O
HO
OH M87 O
O
O OH
O
HO HO
HO GA-O
O
+CH2
O
O
+O
+CH2
+CH2O
O
M113
Oleanolic acid +2 GA ???
Y(Oleanolic acid)+2 GA
M114
Candidoside
Y(Oleanolic acid)_O+2 H+2 Glc+Ara+Xyl
M115
3-O-Glucopyranosyl-glucopyranosyl-glucopyranosylglucopyranoside-12-oleanene-3,28-diol
Pharmaceutical University provide
novel insight into liquid chromatography”为题专文评价了 该项策略
Peer reviewers: The work is important, original and interesting. In my opinion the approach is very clever and original.
Sch is an d rin Sch is an th erin A Sch is an d rin B Deo xy s ch izan d rin γ-Sch is an drin A n g elo y lg o mis in H A n g elo y lg o mis in P
1000.0 100.0 10.0 1.0
确定共有离子化学结构，根据亚结构信息，对数据库中所获得的候 选结构进行再筛选，进而根据碎裂规律推测化合物结构。
1. 中药复杂未知成分快速鉴定技术
基于部分对照品确定各类成分诊断离子
人 参 皂 苷
五 味 子 木 脂 素
J Mass Spectrom, 2009, 44:230-44
1.中药复杂未知成分快速鉴定技术
OH
OO OH P82
-2 O
O-Rha
O-GA O
HO OH
O M37
M5
O
Caffeoyl-O
+2 CH2+AC P75
O-Caffeoyl
Feruloyl-O
M86 O-Feruloyl
Coumaroyl-O
OH
OO
OH OH
CH3Glc-O
M77
Glc-O
M26
O
OH O OH
O
OH O
OH
61 G lc C H 3 O H 71 G lc H O H
R5
R6 OR1
R4
R5
R6
H
OH
H
H
OH
H
OH
H
H
H
OH
H
H
OH
H
H
C H 2O H H
V inyl
OH CH3
OH
C H 2C O O H H
OCH3
OH H
3 ,4-d ih yd ro xy l p h eny l O H
H
D oub le b ond s Δ 7 ,8 Δ 7,8
R 69 H 73 Form yl
4 3
R 1O
R2
R2
R1 49 X yl-G lc R 150 X yl-G lc
R2 H
D ouble bonds Δ 3,4 O
H R 1 G l c －O
6 2 G l c - G l c OO H O Δ 3 ,4 O
R2 OH
OR3
OH
R1 R2 R3 1 CH2 H H 2O H H
M6
4-Hydroxybenzamidoacetic acid
Y3_O+Gly
M7
2-Hydroxy-3-(4-methoxyphenyl)propanoic acid
Y4+2 H+O+CH2
M8
4-(Methoxycarbonyl)-3-(hydroxymethyl)-1H-pyrrole-2-carboxylic acid
549.1 441.1 455.1 525.2 471.1 523.1 559.1
497.1 441.1 555.1 525.2 553.1 537.1 537.1
613.1 455.1 555.1 471.1 553.1 537.1 409.1
浓 度( ng/m l) 浓 度(ng /m l)
1.0
制剂 成分组
不同时相 药效物质组
代谢物归属与 确定代谢途径
应用自编的化学信息处理软件，包括差示谱分析 软件及代谢物与原形成分关联分析软件
脉络宁注射液体内外物质组关联分析
代谢物
代谢物化学结构
代谢途径
M1
5-Hydroxymethyl-2-furancarboxylic acid
Y(5-Hydroxymethyl furaldehyde)+O
R OH
5
OH
4
HO R3 R4
O R1
2 R 2O 3
R 1 R 2 R 3 R 4 D ouble bonds
7 H H H OH
-
10 OH H H O H
Δ 2,3
34 H G lc C H 3 H
-
O
O R2
R1
R3
HO
34 R4
HO HO
HO O
R1 20 H 22 OH 31 H 57 OH
+CH2O -O
O-Glc +CH2
HO
M39
OH
-O+Api
O-Glc
HO
M45
O
O-GA +H2+GA
O -O
O
HO OH M28
HO
P2
OH
HO
P3
OH
HO
P1
OH
OH
-Glc-H2O HO P29OH +Ara
O-Glc +2 O
HO +Rha
O-Glc M25
O-Glc-Api
HO
M60
O-Rha
85 H X 4 H H O H G lc H
Δ 2,3
OH
R4
O
R2
OR1
O
12
O
OR3
OH
R1 R2 R3
R 4 D ouble bonds
32 H H
H
H
Δ 1,2
33 H OH H
H
－
36 H OH H OH
－
39 H OH H
OCH3
－
75 H O H C affeoyl O H
－
OR3
R 2O
Caffeoyl-O
OH OH
-O+Gly
OH
HO OH
H N
O O M4
Glc-O
OH +Glc O
+CH2+GA
P28 OH
O-GA O
O HO
OH
O-GA
M38
HO
HO O-Glc-Ara
OH M69
HO
OH
-CO2
O
HO
OH
HO
O-Glc M41 OH
O
AC-O
O-Glc-Rha P65 OH
2.中药多成分同步定量分析技术
化合物名称
方法
人参皂苷Rg1、Rh1、 PPT
LC-MS
Rg1, Re, Rd, Rb1 , 麦冬皂苷D
丹参酮IIA，IIB,羟基IIA, 紫丹参甲素
隐丹参酮、丹参酮ⅡA
LC-MS LC-MS/MS LC-MS/MS
氧化苦参碱、苦参碱
LC-MS
人参皂苷Rg3、Rh2、ppd
-
48 O H CH 3 CH 3 H O CH 3 CH 3 O CH 3
-
55 H H G lc H H H H
Δ 2,3
63 H H G lc H O H H H
Δ 2 ,3
80 H H G lc-R h a H H H H
Δ 2 ,3
81 H H G lc-R h a H O H H H
Δ 2,3
R2 H H COOH C H 2O H
R3
R4
H CHCOOH
H CHCOOH
E thynyl C H C O O H
H
O -G lc
D ouble bonds
Δ 3,4 Δ 3 ,4 Δ 3 ,4
－
OH
OH
R D ouble bonds
74 H
Δ 4,5
77 OH
-
O OH R
O -G lcA ra
－ Δ 7 ,8 Δ 7,8 Δ 7 ,8 Δ 7,8
－
－ Δ 7,8
R4
R5
R 3O
O
2
OR6
3
R2
R1
R7
OH O
HO
X 4= O
O
OH O
OH OH
R 1 R 2 R 3 R 4 R 5 R 6 R 7 D ou b le b on d s
38 O H O H C H 3 O H V in y l H H
0.1
0.1 0
0.0 0.00
5.00
10.00