中国药学杂志

No.	Name	Place of origin (in Chinese)	Collection or preparation time
S1	Polygonati Rhizoma(SP)	Lueyang Hanzhong Shaanxi (陕西汉中略阳)	2021.10
S2	Polygonati Rhizoma(SP)	Lueyang Hanzhong Shaanxi (陕西汉中略阳)	2021.10
S3	Polygonati Rhizoma(SP)	Lueyang Hanzhong Shaanxi (陕西汉中略阳)	2021.10
S4	Polygonati Rhizoma(SP)	Liuba Hanzhong Shaanxi (陕西汉中留坝)	2021.10
S5	Polygonati Rhizoma(SP)	Liuba Hanzhong Shaanxi (陕西汉中留坝)	2021.10
S6	Polygonati Rhizoma(SP)	Liuba Hanzhong Shaanxi (陕西汉中留坝)	2021.10
S7	Steamed Polygonati Rhizoma (QZP)	Lueyang Hanzhong Shaanxi (陕西汉中略阳)	2021.11
S8	Steamed Polygonati Rhizoma (QZP)	Lueyang Hanzhong Shaanxi (陕西汉中略阳)	2021.11
S9	Steamed Polygonati Rhizoma (QZP)	Lueyang Hanzhong Shaanxi (陕西汉中略阳)	2021.11
S10	Steamed Polygonati Rhizoma (QZP)	Liuba Hanzhong Shaanxi (陕西汉中留坝)	2021.11
S11	Steamed Polygonati Rhizoma (QZP)	Liuba Hanzhong Shaanxi (陕西汉中留坝)	2021.11
S12	Steamed Polygonati Rhizoma (QZP)	Liuba Hanzhong Shaanxi (陕西汉中留坝)	2021.11
S13	Wine-processed Polygonati Rhizoma(JZP)	Lueyang Hanzhong Shaanxi (陕西汉中略阳)	2021.11
S14	Wine-processed Polygonati Rhizoma(JZP)	Lueyang Hanzhong Shaanxi (陕西汉中略阳)	2021.11
S15	Wine-processed Polygonati Rhizoma(JZP)	Lueyang Hanzhong Shaanxi (陕西汉中略阳)	2021.11
S16	Wine-processed Polygonati Rhizoma(JZP)	Liuba Hanzhong Shaanxi (陕西汉中留坝)	2021.11
S17	Wine-processed Polygonati Rhizoma(JZP)	Liuba Hanzhong Shaanxi (陕西汉中留坝)	2021.11
S18	Wine-processed Polygonati Rhizoma(JZP)	Liuba Hanzhong Shaanxi (陕西汉中留坝)	2021.11

No.	Name	Place of origin (in Chinese)	Collection or preparation time
S1	Polygonati Rhizoma(SP)	Lueyang Hanzhong Shaanxi (陕西汉中略阳)	2021.10
S2	Polygonati Rhizoma(SP)	Lueyang Hanzhong Shaanxi (陕西汉中略阳)	2021.10
S3	Polygonati Rhizoma(SP)	Lueyang Hanzhong Shaanxi (陕西汉中略阳)	2021.10
S4	Polygonati Rhizoma(SP)	Liuba Hanzhong Shaanxi (陕西汉中留坝)	2021.10
S5	Polygonati Rhizoma(SP)	Liuba Hanzhong Shaanxi (陕西汉中留坝)	2021.10
S6	Polygonati Rhizoma(SP)	Liuba Hanzhong Shaanxi (陕西汉中留坝)	2021.10
S7	Steamed Polygonati Rhizoma (QZP)	Lueyang Hanzhong Shaanxi (陕西汉中略阳)	2021.11
S8	Steamed Polygonati Rhizoma (QZP)	Lueyang Hanzhong Shaanxi (陕西汉中略阳)	2021.11
S9	Steamed Polygonati Rhizoma (QZP)	Lueyang Hanzhong Shaanxi (陕西汉中略阳)	2021.11
S10	Steamed Polygonati Rhizoma (QZP)	Liuba Hanzhong Shaanxi (陕西汉中留坝)	2021.11
S11	Steamed Polygonati Rhizoma (QZP)	Liuba Hanzhong Shaanxi (陕西汉中留坝)	2021.11
S12	Steamed Polygonati Rhizoma (QZP)	Liuba Hanzhong Shaanxi (陕西汉中留坝)	2021.11
S13	Wine-processed Polygonati Rhizoma(JZP)	Lueyang Hanzhong Shaanxi (陕西汉中略阳)	2021.11
S14	Wine-processed Polygonati Rhizoma(JZP)	Lueyang Hanzhong Shaanxi (陕西汉中略阳)	2021.11
S15	Wine-processed Polygonati Rhizoma(JZP)	Lueyang Hanzhong Shaanxi (陕西汉中略阳)	2021.11
S16	Wine-processed Polygonati Rhizoma(JZP)	Liuba Hanzhong Shaanxi (陕西汉中留坝)	2021.11
S17	Wine-processed Polygonati Rhizoma(JZP)	Liuba Hanzhong Shaanxi (陕西汉中留坝)	2021.11
S18	Wine-processed Polygonati Rhizoma(JZP)	Liuba Hanzhong Shaanxi (陕西汉中留坝)	2021.11

No.	English name	Molecular formula	M_W	m/z (Theoretical) value	m/z (Actual) value	t_R/ min	Deviation /×10^-6	m/z (Fragment ion)
	Amino acids
1¹⁾	Gamma-aminobutyric acid	C₄H₉NO₂	103.062 8	104.070 6	104.071 2	0.77	5.27	53.003,53.690 4,55.018 7, 56.050 3,56.602 2,57.034 6
2¹⁾²⁾	L-arginine	C₆H₁₄N₄O₂	174.111 1	175.119	175.119 1	0.7	0.54	53.498 3,55.055 1,56.050 4, 57.034 3,60.025 8, 60.056 4
3¹⁾²⁾	L-phenylalanine	C₉H₁₁NO₂	165.078 4	166.086 3	166.086 3	1.72	0.33	68.050 3,69.034 2,70.065 8, 79.054 9,80.050 2,80.949 7
4²⁾	L-aminocyclopropane-1-carboxylic acid	C₄H₇NO₂	101.047 1	102.055	102.055 4	0.79	4.52	71.05,56.050 3,60.045 2, 61.028 9,68.050 2,70.065 9
5¹⁾²⁾	2-Pyrrolidone-5-carboxylic acid	C₅H₇NO₃	129.042	130.049 9	130.050 2	1.04	2.38	53.003 1,55.055,56.050 3, 57.070 7,58.065 6,58.744 9
6¹⁾	Aminocaproic acid	C₆H₁₃NO₂	131.094 1	114.091 4	114.091 8	4.6	3.21	53.003 1,53.039 5,54.034 5, 55.018 8,55.054 9,56.050 2
7¹⁾²⁾	Proline	C₅H₉NO₂	115.062 8	116.070 6	116.071	0.84	3.15	51.091 1,53.039 5,53.856 5, 55.018 5,55.055,55.301 8
8¹⁾²⁾	L-valine	C₅H₁₁NO₂	117.078 4	118.086 3	118.086 6	0.91	2.6	56.050 3,50.919 2,53.039 5, 54.203 2,55.055,50.446 2
9¹⁾²⁾	D-alloisoleucine	C₆H₁₃NO₂	131.094 1	132.101 9	132.102	1.05	1.06	51.105 2,51.695 2,55.055 2, 53.039 4,54.476 9,53.002 9
10³⁾	n-(1-deoxy-1-fructosyl)leucine(unconfirmed)	C₁₂H₂₃NO₇	293.146 9	294.154 7	294.154 7	1.31	-0.21	55.018 6,56.050 3,57.034 3, 59.037 4,69.034 5,69.070 7
11³⁾	n-(1-deoxy-1-fructosyl)valine(unconfirmed)	C₁₁H₂₁NO₇	279.131 3	280.139 1	280.139 1	0.93	-0.02	55.018 7,55.055 1,59.050 1, 68.050 2,69.034 3,70.065 9
12³⁾	n-(1-deoxy-1-fructosyl)threonine(unconfirmed)	C₁₀H₁₉NO₈	281.110 5	282.118 3	282.118 3	0.79	-0.14	56.050 2,57.034 4,69.034 4, 74.060 8,81.034 2,84.045
13¹⁾	L-gln	C₅H₁₀N₂O₃	146.068 6	147.076 4	147.076 5	0.78	0.53	50.892 4,52.530 7,52.818, 55.055,56.050 2,58.006 4
14¹⁾	Amfenac	C₁₅H₁₃NO₃	255.089	256.096 8	256.096 8	5.61	-0.16	55.857 8,61.710 4,78.034 5, 81.034 3,83.049 7,94.029 6
15¹⁾	Succinylproline	C₉H₁₃NO₅	215.078 8	216.086 7	216.086 7	0.9	0.34	53.039 3,55.018 7,55.055, 56.050 3,57.034 3,57.070 6
16¹⁾²⁾	Arginine	C₆H₁₄N₄O₂	174.111 1	173.104 4	173.104 9	0.75	2.9	58.029 9,58.041 2,59.013 9, 59.880 6,61.663 3,68.050 5
17¹⁾²⁾	Tryptophan	C₁₁H₁₂N₂O₂	204.089 3	203.082 6	203.083 1	3.83	2.4	50.658 3,51.843 5,57.034 6, 59.013 9,71.014,72.009 2
18¹⁾	n-(1-deoxy-1-fructosyl)tyrosine	C₁₅H₂₁NO₈	343.126 2	388.124 8	388.125 9	1.76	2.72	55.019,57.034 7,59.013 9, 61.988 5,66.035 1,71.014
19¹⁾	Tetrahydrodipicolinate	C₇H₉NO₄	171.052 6	216.051 2	216.051 8	1.03	2.57	57.034 7,59.013 9,69.034 5, 70.029 9,71.013 9,72.009 3
20¹⁾	Glutamylisoleucine	C₁₁H₂₀N₂O₅	260.136 7	259.13	259.130 2	3.93	0.89	57.034 5,59.013 9,68.014 5, 69.034 7,71.013 8,72.008 9
21¹⁾	Prolylyphenylalanine	C₁₄H₁₈N₂O₃	262.131 2	285.120 8	285.123 3	6.49	9.06	55.119 1,57.034 3,57.070 7, 60.902 8,68.972 9,71.049 7
22³⁾	Beta-D-glucopyranosyl anthranilate(unconfirmed)	C₁₃H₁₇NO₇	299.1	344.098 6	344.099 8	1.75	3.5	55.018 8,57.034 4,59.013 9, 69.034 5,71.014,72.993
	Alkaloids
23¹⁾	Feruloyltyramine	C₁₈H₁₉NO₄	313.130 9	314.138 7	314.138 5	6.16	-0.6	51.417 1,53.039 3,81.034 1, 57.763 6,70.065 6,77.039 3
24³⁾	(E)-n-[2-hydroxy-2-(4-hydroxyphenyl)ethyl]-3-(4-hydroxy- 3-methoxyphenyl)prop-2-enamide(unconfirmed)	C₁₈H₁₉NO₅	329.125 8	312.123	312.122 9	5.43	-0.28	81.033 9,89.039 2,91.054 9, 95.049 5,107.049 3,117.033 8
25³⁾	(E)-n-[2-hydroxy-2-(4-hydroxyphenyl)ethyl]-3-(4-hydroxyphenyl) prop-2-enamide(unconfirmed)	C₁₇H₁₇NO₄	299.115 2	282.112 5	282.112 4	5.31	-0.19	55.055 1,56.050 3,58.065 9, 67.055 1,68.050 2,69.070 7
26¹⁾²⁾	Flazine	C₁₇H₁₂N₂O₄	308.079 2	309.087	309.087	6.5	-0.08	55.018 7,55.055 3,57.994 1, 62.451 6,67.055 2,69.070 8
27³⁾	Casuarine 6-alpha-D-glucoside	C₁₄H₂₅NO₁₀	367.147 3	388.122 3	388.125 9	3.77	9.3	55.019,57.034 6,59.013 9, 61.988 5,66.034 9,71.014
28¹⁾	Betaine	C₅H₁₁NO₂	117.078 4	118.086 3	118.086 6	0.81	2.55	56.050 4,56.850 1,57.905 4, 58.037,58.065 9,58.093 2
29¹⁾	Annocherine B	C₁₈H₁₇NO₄	311.115 2	310.108 5	310.109 1	5.57	1.99	56.89,59.013 9,75.617, 93.034 7,107.050 4,108.021 9
	Flavonoid
30³⁾	3-(3,4-Dihydroxybenzyl)-7-hydroxy-5-methoxy-4-chromanone	C₁₇H₁₆O₆	316.094 1	317.102	317.102	6.87	0.17	55.018 6,55.055 1,57.861 8, 65.039 5,60.045 2,59.760 7
31³⁾	5,7-Dihydroxy-2-(4-methoxyphenyl)-3,4-dihydro-2h-1- benzopyran-4-one(unconfirmed)	C₁₆H₁₄O₅	286.083 6	285.076 9	285.077 1	7.06	0.98	55.724 7,59.013 8,65.003 4, 65.039 9,67.019 1,69.034 8
32¹⁾	Calycosin-7-O-β-D-glucoside	C₂₂H₂₂O₁₀	446.120 8	445.114	445.115 1	5.94	2.4	55.018 9,57.034 5,71.014, 63.024 1,65.003 4,59.013 9
33¹⁾	Diosmetin	C₁₆H₁₂O₆	300.062 8	299.056 1	299.056 8	6.88	2.33	59.013 9,63.024 2,65.003 6, 65.734 1,67.375,69.236 1
	Saccharides
34¹⁾²⁾	Raffinose	C₁₈H₃₂O₁₆	504.168 5	539.138 5	539.138 1	0.85	-0.58	55.019 1,58.006 2,59.014, 61.955 3,61.988 5,62.020 5
35¹⁾²⁾	D-arabinose	C₅H₁₀O₅	150.052 3	149.045 6	149.045 9	0.89	2.32	51.015 2,57.034 7,58.017 6, 59.014 2,59.116 9,61.449 9
36¹⁾	Gentiotriose	C₁₈H₃₂O₁₆	504.168 5	485.151 2	485.151 9	0.91	1.39	55.018 9,57.034 6,58.006 1, 59.013 9,69.034 7,71.014
	Organic acids
37³⁾	13S-hydroxyoctadecadienoic acid(unconfirmed)	C₁₈H₃₂O₃	296.234 6	314.269	314.269	7.37	-0.07	55.018 8,55.055,57.034 3, 57.070 7,58.029 5,60.045 2
38¹⁾	Ferulic acid	C₁₀H₁₀O₄	194.057 4	177.054 6	177.054 7	5.43	0.57	53.039 4,55.018 7,55.055, 69.070 7,67.055,63.024 3
39³⁾	Indolelactic acid(unconfirmed)	C₁₁H₁₁NO₃	205.073 3	206.081 2	206.081 4	3.82	1	55.018 6,69.034 3,74.024 4, 79.054 8,80.949 8,81.034
40¹⁾²⁾	Citric acid	C₆H₈O₇	192.026 5	191.019 7	191.020 2	1	2.45	57.034 7,58.029 8,59.013 9, 67.019 1,69.034 9,70.029 9
41³⁾	9,10-Dihode(unconfirmed)	C₁₈H₃₂O₄	312.229 5	311.222 8	311.223 3	8.69	1.63	56.421 1,83.050 5,58.006 1, 59.013 8,75.506 6,57.034 6
42¹⁾	3-Hydroxysebacic acid	C₁₀H₁₈O₅	218.114 9	495.244 6	495.245 1	5.9	1.01	55.018 9,57.034 6,71.014, 59.013 9,69.034 5,58.006 1
	Saponins
43¹⁾	Fistuloside C	C₄₅H₇₂O₁₉	916.466 2	899.463 5	899.463 7	5.41	0.2	69.034 2,69.070 6,71.049 8, 75.044 7,73.065 5,73.029 1
44³⁾	Neogitogenin 3-[glucosyl-(1->2)-glucosyl-(1->4)- galactoside] (unconfirmed)	C₄₅H₇₄O₁₉	918.481 9	901.479 2	901.479 4	5.8	0.24	67.055,69.034 2,69.070 6, 73.029 1,73.065 5,79.054 9
	Coumarins
45²⁾	Coumaroyl tyramine	C₁₇H₁₇NO₃	283.120 3	284.128 1	284.128 1	6.07	-0.22	51.023 9,53.039 5,55.018 7, 55.054 9,56.216 8,65.039 7

No.	English name	Molecular formula	M_W	m/z (Theoretical) value	m/z (Actual) value	t_R/ min	Deviation /×10^-6	m/z (Fragment ion)
	Amino acids
1¹⁾	Gamma-aminobutyric acid	C₄H₉NO₂	103.062 8	104.070 6	104.071 2	0.77	5.27	53.003,53.690 4,55.018 7, 56.050 3,56.602 2,57.034 6
2¹⁾²⁾	L-arginine	C₆H₁₄N₄O₂	174.111 1	175.119	175.119 1	0.7	0.54	53.498 3,55.055 1,56.050 4, 57.034 3,60.025 8, 60.056 4
3¹⁾²⁾	L-phenylalanine	C₉H₁₁NO₂	165.078 4	166.086 3	166.086 3	1.72	0.33	68.050 3,69.034 2,70.065 8, 79.054 9,80.050 2,80.949 7
4²⁾	L-aminocyclopropane-1-carboxylic acid	C₄H₇NO₂	101.047 1	102.055	102.055 4	0.79	4.52	71.05,56.050 3,60.045 2, 61.028 9,68.050 2,70.065 9
5¹⁾²⁾	2-Pyrrolidone-5-carboxylic acid	C₅H₇NO₃	129.042	130.049 9	130.050 2	1.04	2.38	53.003 1,55.055,56.050 3, 57.070 7,58.065 6,58.744 9
6¹⁾	Aminocaproic acid	C₆H₁₃NO₂	131.094 1	114.091 4	114.091 8	4.6	3.21	53.003 1,53.039 5,54.034 5, 55.018 8,55.054 9,56.050 2
7¹⁾²⁾	Proline	C₅H₉NO₂	115.062 8	116.070 6	116.071	0.84	3.15	51.091 1,53.039 5,53.856 5, 55.018 5,55.055,55.301 8
8¹⁾²⁾	L-valine	C₅H₁₁NO₂	117.078 4	118.086 3	118.086 6	0.91	2.6	56.050 3,50.919 2,53.039 5, 54.203 2,55.055,50.446 2
9¹⁾²⁾	D-alloisoleucine	C₆H₁₃NO₂	131.094 1	132.101 9	132.102	1.05	1.06	51.105 2,51.695 2,55.055 2, 53.039 4,54.476 9,53.002 9
10³⁾	n-(1-deoxy-1-fructosyl)leucine(unconfirmed)	C₁₂H₂₃NO₇	293.146 9	294.154 7	294.154 7	1.31	-0.21	55.018 6,56.050 3,57.034 3, 59.037 4,69.034 5,69.070 7
11³⁾	n-(1-deoxy-1-fructosyl)valine(unconfirmed)	C₁₁H₂₁NO₇	279.131 3	280.139 1	280.139 1	0.93	-0.02	55.018 7,55.055 1,59.050 1, 68.050 2,69.034 3,70.065 9
12³⁾	n-(1-deoxy-1-fructosyl)threonine(unconfirmed)	C₁₀H₁₉NO₈	281.110 5	282.118 3	282.118 3	0.79	-0.14	56.050 2,57.034 4,69.034 4, 74.060 8,81.034 2,84.045
13¹⁾	L-gln	C₅H₁₀N₂O₃	146.068 6	147.076 4	147.076 5	0.78	0.53	50.892 4,52.530 7,52.818, 55.055,56.050 2,58.006 4
14¹⁾	Amfenac	C₁₅H₁₃NO₃	255.089	256.096 8	256.096 8	5.61	-0.16	55.857 8,61.710 4,78.034 5, 81.034 3,83.049 7,94.029 6
15¹⁾	Succinylproline	C₉H₁₃NO₅	215.078 8	216.086 7	216.086 7	0.9	0.34	53.039 3,55.018 7,55.055, 56.050 3,57.034 3,57.070 6
16¹⁾²⁾	Arginine	C₆H₁₄N₄O₂	174.111 1	173.104 4	173.104 9	0.75	2.9	58.029 9,58.041 2,59.013 9, 59.880 6,61.663 3,68.050 5
17¹⁾²⁾	Tryptophan	C₁₁H₁₂N₂O₂	204.089 3	203.082 6	203.083 1	3.83	2.4	50.658 3,51.843 5,57.034 6, 59.013 9,71.014,72.009 2
18¹⁾	n-(1-deoxy-1-fructosyl)tyrosine	C₁₅H₂₁NO₈	343.126 2	388.124 8	388.125 9	1.76	2.72	55.019,57.034 7,59.013 9, 61.988 5,66.035 1,71.014
19¹⁾	Tetrahydrodipicolinate	C₇H₉NO₄	171.052 6	216.051 2	216.051 8	1.03	2.57	57.034 7,59.013 9,69.034 5, 70.029 9,71.013 9,72.009 3
20¹⁾	Glutamylisoleucine	C₁₁H₂₀N₂O₅	260.136 7	259.13	259.130 2	3.93	0.89	57.034 5,59.013 9,68.014 5, 69.034 7,71.013 8,72.008 9
21¹⁾	Prolylyphenylalanine	C₁₄H₁₈N₂O₃	262.131 2	285.120 8	285.123 3	6.49	9.06	55.119 1,57.034 3,57.070 7, 60.902 8,68.972 9,71.049 7
22³⁾	Beta-D-glucopyranosyl anthranilate(unconfirmed)	C₁₃H₁₇NO₇	299.1	344.098 6	344.099 8	1.75	3.5	55.018 8,57.034 4,59.013 9, 69.034 5,71.014,72.993
	Alkaloids
23¹⁾	Feruloyltyramine	C₁₈H₁₉NO₄	313.130 9	314.138 7	314.138 5	6.16	-0.6	51.417 1,53.039 3,81.034 1, 57.763 6,70.065 6,77.039 3
24³⁾	(E)-n-[2-hydroxy-2-(4-hydroxyphenyl)ethyl]-3-(4-hydroxy- 3-methoxyphenyl)prop-2-enamide(unconfirmed)	C₁₈H₁₉NO₅	329.125 8	312.123	312.122 9	5.43	-0.28	81.033 9,89.039 2,91.054 9, 95.049 5,107.049 3,117.033 8
25³⁾	(E)-n-[2-hydroxy-2-(4-hydroxyphenyl)ethyl]-3-(4-hydroxyphenyl) prop-2-enamide(unconfirmed)	C₁₇H₁₇NO₄	299.115 2	282.112 5	282.112 4	5.31	-0.19	55.055 1,56.050 3,58.065 9, 67.055 1,68.050 2,69.070 7
26¹⁾²⁾	Flazine	C₁₇H₁₂N₂O₄	308.079 2	309.087	309.087	6.5	-0.08	55.018 7,55.055 3,57.994 1, 62.451 6,67.055 2,69.070 8
27³⁾	Casuarine 6-alpha-D-glucoside	C₁₄H₂₅NO₁₀	367.147 3	388.122 3	388.125 9	3.77	9.3	55.019,57.034 6,59.013 9, 61.988 5,66.034 9,71.014
28¹⁾	Betaine	C₅H₁₁NO₂	117.078 4	118.086 3	118.086 6	0.81	2.55	56.050 4,56.850 1,57.905 4, 58.037,58.065 9,58.093 2
29¹⁾	Annocherine B	C₁₈H₁₇NO₄	311.115 2	310.108 5	310.109 1	5.57	1.99	56.89,59.013 9,75.617, 93.034 7,107.050 4,108.021 9
	Flavonoid
30³⁾	3-(3,4-Dihydroxybenzyl)-7-hydroxy-5-methoxy-4-chromanone	C₁₇H₁₆O₆	316.094 1	317.102	317.102	6.87	0.17	55.018 6,55.055 1,57.861 8, 65.039 5,60.045 2,59.760 7
31³⁾	5,7-Dihydroxy-2-(4-methoxyphenyl)-3,4-dihydro-2h-1- benzopyran-4-one(unconfirmed)	C₁₆H₁₄O₅	286.083 6	285.076 9	285.077 1	7.06	0.98	55.724 7,59.013 8,65.003 4, 65.039 9,67.019 1,69.034 8
32¹⁾	Calycosin-7-O-β-D-glucoside	C₂₂H₂₂O₁₀	446.120 8	445.114	445.115 1	5.94	2.4	55.018 9,57.034 5,71.014, 63.024 1,65.003 4,59.013 9
33¹⁾	Diosmetin	C₁₆H₁₂O₆	300.062 8	299.056 1	299.056 8	6.88	2.33	59.013 9,63.024 2,65.003 6, 65.734 1,67.375,69.236 1
	Saccharides
34¹⁾²⁾	Raffinose	C₁₈H₃₂O₁₆	504.168 5	539.138 5	539.138 1	0.85	-0.58	55.019 1,58.006 2,59.014, 61.955 3,61.988 5,62.020 5
35¹⁾²⁾	D-arabinose	C₅H₁₀O₅	150.052 3	149.045 6	149.045 9	0.89	2.32	51.015 2,57.034 7,58.017 6, 59.014 2,59.116 9,61.449 9
36¹⁾	Gentiotriose	C₁₈H₃₂O₁₆	504.168 5	485.151 2	485.151 9	0.91	1.39	55.018 9,57.034 6,58.006 1, 59.013 9,69.034 7,71.014
	Organic acids
37³⁾	13S-hydroxyoctadecadienoic acid(unconfirmed)	C₁₈H₃₂O₃	296.234 6	314.269	314.269	7.37	-0.07	55.018 8,55.055,57.034 3, 57.070 7,58.029 5,60.045 2
38¹⁾	Ferulic acid	C₁₀H₁₀O₄	194.057 4	177.054 6	177.054 7	5.43	0.57	53.039 4,55.018 7,55.055, 69.070 7,67.055,63.024 3
39³⁾	Indolelactic acid(unconfirmed)	C₁₁H₁₁NO₃	205.073 3	206.081 2	206.081 4	3.82	1	55.018 6,69.034 3,74.024 4, 79.054 8,80.949 8,81.034
40¹⁾²⁾	Citric acid	C₆H₈O₇	192.026 5	191.019 7	191.020 2	1	2.45	57.034 7,58.029 8,59.013 9, 67.019 1,69.034 9,70.029 9
41³⁾	9,10-Dihode(unconfirmed)	C₁₈H₃₂O₄	312.229 5	311.222 8	311.223 3	8.69	1.63	56.421 1,83.050 5,58.006 1, 59.013 8,75.506 6,57.034 6
42¹⁾	3-Hydroxysebacic acid	C₁₀H₁₈O₅	218.114 9	495.244 6	495.245 1	5.9	1.01	55.018 9,57.034 6,71.014, 59.013 9,69.034 5,58.006 1
	Saponins
43¹⁾	Fistuloside C	C₄₅H₇₂O₁₉	916.466 2	899.463 5	899.463 7	5.41	0.2	69.034 2,69.070 6,71.049 8, 75.044 7,73.065 5,73.029 1
44³⁾	Neogitogenin 3-[glucosyl-(1->2)-glucosyl-(1->4)- galactoside] (unconfirmed)	C₄₅H₇₄O₁₉	918.481 9	901.479 2	901.479 4	5.8	0.24	67.055,69.034 2,69.070 6, 73.029 1,73.065 5,79.054 9
	Coumarins
45²⁾	Coumaroyl tyramine	C₁₇H₁₇NO₃	283.120 3	284.128 1	284.128 1	6.07	-0.22	51.023 9,53.039 5,55.018 7, 55.054 9,56.216 8,65.039 7

No.	Metabolite	VIP	FC	P	Ion
1	L-arginine	3.52	0.05	<0.05	+
2	L-phenylalanine	4.61	0.19	<0.05	+
3	1-Aminocyclopropane-1-carboxylic acid	6.46	0.12	<0.05	+
4	2-Pyrrolidone-5-carboxylic acid	4.21	0.18	<0.05	+
5	Aminocaproic acid	2.07	0.32	<0.05	+
6	Proline	2.43	0.26	<0.05	+
7	L-valine	3.85	0.15	<0.05	+
8	D-alloisoleucine	5.58	0.09	<0.05	+
9	n-(1-deoxy-1-fructosyl)leucine	2.51	5.37	<0.05	+
10	n-(1-deoxy-1-fructosyl)valine	3.43	2.42	<0.05	+
11	n-(1-deoxy-1-fructosyl)threonine	4.73	17.95	<0.05	+
12	Tryptophan	3.70	0.001	<0.05	-
13	n-(1-deoxy-1-fructosyl)tyrosine	6.78	521.44	<0.05	-
14	Feruloyltyramine	3.59	0.34	<0.05	+
15	(E)-n-[2-hydroxy-2-(4-hydroxyphenyl)ethyl]-3-(4-hydroxy-3-methoxyphenyl)prop-2-enamide	4.53	0.13	<0.05	+
16	(E)-n-[2-hydroxy-2-(4-hydroxyphenyl)ethyl]-3-(4-hydroxyphenyl)prop-2-enamide	3.63	0.07	<0.05	+
17	Casuarine 6-α-D-glucoside	5.30	197.47	<0.05	-
18	Coumaroyl tyramine	2.46	0.31	<0.05	+
19	Fistuloside C	2.19	0.004	<005	+
20	Citric acid	5.34	2.25	<0.05	-
21	Raffinose	2.84	0.22	<0.05	-
22	D-arabinose	2.01	0.34	<0.05	-

No.	Metabolite	VIP	FC	P	Ion
1	L-arginine	3.52	0.05	<0.05	+
2	L-phenylalanine	4.61	0.19	<0.05	+
3	1-Aminocyclopropane-1-carboxylic acid	6.46	0.12	<0.05	+
4	2-Pyrrolidone-5-carboxylic acid	4.21	0.18	<0.05	+
5	Aminocaproic acid	2.07	0.32	<0.05	+
6	Proline	2.43	0.26	<0.05	+
7	L-valine	3.85	0.15	<0.05	+
8	D-alloisoleucine	5.58	0.09	<0.05	+
9	n-(1-deoxy-1-fructosyl)leucine	2.51	5.37	<0.05	+
10	n-(1-deoxy-1-fructosyl)valine	3.43	2.42	<0.05	+
11	n-(1-deoxy-1-fructosyl)threonine	4.73	17.95	<0.05	+
12	Tryptophan	3.70	0.001	<0.05	-
13	n-(1-deoxy-1-fructosyl)tyrosine	6.78	521.44	<0.05	-
14	Feruloyltyramine	3.59	0.34	<0.05	+
15	(E)-n-[2-hydroxy-2-(4-hydroxyphenyl)ethyl]-3-(4-hydroxy-3-methoxyphenyl)prop-2-enamide	4.53	0.13	<0.05	+
16	(E)-n-[2-hydroxy-2-(4-hydroxyphenyl)ethyl]-3-(4-hydroxyphenyl)prop-2-enamide	3.63	0.07	<0.05	+
17	Casuarine 6-α-D-glucoside	5.30	197.47	<0.05	-
18	Coumaroyl tyramine	2.46	0.31	<0.05	+
19	Fistuloside C	2.19	0.004	<005	+
20	Citric acid	5.34	2.25	<0.05	-
21	Raffinose	2.84	0.22	<0.05	-
22	D-arabinose	2.01	0.34	<0.05	-

No.	Metabolite	VIP	FC	P	Ion
1	L-arginine	3.48	0.21	<0.05	+
2	L-phenylalanine	4.39	0.37	<0.05	+
3	1-aminocyclopropane-1-carboxylic acid	6.46	0.25	<0.05	+
4	2-Pyrrolidone-5-carboxylic acid	4.27	0.28	<0.05	+
5	Aminocaproic acid	2.13	0.39	<0.05	+
6	Proline	2.35	0.41	<0.05	+
7	L-valine	3.87	0.27	<0.05	+
8	D-alloisoleucine	5.74	0.18	<0.05	+
9	n-(1-deoxy-1-fructosyl)leucine	2.54	4.82	<0.05	+
10	n-(1-deoxy-1-fructosyl)valine	4.00	2.65	<0.05	+
11	n-(1-deoxy-1-fructosyl)threonine	4.18	12.35	<0.05	+
12	Tryptophan	3.95	0.03	<0.05	-
13	n-(1-deoxy-1-fructosyl)tyrosine	5.51	293.86	<0.05	-
14	Feruloyltyramine	3.72	0.40	<0.05	+
15	(E)-n-[2-hydroxy-2-(4-hydroxyphenyl)ethyl]-3-(4-hydroxy-3-methoxyphenyl)prop-2-enamide	4.47	0.28	<0.05	+
16	(E)-n-[2-hydroxy-2-(4-hydroxyphenyl)ethyl]-3-(4-hydroxyphenyl)prop-2-enamide	3.81	0.12	<0.05	+
17	Flazine	2.11	165.00	<0.05	+
18	Casuarine 6-α-D-glucoside	3.78	86.55	<0.05	-
19	Coumaroyl tyramine	2.56	0.36	<0.05	+
20	Fistuloside C	2.30	0.06	<0.05	+
21	Citric acid	5.81	2.27	<0.05	-
22	Raffinose	3.16	0.18	<0.05	-
23	D-arabinose	2.04	0.41	<0.05	-

No.	Metabolite	VIP	FC	P	Ion
1	L-arginine	3.48	0.21	<0.05	+
2	L-phenylalanine	4.39	0.37	<0.05	+
3	1-aminocyclopropane-1-carboxylic acid	6.46	0.25	<0.05	+
4	2-Pyrrolidone-5-carboxylic acid	4.27	0.28	<0.05	+
5	Aminocaproic acid	2.13	0.39	<0.05	+
6	Proline	2.35	0.41	<0.05	+
7	L-valine	3.87	0.27	<0.05	+
8	D-alloisoleucine	5.74	0.18	<0.05	+
9	n-(1-deoxy-1-fructosyl)leucine	2.54	4.82	<0.05	+
10	n-(1-deoxy-1-fructosyl)valine	4.00	2.65	<0.05	+
11	n-(1-deoxy-1-fructosyl)threonine	4.18	12.35	<0.05	+
12	Tryptophan	3.95	0.03	<0.05	-
13	n-(1-deoxy-1-fructosyl)tyrosine	5.51	293.86	<0.05	-
14	Feruloyltyramine	3.72	0.40	<0.05	+
15	(E)-n-[2-hydroxy-2-(4-hydroxyphenyl)ethyl]-3-(4-hydroxy-3-methoxyphenyl)prop-2-enamide	4.47	0.28	<0.05	+
16	(E)-n-[2-hydroxy-2-(4-hydroxyphenyl)ethyl]-3-(4-hydroxyphenyl)prop-2-enamide	3.81	0.12	<0.05	+
17	Flazine	2.11	165.00	<0.05	+
18	Casuarine 6-α-D-glucoside	3.78	86.55	<0.05	-
19	Coumaroyl tyramine	2.56	0.36	<0.05	+
20	Fistuloside C	2.30	0.06	<0.05	+
21	Citric acid	5.81	2.27	<0.05	-
22	Raffinose	3.16	0.18	<0.05	-
23	D-arabinose	2.04	0.41	<0.05	-

No.	Metabolite	VIP	FC	P	Ion
1	L-arginine	3.07	0.25	<0.05	+
2	1-aminocyclopropane-1-carboxylic acid	5.19	0.49	<0.05	+
3	(E)-n-[2-hydroxy-2-(4-hydroxyphenyl)ethyl]-3-(4-hydroxy-3-methoxyphenyl)prop-2-enamide	3.96	0.48	<0.05	+
4	Casuarine 6-α-D-glucoside	8.46	2.28	<0.05	-

No.	Metabolite	VIP	FC	P	Ion
1	L-arginine	3.07	0.25	<0.05	+
2	1-aminocyclopropane-1-carboxylic acid	5.19	0.49	<0.05	+
3	(E)-n-[2-hydroxy-2-(4-hydroxyphenyl)ethyl]-3-(4-hydroxy-3-methoxyphenyl)prop-2-enamide	3.96	0.48	<0.05	+
4	Casuarine 6-α-D-glucoside	8.46	2.28	<0.05	-

基于植物代谢组学方法的陕产黄精不同炮制品化学差异研究

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宋艺君 ¹^,² , 孙婧 ¹ , 郭涛 ³ , 高阳丽 ¹ , 宋瑞 ¹ , 卢旭阳 ¹ , 张凯 ¹ , 张桥 ¹^,² , 赵重博 ¹^,² , 孙静 ¹^,²

中国药学杂志 | 论著 2024,59(21): 2011-2021

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中国药学杂志 | 论著 2024, 59(21): 2011-2021

基于植物代谢组学方法的陕产黄精不同炮制品化学差异研究

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宋艺君¹^,², 孙婧¹, 郭涛³, 高阳丽¹, 宋瑞¹, 卢旭阳¹, 张凯¹, 张桥¹^,², 赵重博¹^,², 孙静¹^,²

作者信息

¹ 陕西中医药大学药学院, 陕西咸阳 712046

² 陕西省中药饮片工程技术研究中心, 陕西咸阳 712046

³ 空军第九八六医院, 西安 710054

宋艺君,女,博士,教授研究方向:中药饮片生熟异治炮制机制研究 Tel:(029)38185172

Analysis of Chemical Variability on Different Processed Products of Polygonati Rhizoma Produced in Shaanxi Province Based on Plant Metabolomics

Yijun SONG¹^,², Jing SUN¹, Tao GUO³, Yangli GAO¹, Rui SONG¹, Xuyang LU¹, Kai ZHANG¹, Qiao ZHANG¹^,², Chongbo ZHAO¹^,², Jing SUN¹^,²

Affiliations

¹ College of Pharmacy, Shaanxi University of Chinese Medicine, Xianyang 712046, China

² Shaanxi Engineering Technology Research Center of Prepared Slices, Xianyang 712046, China

³ No.986 Hospital of PLAAF, Xi'an 710054, China

出版时间: 2024-11-08

文章导航

摘要

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目的分析陕产黄精不同炮制品化学成分的差异。方法采用超高效液相色谱-静电场轨道阱高分辨质谱(UPLC-Q-Exactive Orbitrap-MS)技术对陕产黄精不同炮制品的化学成分进行测定,所得数据采用主成分分析(PCA)法与正交偏最小二乘判别分析(OPLS-DA)处理,陕产黄精不同炮制品的差异指标成分通过精准的一级质谱质荷比和二级质谱碎片离子同对照品图谱和软件数据库搜索以及相关文献报道成分进行判别分析。结果共鉴定得到45个成分,通过OPLS-DA,筛选出不同炮制品之间差异性化学成分23个,包括氨基酸类13个,生物碱类5个,糖类2个,香豆素类1个,皂苷类1个,有机酸类1个。。结论黄精、蒸黄精、酒黄精存在一定的化学成分差异,可为黄精炮制品的质量控制和药效研究奠定物质基础。

关键词

黄精 / 蒸黄精 / 酒黄精 / 不同炮制品 / 化学差异 / 植物代谢组学

Abstract

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OBJECTIVE To analyze the difference of chemical components of different processed products of Polygonati Rhizoma produced in Shaanxi Province. METHODS Ultra-high performance liquid chromatography coupled with hybrid quadrupole-orbitrap mass spectrometry (UPLC-Q-Exactive Orbitrap-MS) was developed to determine the chemical components of different processed products of Polygonati Rhizoma produced in Shaanxi Province. The data was analyzed by principal component analysis (PCA) and orthogonal partial least squares discriminant analysis (OPLS-DA). The structures of chemical markers of different processed products of the plants were identified based on accurate primary mass spectrometry and secondary mass spectrometry fragment ion, combined with the reference map, software database searching and related literature. RESULTS A total of 45 components were identified, there were 23 chemical components with significant differences distinguished by the method of OPLS-DA, including 13 amino acids, 5 alkaloids, 2 saccharides, 1 coumarin, 1 saponin, 1 organic acids. CONCLUSION There are some chemical differences among the three products. This study can provide material basis for the quality control and pharmacodynamic research of processed products of Polygonati Rhizoma.

Key words

Polygonati Rhizoma / steamed Polygonati Rhizoma / wine-processed Polygonati Rhizoma / different processed products / chemical difference / plant metabolomics

引用本文

宋艺君, 孙婧, 郭涛, 高阳丽, 宋瑞, 卢旭阳, 张凯, 张桥, 赵重博, 孙静. 基于植物代谢组学方法的陕产黄精不同炮制品化学差异研究. 中国药学杂志, 2024 , 59 (21) : 2011 -2021 .

Yijun SONG, Jing SUN, Tao GUO, Yangli GAO, Rui SONG, Xuyang LU, Kai ZHANG, Qiao ZHANG, Chongbo ZHAO, Jing SUN. Analysis of Chemical Variability on Different Processed Products of Polygonati Rhizoma Produced in Shaanxi Province Based on Plant Metabolomics[J]. Chinese Pharmaceutical Journal, 2024 , 59 (21) : 2011 -2021 .

正文

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黄精为百合科植物滇黄精(Polygonatum kingianum Coll. et Hemsl.)、多花黄精(Polygonatum cyrtonema Hua)、黄精(Polygonatum sibiricum Red.)的干燥根茎^[1],是临床常用的补气养阴类中药,始载于《名医别录》^[2],被列为上品。黄精味甘,性平,归脾、肺、肾经,具补气养阴、健脾、润肺、益肾的功效^[3],是我国大量使用的药食两用品种之一。

唐代《食疗本草》和明代《本草原始》记载黄精生品有“刺人咽喉”的不良反应^[4],清代《医林纂要·药性》^[4]也指出黄精“生用则戟人喉吻”,因此黄精临床上多使用炮制品。自南北朝至近代,黄精的炮制方法可归纳为不加辅料的清蒸法和加辅料的蒸/煮法,包括单蒸法(蒸晒)、重蒸法、九蒸九晒法、酒制法、黑豆汁制法等^[2],根据应用目的不同而采用具体的炮制方法。据考证^[1],蒸制能增强黄精补脾润肺益肾的作用,并可除去麻味,以免刺激咽喉,而酒制能助其药势,使其滋而不腻,更好地发挥补益作用。现代中医临床多使用蒸黄精和酒黄精^[5]。《中国药典》2020年版收录的黄精炮制品为酒黄精^[6],《全国中药炮制规范》1988年版收录的黄精炮制品为蒸黄精和酒黄精^[7],说明蒸黄精和酒黄精为应用较广泛的黄精炮制品。在陕卫中医药发〔2020〕24号文件中明确规定,黄精属于45种秦药品种下属的10种区域特色中草药之一,为了进一步促进黄精不同炮制品在中医临床的安全、有效应用,本实验拟比较陕产黄精(Polygonatum sibiricum Red.) 不同炮制品的化学成分差异。

植物代谢组学是采用高通量分析技术,以代谢组群指标分析为基础,从而对中药的代谢成分进行无差别、整体、全面地分析^[8-9]。近几年,植物代谢组学技术广泛应用于中药研究,如不同药用部位的鉴别^[8,10],药用植物最佳采收期确定^[11-12],不同基原的鉴别^[13-14],中药炮制机制研究^[15-16],不同产地和生长方式药材的品质差异^[17-18],不同炮制品的成分差异^[19-20]等。本实验基于UPLC-Q-Exactive Orbitrap-MS代谢组学技术对陕产黄精不同炮制品的化学成分进行对比研究,为阐明陕产黄精不同炮制品的成分差异以及黄精炮制品的质量控制和药效研究奠定物质基础。

1 仪器与材料

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1.1 仪器

Vanquish超高效液相色谱仪(Thermo公司,USA);Q Exactive HFX高分辨质谱仪(Thermo公司,USA);梅特勒MS105/A型十万分之一电子天平(北京明宸中寰科技有限公司);H2-16KR台式高速冷冻离心机(湖南可成仪器设备有限公司);SK-1型快速混匀器(武汉格莱莫检测设备有限公司);FW135型中草药粉碎机(天津市泰斯特仪器有限公司);KQ5200E型超声波清洗器(昆山超声仪器有限公司);真空干燥箱(天津泰斯特仪器有限公司)。

1.2 试药

对照品L-精氨酸(批号H11M10Y82633)、L-苯丙氨酸(批号N26GB169364)、L-氨基环丙烷羧酸(批号D03GB170196)、DL-焦谷氨酸(批号YM0327JA14)、L-缬氨酸(批号S05J12I135887)、D-别异亮氨酸(批号B13J9D52846)、L-色氨酸(批号M20IB210217)、枸橼酸(批号N07IB231318)、棉籽糖(批号S02F12G139355)、D-阿拉伯糖(批号A10GB144812)、对香豆酰酪胺(批号Y30S11W126554)、酒渣碱(批号N25IB233222)、脯氨酸(批号Z12O11H127142)(上海源叶生物科技有限公司,纯度均≥98%);甲醇、乙腈为色谱纯;甲酸、异丙醇为色谱纯,均为色谱级;黄酒(绍兴黄酒酿造有限公司,酒精度12%,批号20210306);纯净水(Milli-Q^®HX 7000纯水仪,美国默克公司)。

1.3 植物样本

6批黄精药材于2021年10月采自陕西省汉中市略阳县(编号1,2,3)和留坝县(编号4,5,6)黄精种植基地,经陕西中医药大学药学院张岗教授鉴定为百合科植物黄精(Polygonatum sibiricum Red.)的新鲜根茎,除去须根,洗净,置沸水中略烫至透心,阴干后得黄精。对黄精进行清蒸^[7]和酒蒸^[6]炮制得到蒸黄精和酒黄精。对黄精、蒸黄精和酒黄精分别切制得到相应饮片,干燥,保存备用。样品信息见表1。

2 方法

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2.1 黄精炮制品的制备^[6-7]

黄精:取黄精药材,除去杂质,洗净,略润,切厚片,干燥。

蒸黄精:取净黄精,洗净,蒸至色棕黑滋润时取出,切厚片,干燥。

酒黄精:取净黄精,照酒炖法或酒蒸法(通则0213)炖透或蒸透,稍晾,切厚片,干燥。每100 kg黄精,用黄酒20 kg。

2.2 供试品溶液制备

在参考文献[20]的基础上改良方法来制备供试品。将黄精不同炮制品在50 ℃烘箱干燥5 h,将干品粉碎后过4号筛。分别称取黄精不同炮制品粉末0.1 g,精密称定,分别加入100 μL预冷水,涡旋60 s,加入400 μL预冷甲醇乙腈溶液(1∶1),涡旋60 s,低温超声30 min,2次,-20 ℃放置1 h沉淀蛋白,12 000 r·min^-1,4 ℃离心20 min,取上清液真空干燥后复溶于200 μL体积分数30%乙腈,涡旋,14 000×g 4 ℃离心15 min,取上清液,用0.22 μm微孔滤膜滤过,取续滤液,即得。另取上述测试样品各10 μL混合,制备质量控制(QC)样本,用于检测仪器的稳定性。

2.3 对照品溶液制备

分别精密称取各对照品适量,置于10 mL的量瓶中,用甲醇溶解定容,制备单一对照品储备液,混合对照品溶液储备液由各对照品储备液混合并稀释得到,均置于4 ℃保存。

2.4 色谱条件

色谱柱为Waters HSS T3 (2.1 mm×100 mm,1.8 μm),流动相A为体积分数0.1%甲酸-水溶液,B为0.1%甲酸,乙腈-异丙醇(1∶1)。梯度洗脱条件:0~2 min,90%A;2~6 min,90%~40%A;6~15 min,40%A。流速0.3 mL·min^-1,柱温40 ℃,进样室温度4 ℃,进样量2 μL。

2.5 质谱条件

离子源为ESI源,正/负离子检测模式,鞘气压力275.8 kPa,辅助气是氮气,压力68.95 kPa;离子喷雾电压3 000~2 800 V;离子传输管温度320 ℃;辅助气温度350 ℃;扫描模式为Full-scan MS²模式,一级扫描范围m/z 70~1 050,二级扫描范围m/z 200~2 000,一级分辨率70 000,二级分辨率17 500。MS/MS模式时,碰撞能为60 eV。

2.6 数据处理

原始数据用代谢组学处理软件Progenesis QI(美国Waters公司)进行基线过滤、保留时间校正、峰对齐、峰识别、积分和归一化等预处理,主要参数设置如下:保留时间范围为0~17 min,m/z 70~1 050,保留时间和m/z允许偏差分别为0.1 min、5×10^-6,最终得到一个保留时间、质荷比和峰强度的数据矩阵。将所得数据导入Simca-p14.0软件进行无监督的主成分分析(PCA),初步观察陕产黄精不同炮制品的聚集情况,再根据t检验(P<0.05),正交偏最小二乘判别分析(OPLS-DA)模型得到的变量权重值(VIP≥2),差异倍数FC≥2或≤0.5,寻找差异化学成分,从整体到部分更全面分析陕产黄精不同炮制品化学成分的差异。OPLS-DA模型通过CV-ANOVA验证,P<0.05说明该模型预测性能强,差异具有统计学意义。

3 结果与分析

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3.1 陕产黄精不同炮制品的基峰离子流图谱分析

具有代表性的黄精不同炮制品的UPLC-Q-Exactive Orbitrap-MS基峰离子流图见图1~2,直观显示其不同炮制品的化学成分之间存在明显差异。将对照品图谱、数据库搜索(HMDB、Mass Bank、Thermo mzcloud、PubChem)和相关文献报道的化合物同检测到的化合物保留时间、相对分子质量、碎片离子等信息进行对照,共鉴定出45个代谢物,其中包括氨基酸类22个,生物碱类7个,黄酮类4个,糖类3个,皂苷类2个,有机酸类6个,香豆素类1个。结果见表2。

3.2 多元统计分析结果

图1~2表明,陕产黄精不同炮制品的化学成分存在差异,为确定黄精不同炮制品的化学成分差异,根据“2.5”项下对黄精生品、清蒸品、酒蒸品UPLC色谱图处理,得627个变量,样品为3组(每组样品数n=6),得数据矩阵18×627,对其进行PCA分析。图3为生黄精、蒸黄精和酒黄精UPLC色谱图的PCA分析散点图。从图3中可看出,生黄精、蒸黄精和酒黄精三者明显分开,蒸黄精和酒黄精相对靠近一些,说明三者代谢组之间存在一定的差异,蒸黄精和酒黄精的差异小一些,进一步地说明生黄精和炮制品之间化学组成存在一定的差异,同时不同的炮制方法对生黄精化学组成的改变不同。

3.2.1 生、酒黄精代谢组差异分析

对生黄精和酒黄精的UPLC色谱图进行PCA分析,数据矩阵为12×627。图4为生黄精和酒黄精UPLC色谱图PCA分析的散点图。图4显示,生黄精和酒黄精沿t[1]轴明显分开,两者代谢组明显不同,所含成分差异较大。采用OPLS-DA进行比较,OPLS-DA模型验证结果表明,其未过度拟合(

R X 2

=0.97,

R Y 2

=1.00,Q²=1.00,P<0.05),质量良好。其OPLS-DA得分图见图5A,可看出生黄精和酒黄精更明显区分开来。S-plot图能够通过对变量的量级与其可靠性进行比较来预测差异成分,主要用于从组学数据中筛选出指定的代谢物。S-plot图中的每一个点代表一个变量,在S-plot(图5B)图中位于“S”两端的变量属于关键变量。根据t检验(P<0.05)、变量权重值VIP≥2结合差异倍数FC≥2或≤0.5进行筛选,结合已鉴定成分得到黄精和酒黄精22个差异指标成分(表3)。

3.2.2 生、蒸黄精UPLC代谢组差异分析

对生黄精和蒸黄精的UPLC色谱图进行PCA分析,数据矩阵为12×627。图6为生黄精和蒸黄精UPLC色谱图PCA分析的散点图。图6显示,生黄精和蒸黄精沿t1轴明显分开,两者代谢组明显不同,所含成分差异较大。采用OPLS-DA进行比较,OPLS-DA模型验证结果表明,其未过度拟合(

R X 2

=0.969,

R Y 2

=1.00,Q²=1.00,P<0.05),质量良好。其OPLS-DA得分图见图7A,可看出生黄精和蒸黄精更明显区分开来。S-plot图能够通过对变量的量级与其可靠性进行比较来预测差异成分,主要用于从组学数据中筛选出指定的代谢物。S-plot图中的每一个点代表一个变量,在S-plot(图7B)图中位于“S”两端的变量属于关键变量。根据t检验(P<0.05)、变量权重值VIP≥2结合差异倍数FC≥2或≤0.5进行筛选,结合已鉴定成分得到黄精和蒸黄精23个差异指标成分(表4)。

3.2.3 蒸、酒黄精UPLC代谢组差异分析

对蒸黄精和酒黄精的UPLC色谱图进行PCA分析,数据矩阵为12×627。图8为蒸黄精和酒黄精UPLC色谱图PCA分析的散点图。图8显示,蒸黄精和酒黄精沿t1轴明显分开,两者代谢组明显不同,所含成分差异较大。采用OPLS-DA进行比较,OPLS-DA模型验证结果表明,其未过度拟合(

R X 2

=0.856,

R Y 2

=1.00,Q²=0.999,P<0.05),质量良好。其OPLS-DA得分图见图9A,可看出蒸黄精和酒黄精更明显区分开来。S-plot图能够通过对变量的量级与其可靠性进行比较来预测差异成分,主要用于从组学数据中筛选出指定的代谢物。S-plot图中的每一个点代表一个变量,在S-plot(图9B)图中位于“S”两端的变量属于关键变量。根据t检验(P<0.05)、变量权重值VIP≥2结合差异倍数FC≥2或≤0.5进行筛选,结合已鉴定成分得到蒸黄精和酒黄精4个差异指标成分(表5)。

根据t检验(P<0.05)、变量权重值VIP≥2结合差异倍数FC≥2或≤0.5进行筛选,结合已鉴定成分明确黄精、蒸黄精和酒黄精23个差异指标成分:L-精氨酸(t_R=0.70 min,m/z 175.119 1),L-苯丙氨酸(t_R=1.72 min,m/z 166.086 3),L-氨基环丙烷羧酸(t_R=0.79 min,m/z 102.055 4),DL-焦谷氨酸(t_R=1.04 min,m/z 130.050 2),氨基己酸(t_R=4.60 min,m/z 114.091 8),脯氨酸(t_R=0.84 min,m/z 116.071 0),L-缬氨酸(t_R=0.91 min,m/z 118.086 6),D-别异亮氨酸(t_R=1.05 min,m/z 132.102 0),n-(1-deoxy-1-fructosyl)leucine(t_R=1.31 min,m/z 294.154 7), n-(1-deoxy-1-fructosyl)valine(t_R=0.93 min,m/z 280.139 1),n-(1-deoxy-1-fructosyl)threonine(t_R=0.79 min,m/z 282.118 3),L-色氨酸(t_R=3.83 min,m/z 203.083 1),N-苷(t_R=1.76 min,m/z 388.125 9),阿魏酰酪胺(t_R=6.16 min,m/z 314.138 5),(e)-n-[2-hydroxy-2-(4-hydroxyphenyl)ethyl]-3-(4-hydroxy-3-methoxyphenyl)prop-2-enamide(t_R=5.43 min,m/z 312.122 9), (e)-n-[2-hydroxy-2-(4-hydroxyphenyl)ethyl]-3-(4-hydroxyphenyl) prop-2-enamide(t_R=5.31 min,m/z 282.112 5),酒渣碱(t_R=6.50 min,m/z 309.087 0),木麻黄-6-α-D-葡糖苷(t_R=3.77 min,m/z 388.125 9),对香豆酰酪胺(t_R=6.07 min,m/z 284.128 1),fistuloside c(t_R=5.41 min,m/z 899.463 7),柠檬酸(t_R=1.00 min,m/z 191.020 2),棉籽糖(t_R=0.85 min,m/z 539.138 1),D-阿拉伯糖(t_R=0.89 min,m/z 149.045 9)。

3.3 差异代谢物的聚类热图分析

为进一步了解SP、QZP和JZP代谢成分的变化规律,对3组样本的23种显著性差异变量绘制聚类热图,见图10。红色部分表示上调差异表达变量,蓝色部分表示下调差异表达变量,且颜色越深的部分表明差异越显著。其中,QZP和JZP聚为一类,SP相对于这两组有14种差异变量上调,即相对含量增加,占到全部差异变量的60.87%,包括DL-焦谷氨酸,D-别异亮氨酸,L-缬氨酸,氨基己酸,对香豆酰酪胺,阿魏酰酪胺,L-氨基环丙烷羧酸,L-精氨酸, 脯氨酸,棉籽糖,L-色氨酸,fistuloside c,(e)-n-[2-hydroxy-2-(4-hydroxyphenyl)ethyl]-3-(4-hydroxy-3-methoxyphenyl)prop-2-enamide,(e)-n-[2-hydroxy-2-(4-hydroxyphenyl)ethyl]-3-(4-hydroxyphenyl)prop-2-enamide;有9种差异变量下调,即相对含量减少,占到全部差异变量的39.13%,包括L-苯丙氨酸,N-苷,枸橼酸,酒渣碱,木麻黄-6-α-D-葡糖苷,D-阿拉伯糖,n-(1-deoxy-1-fructosyl)leucine,n-(1-deoxy-1-fructosyl)valine,n-(1-deoxy-1-fructosyl)threonine。

将23种差异变量按结构分类,得到氨基酸类13个,生物碱类5个,糖类2个,有机酸类1个,皂苷类1个,香豆素类1个,各类化合物的占比情况分别为氨基酸类56.52%,生物碱类21.74%,糖类8.70%,有机酸类4.35%,皂苷类4.35%,香豆素类4.35%。

4 讨论

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黄精的炮制方法历代本草均有记载,演变至今以蒸黄精、酒黄精^[7]应用较为广泛。中药炮制理论认为蒸制炮制后能增强药物补益作用^[21],黄精最早的炮制方法见于《雷公炮灸论》的单蒸法^[22],即蒸黄精,《太平圣惠方》独创了黄精与酒共制的方法^[23],即酒黄精,这些为黄精清蒸、酒蒸提供依据。同时,生黄精从《雷公炮炙论》雷氏之法之“溪水洗净”,“刀薄切”沿用至今。以上说明黄精生品、清蒸品、酒蒸品在中医临床使用都具有悠久的历史,本实验旨在为黄精不同炮制品的临床分别使用提供化学支持。

本实验采用UPLC-Q-Exactive Orbitrap-MS代谢组学技术对陕产黄精不同炮制品的化学成分进行了比较研究,从黄精炮制品中指认化学成分45个,包括氨基酸类成分22个,生物碱类成分7个,有机酸类成分6个,黄酮类成分4个,糖类成分3个,皂苷类成分2个,香豆素类成分1个。经t检验、多元统计分析结合FC值分析结果,得到黄精不同炮制品的显著性差异化学成分23个,氨基酸、糖等初级代谢产物以及生物碱、皂苷等次级代谢产物的相对含量存在较大差异。与生黄精相比,酒黄精所含n-(1-deoxy-1-fructosyl)leucine,n-(1-deoxy-1-fructosyl)valine,枸橼酸,n-(1-deoxy-1-fructosyl)threonine,n-(1-deoxy-1-fructosyl)tyrosine,木麻黄-6-α-D-葡糖苷,酒渣碱,D-阿拉伯糖的含量增加,L-精氨酸,L-苯丙氨酸,L-氨基环丙烷羧酸,D,L-焦谷氨酸,氨基己酸,脯氨酸,L-缬氨酸,D-别异亮氨酸,L-色氨酸,阿魏酰酪胺,(E)-n-[2-hydroxy-2-(4-hydroxyphenyl)ethyl]-3-(4-hydroxy-3-methoxyphenyl)prop-2-enamide,(E)-n-[2-hydroxy-2-(4-hydroxyphenyl)ethyl]-3-(4-hydroxyphenyl)prop-2-enamide,对香豆酰酪胺,fistuloside C,棉籽糖的含量减少;与生黄精相比,蒸黄精所含酒渣碱,n-(1-deoxy-1-fructosyl)leucine,木麻黄-6-α-D-葡糖苷,枸橼酸,D-阿拉伯糖,n-(1-deoxy-1-fructosyl)valine,n-(1-deoxy-1-fructosyl)threonine,n-(1-deoxy-1-fructosyl)tyrosine的含量增加,L-精氨酸,L-苯丙氨酸,L-氨基环丙烷羧酸,D,L-焦谷氨酸,氨基己酸,脯氨酸,L-缬氨酸,D-别异亮氨酸,阿魏酰酪胺,对香豆酰酪胺,fistuloside C,L-色氨酸,(e)-n-[2-hydroxy-2-(4-hydroxyphenyl)ethyl]-3-(4-hydroxy-3-methoxyphenyl)prop-2-enamide,(e)-n-[2-hydroxy-2-(4-hydroxyphenyl)ethyl]-3-(4-hydroxyphenyl)prop-2-enamide,棉籽糖的含量减少;与蒸黄精相比,酒黄精所含木麻黄-6-α-D-葡糖苷,n-(1-deoxy-1-fructosyl)leucine,n-(1-deoxy-1-fructosyl)threonine,N-苷,D-阿拉伯糖,棉籽糖的含量增加,L-精氨酸,L-氨基环丙烷羧酸,L-苯丙氨酸,D,L-焦谷氨酸,氨基己酸,脯氨酸,L-缬氨酸,D-别异亮氨酸,L-色氨酸,阿魏酰酪胺,对香豆酰酪胺,(E)-n-[2-hydroxy-2-(4-hydroxyphenyl)ethyl]-3-(4-hydroxy-3-methoxyphenyl)prop-2-enamide,(E)-n-[2-hydroxy-2-(4-hydroxyphenyl)ethyl]-3-(4-hydroxyphenyl)prop-2-enamide,n-(1-deoxy-1-fructosyl)valine,酒渣碱,fistuloside C,枸橼酸的含量减少。

综上所述,生黄精、蒸黄精和酒黄精化学成分各不相同,导致其药理活性可能也不尽相同。其中,生黄精中氨基酸类成分质量分数高,炮制品中单糖的质量分数高,可能因为在加热蒸制的过程中,黄精多糖水解为单糖和寡糖等小分子糖类成分,虽然随着反应的进行,小分子糖类和氨基酸类成分发生美拉德反应,使小分子糖类和氨基酸类成分含量减少,但是总的来说,小分子糖类还是增加的,因为小分子糖类容易被人体吸收,所以炮制品的补益作用增强;另外,炮制品中酒渣碱的质量分数高于生品,其可能更有利于提高免疫作用^[24],因此三者在应用时可根据用途不同而适当选取,即所谓的对症下药。实验结果表明,中药成分复杂,不同成分的变化可能改变其药理活性,同时从炮制化学角度证明炮制可整体改变药效。本实验从新的角度对黄精生品和炮制品进行评价,为药物炮制研究提供了新的思路。

基金

收起

国家自然科学基金项目(82104395)
陕西省科技厅项目(2024SF-YBXM-456)
陕西省高水平中医药重点学科资助(中药炮制学)(174010324027/2024)

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2024年第59卷第21期

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接收时间：2024-04-23
首发时间：2025-11-16
出版时间：2024-11-08

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收稿日期：2024-04-23

基金

国家自然科学基金项目(82104395)

陕西省科技厅项目(2024SF-YBXM-456)

陕西省高水平中医药重点学科资助(中药炮制学)(174010324027/2024)

作者信息

¹ 陕西中医药大学药学院, 陕西咸阳 712046

² 陕西省中药饮片工程技术研究中心, 陕西咸阳 712046

³ 空军第九八六医院, 西安 710054

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2种不同金属材料的力学参数

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

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TxT

No.	Name	Place of origin (in Chinese)	Collection or preparation time
S1	Polygonati Rhizoma(SP)	Lueyang Hanzhong Shaanxi (陕西汉中略阳)	2021.10
S2	Polygonati Rhizoma(SP)	Lueyang Hanzhong Shaanxi (陕西汉中略阳)	2021.10
S3	Polygonati Rhizoma(SP)	Lueyang Hanzhong Shaanxi (陕西汉中略阳)	2021.10
S4	Polygonati Rhizoma(SP)	Liuba Hanzhong Shaanxi (陕西汉中留坝)	2021.10
S5	Polygonati Rhizoma(SP)	Liuba Hanzhong Shaanxi (陕西汉中留坝)	2021.10
S6	Polygonati Rhizoma(SP)	Liuba Hanzhong Shaanxi (陕西汉中留坝)	2021.10
S7	Steamed Polygonati Rhizoma (QZP)	Lueyang Hanzhong Shaanxi (陕西汉中略阳)	2021.11
S8	Steamed Polygonati Rhizoma (QZP)	Lueyang Hanzhong Shaanxi (陕西汉中略阳)	2021.11
S9	Steamed Polygonati Rhizoma (QZP)	Lueyang Hanzhong Shaanxi (陕西汉中略阳)	2021.11
S10	Steamed Polygonati Rhizoma (QZP)	Liuba Hanzhong Shaanxi (陕西汉中留坝)	2021.11
S11	Steamed Polygonati Rhizoma (QZP)	Liuba Hanzhong Shaanxi (陕西汉中留坝)	2021.11
S12	Steamed Polygonati Rhizoma (QZP)	Liuba Hanzhong Shaanxi (陕西汉中留坝)	2021.11
S13	Wine-processed Polygonati Rhizoma(JZP)	Lueyang Hanzhong Shaanxi (陕西汉中略阳)	2021.11
S14	Wine-processed Polygonati Rhizoma(JZP)	Lueyang Hanzhong Shaanxi (陕西汉中略阳)	2021.11
S15	Wine-processed Polygonati Rhizoma(JZP)	Lueyang Hanzhong Shaanxi (陕西汉中略阳)	2021.11
S16	Wine-processed Polygonati Rhizoma(JZP)	Liuba Hanzhong Shaanxi (陕西汉中留坝)	2021.11
S17	Wine-processed Polygonati Rhizoma(JZP)	Liuba Hanzhong Shaanxi (陕西汉中留坝)	2021.11
S18	Wine-processed Polygonati Rhizoma(JZP)	Liuba Hanzhong Shaanxi (陕西汉中留坝)	2021.11

No.

Name

Place of origin
(in Chinese)

Collection or
preparation time

Polygonati Rhizoma(SP)

Lueyang Hanzhong Shaanxi
(陕西汉中略阳)

2021.10

Polygonati Rhizoma(SP)

Lueyang Hanzhong Shaanxi
(陕西汉中略阳)

2021.10

Polygonati Rhizoma(SP)

Lueyang Hanzhong Shaanxi
(陕西汉中略阳)

2021.10

Polygonati Rhizoma(SP)

Liuba Hanzhong Shaanxi
(陕西汉中留坝)

2021.10

Polygonati Rhizoma(SP)

Liuba Hanzhong Shaanxi
(陕西汉中留坝)

2021.10

Polygonati Rhizoma(SP)

Liuba Hanzhong Shaanxi
(陕西汉中留坝)

2021.10

Steamed Polygonati Rhizoma
(QZP)

Lueyang Hanzhong Shaanxi
(陕西汉中略阳)

2021.11

Steamed Polygonati Rhizoma
(QZP)

Lueyang Hanzhong Shaanxi
(陕西汉中略阳)

2021.11

Steamed Polygonati Rhizoma
(QZP)

Lueyang Hanzhong Shaanxi
(陕西汉中略阳)

2021.11

S10

Steamed Polygonati Rhizoma
(QZP)

Liuba Hanzhong Shaanxi
(陕西汉中留坝)

2021.11

S11

Steamed Polygonati Rhizoma
(QZP)

Liuba Hanzhong Shaanxi
(陕西汉中留坝)

2021.11

S12

Steamed Polygonati Rhizoma
(QZP)

Liuba Hanzhong Shaanxi
(陕西汉中留坝)

2021.11

S13

Wine-processed Polygonati
Rhizoma(JZP)

Lueyang Hanzhong Shaanxi
(陕西汉中略阳)

2021.11

S14

Wine-processed Polygonati
Rhizoma(JZP)

Lueyang Hanzhong Shaanxi
(陕西汉中略阳)

2021.11

S15

Wine-processed Polygonati
Rhizoma(JZP)

Lueyang Hanzhong Shaanxi
(陕西汉中略阳)

2021.11

S16

Wine-processed Polygonati
Rhizoma(JZP)

Liuba Hanzhong Shaanxi
(陕西汉中留坝)

2021.11

S17

Wine-processed Polygonati
Rhizoma(JZP)

Liuba Hanzhong Shaanxi
(陕西汉中留坝)

2021.11

S18

Wine-processed Polygonati
Rhizoma(JZP)

Liuba Hanzhong Shaanxi
(陕西汉中留坝)

2021.11

No.	English name	Molecular formula	M_W	m/z (Theoretical) value	m/z (Actual) value	t_R/ min	Deviation /×10^-6	m/z (Fragment ion)
	Amino acids
1¹⁾	Gamma-aminobutyric acid	C₄H₉NO₂	103.062 8	104.070 6	104.071 2	0.77	5.27	53.003,53.690 4,55.018 7, 56.050 3,56.602 2,57.034 6
2¹⁾²⁾	L-arginine	C₆H₁₄N₄O₂	174.111 1	175.119	175.119 1	0.7	0.54	53.498 3,55.055 1,56.050 4, 57.034 3,60.025 8, 60.056 4
3¹⁾²⁾	L-phenylalanine	C₉H₁₁NO₂	165.078 4	166.086 3	166.086 3	1.72	0.33	68.050 3,69.034 2,70.065 8, 79.054 9,80.050 2,80.949 7
4²⁾	L-aminocyclopropane-1-carboxylic acid	C₄H₇NO₂	101.047 1	102.055	102.055 4	0.79	4.52	71.05,56.050 3,60.045 2, 61.028 9,68.050 2,70.065 9
5¹⁾²⁾	2-Pyrrolidone-5-carboxylic acid	C₅H₇NO₃	129.042	130.049 9	130.050 2	1.04	2.38	53.003 1,55.055,56.050 3, 57.070 7,58.065 6,58.744 9
6¹⁾	Aminocaproic acid	C₆H₁₃NO₂	131.094 1	114.091 4	114.091 8	4.6	3.21	53.003 1,53.039 5,54.034 5, 55.018 8,55.054 9,56.050 2
7¹⁾²⁾	Proline	C₅H₉NO₂	115.062 8	116.070 6	116.071	0.84	3.15	51.091 1,53.039 5,53.856 5, 55.018 5,55.055,55.301 8
8¹⁾²⁾	L-valine	C₅H₁₁NO₂	117.078 4	118.086 3	118.086 6	0.91	2.6	56.050 3,50.919 2,53.039 5, 54.203 2,55.055,50.446 2
9¹⁾²⁾	D-alloisoleucine	C₆H₁₃NO₂	131.094 1	132.101 9	132.102	1.05	1.06	51.105 2,51.695 2,55.055 2, 53.039 4,54.476 9,53.002 9
10³⁾	n-(1-deoxy-1-fructosyl)leucine(unconfirmed)	C₁₂H₂₃NO₇	293.146 9	294.154 7	294.154 7	1.31	-0.21	55.018 6,56.050 3,57.034 3, 59.037 4,69.034 5,69.070 7
11³⁾	n-(1-deoxy-1-fructosyl)valine(unconfirmed)	C₁₁H₂₁NO₇	279.131 3	280.139 1	280.139 1	0.93	-0.02	55.018 7,55.055 1,59.050 1, 68.050 2,69.034 3,70.065 9
12³⁾	n-(1-deoxy-1-fructosyl)threonine(unconfirmed)	C₁₀H₁₉NO₈	281.110 5	282.118 3	282.118 3	0.79	-0.14	56.050 2,57.034 4,69.034 4, 74.060 8,81.034 2,84.045
13¹⁾	L-gln	C₅H₁₀N₂O₃	146.068 6	147.076 4	147.076 5	0.78	0.53	50.892 4,52.530 7,52.818, 55.055,56.050 2,58.006 4
14¹⁾	Amfenac	C₁₅H₁₃NO₃	255.089	256.096 8	256.096 8	5.61	-0.16	55.857 8,61.710 4,78.034 5, 81.034 3,83.049 7,94.029 6
15¹⁾	Succinylproline	C₉H₁₃NO₅	215.078 8	216.086 7	216.086 7	0.9	0.34	53.039 3,55.018 7,55.055, 56.050 3,57.034 3,57.070 6
16¹⁾²⁾	Arginine	C₆H₁₄N₄O₂	174.111 1	173.104 4	173.104 9	0.75	2.9	58.029 9,58.041 2,59.013 9, 59.880 6,61.663 3,68.050 5
17¹⁾²⁾	Tryptophan	C₁₁H₁₂N₂O₂	204.089 3	203.082 6	203.083 1	3.83	2.4	50.658 3,51.843 5,57.034 6, 59.013 9,71.014,72.009 2
18¹⁾	n-(1-deoxy-1-fructosyl)tyrosine	C₁₅H₂₁NO₈	343.126 2	388.124 8	388.125 9	1.76	2.72	55.019,57.034 7,59.013 9, 61.988 5,66.035 1,71.014
19¹⁾	Tetrahydrodipicolinate	C₇H₉NO₄	171.052 6	216.051 2	216.051 8	1.03	2.57	57.034 7,59.013 9,69.034 5, 70.029 9,71.013 9,72.009 3
20¹⁾	Glutamylisoleucine	C₁₁H₂₀N₂O₅	260.136 7	259.13	259.130 2	3.93	0.89	57.034 5,59.013 9,68.014 5, 69.034 7,71.013 8,72.008 9
21¹⁾	Prolylyphenylalanine	C₁₄H₁₈N₂O₃	262.131 2	285.120 8	285.123 3	6.49	9.06	55.119 1,57.034 3,57.070 7, 60.902 8,68.972 9,71.049 7
22³⁾	Beta-D-glucopyranosyl anthranilate(unconfirmed)	C₁₃H₁₇NO₇	299.1	344.098 6	344.099 8	1.75	3.5	55.018 8,57.034 4,59.013 9, 69.034 5,71.014,72.993
	Alkaloids
23¹⁾	Feruloyltyramine	C₁₈H₁₉NO₄	313.130 9	314.138 7	314.138 5	6.16	-0.6	51.417 1,53.039 3,81.034 1, 57.763 6,70.065 6,77.039 3
24³⁾	(E)-n-[2-hydroxy-2-(4-hydroxyphenyl)ethyl]-3-(4-hydroxy- 3-methoxyphenyl)prop-2-enamide(unconfirmed)	C₁₈H₁₉NO₅	329.125 8	312.123	312.122 9	5.43	-0.28	81.033 9,89.039 2,91.054 9, 95.049 5,107.049 3,117.033 8
25³⁾	(E)-n-[2-hydroxy-2-(4-hydroxyphenyl)ethyl]-3-(4-hydroxyphenyl) prop-2-enamide(unconfirmed)	C₁₇H₁₇NO₄	299.115 2	282.112 5	282.112 4	5.31	-0.19	55.055 1,56.050 3,58.065 9, 67.055 1,68.050 2,69.070 7
26¹⁾²⁾	Flazine	C₁₇H₁₂N₂O₄	308.079 2	309.087	309.087	6.5	-0.08	55.018 7,55.055 3,57.994 1, 62.451 6,67.055 2,69.070 8
27³⁾	Casuarine 6-alpha-D-glucoside	C₁₄H₂₅NO₁₀	367.147 3	388.122 3	388.125 9	3.77	9.3	55.019,57.034 6,59.013 9, 61.988 5,66.034 9,71.014
28¹⁾	Betaine	C₅H₁₁NO₂	117.078 4	118.086 3	118.086 6	0.81	2.55	56.050 4,56.850 1,57.905 4, 58.037,58.065 9,58.093 2
29¹⁾	Annocherine B	C₁₈H₁₇NO₄	311.115 2	310.108 5	310.109 1	5.57	1.99	56.89,59.013 9,75.617, 93.034 7,107.050 4,108.021 9
	Flavonoid
30³⁾	3-(3,4-Dihydroxybenzyl)-7-hydroxy-5-methoxy-4-chromanone	C₁₇H₁₆O₆	316.094 1	317.102	317.102	6.87	0.17	55.018 6,55.055 1,57.861 8, 65.039 5,60.045 2,59.760 7
31³⁾	5,7-Dihydroxy-2-(4-methoxyphenyl)-3,4-dihydro-2h-1- benzopyran-4-one(unconfirmed)	C₁₆H₁₄O₅	286.083 6	285.076 9	285.077 1	7.06	0.98	55.724 7,59.013 8,65.003 4, 65.039 9,67.019 1,69.034 8
32¹⁾	Calycosin-7-O-β-D-glucoside	C₂₂H₂₂O₁₀	446.120 8	445.114	445.115 1	5.94	2.4	55.018 9,57.034 5,71.014, 63.024 1,65.003 4,59.013 9
33¹⁾	Diosmetin	C₁₆H₁₂O₆	300.062 8	299.056 1	299.056 8	6.88	2.33	59.013 9,63.024 2,65.003 6, 65.734 1,67.375,69.236 1
	Saccharides
34¹⁾²⁾	Raffinose	C₁₈H₃₂O₁₆	504.168 5	539.138 5	539.138 1	0.85	-0.58	55.019 1,58.006 2,59.014, 61.955 3,61.988 5,62.020 5
35¹⁾²⁾	D-arabinose	C₅H₁₀O₅	150.052 3	149.045 6	149.045 9	0.89	2.32	51.015 2,57.034 7,58.017 6, 59.014 2,59.116 9,61.449 9
36¹⁾	Gentiotriose	C₁₈H₃₂O₁₆	504.168 5	485.151 2	485.151 9	0.91	1.39	55.018 9,57.034 6,58.006 1, 59.013 9,69.034 7,71.014
	Organic acids
37³⁾	13S-hydroxyoctadecadienoic acid(unconfirmed)	C₁₈H₃₂O₃	296.234 6	314.269	314.269	7.37	-0.07	55.018 8,55.055,57.034 3, 57.070 7,58.029 5,60.045 2
38¹⁾	Ferulic acid	C₁₀H₁₀O₄	194.057 4	177.054 6	177.054 7	5.43	0.57	53.039 4,55.018 7,55.055, 69.070 7,67.055,63.024 3
39³⁾	Indolelactic acid(unconfirmed)	C₁₁H₁₁NO₃	205.073 3	206.081 2	206.081 4	3.82	1	55.018 6,69.034 3,74.024 4, 79.054 8,80.949 8,81.034
40¹⁾²⁾	Citric acid	C₆H₈O₇	192.026 5	191.019 7	191.020 2	1	2.45	57.034 7,58.029 8,59.013 9, 67.019 1,69.034 9,70.029 9
41³⁾	9,10-Dihode(unconfirmed)	C₁₈H₃₂O₄	312.229 5	311.222 8	311.223 3	8.69	1.63	56.421 1,83.050 5,58.006 1, 59.013 8,75.506 6,57.034 6
42¹⁾	3-Hydroxysebacic acid	C₁₀H₁₈O₅	218.114 9	495.244 6	495.245 1	5.9	1.01	55.018 9,57.034 6,71.014, 59.013 9,69.034 5,58.006 1
	Saponins
43¹⁾	Fistuloside C	C₄₅H₇₂O₁₉	916.466 2	899.463 5	899.463 7	5.41	0.2	69.034 2,69.070 6,71.049 8, 75.044 7,73.065 5,73.029 1
44³⁾	Neogitogenin 3-[glucosyl-(1->2)-glucosyl-(1->4)- galactoside] (unconfirmed)	C₄₅H₇₄O₁₉	918.481 9	901.479 2	901.479 4	5.8	0.24	67.055,69.034 2,69.070 6, 73.029 1,73.065 5,79.054 9
	Coumarins
45²⁾	Coumaroyl tyramine	C₁₇H₁₇NO₃	283.120 3	284.128 1	284.128 1	6.07	-0.22	51.023 9,53.039 5,55.018 7, 55.054 9,56.216 8,65.039 7

No.

English
name

Molecular
formula

M_W

m/z
(Theoretical)
value

m/z
(Actual)
value

t_R/
min

Deviation
/×10^-6

m/z
(Fragment ion)

Amino acids

1¹⁾

Gamma-aminobutyric acid

C₄H₉NO₂

103.062 8

104.070 6

104.071 2

0.77

5.27

53.003,53.690 4,55.018 7,
56.050 3,56.602 2,57.034 6

2¹⁾²⁾

L-arginine

C₆H₁₄N₄O₂

174.111 1

175.119

175.119 1

0.7

0.54

53.498 3,55.055 1,56.050 4,
57.034 3,60.025 8, 60.056 4

3¹⁾²⁾

L-phenylalanine

C₉H₁₁NO₂

165.078 4

166.086 3

1.72

0.33

68.050 3,69.034 2,70.065 8,
79.054 9,80.050 2,80.949 7

4²⁾

L-aminocyclopropane-1-carboxylic acid

C₄H₇NO₂

101.047 1

102.055

102.055 4

0.79

4.52

71.05,56.050 3,60.045 2,
61.028 9,68.050 2,70.065 9

5¹⁾²⁾

2-Pyrrolidone-5-carboxylic acid

C₅H₇NO₃

129.042

130.049 9

130.050 2

1.04

2.38

53.003 1,55.055,56.050 3,
57.070 7,58.065 6,58.744 9

6¹⁾

Aminocaproic acid

C₆H₁₃NO₂

131.094 1

114.091 4

114.091 8

4.6

3.21

53.003 1,53.039 5,54.034 5,
55.018 8,55.054 9,56.050 2

7¹⁾²⁾

Proline

C₅H₉NO₂

115.062 8

116.070 6

116.071

0.84

3.15

51.091 1,53.039 5,53.856 5,
55.018 5,55.055,55.301 8

8¹⁾²⁾

L-valine

C₅H₁₁NO₂

117.078 4

118.086 3

118.086 6

0.91

2.6

56.050 3,50.919 2,53.039 5,
54.203 2,55.055,50.446 2

9¹⁾²⁾

D-alloisoleucine

C₆H₁₃NO₂

131.094 1

132.101 9

132.102

1.05

1.06

51.105 2,51.695 2,55.055 2,
53.039 4,54.476 9,53.002 9

10³⁾

n-(1-deoxy-1-fructosyl)leucine(unconfirmed)

C₁₂H₂₃NO₇

293.146 9

294.154 7

1.31

-0.21

55.018 6,56.050 3,57.034 3,
59.037 4,69.034 5,69.070 7

11³⁾

n-(1-deoxy-1-fructosyl)valine(unconfirmed)

C₁₁H₂₁NO₇

279.131 3

280.139 1

0.93

-0.02

55.018 7,55.055 1,59.050 1,
68.050 2,69.034 3,70.065 9

12³⁾

n-(1-deoxy-1-fructosyl)threonine(unconfirmed)

C₁₀H₁₉NO₈

281.110 5

282.118 3

0.79

-0.14

56.050 2,57.034 4,69.034 4,
74.060 8,81.034 2,84.045

13¹⁾

L-gln

C₅H₁₀N₂O₃

146.068 6

147.076 4

147.076 5

0.78

0.53

50.892 4,52.530 7,52.818,
55.055,56.050 2,58.006 4

14¹⁾

Amfenac

C₁₅H₁₃NO₃

255.089

256.096 8

5.61

-0.16

55.857 8,61.710 4,78.034 5,
81.034 3,83.049 7,94.029 6

15¹⁾

Succinylproline

C₉H₁₃NO₅

215.078 8

216.086 7

0.9

0.34

53.039 3,55.018 7,55.055,
56.050 3,57.034 3,57.070 6

16¹⁾²⁾

Arginine

C₆H₁₄N₄O₂

174.111 1

173.104 4

173.104 9

0.75

2.9

58.029 9,58.041 2,59.013 9,
59.880 6,61.663 3,68.050 5

17¹⁾²⁾

Tryptophan

C₁₁H₁₂N₂O₂

204.089 3

203.082 6

203.083 1

3.83

2.4

50.658 3,51.843 5,57.034 6,
59.013 9,71.014,72.009 2

18¹⁾

n-(1-deoxy-1-fructosyl)tyrosine

C₁₅H₂₁NO₈

343.126 2

388.124 8

388.125 9

1.76

2.72

55.019,57.034 7,59.013 9,
61.988 5,66.035 1,71.014

19¹⁾

Tetrahydrodipicolinate

C₇H₉NO₄

171.052 6

216.051 2

216.051 8

1.03

2.57

57.034 7,59.013 9,69.034 5,
70.029 9,71.013 9,72.009 3

20¹⁾

Glutamylisoleucine

C₁₁H₂₀N₂O₅

260.136 7

259.13

259.130 2

3.93

0.89

57.034 5,59.013 9,68.014 5,
69.034 7,71.013 8,72.008 9

21¹⁾

Prolylyphenylalanine

C₁₄H₁₈N₂O₃

262.131 2

285.120 8

285.123 3

6.49

9.06

55.119 1,57.034 3,57.070 7,
60.902 8,68.972 9,71.049 7

22³⁾

Beta-D-glucopyranosyl anthranilate(unconfirmed)

C₁₃H₁₇NO₇

299.1

344.098 6

344.099 8

1.75

3.5

55.018 8,57.034 4,59.013 9,
69.034 5,71.014,72.993

Alkaloids

23¹⁾

Feruloyltyramine

C₁₈H₁₉NO₄

313.130 9

314.138 7

314.138 5

6.16

-0.6

51.417 1,53.039 3,81.034 1,
57.763 6,70.065 6,77.039 3

24³⁾

(E)-n-[2-hydroxy-2-(4-hydroxyphenyl)ethyl]-3-(4-hydroxy-
3-methoxyphenyl)prop-2-enamide(unconfirmed)

C₁₈H₁₉NO₅

329.125 8

312.123

312.122 9

5.43

-0.28

81.033 9,89.039 2,91.054 9,
95.049 5,107.049 3,117.033 8

25³⁾

(E)-n-[2-hydroxy-2-(4-hydroxyphenyl)ethyl]-3-(4-hydroxyphenyl) prop-2-enamide(unconfirmed)

C₁₇H₁₇NO₄

299.115 2

282.112 5

282.112 4

5.31

-0.19

55.055 1,56.050 3,58.065 9,
67.055 1,68.050 2,69.070 7

26¹⁾²⁾

Flazine

C₁₇H₁₂N₂O₄

308.079 2

309.087

6.5

-0.08

55.018 7,55.055 3,57.994 1,
62.451 6,67.055 2,69.070 8

27³⁾

Casuarine 6-alpha-D-glucoside

C₁₄H₂₅NO₁₀

367.147 3

388.122 3

388.125 9

3.77

9.3

55.019,57.034 6,59.013 9,
61.988 5,66.034 9,71.014

28¹⁾

Betaine

C₅H₁₁NO₂

117.078 4

118.086 3

118.086 6

0.81

2.55

56.050 4,56.850 1,57.905 4,
58.037,58.065 9,58.093 2

29¹⁾

Annocherine B

C₁₈H₁₇NO₄

311.115 2

310.108 5

310.109 1

5.57

1.99

56.89,59.013 9,75.617,
93.034 7,107.050 4,108.021 9

Flavonoid

30³⁾

3-(3,4-Dihydroxybenzyl)-7-hydroxy-5-methoxy-4-chromanone

C₁₇H₁₆O₆

316.094 1

317.102

6.87

0.17

55.018 6,55.055 1,57.861 8,
65.039 5,60.045 2,59.760 7

31³⁾

5,7-Dihydroxy-2-(4-methoxyphenyl)-3,4-dihydro-2h-1-
benzopyran-4-one(unconfirmed)

C₁₆H₁₄O₅

286.083 6

285.076 9

285.077 1

7.06

0.98

55.724 7,59.013 8,65.003 4,
65.039 9,67.019 1,69.034 8

32¹⁾

Calycosin-7-O-β-D-glucoside

C₂₂H₂₂O₁₀

446.120 8

445.114

445.115 1

5.94

2.4

55.018 9,57.034 5,71.014,
63.024 1,65.003 4,59.013 9

33¹⁾

Diosmetin

C₁₆H₁₂O₆

300.062 8

299.056 1

299.056 8

6.88

2.33

59.013 9,63.024 2,65.003 6,
65.734 1,67.375,69.236 1

Saccharides

34¹⁾²⁾

Raffinose

C₁₈H₃₂O₁₆

504.168 5

539.138 5

539.138 1

0.85

-0.58

55.019 1,58.006 2,59.014,
61.955 3,61.988 5,62.020 5

35¹⁾²⁾

D-arabinose

C₅H₁₀O₅

150.052 3

149.045 6

149.045 9

0.89

2.32

51.015 2,57.034 7,58.017 6,
59.014 2,59.116 9,61.449 9

36¹⁾

Gentiotriose

C₁₈H₃₂O₁₆

504.168 5

485.151 2

485.151 9

0.91

1.39

55.018 9,57.034 6,58.006 1,
59.013 9,69.034 7,71.014

Organic acids

37³⁾

13S-hydroxyoctadecadienoic acid(unconfirmed)

C₁₈H₃₂O₃

296.234 6

314.269

7.37

-0.07

55.018 8,55.055,57.034 3,
57.070 7,58.029 5,60.045 2

38¹⁾

Ferulic acid

C₁₀H₁₀O₄

194.057 4

177.054 6

177.054 7

5.43

0.57

53.039 4,55.018 7,55.055,
69.070 7,67.055,63.024 3

39³⁾

Indolelactic acid(unconfirmed)

C₁₁H₁₁NO₃

205.073 3

206.081 2

206.081 4

3.82

55.018 6,69.034 3,74.024 4,
79.054 8,80.949 8,81.034

40¹⁾²⁾

Citric acid

C₆H₈O₇

192.026 5

191.019 7

191.020 2

2.45

57.034 7,58.029 8,59.013 9,
67.019 1,69.034 9,70.029 9

41³⁾

9,10-Dihode(unconfirmed)

C₁₈H₃₂O₄

312.229 5

311.222 8

311.223 3

8.69

1.63

56.421 1,83.050 5,58.006 1,
59.013 8,75.506 6,57.034 6

42¹⁾

3-Hydroxysebacic acid

C₁₀H₁₈O₅

218.114 9

495.244 6

495.245 1

5.9

1.01

55.018 9,57.034 6,71.014,
59.013 9,69.034 5,58.006 1

Saponins

43¹⁾

Fistuloside C

C₄₅H₇₂O₁₉

916.466 2

899.463 5

899.463 7

5.41

0.2

69.034 2,69.070 6,71.049 8,
75.044 7,73.065 5,73.029 1

44³⁾

Neogitogenin 3-[glucosyl-(1->2)-glucosyl-(1->4)-
galactoside] (unconfirmed)

C₄₅H₇₄O₁₉

918.481 9

901.479 2

901.479 4

5.8

0.24

67.055,69.034 2,69.070 6,
73.029 1,73.065 5,79.054 9

Coumarins

45²⁾

Coumaroyl tyramine

C₁₇H₁₇NO₃

283.120 3

284.128 1

6.07

-0.22

51.023 9,53.039 5,55.018 7,
55.054 9,56.216 8,65.039 7

No.	Metabolite	VIP	FC	P	Ion
1	L-arginine	3.52	0.05	<0.05	+
2	L-phenylalanine	4.61	0.19	<0.05	+
3	1-Aminocyclopropane-1-carboxylic acid	6.46	0.12	<0.05	+
4	2-Pyrrolidone-5-carboxylic acid	4.21	0.18	<0.05	+
5	Aminocaproic acid	2.07	0.32	<0.05	+
6	Proline	2.43	0.26	<0.05	+
7	L-valine	3.85	0.15	<0.05	+
8	D-alloisoleucine	5.58	0.09	<0.05	+
9	n-(1-deoxy-1-fructosyl)leucine	2.51	5.37	<0.05	+
10	n-(1-deoxy-1-fructosyl)valine	3.43	2.42	<0.05	+
11	n-(1-deoxy-1-fructosyl)threonine	4.73	17.95	<0.05	+
12	Tryptophan	3.70	0.001	<0.05	-
13	n-(1-deoxy-1-fructosyl)tyrosine	6.78	521.44	<0.05	-
14	Feruloyltyramine	3.59	0.34	<0.05	+
15	(E)-n-[2-hydroxy-2-(4-hydroxyphenyl)ethyl]-3-(4-hydroxy-3-methoxyphenyl)prop-2-enamide	4.53	0.13	<0.05	+
16	(E)-n-[2-hydroxy-2-(4-hydroxyphenyl)ethyl]-3-(4-hydroxyphenyl)prop-2-enamide	3.63	0.07	<0.05	+
17	Casuarine 6-α-D-glucoside	5.30	197.47	<0.05	-
18	Coumaroyl tyramine	2.46	0.31	<0.05	+
19	Fistuloside C	2.19	0.004	<005	+
20	Citric acid	5.34	2.25	<0.05	-
21	Raffinose	2.84	0.22	<0.05	-
22	D-arabinose	2.01	0.34	<0.05	-

No.

Metabolite

VIP

Ion

L-arginine

3.52

0.05

<0.05

L-phenylalanine

4.61

0.19

<0.05

1-Aminocyclopropane-1-carboxylic acid

6.46

0.12

<0.05

2-Pyrrolidone-5-carboxylic acid

4.21

0.18

<0.05

Aminocaproic acid

2.07

0.32

<0.05

Proline

2.43

0.26

<0.05

L-valine

3.85

0.15

<0.05

D-alloisoleucine

5.58

0.09

<0.05

n-(1-deoxy-1-fructosyl)leucine

2.51

5.37

<0.05

n-(1-deoxy-1-fructosyl)valine

3.43

2.42

<0.05

n-(1-deoxy-1-fructosyl)threonine

4.73

17.95

<0.05

Tryptophan

3.70

0.001

<0.05

n-(1-deoxy-1-fructosyl)tyrosine

6.78

521.44

<0.05

Feruloyltyramine

3.59

0.34

<0.05

(E)-n-[2-hydroxy-2-(4-hydroxyphenyl)ethyl]-3-(4-hydroxy-3-methoxyphenyl)prop-2-enamide

4.53

0.13

<0.05

(E)-n-[2-hydroxy-2-(4-hydroxyphenyl)ethyl]-3-(4-hydroxyphenyl)prop-2-enamide

3.63

0.07

<0.05

Casuarine 6-α-D-glucoside

5.30

197.47

<0.05

Coumaroyl tyramine

2.46

0.31

<0.05

Fistuloside C

2.19

0.004

<005

Citric acid

5.34

2.25

<0.05

Raffinose

2.84

0.22

<0.05

D-arabinose

2.01

0.34

<0.05

No.	Metabolite	VIP	FC	P	Ion
1	L-arginine	3.48	0.21	<0.05	+
2	L-phenylalanine	4.39	0.37	<0.05	+
3	1-aminocyclopropane-1-carboxylic acid	6.46	0.25	<0.05	+
4	2-Pyrrolidone-5-carboxylic acid	4.27	0.28	<0.05	+
5	Aminocaproic acid	2.13	0.39	<0.05	+
6	Proline	2.35	0.41	<0.05	+
7	L-valine	3.87	0.27	<0.05	+
8	D-alloisoleucine	5.74	0.18	<0.05	+
9	n-(1-deoxy-1-fructosyl)leucine	2.54	4.82	<0.05	+
10	n-(1-deoxy-1-fructosyl)valine	4.00	2.65	<0.05	+
11	n-(1-deoxy-1-fructosyl)threonine	4.18	12.35	<0.05	+
12	Tryptophan	3.95	0.03	<0.05	-
13	n-(1-deoxy-1-fructosyl)tyrosine	5.51	293.86	<0.05	-
14	Feruloyltyramine	3.72	0.40	<0.05	+
15	(E)-n-[2-hydroxy-2-(4-hydroxyphenyl)ethyl]-3-(4-hydroxy-3-methoxyphenyl)prop-2-enamide	4.47	0.28	<0.05	+
16	(E)-n-[2-hydroxy-2-(4-hydroxyphenyl)ethyl]-3-(4-hydroxyphenyl)prop-2-enamide	3.81	0.12	<0.05	+
17	Flazine	2.11	165.00	<0.05	+
18	Casuarine 6-α-D-glucoside	3.78	86.55	<0.05	-
19	Coumaroyl tyramine	2.56	0.36	<0.05	+
20	Fistuloside C	2.30	0.06	<0.05	+
21	Citric acid	5.81	2.27	<0.05	-
22	Raffinose	3.16	0.18	<0.05	-
23	D-arabinose	2.04	0.41	<0.05	-

No.

Metabolite

VIP

Ion

L-arginine

3.48

0.21

<0.05

L-phenylalanine

4.39

0.37

<0.05

1-aminocyclopropane-1-carboxylic acid

6.46

0.25

<0.05

2-Pyrrolidone-5-carboxylic acid

4.27

0.28

<0.05

Aminocaproic acid

2.13

0.39

<0.05

Proline

2.35

0.41

<0.05

L-valine

3.87

0.27

<0.05

D-alloisoleucine

5.74

0.18

<0.05

n-(1-deoxy-1-fructosyl)leucine

2.54

4.82

<0.05

n-(1-deoxy-1-fructosyl)valine

4.00

2.65

<0.05

n-(1-deoxy-1-fructosyl)threonine

4.18

12.35

<0.05

Tryptophan

3.95

0.03

<0.05

n-(1-deoxy-1-fructosyl)tyrosine

5.51

293.86

<0.05

Feruloyltyramine

3.72

0.40

<0.05

(E)-n-[2-hydroxy-2-(4-hydroxyphenyl)ethyl]-3-(4-hydroxy-3-methoxyphenyl)prop-2-enamide

4.47

0.28

<0.05

(E)-n-[2-hydroxy-2-(4-hydroxyphenyl)ethyl]-3-(4-hydroxyphenyl)prop-2-enamide

3.81

0.12

<0.05

Flazine

2.11

165.00

<0.05

Casuarine 6-α-D-glucoside

3.78

86.55

<0.05

Coumaroyl tyramine

2.56

0.36

<0.05

Fistuloside C

2.30

0.06

<0.05

Citric acid

5.81

2.27

<0.05

Raffinose

3.16

0.18

<0.05

D-arabinose

2.04

0.41

<0.05

No.	Metabolite	VIP	FC	P	Ion
1	L-arginine	3.07	0.25	<0.05	+
2	1-aminocyclopropane-1-carboxylic acid	5.19	0.49	<0.05	+
3	(E)-n-[2-hydroxy-2-(4-hydroxyphenyl)ethyl]-3-(4-hydroxy-3-methoxyphenyl)prop-2-enamide	3.96	0.48	<0.05	+
4	Casuarine 6-α-D-glucoside	8.46	2.28	<0.05	-

No.

Metabolite

VIP

Ion

L-arginine

3.07

0.25

<0.05

1-aminocyclopropane-1-carboxylic acid

5.19

0.49

<0.05

(E)-n-[2-hydroxy-2-(4-hydroxyphenyl)ethyl]-3-(4-hydroxy-3-methoxyphenyl)prop-2-enamide

3.96

0.48

<0.05

Casuarine 6-α-D-glucoside

8.46

2.28

<0.05