.399 7	0.066 5	1.265 9	7.454 1	1.433 8
S12	0.337 5	0.253 3	0.458 7	0.235 4	0.024 3	1.558 6	10.447 4	0.497 5
S13	0.302 1	0.305 7	0.368 6	0.429 8	0.075 1	1.335 3	10.655 7	1.159 9
S14	0.502 7	0.516 4	0.443 2	0.460 6	0.073 7	0.899 6	7.694 6	1.682 2
S15	0.309 3	0.255 7	0.407 9	0.295 7	0.053 1	1.468 1	7.693 5	1.573 9
S16	0.388 7	0.157 2	0.420 5	0.409 5	0.069 2	0.620 3	6.165 2	1.720 4
T1	0.644 9	0.277 5	0.434 7	0.109 7	0.019 9	0.440 9	5.266 6	0.242 8
T2	0.543 2	0.168 5	0.488 7	0.143 4	0.025 6	0.390 3	5.795 0	0.605 8
T3	0.698 5	0.183 9	0.409 2	0.231 4	0.037 3	0.769 2	5.895 7	0.863 7
T4	0.723 0	0.234 7	0.360 0	0.189 7	0.031 9	0.511 0	4.653 8	0.809 6
T5	0.658 8	0.143 5	0.351 1	0.184 1	0.030 4	0.499 2	4.662 3	0.688 6
T6	0.732 6	0.688 3	0.496 4	0.222 5	0.039 0	0.789 9	6.762 7	0.927 4
T7	0.276 3	0.249 2	0.422 1	0.152 4	0.029 2	0.561 5	6.777 5	0.249 1
T8	0.523 7	0.199 2	0.422 1	0.139 4	0.025 0	0.547 8	6.013 9	0.293 7
T9	0.410 0	0.254 9	0.415 6	0.130 8	0.024 0	0.397 4	5.303 0	0.621 7
T10	0.586 6	0.158 0	0.442 0	0.170 9	0.031 8	0.323 7	4.992 4	0.777 8
T11	0.506 2	0.239 6	0.330 4	0.221 1	0.033 8	0.437 7	6.886 1	0.902 0
T12	0.585 5	0.192 7	0.397 4	0.091 3	0.040 6	0.565 0	5.532 4	0.914 7
T13	0.457 7	0.211 3	0.382 4	0.246 6	0.043 1	0.457 7	4.748 7	0.863 7
T14	0.440 6	0.531 7	0.405 1	0.317 1	0.054 6	0.460 0	4.506 7	0.959 3
T15	0.244 3	0.390 5	0.420 1	0.285 9	0.049 0	0.782 9	3.969 8	0.921 1
T16	0.471 3	0.258 1	0.425 8	0.185 9	0.030 6	0.606 6	6.038 7	0.835 1

HPLC指纹图谱结合化学计量学研究当归土炒前后主要成分变化

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孟子盈 ¹^,² , 杨倩倩 ¹^,² , 石玉存 ¹^,² , 杜丽东 ¹^,²^,³ , 王瑞琼 ¹^,²^,⁴^,⁵ , 吴国泰 ²^,³^,⁴^,⁵^,^*

中国药学杂志 | 论著 2025,60(5): 522-531

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中国药学杂志 | 论著 2025, 60(5): 522-531

HPLC指纹图谱结合化学计量学研究当归土炒前后主要成分变化

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孟子盈¹^,², 杨倩倩¹^,², 石玉存¹^,², 杜丽东¹^,²^,³, 王瑞琼¹^,²^,⁴^,⁵, 吴国泰²^,³^,⁴^,⁵^,^*

作者信息

¹ 甘肃中医药大学药学院, 兰州 730000

² 陇药产业创新研究院, 兰州 730000

³ 甘肃省中药药理与毒理学重点实验室, 兰州 730000

⁴ 西北中藏药省部共建协同创新中心, 兰州 730000

⁵ 国家中药炮制技术传承基地, 兰州 730000

孟子盈,女,硕士研究生研究方向:中药药理与毒理研究

通讯作者:

^* 吴国泰,男,博士,副教授,硕士生导师研究方向:中药炮制药理与中药大健康产品研发研究 Tel:(0931)5109816

Changes of Main Components in Angelica sinensis After Stir Frying by HPLC Fingerprint Combined with Chemometrics

Ziying MENG¹^,², Qianqian YANG¹^,², Yucun SHI¹^,², Lidong DU¹^,²^,³, Ruiqiong WANG¹^,²^,⁴^,⁵, Guotai WU²^,³^,⁴^,⁵^,^*

Affiliations

¹ School of Pharmacy, Gansu University of Traditional Chinese Medicine (TCM), Lanzhou 730000, China

² Longyao Industry Innovation Research Institute, Lanzhou 730000, China

³ Gansu Provincial Key Laboratory of Pharmacology and Toxicology of TCM, Lanzhou 730000, China

⁴ Collaborative Innovation Center for Northwest Chinese and Tibetan Medicine, Lanzhou 730000, China

⁵ National Traditional Chinese Medicine Processing Technology Inheritance Base, Lanzhou 730000, China

出版时间: 2025-03-08 doi: 10.11669/cpj.2025.05.010

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摘要

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目的用高效液相色谱(high performance liquid chromatography,HPLC)指纹图谱结合化学计量学(chemometrics)研究当归土炒前后主要成分变化。方法建立当归土炒前后HPLC指纹图谱并用相似度评价、主成分分析(principal component analysis,PCA)、正交偏最小二乘判别分析(orthogonal partial least squares discriminant analysis,OPLS-DA)等方法对当归土炒前后HPLC指纹图谱分析评价,以变量重要性投影(variable importance in the projection,VIP)值>1为标准筛选当归土炒前后的差异性成分,并对差异性成分进行配对t检验。结果生当归和土炒当归指纹图谱均标定了20个共有峰,经混合对照品比对,指认其中8个色谱峰,分别为色氨酸、绿原酸、阿魏酸、洋川芎内酯 I、洋川芎内酯 H、阿魏酸松柏酯、藁本内酯、丁烯基苯酞,PCA显示生当归、土炒当归样品在主成分空间的分布上有特定区域,OPLS-DA以VIP值>1为标准共筛选出藁本内酯、洋川芎内酯I、阿魏酸松柏酯3个差异性成分,经配对t检验当归土炒后藁本内酯、洋川芎内酯I、阿魏酸松柏酯峰面积显著降低(P<0.001),化学计量学分析可有效区分生当归和土炒当归。结论生当归经土炒后化学成分发生了一定程度的改变,建立的HPLC指纹图谱相似度较高,无法显著区分生当归及土炒当归,结合化学计量学方法PCA、OPLS-DA及差异性成分配对t检验后能够明显区分生当归及土炒当归,为研究土炒当归的炮制原理提供了参考,并为后续炮制前后药理作用的研究提供数据支持。

关键词

当归 / 土炒当归 / 成分变化 / 高效液相色谱指纹图谱 / 含量测定

Abstract

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OBJECTIVE To study the changes of main components of Angelica sinensis(A.sinensis) after stir-frying high performance liquid chromatography(HPLC) fingerprint combined with chemometrics. METHODS The HPLC fingerprints of A. sinensis before and after stir-frying were established. The fingerprints were analyzed and evaluated by similarity evaluation,principal component analysis(PCA)and orthogonal partial least squares discriminant analysis(OPLS-DA).The variable importance in the projection(VIP)value> 1 was used as the standard to screen the different components before and after stir-frying of A. sinensis,and paired t-test was performed on the different components. RESULTS There were 20 common peaks in the fingerprints of raw A. sinensis(RAS)and stir-fried A. sinensis(SFAS). After comparison with mixed reference substances, eight chromatographic peaks were identified as tryptophan, chlorogenic acid, ferulic acid, senkyunolide I, senkyunolide H, coniferyl ferulate, ligustilide, and butyliden phthalide.PCA(SFAS)showed that there were specific regions in the spatial distribution of principal components in the samples of RAS and SFAS. OPLS-DA screened out three differential components of ligustilide,senkyunolide I and coniferyl ferulate with VIP value> 1 as the standard.The peak areas of ligustilide,senkyunolide I and coniferyl ferulate were significantly reduced by paired t test (P<0.001). Chemometric analysis could effectively distinguish RAS and SFAS. CONCLUSION The chemical composition of RAS changes to a certain extent after stir-frying with soil.The established HPLC fingerprint had high similarity and could not significantly distinguish between RAS and SFAS. When combining HPLC fingerprint with stoichiometric analysis PCA,OPLS-DA and differential component distribution t test, RAS and SFAS can be obviously distinguished,which provides a reference for studying the processing principle of SFAS as well as data support for subsequent studies on pharmacological effects before and after processing.

Key words

Angelica sinensis / stir-fried A. sinensis / composition changes / HPLC fingerprint / content determination

引用本文

孟子盈, 杨倩倩, 石玉存, 杜丽东, 王瑞琼, 吴国泰. HPLC指纹图谱结合化学计量学研究当归土炒前后主要成分变化. 中国药学杂志, 2025 , 60 (5) : 522 -531 . DOI: 10.11669/cpj.2025.05.010

Ziying MENG, Qianqian YANG, Yucun SHI, Lidong DU, Ruiqiong WANG, Guotai WU. Changes of Main Components in Angelica sinensis After Stir Frying by HPLC Fingerprint Combined with Chemometrics[J]. Chinese Pharmaceutical Journal, 2025 , 60 (5) : 522 -531 . DOI: 10.11669/cpj.2025.05.010

正文

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当归为中医临床常用中药,具有补血活血、调经止痛、润肠通便的功效,用于血虚萎黄,眩晕心悸,月经不调,肠燥便秘等^[1]。当归土炒后入脾补血的作用增强,刺激性降低,补血而不致滑肠,善治血虚便溏、中焦虚寒、腹痛等。清代《医宗金鉴》始载当归土炒炮制的方法,提出“土炒至老黄色”,将土炒当归配伍用于治疗寒痢、飧泄^[2]。土炒当归在传统中医中沿用至今,但《中国药典》2020年版仅收载当归和酒当归2个品种,以挥发油(不得少于0.4%)和阿魏酸(不得少于0.050%)含量作为评定指标^[1];现行各地中药饮片炮制规范对土炒当归的收载较少,仅在甘肃、河南、湖南等地的中药炮制规范中持续更新,且大多只有当归土炒饮片的外观性状描述,无定量化评价指标。研究发现当归的化学成分包括挥发油、多糖、有机酸、氨基酸、黄酮类以及微量元素等,其中挥发油、多糖及有机酸为当归药材及饮片的主要质控指标^[3-5]。目前对当归的HPLC指纹图谱研究多集中于当归药材^[6]、饮片^[7]及其经典名方^[8-9],对于当归炮制品如土炒当归的指纹图谱及炮制前后成分变化研究明显不足,未能系统分析当归土炒前后的成分变化规律。本研究建立生当归和土炒当归的HPLC指纹图谱,并进行相似度评价、主成分分析(PCA)、正交偏最小二乘判别分析(OPLS-DA)、差异性成分配对t检验等化学计量学分析,以期发现生当归和土炒当归的主要成分差异,为当归土炒炮制原理解析提供参考,并为后续炮制前后药理作用的研究提供数据支持。

1 仪器与材料

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1.1 仪器

Agilent infinity 1290 Ⅱ型高效液相色谱仪、Agilent Eclipse XDB-C₁₈ (4.6 mm×150 mm,5 μm)色谱柱(美国安捷伦公司);扫频超声波清洗机(宁波新芝生物科技股份有限公司);赛多利斯BCE224i-1CCN型电子天平、赛多利斯Secura125-1CN电子天平[赛多利斯(北京)科学仪器有限公司];Smart-N超纯水机(上海康雷分析仪器有限公司)。

1.2 对照品与试剂

对照品色氨酸(批号140686-202205,含量以100%计)、绿原酸(批号110753-202119,含量以96.3%计)、阿魏酸(批号110773-202316,含量以99.3%计)、藁本内酯(批号111731-202311)、洋川芎内酯I(批号112071-202101,含量以99.2%计)(中国食品药品检定研究院);对照品阿魏酸松柏酯(批号J14HB188619,)、洋川芎内酯H(批号S25 GB162334)、丁烯基苯酞(批号Y21J10W88899)(上海源叶生物科技有限公司,纯度均≥98%)。

甲醇(分析纯、色谱纯);乙腈、磷酸为色谱纯;水为超纯水。

1.3 药材与饮片

16批当归药材来自不同产地,来源信息见表1,经甘肃中医药大学强正泽副教授鉴定为伞形科植物当归[Angelica sinensis(Oliv.) Diels]的干燥根,16批当归药材按《中国药典》2020年版当归项下切制成饮片,分别留取一半约200 g用作生当归饮片(编号S1~S16),另一半约200 g按《甘肃省中药炮制规范》(2022年版)制备土炒当归^[10],将20 g灶心土置锅中用文火加热,待土炒至灵活状态加入生当归饮片100 g,炒至表面挂土色,筛去土粉,取出晾凉,即得(编号T1~T16),所有样品均于4 ℃冰箱中密封冷藏。

2 方法与结果

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2.1 供试品溶液的制备

参考文献[11]方法,取生当归、土炒当归粉末(过3号筛)约0.5 g,精密称定,置于50 mL具塞锥形瓶中,加入20 mL 体积分数70%甲醇,称定质量,超声(功率99 W,频率59 kHz)处理40 min,放凉至室温,再次称定质量,用体积分数70%甲醇进行补足,摇匀滤过,取续滤液,即得生当归、土炒当归供试品溶液。

2.2 混合对照品溶液的制备

参考文献方[11]法,取色氨酸、阿魏酸、绿原酸、阿魏酸松柏酯、洋川芎内酯I、洋川芎内酯H、藁本内酯、丁烯基苯酞适量,精密称定,加入甲醇制成质量浓度分别为15.83、15.13、6.54、6.82、2.07、3.38、59.13、13.79 μg·mL^-1的混合对照品溶液,保存于冰箱备用。

2.3 色谱条件

参考文献[12]方法并作优化,Agilent Ecipse XDB-C₁₈(4.6 mm×150 mm,5 μm)色谱柱; 0.085%磷酸溶液(A)-乙腈(B)为流动相;梯度洗脱:0~20 min,10%~26%B;20~25 min,26%~46%B;25~45 min,46%B;45~52 min,46%~76%B;52~60 min,76%~85%B;60~65 min,85%~90%B;检测波长280 nm;流速为1.0 mL·min^-1;柱温30 ℃;进样量10 μL。

2.4 指纹图谱方法学考查

2.4.1 精密度

取生当归(S4)和土炒当归(T4)供试品溶液,按“2.3”项下色谱条件,连续进样6次,洋川芎内酯I色谱峰为参照,计算获得7个共有峰的相对保留时间相对标准偏差(RSD)均小于0.25%,相对峰面积的RSD均小于2.15%,表明仪器精密度良好,符合HPLC指纹图谱测定要求。

2.4.2 重复性

取生当归(S4)和土炒当归(T4)粉末约0.5 g,精密称定,平行6份,按“2.1”项下方法制备供试品溶液,按“2.3”项下色谱条件进样测定,以洋川芎内酯I色谱峰为参照,计算获得7个共有峰的相对保留时间RSD均小于0.23%,相对峰面积的RSD均小于1.60%,表明本方法重复性良好,符合HPLC指纹图谱测定要求。

2.4.3 稳定性

取生当归(S4)和土炒当归(T4)供试品溶液,按“2.3”项下色谱条件,分别于0、2、4、8、16、24 h进样,以洋川芎内酯I色谱峰为参照,计算获得7个共有峰的相对保留时间RSD均小于0.38%,相对峰面积的RSD均小于2.57%,表明供试品溶液在24 h内基本稳定,符合HPLC指纹图谱测定要求。

2.5 指纹图谱的建立及化学模式识别

2.5.1 生当归及土炒当归HPLC指纹图谱建立

参考文献[13],取“2.2”项下混合对照品溶液按“2.3”项下色谱条件进样测定,得到混合对照品HPLC色谱图(图1)。取16批生当归(S1~S16)和16批土炒当归(T1~T16)饮片,按“2.1”项下方法制备供试品溶液,按“2.3”项下色谱条件进样测定,得到HPLC色谱图。将16批生当归和16批土炒当归HPLC色谱图数据分别导入《中药色谱指纹图谱相似度评价系统》(2012年版)进行图谱分析,分别以S4和T4为参照图谱,设置时间窗宽度为0.1 min,采用中位数法和多点校正,对色谱图进行色谱峰匹配,生成16批生当归HPLC指纹图谱叠加图、16批土炒当归HPLC指纹图谱叠加图以及生当归、土炒当归、混合对照品HPLC色谱图(图2~4),生当归和土炒当归HPLC指纹图谱均标定20个共有峰,经混合对照品比对,指认其中8个色谱峰,依次为色氨酸(峰3)、绿原酸(峰4)、阿魏酸(峰6)、洋川芎内酯 I(峰8)、洋川芎内酯 H(峰9)、阿魏酸松柏酯(峰11)、藁本内酯(峰13)、丁烯基苯酞(峰14)。

2.5.2 相似度评价

将生当归、土炒当归UPLC指纹图谱分别导入《中药色谱指纹图谱相似度评价系统(2012版)》进行特征峰匹配,生成对照指纹图谱(RAS-R、SFAS-R),分别计算16批生当归和16批土炒当归样品(S1~S16、T1~T16)与对照指纹图谱(RAS-R、SFAS-R)的相似度,评价结果见表2。16批生当归样品与其对照图谱的相似度在0.928~0.997, 与土炒当归对照图谱相似度在0.929~0.998,16批土炒当归样品与其对照图谱相似度在0.990~0.999,与生当归对照图谱相似度在0.990~0.999,相似度评价结果表明炮制品之间样品差异不大,所建立的指纹图谱可用于当归饮片的整体控制,但无法有效区分生当归和土炒当归。

2.5.3 生当归和土炒当归HPLC指纹图谱PCA

将生当归、土炒当归指纹图谱共有峰峰面积数据导入SIMCA 14.1软件,建立无监督的识别模式,以95%置信区间观察样品分布趋势,PCA三维投影见图5。PCA结果显示生当归、土炒当归样品在主成分空间的分布上有特定区域,存在聚集,表明生当归和土炒当归化学成分可能存在差异。

2.5.4 生当归和土炒当归HPLC指纹图谱OPLS-DA

为了进一步筛选对2种饮片分类贡献较大的成分,根据PCA结果,采用SIMCA 14.1软件进行有监督模式识别分析,建立OPLS-DA分析模型,模型在X、Y轴方向上对变量解释能力参数R²X(cum)=0.826,R²Y(cum)=0.877,模型分组预测能力参Q²(cum)=0.662,R²>0.5,Q²>0.5,可用于区分生当归和土炒当归。OPLS-DA得分图见图6,图6中生当归和土炒当归区分明显。经200次排列检验,R²和Q²的截距分别为0.327,-0.663,所有R²和Q²的左边的值均低于最右边,排列检验确保了模型没有过度拟合,因此,所建立的模型可靠(图7)。以VIP值>1为标准共筛选出3个差异成分,影响显著性排序为13号峰(藁本内酯)>8号峰(洋川芎内酯I)>11号峰(阿魏酸松柏酯),这3个成分是造成生当归和土炒当归含量差异的主要成分(图8)。

2.5.5 差异性成分配对t检验

以峰面积为变量,对16批生当归和16批土炒当归的3个差异性成分色谱峰的峰面积进行配对t检验,利用Graphpad Prism 10软件绘制t检验图,结果见图9。表3结果显示各配对变量的P值均<0.001,即3个配对成分炮制前后各峰峰面积具有显著性差异,炮制后峰面积显著低于炮制前,3个差异特征峰峰面积土炒后均显著降低。

2.6 不同批次当归和土炒当归中8个成分含量测定

2.6.1 线性关系

参考文献[14]方法,取色氨酸、阿魏酸、绿原酸、阿魏酸松柏酯、洋川芎内酯I、洋川芎内酯H、藁本内酯、丁烯基苯酞适量,精密称定,加入甲醇制成质量浓度分别为89.60、105.50、79.4、43.16、16.74、99.30、473.00、262.33 μg·mL^-1的混合对照品溶液。精密移取混合对照品溶液,用甲醇以倍比稀释的方法制成不同浓度的对照品溶液,按“2.3”项下色谱条件进样测定,记录各色谱峰峰面积值,以进样浓度对峰面积进行线性回归,得到色氨酸、绿原酸、阿魏酸、洋川芎内酯Ⅰ、洋川芎内酯 H、阿魏酸松柏酯、藁本内酯、丁烯基苯酞回归方程及线性范围,见表4。

2.6.2 精密度试验

按“2.4.1”方法测定,混合对照品溶液峰面积RSD分别为藁本内酯0.85%、色氨酸 0.57%、绿原酸0.94%、洋川芎内酯H 0.85%、阿魏酸0.83%、洋川芎内酯Ⅰ 0.66%、丁烯基苯酞1.63%、阿魏酸松柏酯1.37%,表明仪器精密度良好。

2.6.3 重复性试验

按“2.4.2”方法,取编号为S4的当归样品测定,样品藁本内酯、洋川芎内酯H、色氨酸、丁烯基苯酞、洋川芎内酯Ⅰ、绿原酸、阿魏酸、阿魏酸松柏酯含量平均值分别为7.614 4、0.060 7、0.493 7、1.423 1、0.370 1、0.228 1、0.416 9、1.069 7 mg·g^-1,峰面积RSD分别为0.79%、1.19%、0.89%、1.18%、0.49%、0.75%、0.72%、1.17%,表明本方法重复性良好。

2.6.4 稳定性试验

按“2.4.3”方法,取编号为S4的当归样品测定,分别于0、2、4、8、16、24 h进样,结果显示样品峰面积RSD分别为藁本内酯0.93%、阿魏酸1.14%、阿魏酸松柏酯2.02%、丁烯基苯酞1.95%、洋川芎内酯H 1.07%、洋川芎内酯 Ⅰ 0.63%、绿原酸 0.82%、色氨酸0.55%,表明供试品溶液在24 h内稳定。

2.6.5 加样回收率

精密称定已知含量的S4当归样品粉末0.5 g,共9份,每份供试品中加入各成分含量50%、100%、150%的对照品,按“2.4.1”方法测定,计算得到上述8个成分的平均加样回收率分别为98.98%、99.28%、99.25%、100.69%、98.59%、99.78%、101.06%、100.52%,RSD值分别为1.82%、2.31%、2.04%、1.32%、1.55%、1.65%、1.32%、1.93%,见表5。

2.6.6 含量测定

取16批生当归及16批土炒当归样品,按“2.4.1”方法测定,外标法计算样品中藁本内酯、丁烯基苯酞、阿魏酸松柏酯、洋川芎内酯I、洋川芎内酯H、色氨酸、阿魏酸、绿原酸8个成分的含量16批生当归样品藁本内酯、丁烯基苯酞、阿魏酸松柏酯、洋川芎内酯I、洋川芎内酯H、色氨酸、阿魏酸、绿原酸含量测定平均值为7.962 6、1.127 5、1.108 4、0.308 6、0.052 7、0.468 4、0.384 0、0.268 7 mg·g^-1,16批土炒当归样品含量测定平均值为5.487 8、0.717 3、0.533 8、0.188 9、0.034 1、0.531 4、0.412 7、0.273 9 mg·g^-1,其中藁本内酯、阿魏酸松柏酯、洋川芎内酯I含量变化较大,与PCA、OPLS-DA、差异性配对t检验结果一致,含量测定结果见表6。

3 讨论

收起

实验前期以生当归药材提取效率、色谱峰峰形、分离效果等为指标,考察了体积分数60%、70%、80%甲醇、无水甲醇和30、40、50 min超声时间对生当归提取效率的影响,发现体积分数70%甲醇超声40 min提取效率最高;通过观察250、260、270、280、290、300 nm不同检测波长下各色谱峰响应值情况,发现在280 nm下色谱峰数目较多且分离度及峰形对称度较好;对乙腈-水、乙腈-1%冰乙酸水、乙腈-0.5%冰乙酸水、乙腈-0.1%磷酸水、乙腈-0.085%磷酸水不同流动相和柱温(30、35、40 ℃)、进样量(5、10、15、20 μL)进行了系统考察,最终确定乙腈-0.085%磷酸水为流动相,进样量10 μL,柱温30 ℃作为HPLC条件。洗脱过程中藁本内酯和丁烯基苯酞的分离程度较差,可能与色谱柱分离性能相关,20~52 min梯度洗脱比例经过多次调整,最终确定比例为20~25 min,26%~46%B;25~45 min,46%B;45~52 min,46%~76%B,在此条件下,藁本内酯和丁烯基苯酞分离度符合要求,峰形较好。

通过PCA可观察到生当归、土炒当归样品在主成分空间的分布,可将生当归与土炒当归大致区分,但当变量相关性较小时,PCA分析存在局限性,可进一步采用OPLS-DA分析法,OPLS-DA得分图显示了生当归及土炒当归区分明显,按VIP>1发现3个差异性成分分别为13号峰(藁本内酯)>8号峰(洋川芎内酯I)>11号峰(阿魏酸松柏酯)。藁本内酯是当归药材最主要的挥发油成分,其与阿魏酸和阿魏酸松柏酯在当归药材的质量控制和药效成分开发方面具有重要地位。藁本内酯结构上存在活泼的丁烯基,室温放置易发生水解、脱氢、氧化等反应,光照和氧气等外部条件均会加速其异构化进程,稳定性较差^[15]。研究发现,当归中的阿魏酸以游离和结合型共同存在,即阿魏酸和阿魏酸松柏酯,但以阿魏酸松柏酯为主^[16]。结合型的阿魏酸松柏酯性质不稳定,在甲醇、强酸、弱碱、受热或受光等情况下易分解成阿魏酸和松柏醇^[17]。苯酞类多为油状,且容易通过氧化、水解、光解和异构化等反应发生结构改变,洋川芎内酯I属于当归中的主要苯酞类成分。研究发现在有氧的条件下,光照及随之升高的温度对洋川芎内酯I稳定性影响较大,无氧条件下则相反,说明氧是影响其稳定性的主要因素,光照和温度能加速有氧条件下洋川芎内酯I降解^[18]。当归经土炒后,藁本内酯、洋川芎内酯I及阿魏酸松柏酯含量显著降低,可能与炮制过程受热,藁本内酯分解或异构化为其他苯酞类化合物,阿魏酸松柏酯分解、洋川芎内酯I降解或炮制过程当归的组织结构被破坏,挥发油逸散导致含量降低有关。配对t检验可用于同一组个体处理前后的差异比较,对OPLS-DA分析的三个差异性成分进一步检验分析,结果表明生当归经土炒后,藁本内酯、洋川芎内酯I、阿魏酸松柏酯峰面积显著降低,含量下降较多。阿魏酸是评价当归质量的重要指标,研究发现,阿魏酸性质不稳定,易受加热和炮制方法等多种因素的影响,但化学计量学分析实验结果显示土炒当归相比当归阿魏酸含量无明显变化,可能是因为阿魏酸松柏酯分解产生部分阿魏酸。

洋川芎内酯H、藁本内酯为代表的苯酞类成分是当归挥发油中的重要组成部分^[19],研究发当归挥发油可调节胃肠动力、调节胃肠肌电、影响胃肠平滑肌。当归挥发油调节胃肠道平滑肌的作用与当归挥发油的浓度、胃肠道平滑肌的状态有关^[20],改善实验性胃肠动力障碍,可能与促进乙酰胆碱(Ach)和胃肠激素的分泌有关^[21]。当归炮制传统理论认为生当归补血又润肠,当归土炒后补血而不滑肠,当归经土炒后藁本内酯、洋川芎内酯I等挥发油成分含量显著下降,对胃肠道的调节作用改变,其缓和油润而不滑肠的功效可能与挥发油成分含量变化有关,但仍需进一步结合药理试验研究当归土炒前后成分变化与功效差异的相关性。

基金

收起

国家自然科学基金项目资助(82260772)
甘肃省药品监督管理局科研项目资助(2023GSMPA026)

参考文献

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文献

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参考文献引证文献

排序方式：

[1]

Ch.P(2020)Vol Ⅰ(中国药典2020年版. 一部)[S]. 2020:139.

[2]

. Golden Mirror of Medicine(医宗金鉴)[M]. Shenyang: Liaoning Science and Technology Publishing House, 1997:486-491.

[3]

FENG

H M

, LI

, LUO

X D

, et al. Research progress on chemical constituents and pharmacological effects of danggui(Radix Angelicae Sinensis)and prediction analysis on its quality markers[J]. Chin Arch Tradit Chin Med(中华中医药学刊), 2022, 40(4):159-166.

[4]

, ZHANG

Y G

, SHI

L P

, et al. Research progress in pharmacological effects and chemical components of processed Angelicae Sinensis Radix products[J]. China J Chin Mater Med(中国中药杂志), 2023, 48(22):6003-6010.

[5]

LYU

C L

, LI

H H

, SHI

Y J

, et al. Research progress of Angelicae Sinensis Radix and predictive analysis on its quality markers[J]. China J Chin Mater Med(中国中药杂志), 2023, 48(22):6003-6010.

[6]

ZHANG

M H

, ZHU

T T

, JIN

, et al. Quality differences of different origins and varieties of Angelicae sinensis based on HPLC multi-index composition determination and multi-pattern recognition method of fingerprint[J]. Chin Tradit Herb Drugs(中草药), 2022, 53(19):6187-6199.

[7]

, YANG

X J

, LI

, et al. Establishment of fingerprint and contents determination of four components of Angelicae Sinensis Precision boiled powder decoction pieces[J]. Chin J Inf Tradit Chin Med(中国中医药信息杂志), 2022, 29(2):93-97.

[8]

ZHOU

, LI

, WEI

B B

, et al. Research on differential quality markers of medicine herbs for Danggui Buxue Decoction before and after processing based on fingerprint and network pharmacology[J]. China J Chin Mater Med(中国中药杂志), 2024, 49(9):2451-2460.

[9]

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.

[10]

Gansu Medical Products Administration. Gansu Province Chinese medicine processing specification (甘肃省中药炮制规范2022版)[M]. Lanzhou: Lanzhou University Press, 2022:15-16.

[11]

YAO

Y Y

, MU

X Q

, PENG

, et al. HPLC analysis and study of the content determination of 7 components of Angelica sinensis in four producing areas in different treatments[J]. Lishizhen Med Mater Med Res(时珍国医国药), 2022, 33(8):1987-1990.

[12]

WANG

Y J

, YAN

, HUANG

S L

, et al. Establishment of HPLC fingerprint and chemometrics evaluation of Angelica sinensis[J]. Chin Tradit Pat Med(中成药), 2020, 42(2):514-519.

[13]

DENG

H S

, LI

X X

, WANG

, et al. Quality evaluation of forsythiae fructus based on HPLC fingerprint and QAMS multi-component content determination[J]. Chin Pharm J(中国药学杂志), 2024, 59(15):1429-1437.

[14]

YAN

W H

, CAO

H H

, GUO

, et al. UPLC fingerprint and multi-components content determination of different processed products of Angelica sinensis[J]. China J Chin Mater Med(中国中药杂志), 2019, 44(12):2499-2510.

[15]

CHEN

Z H

, WU

G T

, SUN

, et al. Research progress of ligustilide in Angelica Sinensis[J]. J Gansu Univ Chin Med(甘肃中医药大学学报), 2018, 35(2):102-105.

[16]

FUENTES

, CABALLERO

, ALARCÓN

, et al. Chlorogenic acid inhibits human platelet activation and thrombus formation[J]. PLoS One, 2014, 9(3):e90699.

[17]

S Q

, ZHANG

Y C

, SU

P Y

, et al. Advances in research of on coniferyl ferulate[J]. Chin J Exp Tradit Med Form(中国实验方剂学杂志), 2011, 17(3):229-231.

[18]

ZUO

A H

, WANG

, XIAO

H B

. Study on degradation products of senkyunolide A and senkyunolide I[J]. Chin Tradit Herb Drugs(中草药), 2012, 43(11):2127-2131.

[19]

ZHANG

L B

, LYU

J L

, CHEN

H L

, et al. Research progress of structures and pharmacological activities of phthalides from Angelica sinensis[J]. China J Chin Mater Med(中国中药杂志), 2016, 41(2):167-176.

[20]

YAO

, WANG

Z W

, FU

X Y

, et al. Advances in research on effects of the essential oil of Angelicae Sinensis Radix and its phthalide constituents on smooth muscle[J]. Chin J Mod Appl Pharm(中国现代应用药学), 2019, 36(21):2738-2742.

[21]

CHENG

X P

, WU

G T

, LIU

F L

, et al. Study on the effect and mechanism of angelica volatile oil on experimental gastrointestinal motility disorder[J]. Pharm Clin Chin Mater Med(中药药理与临床), 2011, 27(4):54-56.

2025年第60卷第5期

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doi: 10.11669/cpj.2025.05.010

接收时间：2024-09-23
首发时间：2025-11-07
出版时间：2025-03-08

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收稿日期：2024-09-23

基金

国家自然科学基金项目资助(82260772)

甘肃省药品监督管理局科研项目资助(2023GSMPA026)

作者信息

¹ 甘肃中医药大学药学院, 兰州 730000

² 陇药产业创新研究院, 兰州 730000

³ 甘肃省中药药理与毒理学重点实验室, 兰州 730000

⁴ 西北中藏药省部共建协同创新中心, 兰州 730000

⁵ 国家中药炮制技术传承基地, 兰州 730000

通讯作者:

^* 吴国泰,男,博士,副教授,硕士生导师研究方向:中药炮制药理与中药大健康产品研发研究 Tel:(0931)5109816

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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(in Chinese)	Collection time	No.	Origin(in Chinese)	Collection time
S1	Shendu,Minxian,Gansu(甘肃省岷县申都乡)	2022.10	S9	Dacaotan,Zhangxian,Gansu(甘肃省漳县大草滩镇)	2023.10
S2	Zichuan,Minxian,Gansu(甘肃省岷县麻子川镇)	2022.10	S10	Sancha,Zhangxian,Gansu(甘肃省漳县三岔镇)	2023.10
S3	Qingshui,Minxian,Gansu(甘肃省岷县清水镇)	2022.10	S11	Nanfeng,Minle,Gansu(甘肃省民乐县南丰镇)	2022.09
S4	Shili,Minxian,Gansu(甘肃省岷县十里镇)	2022.10	S12	Fengle,Minle,Gansu(甘肃省民乐县丰乐镇)	2022.09
S5	Puma,Minxian,Gansu(甘肃省岷县蒲麻镇)	2022.10	S13	Xinzhuang,Datong,Qinghai(青海省大通县新庄镇)	2022.09
S6	Lyujing,Minxian,Gansu(甘肃省岷县闾井镇)	2022.10	S14	Gonghe,Huangzhong,Qinghai(青海省湟中区共和镇)	2022.09
S7	Huichuan,Weiyuan,Gansu(甘肃省渭源县会川镇)	2023.10	S15	Mapo,Yuzhong,Gansu(甘肃省榆中县马坡乡)	2022.09
S8	Tianjiahe,Weiyuan,Gansu(甘肃省渭源县田家河乡)	2023.10	S16	Heping,Yuzhong,Gansu(甘肃省榆中县和平镇)	2022.10

No.

Origin(in Chinese)

Collection time

No.

Origin(in Chinese)

Collection time

Shendu,Minxian,Gansu(甘肃省岷县申都乡)

2022.10

Dacaotan,Zhangxian,Gansu(甘肃省漳县大草滩镇)

2023.10

Zichuan,Minxian,Gansu(甘肃省岷县麻子川镇)

2022.10

S10

Sancha,Zhangxian,Gansu(甘肃省漳县三岔镇)

2023.10

Qingshui,Minxian,Gansu(甘肃省岷县清水镇)

2022.10

S11

Nanfeng,Minle,Gansu(甘肃省民乐县南丰镇)

2022.09

Shili,Minxian,Gansu(甘肃省岷县十里镇)

2022.10

S12

Fengle,Minle,Gansu(甘肃省民乐县丰乐镇)

2022.09

Puma,Minxian,Gansu(甘肃省岷县蒲麻镇)

2022.10

S13

Xinzhuang,Datong,Qinghai(青海省大通县新庄镇)

2022.09

Lyujing,Minxian,Gansu(甘肃省岷县闾井镇)

2022.10

S14

Gonghe,Huangzhong,Qinghai(青海省湟中区共和镇)

2022.09

Huichuan,Weiyuan,Gansu(甘肃省渭源县会川镇)

2023.10

S15

Mapo,Yuzhong,Gansu(甘肃省榆中县马坡乡)

2022.09

Tianjiahe,Weiyuan,Gansu(甘肃省渭源县田家河乡)

2023.10

S16

Heping,Yuzhong,Gansu(甘肃省榆中县和平镇)

2022.10

No.	Similarity	No.	Similarity
S1	0.989	0.99	T1	0.99	0.991
S2	0.997	0.998	T2	0.996	0.997
S3	0.992	0.992	T3	0.995	0.995
S4	0.993	0.993	T4	0.99	0.990
S5	0.989	0.989	T5	0.991	0.992
S6	0.996	0.997	T6	0.998	0.998
S7	0.995	0.995	T7	0.992	0.992
S8	0.996	0.997	T8	0.997	0.997
S9	0.992	0.992	T9	0.994	0.995
S10	0.995	0.994	T10	0.996	0.997
S11	0.990	0.989	T11	0.995	0.995
S12	0.974	0.973	T12	0.997	0.997
S13	0.988	0.988	T13	0.992	0.992
S14	0.928	0.929	T14	0.996	0.996
S15	0.950	0.949	T15	0.993	0.992
S16	0.978	0.978	T16	0.999	0.999

No.

Similarity

No.

Similarity

RAS-R

SFAS-R

RAS-R

SFAS-R

0.989

0.99

0.991

0.997

0.998

0.996

0.997

0.992

0.995

0.993

0.99

0.990

0.989

0.991

0.992

0.996

0.997

0.998

0.995

0.992

0.996

0.997

0.992

0.994

0.995

S10

0.995

0.994

T10

0.996

0.997

S11

0.990

0.989

T11

0.995

S12

0.974

0.973

T12

0.997

S13

0.988

T13

0.992

S14

0.928

0.929

T14

0.996

S15

0.950

0.949

T15

0.993

0.992

S16

0.978

T16

0.999

Peak	Component	Paired-sample test	t value	df	P value	Effective dose
13	Ligustilide	RAS-SFAS	5.249	15	<0.001	1.35
8	Senkyunolide I	RAS-SFAS	6.907	15	<0.001	1.726
11	Coniferyl ferulate	RAS-SFAS	8.114	15	<0.001	2.028

Peak

Component

Paired-sample test

t value

P value

Effective dose

Ligustilide

RAS-SFAS

5.249

<0.001

1.35

Senkyunolide I

RAS-SFAS

6.907

<0.001

1.726

Coniferyl ferulate

RAS-SFAS

8.114

<0.001

2.028

Component	Regressione quation	r²	Linear range/μg·mL^-1
Tryptophan	Y=15.016X-4.610 9	0.999 7	2.80	-89.60
Chlorogenic acid	Y=4.956 1X-2.281 4	0.999 6	3.30	-105.50
Ferulic acid	Y=9.855X+0.695 5	0.999 8	2.48	-79.4
Senkyunolide I	Y=50.366X+5.471 6	0.999 8	1.35	-43.16
Senkyunolide H	Y=62.848X+2.554 7	0.999 8	0.52	-16.74
Coniferyl ferulate	Y=10.21X+6.472 8	0.999 8	3.10	-99.30
Ligustilide	Y=7.585X+22.72	0.999 8	14.78	-473.00
Butyliden phthalide	Y=1.256 1X+5.776 2	0.999 4	8.20	-262.33

Component

Regressione quation

r²

Linear range/μg·mL^-1

Tryptophan

Y=15.016X-4.610 9

0.999 7

2.80

-89.60

Chlorogenic acid

Y=4.956 1X-2.281 4

0.999 6

3.30

-105.50

Ferulic acid

Y=9.855X+0.695 5

0.999 8

2.48

-79.4

Senkyunolide I

Y=50.366X+5.471 6

0.999 8

1.35

-43.16

Senkyunolide H

Y=62.848X+2.554 7

0.999 8

0.52

-16.74

Coniferyl ferulate

Y=10.21X+6.472 8

0.999 8

3.10

-99.30

Ligustilide

Y=7.585X+22.72

0.999 8

14.78

-473.00

Butyliden phthalide

Y=1.256 1X+5.776 2

0.999 4

8.20

-262.33

Components	m(Sample)/g	m(Original)/μg	m(Added)/μg	m(Found)/μg	Recovery/%	Mean recovery/%	RSD/%
Tryptophan	0.501 5	244.49	122.15	364.71	98.42	98.98	1.82
	0.502 0	244.73	122.15	366.15	99.40
	0.500 1	243.80	122.15	365.21	99.39
	0.501 2	244.34	244.3	480.45	96.65
	0.500 9	244.19	244.3	481.26	97.04
	0.501 3	244.39	244.3	490.19	100.61
	0.501 8	244.63	366.45	618.56	102.04
	0.500 5	244.00	366.45	610.47	100.01
	0.500 2	243.85	366.45	600.26	97.26
Chlorogenic acid	0.501 5	115.28	57.6	173.88	101.74	99.28	2.31
	0.502 0	115.39	57.6	171.27	97.01
	0.500 1	114.96	57.6	170.59	96.58
	0.501 2	115.21	115.20	230.69	100.24
	0.500 9	115.14	115.2	232.86	102.19
	0.501 3	115.23	115.2	226.01	96.16
	0.501 8	115.35	172.8	288.10	99.97
	0.500 5	115.05	172.8	289.68	101.06
	0.500 2	114.98	172.8	285.3	98.56
Ferulic acid	0.501 5	209.87	104.85	314.85	100.12	99.25	2.04
	0.502 0	210.08	104.85	313.67	98.80
	0.500 1	209.29	104.85	312.19	98.14
	0.501 2	209.75	209.7	414.46	97.62
	0.500 9	209.62	209.7	415.70	98.27
	0.501 3	209.79	209.7	421.96	101.18
	0.501 8	210.00	314.55	525.15	100.19
	0.500 5	209.45	314.55	523.97	99.99
	0.500 2	209.33	314.55	520.55	98.94
Senkyunolide I	0.501 5	186.53	93.2	281.13	101.50	100.69	1.32
	0.502 0	186.71	93.2	279.67	99.74
	0.500 1	186.01	93.2	280.45	101.33
	0.501 2	186.42	186.4	372.89	100.04
	0.500 9	186.30	186.4	378.86	103.30
	0.501 3	186.45	186.4	375.16	101.24
	0.501 8	186.64	279.6	466.10	99.95
	0.500 5	186.16	279.6	462.23	98.74
	0.500 2	186.04	279.6	466.67	100.37
Senkyunolide H	0.501 5	30.63	15.3	45.80	99.17	98.59	1.55
	0.502 0	30.66	45.61	15.3	97.73
	0.500 1	30.54	45.35	15.3	96.79
	0.501 2	30.61	60.85	30.6	98.83
	0.500 9	30.59	60.74	30.6	98.53
	0.501 3	30.61	60.08	30.6	96.29
	0.501 8	30.64	75.87	45.9	98.53
	0.500 5	30.57	76.76	45.9	100.64
	0.500 2	30.55	76.80	45.9	100.77
Coniferyl ferulate	0.501 5	566.88	846.4	283.2	98.70	99.78	1.65
	0.502 0	567.45	850.2	283.2	99.84
	0.500 1	565.30	849.52	283.2	100.36
	0.501 2	566.54	1 132.6	566.4	99.94
	0.500 9	566.20	1 134.5	566.4	100.34
	0.501 3	566.65	1 124.9	566.4	98.56
	0.501 8	567.22	1 420.45	849.6	100.43
	0.500 5	565.75	1 389.42	849.6	96.95
	0.500 2	565.41	1 439.87	849.8	102.90
Ligustilide	0.501 5	3 849.03	5 835.19	1 920.3	103.43	101.06	1.32
	0.502 0	3 852.87	5 789.83	1 920.3	100.87
	0.500 1	3 838.29	5 794.59	1 920.3	101.87
	0.501 2	3 846.73	7 655.34	3 840.6	99.17
	0.500 9	3 844.43	7 689.59	3 840.6	100.12
	0.501 3	3 847.50	7 737.91	3 840.6	101.30
	0.501 8	3 851.34	9 581.32	5 760.9	99.46
	0.500 5	3 841.36	9 695.52	5 760.9	101.62
	0.500 2	3 839.06	9 699.85	5 760.9	101.73
Butyliden phthalide	0.501 5	719.03	1 088.67	359.2	102.91	100.52	1.93
	0.502 0	719.75	1 074.95	359.2	98.89
	0.500 1	717.02	1 075.69	359.2	99.85
	0.501 2	718.60	1 449.68	718.4	101.76
	0.500 9	718.17	1 460.93	718.4	103.39
	0.501 3	718.74	1 428.56	718.4	98.81
	0.501 8	719.46	1 796.88	1 077.6	99.98
	0.500 5	717.60	1 809.74	1 077.6	101.35
	0.500 2	717.17	1 770.75	1 077.6	97.77

Components

m(Sample)/g

m(Original)/μg

m(Added)/μg

m(Found)/μg

Recovery/%

Mean recovery/%

RSD/%

Tryptophan

0.501 5

244.49

122.15

364.71

98.42

98.98

1.82

0.502 0

244.73

122.15

366.15

99.40

0.500 1

243.80

122.15

365.21

99.39

0.501 2

244.34

244.3

480.45

96.65

0.500 9

244.19

244.3

481.26

97.04

0.501 3

244.39

244.3

490.19

100.61

0.501 8

244.63

366.45

618.56

102.04

0.500 5

244.00

366.45

610.47

100.01

0.500 2

243.85

366.45

600.26

97.26

Chlorogenic acid

0.501 5

115.28

57.6

173.88

101.74

99.28

2.31

0.502 0

115.39

57.6

171.27

97.01

0.500 1

114.96

57.6

170.59

96.58

0.501 2

115.21

115.20

230.69

100.24

0.500 9

115.14

115.2

232.86

102.19

0.501 3

115.23

115.2

226.01

96.16

0.501 8

115.35

172.8

288.10

99.97

0.500 5

115.05

172.8

289.68

101.06

0.500 2

114.98

172.8

285.3

98.56

Ferulic acid

0.501 5

209.87

104.85

314.85

100.12

99.25

2.04

0.502 0

210.08

104.85

313.67

98.80

0.500 1

209.29

104.85

312.19

98.14

0.501 2

209.75

209.7

414.46

97.62

0.500 9

209.62

209.7

415.70

98.27

0.501 3

209.79

209.7

421.96

101.18

0.501 8

210.00

314.55

525.15

100.19

0.500 5

209.45

314.55

523.97

99.99

0.500 2

209.33

314.55

520.55

98.94

Senkyunolide I

0.501 5

186.53

93.2

281.13

101.50

100.69

1.32

0.502 0

186.71

93.2

279.67

99.74

0.500 1

186.01

93.2

280.45

101.33

0.501 2

186.42

186.4

372.89

100.04

0.500 9

186.30

186.4

378.86

103.30

0.501 3

186.45

186.4

375.16

101.24

0.501 8

186.64

279.6

466.10

99.95

0.500 5

186.16

279.6

462.23

98.74

0.500 2

186.04

279.6

466.67

100.37

Senkyunolide H

0.501 5

30.63

15.3

45.80

99.17

98.59

1.55

0.502 0

30.66

45.61

15.3

97.73

0.500 1

30.54

45.35

15.3

96.79

0.501 2

30.61

60.85

30.6

98.83

0.500 9

30.59

60.74

30.6

98.53

0.501 3

30.61

60.08

30.6

96.29

0.501 8

30.64

75.87

45.9

98.53

0.500 5

30.57

76.76

45.9

100.64

0.500 2

30.55

76.80

45.9

100.77

Coniferyl ferulate

0.501 5

566.88

846.4

283.2

98.70

99.78

1.65

0.502 0

567.45

850.2

283.2

99.84

0.500 1

565.30

849.52

283.2

100.36

0.501 2

566.54

1 132.6

566.4

99.94

0.500 9

566.20

1 134.5

566.4

100.34

0.501 3

566.65

1 124.9

566.4

98.56

0.501 8

567.22

1 420.45

849.6

100.43

0.500 5

565.75

1 389.42

849.6

96.95

0.500 2

565.41

1 439.87

849.8

102.90

Ligustilide

0.501 5

3 849.03

5 835.19

1 920.3

103.43

101.06

1.32

0.502 0

3 852.87

5 789.83

1 920.3

100.87

0.500 1

3 838.29

5 794.59

1 920.3

101.87

0.501 2

3 846.73

7 655.34

3 840.6

99.17

0.500 9

3 844.43

7 689.59

3 840.6

100.12

0.501 3

3 847.50

7 737.91

3 840.6

101.30

0.501 8

3 851.34

9 581.32

5 760.9

99.46

0.500 5

3 841.36

9 695.52

5 760.9

101.62

0.500 2

3 839.06

9 699.85

5 760.9

101.73

Butyliden phthalide

0.501 5

719.03

1 088.67

359.2

102.91

100.52

1.93

0.502 0

719.75

1 074.95

359.2

98.89

0.500 1

717.02

1 075.69

359.2

99.85

0.501 2

718.60

1 449.68

718.4

101.76

0.500 9

718.17

1 460.93

718.4

103.39

0.501 3

718.74

1 428.56

718.4

98.81

0.501 8

719.46

1 796.88

1 077.6

99.98

0.500 5

717.60

1 809.74

1 077.6

101.35

0.500 2

717.17

1 770.75

1 077.6

97.77

No.	Tryptophan	Chlorogenic acid	Ferulic acid	Senkyunolide I	Senkyunolide H	Coniferyl ferulate	Ligustilide	Butyliden phthalide
S1	0.520 5	0.243 6	0.351 1	0.212 0	0.039 2	0.785 2	7.237 3	0.497 5
S2	0.579 4	0.198 4	0.430 3	0.218 3	0.038 7	0.970 1	7.718 3	0.962 5
S3	0.674 0	0.162 9	0.332 4	0.239 6	0.040 5	1.135 1	6.775 4	1.038 9
S4	0.487 5	0.229 9	0.418 5	0.371 9	0.061 1	1.130 4	7.675 0	1.433 8
S5	0.489 4	0.208 1	0.355 6	0.399 7	0.066 5	1.265 9	7.454 1	1.433 8
S6	0.631 6	0.599 5	0.336 9	0.268 5	0.048 0	1.082 2	7.142 4	0.994 3
S7	0.249 9	0.250 9	0.365 7	0.251 1	0.047 3	1.390 5	9.335 7	0.914 7
S8	0.531 5	0.204 0	0.326 4	0.217 5	0.041 3	0.933 7	7.029 0	0.914 7
S9	0.546 1	0.210 5	0.329 2	0.193 9	0.037 8	0.658 7	6.072 4	0.987 9
S10	0.455 5	0.295 2	0.443 2	0.335 3	0.060 9	1.235 0	10.852 4	0.793 7
S11	0.489 4	0.208 1	0.355 6	0.399 7	0.066 5	1.265 9	7.454 1	1.433 8
S12	0.337 5	0.253 3	0.458 7	0.235 4	0.024 3	1.558 6	10.447 4	0.497 5
S13	0.302 1	0.305 7	0.368 6	0.429 8	0.075 1	1.335 3	10.655 7	1.159 9
S14	0.502 7	0.516 4	0.443 2	0.460 6	0.073 7	0.899 6	7.694 6	1.682 2
S15	0.309 3	0.255 7	0.407 9	0.295 7	0.053 1	1.468 1	7.693 5	1.573 9
S16	0.388 7	0.157 2	0.420 5	0.409 5	0.069 2	0.620 3	6.165 2	1.720 4
T1	0.644 9	0.277 5	0.434 7	0.109 7	0.019 9	0.440 9	5.266 6	0.242 8
T2	0.543 2	0.168 5	0.488 7	0.143 4	0.025 6	0.390 3	5.795 0	0.605 8
T3	0.698 5	0.183 9	0.409 2	0.231 4	0.037 3	0.769 2	5.895 7	0.863 7
T4	0.723 0	0.234 7	0.360 0	0.189 7	0.031 9	0.511 0	4.653 8	0.809 6
T5	0.658 8	0.143 5	0.351 1	0.184 1	0.030 4	0.499 2	4.662 3	0.688 6
T6	0.732 6	0.688 3	0.496 4	0.222 5	0.039 0	0.789 9	6.762 7	0.927 4
T7	0.276 3	0.249 2	0.422 1	0.152 4	0.029 2	0.561 5	6.777 5	0.249 1
T8	0.523 7	0.199 2	0.422 1	0.139 4	0.025 0	0.547 8	6.013 9	0.293 7
T9	0.410 0	0.254 9	0.415 6	0.130 8	0.024 0	0.397 4	5.303 0	0.621 7
T10	0.586 6	0.158 0	0.442 0	0.170 9	0.031 8	0.323 7	4.992 4	0.777 8
T11	0.506 2	0.239 6	0.330 4	0.221 1	0.033 8	0.437 7	6.886 1	0.902 0
T12	0.585 5	0.192 7	0.397 4	0.091 3	0.040 6	0.565 0	5.532 4	0.914 7
T13	0.457 7	0.211 3	0.382 4	0.246 6	0.043 1	0.457 7	4.748 7	0.863 7
T14	0.440 6	0.531 7	0.405 1	0.317 1	0.054 6	0.460 0	4.506 7	0.959 3
T15	0.244 3	0.390 5	0.420 1	0.285 9	0.049 0	0.782 9	3.969 8	0.921 1
T16	0.471 3	0.258 1	0.425 8	0.185 9	0.030 6	0.606 6	6.038 7	0.835 1

No.

Tryptophan

Chlorogenic acid

Ferulic acid

Senkyunolide I

Senkyunolide H

Coniferyl ferulate

Ligustilide

Butyliden phthalide

0.520 5

0.243 6

0.351 1

0.212 0

0.039 2

0.785 2

7.237 3

0.497 5

0.579 4

0.198 4

0.430 3

0.218 3

0.038 7

0.970 1

7.718 3

0.962 5

0.674 0

0.162 9

0.332 4

0.239 6

0.040 5

1.135 1

6.775 4

1.038 9

0.487 5

0.229 9

0.418 5

0.371 9

0.061 1

1.130 4

7.675 0

1.433 8

0.489 4

0.208 1

0.355 6

0.399 7

0.066 5

1.265 9

7.454 1

1.433 8

0.631 6

0.599 5

0.336 9

0.268 5

0.048 0

1.082 2

7.142 4

0.994 3

0.249 9

0.250 9

0.365 7

0.251 1

0.047 3

1.390 5

9.335 7

0.914 7

0.531 5

0.204 0

0.326 4

0.217 5

0.041 3

0.933 7

7.029 0

0.914 7

0.546 1

0.210 5

0.329 2

0.193 9

0.037 8

0.658 7

6.072 4

0.987 9

S10

0.455 5

0.295 2

0.443 2

0.335 3

0.060 9

1.235 0

10.852 4

0.793 7

S11

0.489 4

0.208 1

0.355 6

0.399 7

0.066 5

1.265 9

7.454 1

1.433 8

S12

0.337 5

0.253 3

0.458 7

0.235 4

0.024 3

1.558 6

10.447 4

0.497 5

S13

0.302 1

0.305 7

0.368 6

0.429 8

0.075 1

1.335 3

10.655 7

1.159 9

S14

0.502 7

0.516 4

0.443 2

0.460 6

0.073 7

0.899 6

7.694 6

1.682 2

S15

0.309 3

0.255 7

0.407 9

0.295 7

0.053 1

1.468 1

7.693 5

1.573 9

S16

0.388 7

0.157 2

0.420 5

0.409 5

0.069 2

0.620 3

6.165 2

1.720 4

0.644 9

0.277 5

0.434 7

0.109 7

0.019 9

0.440 9

5.266 6

0.242 8

0.543 2

0.168 5

0.488 7

0.143 4

0.025 6

0.390 3

5.795 0

0.605 8

0.698 5

0.183 9

0.409 2

0.231 4

0.037 3

0.769 2

5.895 7

0.863 7

0.723 0

0.234 7

0.360 0

0.189 7

0.031 9

0.511 0

4.653 8

0.809 6

0.658 8

0.143 5

0.351 1

0.184 1

0.030 4

0.499 2

4.662 3

0.688 6

0.732 6

0.688 3

0.496 4

0.222 5

0.039 0

0.789 9

6.762 7

0.927 4

0.276 3

0.249 2

0.422 1

0.152 4

0.029 2

0.561 5

6.777 5

0.249 1

0.523 7

0.199 2

0.422 1

0.139 4

0.025 0

0.547 8

6.013 9

0.293 7

0.410 0

0.254 9

0.415 6

0.130 8

0.024 0

0.397 4

5.303 0

0.621 7

T10

0.586 6

0.158 0

0.442 0

0.170 9

0.031 8

0.323 7

4.992 4

0.777 8

T11

0.506 2

0.239 6

0.330 4

0.221 1

0.033 8

0.437 7

6.886 1

0.902 0

T12

0.585 5

0.192 7

0.397 4

0.091 3

0.040 6

0.565 0

5.532 4

0.914 7

T13

0.457 7

0.211 3

0.382 4

0.246 6

0.043 1

0.457 7

4.748 7

0.863 7

T14

0.440 6

0.531 7

0.405 1

0.317 1

0.054 6

0.460 0

4.506 7

0.959 3

T15

0.244 3

0.390 5

0.420 1

0.285 9

0.049 0

0.782 9

3.969 8

0.921 1

T16

0.471 3

0.258 1

0.425 8

0.185 9

0.030 6

0.606 6

6.038 7

0.835 1