高效能液相層析法 (HPLC) 是目前最為普通中藥的分析
方法。本論文包含三部分，第一部分是開發出分析人參、芍藥和吳茱萸的
HPLC 分析方法，並對流動相的組成與管柱的選擇作一系統探討。人參中
的十二個人參皂素 (ginsenoside Rb1、 Rb2、 Rc、 Rd、 Re、 Rf、
Rg1、 Rg2、 Ro 、mRb1、 mRb2、 mRc) 可用 Cosmosil 5C18 分離管柱
在 10 mM KH2PO4-CH3CN 流動相系統，配合梯度沖提在 45 分鐘內完成分
析定量。芍藥中的八個藥效成分 (gallic acid、 oxypaeoniflorin、
albiflorin、 paeoniflorin、 benzoic acid、 pentagalloylglucose、
paeonol、 benzoylalbiflorin) 可用 Cosmosil 5C18-MS 分離管柱在
0.1% H3PO4-50 mM KH2PO4-CH3CN 流動相系統，配合梯度沖提在 60 分鐘
內完成分析定量。吳茱萸中的十二個生物鹼成分 (carboxyevodiamine、
dehydroevodiamine、 evodiamine、 rutaecarpine、 1-methyl-2-
nonyl-4(1H)-quinolone、 1-methyl-2-[(Z)-6-undecenyl]-4(1H)-
quinolone、 1-methyl-2-undecyl-4(1H)-quinolone、 evocarpine、
1-methyl-2-[(6Z,9Z)-6,9-pentadecadienyl]-4(1H)-quinolone、
dihydroevocarpine、 1-methyl-2-[(Z)-10-pentadecenyl]-4(1H)-
quinolone、 1-methyl-2-[(Z)-6-pentadecenyl]-4(1H)-quinolone) 可
用 Capcell SG-120 分離管柱在 1.25% HOAC-30 mM NaOAc-CH3CN-CH3OH
流動相系統，配合梯度沖提在 45 分鐘內完成分析定量。第二部分是將由
第一部分所開發的分析方法應用於市售藥材的比較研究，利用特有成分的
定量結果及各成分間的比例關係，建立植物的化學成分指紋圖譜，推斷藥
材基源，並獲知藥物品質。粉光參和三七人參的人參皂素總含量高於高麗
人參，白參、紅參和石柱參中較高含量的成分是 Rb1 和 Rg1 ，參鬚則是
Rb1 和 Re，三七人參是 Rb1、 Rg1 和 Rd，粉光參是 Rb1、 Re 和 mRb1
，另外粉光參中不含 Rf 和 Rg2，紅參和石柱參中幾不含
malonylginsenosides。白芍的藥效成分總含量高於赤芍，白芍中較高含
量的成分為 paeoniflorin、 albiflorin 和 pentagalloylglucose，赤
芍中為 paeoniflorin、 pentagalloylglucose 和 oxypaeoniflorin，白
芍的 albiflorin/oxypaeoniflorin 比值高於 1，而赤芍則是小於 1，可
用來區辨兩者。吳茱萸藥材中開口者的含量遠高於閉口者，開口者中含量
較高者為 dehydroevodiamine、 evodiamine、 evocarpine 和
rutaecarpine，閉口者中含量較高者則為 dehydroevodiamine、
evodioside B 和 epimedoside C。液相層析質譜法 (LC/MS) 是將液相層
析儀 (LC) 和質譜儀 (MS) 相銜接的一種分析技術，第三部分乃利用 LC-
UV-ESI-MS 的連線作業發展一種分析鑑定黃連中七個生物鹼 (berberine
、 palmatine、 coptisine、 epiberberine、 jatrorrhizine、
columbamine 和 berberastine) 的方法，萃取液不需經前處理，可直接
分析。並利用此方法辨識黃連成分熱解產物 berberrubine、
palmatrubine、 jatrorrhizrubine 和 columbamrubine。

The chemical constituents in Chinese herb drugs are
always very complicated and HPLC is regarded as their most
conveniently analytical tool up to now. This dissertation
contains three parts. The first part concerns the development of
three direct and rapid HPLC methods for determining the chemical
constituents in Ginseng Radix, Paeoniae Radix and Evodiae
Fructus respectively. The effects of mobile phase and column
selectivity and the validation of of these methods are also
discussion.In Ginseng Radix, components such as ginsnosides-Rb1,
Rb2, Rc, Rd, Re, Rf, Rg1, Rg2, Ro and malonylginsenosides Rb1,
Rb2 and mRc could be separated successfully. Detection at 198 nm
by using a Cosmosil 5C18 column with a linear gradient elution
of 10 mM KH2PO4-CH3CN (far-UV grade) was found to be the most
suitable and the contents of the ginsenosides in a non-
pretreated methanol-water extract could easily be determined
within 45 min. In Paeoniae Radix, eight compounds (gallic acid,
oxypaeoniflorin, albiflorin, paeoniflorin, benzoic acid,
pentagalloylglucose, paeonol and benzoylalbiflorin) could be
determined easily within 40 min. The method is carried out by
using a Cosmosil 5C18-MS column with a gradient solvent system
of 0.1% H3PO4-50 mM KH2PO4-CH3CN and a UV detector (254 nm). And
a method for the simultaneous determination of four
indolequinazoline alkaloids (carboxyevodiamine,
dehydroevodiamine, evodiamine and rutaecarpine) and eight
quinolone alkaloids (1-methyl-2-nonyl-4(1H)-quinolone,
1-methyl-2-[(Z)-6-undecenyl]-4(1H)-quinolone, 1-methyl-2-
undecyl-4(1H)-quinolone, evocarpine, 1-methyl-2-[(6Z,9Z)-6,9-
pentadecadienyl]-4(1H)-quinolone, dihydroevocarpine, 1-methyl-2-
[(Z)-10-pentadecenyl]-4(1H)-quinolone and 1-methyl-2-[(Z)-6-
pentadecenyl]-4(1H)-quinolone) in Evodiae Fructus was also
developed. The method was carried out by using a Capcell C18
SG-120 column with a gradient solvent system of acetate buffer-
acetonitrile-methanol and a UV detector (250 nm), and the
contents of the alkaloids in a non-pretreatment Evodiae Fructus
extract could easily be determined within 40 minutes. In the
second part, we used these methods listed above to evaluate the
three Chinese herb drugs and found that there were great
difference existed in each herb either the ratios or amounts of
the individual constituents. After closely comparing the HPLC
chromatogram and the morphological characters of various
samples, a significant relationship between the species and the
chemical constituents have been postulated. It was found that
the saponin contents in P. notoginseng and P. quinquefolia were
generally higher than in P. ginseng. The ginsenosides that were
of the highest contents in the white-ginseng, red-ginseng and
shihchu-ginseng samples of P. ginseng were Rb1 and Rg1, that in
the root-hair of P. ginseng were Rb1 and Re, that in P.
notoginseng were Rb1, Rg1 and Rd, and that in P. quinquefolia
were Rb1, Re and mRb1. Among the samples, those of P.
quinquefolia did not contain Rf and Rg2, whilst those of
shihchu-ginseng and red-ginseng of P. ginseng contained none or
only trace of malonylginsenosides. In Paeoniae Radix, P.
lactiflora articles were generally higher than in P. vitchii
articles in constituent contents except the albiflorin/
oxypaeoniflorin ratio and paeonol content. The top high contents
of in P. lactiflora were paeoniflorin, albiflorin and
pentagalloylglucose in the order named, but those in P. vitchii
were paeoniflorin, pentagalloylglucose and oxypaeoniflorin. The
peak-area ratio of albiflorin/oxypaeoniflorin was higher than
unity in P. lactiflora samples but lower than unity in P.
vitchii samples. Among the samples of Evodiae Fructus, there
included mainly two categories: opened tip and unopened tip. The
former had dehydroevodiamine, evodiamine, evocarpine and
rutaecarpine as the most aboundant components. And the latter,
however, had higher contents in dehydroevodiamine、 evodioside
B and epimedoside C。By use of this LC-UV-ESI-MS method, these
protoberberine alkaloids (berberine, palmatine, coptisine,
epiberberine, jatrorrhizine, columbamine and berberastine) in a
crude extract of Coptidis Rhizoma can be easily separated and
identified within 50 minutes. And the method had been used to
identify the pyrolyzed products, berberrubine, palmatrubine,
jatrorrhizrubine and columbamrubine。
The chemical constituents in Chinese herb drugs are