Chinese Medicine, 2011, 2, 143-153
doi:10.4236/cm.2011.24024 Published Online December 2011 (http://www.SciRP.org/journal/cm)
Copyright © 2011 SciRes. CM
143
Discrimination of 11 Chinese Materia Medica from
Umbelliferae by Electronic Nose
Qingmao Fang1, Mei Zhang1, Yuxia Yang1, Xianjian Zhou1, Hongfeng Jia2, P in g Fu1, Luqi Huang3
1Sichuan Academy of Chinese Medical and Materia Medica Sciences, Chengdu, China
2Department of Food Science, Sichuan Higher Institute of Cuisine, Chengdu, China
3Institute of Chinese Materia Medica, China Academy of Chinese Medical Sciences, Beijing, China
E-mail: fangqm196938@sina.com
Received July 31, 2011; revised August 24, 2011; accepted September 10, 2011
Abstract
In this paper, electronic nose (E-nose) was used to discriminate the 11 Chinese Materia Medica (CMM) from
Umbelliferae by the difference of their odors. The E-nose generated data were analyzed by discriminant
function analysis (DFA) and the responses of 18 sensors of E-nose were evaluated by CA analysis. Results
showed that a rapid evaluation of complex response of the samples could be obtained, in combination with
DFA, SQC and the CA analysis of the E-nose was given better results in the recognition values of the odor of
the 11 CMM. All the 11 CMM could be distinguished by E-nose coupled with DFA, sensor 2, 3, 4, 5, 11, 13
and 15 were found to be able to better discriminate between the CMM samples. The CMM from Um-
belliferae produced from different areas and processed with different methods could be distinguished by the
E-nose, too. The results of the similarity of fingerprints of the E-nose are fitted with the TCM records about
the property (yaoxing), channel tropism (guijing), function and usage of the CMM. The E-nose is a technol-
ogy that can reflect the holistic odor of a CMM and is relevant to the TCM doctor’s practical identification.
The odor of CMM can be expressed by objective data instead of subjective sense by human nose. Based on
the sensor`s intensity of E-nose, the fingerprint of a CMM can be established, too. Although the E-nose has
so many advantages, only use E-nose technology is not enough to control the quality of a CMM. It must be
combined with the other macroscopic discriminating technology, such as the E-tongue, the E-eye, to have a
holistic evaluation of a CMM.
Keywords: Chinese Materia Medica from Umbelliferae, Electronic Nose, Discrimination, Odor
1. Introduction
Chinese Materia Medica (CMM) are materials, which the
Traditional Chinese Medicine (TCM) doctors used to
treat diseases of the human being for thousand years. In
ancient China, macroscopic characteristics, such as shape,
size, color, smell and taste were used by TCM doctors
used to identify CMM and to evaluate their quality. Mac-
roscopic identication relies on the naked senses, and is
therefore a simple, fast and easy way to authenticate
CMM [1].The odor of CMM refers to the olfactory stim-
uli, such as aromatic, distinctive, or unpleasant smells [2].
Each CMM has its own special odor to some extent, espe-
cially those containing volatiles, such as Szechwan lovage
rhizome (Rhizoma chuanxiong, chuanxiong, RCX), Chi-
nese angelica (Radix angeicace sinensis, danggui). Tra-
ditionally, for the same CMM, samples with strong odors
are considered to be superior in quality. In the modern
day, it is understood that the strength of the odor often
reects the volatiles` content. As the CMM from Umbel-
liferae is considered, each CMM contains many kinds of
volatiles, such as, coumarins, phenolsacids, etc [3]. The
odor is reflecting all the volatiles of the CMM. Most of
the CMM from Umbelliferae have strong odors, and their
odors are mostly xin (pungent) in nature, they are classi-
fied as balmy by TCM doctor. That is why traditionally
odor was used as an important standard to evaluate the
quality of the CMM from Umbelliferae.
Usually, CMM are used as whole plant and/or combi-
nation of several herbs, and multiple constituents are res-
ponsible for the therapeutic effects. Therefore, quality
control of CM is very difcult. To date, the valid method
for quantitatively evaluating the quality of the CMM is
poor [4]. Today, in China Pharmacopea, chemical analy-
Q. M. FANG ET AL.
144
sis of volatiles which have odors, by HPLC and TLC, are
used to control quality of the CMM from Umbelliferae.
And the volatiles, such as, ferulic acid, is used as a refer-
ence compound to control the quality of RCX, Radix an-
gelicae ainensis (danggui) and Rhizoma et Radix ligu-
stici (gaoben) [5]. We think this method can not object-
tively reflect the quality of a CMM from Umbelliferae.
First of all, the method based on the chemical component
analysis has no relationship with the traditional TCM
doctor’s experience identification, a technology based on
the macroscopic characteristics of a CMM, including ap-
pearance, color, odor and taste. The second is that there
are many components in a CMM, only use one or two
component(s) can not reflect the holistic quality of a
CMM. For example, RCX contains more than fifty kinds
of chemical components. It contains 40 kinds of volatile
oil, such as ligustilide (58%), 3-butylphthalide (5.29%),
etc. And it contains lactones, alkloids, phenols and acids,
too [3]. But only ferulic acid was used as a reference
compound to control the quality of RCX in China Phar-
macopoeia [5]. The ferulic acid is not the main active
component of this CMM, why is it used as a reference
compound? Because although it is known that the main
active component of RCX is ligustilide, but this compo-
nent is not stable, it is very easy to break down when
exposed to air or light. Even use ligustilide as a reference
compound can not reflect the whole odor of RCX, be-
cause the odor of RCX is made up of the volatile oil, the
lactones, the phenols and the acids. Another example is
ginseng (Radix ginseng, renshen). In traditional experi-
ences, ginseng of a large size is thought to be of superior
quality. However, modern studies have indicated that the
content of ginsenoside in the berous roots is higher than
that in the main root [6]. It seems that not all the ancient
statements on the genuineness and quality based on mac-
roscopic characteristics are correct. But the actual expla-
nation for this phenomenon is that only use ginseside as
reference compounds can not reveal the genuineness of the
ancient statement about ginseng. Why? Because ginseng
has many components and the superior quality of ginseng
is based on the macroscopic characteristics that all the
components contained in ginseng displayed.
In China, Daodiyaocai (Genuine Traditional CMM) is
a most important concept in the TCM theory. In another
word, a CMM produced from a special area is better than
the CMM produced from the other areas. For example,
RCX produced from Dujiangyan county is a Genuine
Traditional CMM [7]. Another example is Radix angeli-
cae sinensis (danggui), this CMM produced in Ming cou-
nty, Gansu is better than produced form other areas such
as Sichuan and Yunnan provinces [7]. For a long time,
painstaking efforts were done to reveal the connotation
of the Daodiyaocai, but there is no ideal results to this
puzzle. Because except the production area difference,
e.g. climate, soil, there are many other factors, such as
cultivating technology, the field management, the proc-
essing method, etc, can effect the quality of the CMM,
too [2]. An objective method, which is closely related
with the traditionally macroscopic identification and
quality evaluation is needed to express the quality of
CMM changes with the variations of the factors men-
tioned above.
The E-nose is an instrument that mimics the TCM
doctor’s olfactory perception and provides an odor fin-
gerprint of the sample, it is equipped with an array of
non-selective and broad-spectrum chemical sensors use-
ful for the analysis of headspace of liquid or solid sam-
ples [8].Therefore it is a technology that can reflect the
macroscopic characteristic of a CMM. As a non-invasive
method, the E-nose has gradually being applied in the
quality assessment of Chinese medicine [9-13]. The E-
nose has been appropriately used in the quality assess-
ment of precious traditional Chinese medicines, such as
musk, too [14].
Is the electronic nose (E-nose) can correctly explain
the property (yaoxing) of the CMM? Is the E-nose can
correctly explain the genuineness and quality based on
macroscopic characteristics? Is the E-nose can reveal one
aspects of the connotation of the Daodiyaocai? In this
paper, E-nose was used to identify 11 CMM from Um-
belliferae and the quality control of a CMM based on the
holistic theory of TCM is discussed.
2. Materials and Methods
2.1. Experimental Material
9 of the CMM purchased in Chengdu Hehuachi market
of CMM and 2 of the CMM collected in their produced
areas were used as testing samples. The samples were
identified by Professor Guangming Shu from Sichuan
Academy of Chinese Medical and Materia Medica Scien-
ces. The name, the production area, the property (yaox-
ing) in nature, the channel tropism (guijing), the function,
the usage, the components and the reference compounds
were listed in Table 1.
2.2. Electronic Nose
FOX-4000 (Alpha-M.O.S., France) consists of a sampl-
ing apparatus, a detector unit containing an array of 18
sensors, air generator equipment, HS-100 autosampler
and pattern recognition software (SOFTV12) for data re-
cording. The sensor array is composed of 18 metal oxide
semiconductors (MOSs) chemical sensors divided into
chambers as three types: T, P, and LY.
Copyright © 2011 SciRes. CM
Q. M. FANG ET AL.
Copyright © 2011 SciRes. CM
145
Table 1. The details of the CMM samples utilized in the experiment.
No. Sample
name [5]
Production
area
Reference
compound [5]
Property
(odor and taste) in
nature
Components [3] Channel
tropism [6] Usage [5] Function [5]
1 Fructus
foeniculi
Neimenggu
province Trans-anethole Pungent and
balmy
trans-anethole, anisaldehyde, anisole,
α-fenchone, methylchavicol, fenchone,
limonene, α-pinene, xanthotoxin,
α-amyrin, coumarins: imperatorin,
bergapten, 7-hydroxycoumarin, ara-
chic acid, behenic acid
6,7-dihydroxycoumarin, oleanolic
acid, linoleic acid,
petroselinic acid, palmitic acid
liver, kidney,
spleen, stom-
ach
Abdominal pain
caused by inva-
sion of
the pathogenic
cold, dysmenor-
rheal,
cold pain in the
lower abdomen
Clearing away
cold, alleviating
pain,
regulating the
flow of qi,
normalizing the
function of
stomach
and spleen
2 Fructus
cnidii
Gansu
province Osthol bitter, pungent
and balmy
Coumarins: osthol, imperatorin, ber-
gapten, isopimpinellin, xanthotoxin,
xanthotoxol; biscoumarins:
cnidimonal, cnidimarin;
coumarin derivatives:
5-formylxanthotoxol,
2-deoxymeranzin hydrate, volatile oil:
L-pinene, L-camphene, bornyl is-
ovalerate, isoborneol, dihydrooroselol,
columbianadin, ciniadin, palmitic acid
kidney
skin ailments
(itchy, “wet”
skin conditions,
eczema, scabies
and acne), vulval
and
vaginal itching
and infections,
sexual dysfunc-
tion, allergy,
sexual
Malaise, frigity
and female
sterility
eliminating
dampness,
dispersing
pathogenic
wind, destroy-
ing parasites,
relieving itch-
ing, warming
kidney and
invigorating
kidney-yang
3
Radix
angeli-
cae
pubes-
centis
Sichuan
province
osthol,
columbianetin
acetate
bitter, pungent
and a little balmy
coumarins: osthol, bergapten, xan-
thotoxin, angelols A,B, C, D, E, F, G,
H, J, angelitriol, angelin, columbi-
anetin, columbianetin acetate,
columbianadin,
isoimperatorin, columbi-
anetin-β-D-glucopyranoside, umbelli-
ferone, nodakenin, angelidiol,
oxypeucedaninhydrate, columbianetin
propionate, isoangelol, anoupubesol;
essential oil:
1-Methyl-2-isopropylbenzene,
α-pinene, himachalol,
2,3,5,6-tetramethylphenol, longi-
folene, palmitic acid, α-phellandrene,
humulene, sylvestrene
kidney bladder
Numbness
caused by
wind-cold-damp
ness,
lambago,
Shaoyin head-
ache, headache
due to patho-
genic
wind-cold-damp
ness
dispersing
pathogenic
wind,
removing
dampness,
relieving
stagnation and
alleviating pain
4 Radix
glehniae
Jilin prov-
ince -
sweet, a little
bitter and a little
balmy
Isoimperatorin, lupine, betulin,
β-sitosterol, daucosterol, panaxynol,
facarindiol, (8E)-1,8-hepta-decadiene
-4,6-diyne-3,10-dioland, α-pinene,
β-phellandrene, germacrene B, phel-
lopterin, bergapten, xanthotoxin,
psoralen, scopoletin, xanthotoxol,
9-geranyloxypsoralen,
marmesin, ber-
gaptin,7-O-3,3-dimethylallyl
scopletin, os-
thenol-7-O-β-gentiobioside, impera-
torin, isoimperatorin, alloisoimpera-
torin, cnidilin, poly-saccharides
lung and stom-
ach
cough caused by
lung-heat, defi-
ciency
of the stom-
ach-yin and
consumption
of body fluid
caused by febrile
disease, thirsty
Nourishing
Yin, Clearing
away
the lung heat,
reinforcing
stomach,
promoting the
production
of body fluid
Q. M. FANG ET AL.
146
5
Radix
peuceda
ni
Guizhou
province
praeruptorin
a,b
bitter, pungent
and a little cold
praeruptorin a,b,c,d,e,
pteryxin, scopolin,
3'(S)-angeloyloxy-4(R)-isovalery-
loxy-3,4-dihydroseselin , decursin,
peucedanocoumarin I-III, nodakenin,
5,8-dimethoxypsoralen, anchoic acid,
isoscopoletin, umbelliferone,
praeroside I-V
lung
cough and
tachypnea due to
pathogenic
wind-heat,
phlegm, Asthma
due to excessive
phlegm caused
by pathogenic
heat, cough and
phlegm caused
by pathogenic
wind-heat
Depressing
upward-reverse
flow of qi,
resolving
phlegm,
clearing the
wind and clear-
ing
away heat
6
Radix
chuan-
ming-shi
nis
violacei
Lanzhong
Sichuan
province,
without
cortex
- Sweet, mild, a
little balmy
5,8-dimethyoxy-psoracen, umberlli-
ferone, 5-pentenyl-8-
methoxy-psoracen,
deltoin, marmesin, ammijin; feruic
acid, octadecoic acid, polysaccharides
Lung,
spleen,
stomach
cough caused by
lung-heat,
consumption of
yin caused by
febrile disease
nourishing Yin,
reinforcing
the lung, in-
vigorating
spleen
7
Radix
saposh-
niko-
viae
Liaolin
province
prim-O-glucos
ylcimicifugin,
5-O-methylvis
ammiosode
pungent, sweet
and a little balmy
octanal, β-bisabolene, nonanal, im-
peratorin, 3’-o-acetylhamaudol,
scopoletin, cimicifugin
prim-o-glucasylcimifugin, anomalin,
5-O-methylvisammiosode, bergapten,
psoralen,
xanthotoxin
bladder,
liver, spleen
wind-cold type
common cold,
headache, acute
tonsillitis caused
by pathogenic
wind-cold
Promoting
blood circula-
tion,
promoting the
circulation of
qi,
dispersing
pathogenic
wind,
and alleviating
pain
8
Rhizoma
chuanx-
iong
Dujianyan
county,
Sichuan
province,
sun dried
ferulic acid pungent and
balmy
ligustilide, ferulic acid,
neocnidilide,
3-butylphthalide,3-butylidene
phthalide, cnidiumlactone,
4-hydroxy-3-butylphthalide,
ligustilidiol,
vanillic acid, vanillin,
chuanxiongzine,
bis-5,5’-formylfurperyeether,spathulen
l,sabinene,chuanxiongol,
2,2’-ligustilide, linoleic acid, palmitic
acid, 4-hydroxy-3-methoxy
styrene
liver,
gallbladder,
pericard-
ium
Numbness of
chest, cardialgia,
sternocastal
pain, amenor-
rhoea, dys-
menorrheal,
headache, ir-
regular men-
struation, ab-
dominal pain,
acute tonsillitis
caused by
pathogenic
wind-cold, head-
ache, swollen
due to tumble
Promoting
blood circula-
tion,
promoting the
circulation of
qi,
dispersing
pathogenic
wind,
nd alleviating
pain
9
Rhizoma
et Radix
ligustici
Kangding
county,
Sichuan
province
ferulic acid pungent and
balmy
ligusinenoside A,B,C, Ligusinenosides
A-C, ferulaic acid, ligustilide
3-butylidene phthalide,neocnidilide,
cnidilide, palmitic acid,
terpineol-4,
4-terpinylacetate,α-cedrene,
3-butylidene-4,5-dihydrophthalide,
myristicine, spathulenol,
β-phellandrene, β-selinene, me-
thyleugenol, bergapten, scopoletin ,
5-Oxo-δ-4-decahydrobenzindene
bladder
wind-cold type
common cold,
headache, acute
tonsillitis caused
by pathogenic
wind-cold
Dispersing
pathogenic
wind,
clearing away
cold, removing
dampness,
alleviating pain
10
Radix
angeli-
cae
sinensis
Ming
county,
Gansu
province
ferulic acid sweet, pungent
and balmy
ligustilide, n-butylidene phthalide,
carvacrol, camphoric acid, anisic acid,
azelaic acid,
6-methoxy-7-hydroxycoumarin,
palmitic acid, ferulaic
acid,angelicide,vanillic acid, brefeldin,
phosphatidylcholine, poly-saccharides
liver,
spleen heart
Deficiency of
blood, atrophy,
irregular
menstruation,
acute tonsillitis
caused
by pathogenic
wind-cold, con-
tipation
Enriching
blood, promot-
ing blood
circulation,
regulating
menstruation,
loosening the
bowel and
relieving
constipation
Copyright © 2011 SciRes. CM
Q. M. FANG ET AL.
Copyright © 2011 SciRes. CM
147
11
Rhizoma
et Radix
notop-
terygh
Sichuan
province
Notopterol,
isoimperatorin
Pungent, bitter
and balmy
α-pinene, β-pinene, α-copaene,
trans-β-farnesene, benzyl benzoate,
limonene, p-hydroxyphenthyl anisate,
ferulic acid, oleic acid, linoleic acid,
sabinene, notopterol, isoimperatorin,
cnidilin, nodakenin, ehtylnotopterol,
notopterol,
5-hydroxy-8-(1,1’-dimenthylallyl)
psoralen, bergaptern, osthenol,
phenethyl, ferulate, trans-ferulic acid
bladder
wind-cold type
common cold,
headache, acute
tonsillitis caused
by pathogenic
wind-cold,
Relieving exte-
rior syndrome,
clearing away
cold, dispersing
pathogenic
wind, removing
dampness,
alleviating pain
12
Radix
chuan-
ming-
shinis
violacei
Qingbaiji-
ang, Si-
chuan,
without
cortex
the same as
No. 6
Sweet, mild, a
little balmy the same as No. 6
Lung,
spleen,
stomach
the same as No.
6
the same as No.
6
13
Rhizoma
chuanx-
iong
Penshan,
Sichuan,
sun dried
ferulic acid pungent and
balmy the same as No. 8 the same as
No. 8
the same as No.
8
the same as No.
8
14
Rhizoma
chuanx-
iong
Penshan,
Sichuan
province,
coal heated
ferulic acid pungent and
balmy the same as No. 8 the same as
No. 8
the same as No.
8
the same as No.
8
15
Radix
chuan-
ming-
shinis
violacei
Qingbaiji-
ang,
Sichuan
province,
with cortex
- Sweet, mild, a
little balmy the same as No. 6 the same as
No. 6
the same as No.
6
the same as No.
6
2.3. Experiment Procedure
Experiments were performed on FOX-4000. The samples
were accurately weighed for 0.5 g and placed in 10 ml
sealed headspace vials and loaded into the autosampler
tray; then 1000 μl of headspace air was automatically in-
jected into E-nose by a syringe and ow-injected into the
carrier gas ow.
In the testing process, distilled water was used to ad-
just the carrier gas humidity. The synthetic dry air was
pumped into the sensor chambers with a constant rate of
150 ml/min via an air transformer connected to a syringe
during the measurement process. The injection volume
was 1ml, injection rate of 1ml/s, the total syringe volume
of 2.5 ml, while the syringe temperature was maintained
at 35˚C. The time of acquisition parameters and the time
between injections are respective 120 s and 600 s. Each
sample was measured four times based on highly accu-
rate repeatability. The maximum response points auto-
matically recorded for each 18 sensors were used as the
E-nose response.
2.4. Data Analysis
The responses of the electronic nose were at rst ana-
lyzed by DFA to investigate the presence of classes in-
side the samples population. The DFA results were dis-
cussed in details according to the property, the chemical
components, the channel tropism, the function and the
usage, production areas and processing methods of the
samples to characterize the CMM by the electronic nose.
CA was employed to examine the sensorial data and test
the relationships of various CMM. Finally, SQC was
used to perform the classication of the CMM samples
[15]. All calculations were performed in SOFTV 12 and
SPSS software.
3. Results and Discussion
3.1. The Common Characteristics among the 11
CMM from Umbelliferae
There are many common characteristic among the 11
Q. M. FANG ET AL.
148
CMM from Umbelliferae as shown in Table 1. There
exist differences between the TCM and the Western me-
dicine, such as the yaoxing (property), the guijing (chan-
nel tropism), the function and the usage, etc. The yaox-
ing (property) and guijing (channel tropism) are the uni-
que characteristics of TCM.
First, we can find that all the 11 species have pungent
and bitter odors, their yaoxing (property) are mostly bal-
my or a little balmy in nature, only Radix peucedani
(qianhu, N5) has a property of a little cold in nature. In
TCM theory, the CMM which has strong pungent or
sweet odors and dispersing characteristics has a yaoxing
(property) of mostly balmy or hot in nature [16], such as
RCX (N8, N13 and N14). Traditionally, for the same
CMM, sample with the strongest odor is considered to be
superior in quality [2].
Second, it can be found in Table 1, there are many
components in the sample of the 11 CMM from Umbel-
liferae [4]. Furthermore, there are many common com-
ponents, e.g. volatile oils, coumarins , phenols, acids and
lactones in the 11 CMM as listed in Table 1. For exam-
ple, coumarins can be found in all of the 11 CMM except
RCX; sample 1, 2, 3, 4, 8, 10 contain α-pinene; sample 1,
2, 3, 4, 7, 8 contain bergapten, etc. It is understood that
the odor reflects all volatiles contained in a CMM and
the strength of the odor often reects the content of all
the volatiles. The odor is a holistic expression of all the
volatiling components which can be smelled by nose and
the E-nose, such as volatile oils, courmins, lactones, phe-
nols and acids, etc. In China, quality assessment of the
CMM from Umbelliferae based on macroscopic charac-
teristics, such as odor, is widely used in the CMM markets.
Similarly, medicinal vendors classify and price CMM
from Umbelliferae based on the strength of the odor of
the CMM from Umbelliferae, and consumers also pri-
marily evaluate the quality of CMM from Umbelliferae
on the basis of the odor of them. Therefore, use the ho-
listic odor of the CMM from Umbelliferae as a standard
to evaluate its quality is better than just only use one or a
few components as standards. Because there is no rela-
tionship between the analysis of a CMM based on the
component(s) and the doctor’s practical identification.
On the contrary, the use of the odor as a standard to
evaluate a CMM is relevant to the doctor’s practical
identification and it is more close to the holism of the
TCM theory. The E-nose technology can identify the dif-
ferent odors of volatiles, such as, musk, vinegar, etc [14,
17]. That is why we use E-nose as a tool to discriminate
the 11 CMM from Umbelliferae.
Third, there are also some common phenomenon of
the guijing (channel tropism) of the 11 CMM. In TCM
theory, there are 18 invisible channels (jinluo) [16], such
as kidney channel, bladder channel, heart channel, lung
channel, etc, in the human body. The CMM has special
property and can go into the special channel, such as
kidney channel. This characteristic of the CMM is called
guijing (channel tropism). Three of the CMM (Fructus
foeniculi, xiaohuixiang, Fructus cnidii, shechuangzi,
Radix angelicae pubescentis, duhuo) can go into the kid-
ney channel, four of the CMM (Radix angelicae pubes-
centis, duhuo, Radix saposhnikoviae, fangfeng; RCX,
Radix angelicae sinensis, danggui) can go into the blad-
der channel. And four of the CMM (Fructus foeniculi,
xiaohuixiang, RCX, Rhizoma et Radix ligustici, gaoben,
Radix angelicae sinensis, danggui, Rhizoma et Radix
notopterygh, qianghuo) can go into the spleen channel.
Off course, there are other channels that the 11 CMM
can go into, such as, liver channel, lung channel, heart
channel and the gallbladder, etc.
Forth, the functions of most of the 11 CMM are some-
what similar to each other. In Table 1, Sample 2, 3, 6, 7,
8, 10 have the same function of “dispersing pathogenic
wind”; sample 1, 3, 6, 7, 8, 10 have the same function of
“alleviating pain”.
Fifth, the usages of the 11 CMM are similar, too. For
example, sample 6, 7, 8, 9, 10 have the usage to cure
acute tonsillitis caused by pathogenic wind-cold; sample
1, 2, 3, 6, 7, 8, 9, 10 have the usage to cure many kinds
of pain caused by pathogenic wind-cold, such as head-
ache, lambago and knee pain, etc. Sample 7 and 10 have
the usage to cure cold due to pathogenic wind-cold.
Last, from Table 1, it can be found that some reference
compounds are used to control the quality of two or three
CMM. For example, ferulic acid is used as reference
compound to control the quality of RCX, Rhizoma et
Radix ligustici and Radix angelicae sinensis; and Osthol
is used as reference compound to control the quality of
Fructus cnidii and Radix angelicae pubescentis [5].
3.2. E-Nose Responses to Samples of the 11
CMM from Umbelliferae
Figure 1 shows the typical responses of sensors with
RCX (N8). Each line represented the average signal
variation of RCX (N8), respectively for one sensor of the
18 sensors. The curves represented the intensity of each
sensor against time due to the electro-valve action when
the volatiles reached the measurement chamber [15]. In
the initial period, the intensity of each sensor was low,
then increased continuously, and nally stabilized after a
few seconds or minutes. The horizontal axis was the
timeline, a total of 120 s; the vertical axis was the inten-
sity of the response, each curve on behalf of a sensor in
response to the changes within 120 s. In this study, the
maximum response values of each sensor was extracted
and analyzed individually. In this way, response values
Copyright © 2011 SciRes. CM
149
Q. M. FANG ET AL.
represented in different curves were explored and other
response values with little signicance were discarded.
By CA analysis, the relative importance of the sensors
in the array was identied. As shown in Figure 2, Sensor
2, 3, 4, 5, 11, 13 and 15 have the highest inuence on the
discrimination of the 11 CMM from Umbelliferae family.
When compared this result with that of the musk, shex-
iang [15], senor 2, 3, 5, 15 are the common senors which
have the highest influence on the intensity of the E-nose
on the two kinds of CMM. While the senor 4, 11, 12, 13,
17 are the different highest influence sensors that can
discriminate the CMM from Umbelliferae family with
the musk, shexiang. Sensor 6 (T30/1) is misclassified to
have strong influence on the discrimination of the 11
CMM from Umbelliferae family, because its intensity is
very low as shown in Figure 1. For example, the inten-
sity of sensor 6 (T30/1) of RCX, Dujiangyan (N8) is only
0.0781. In contrast, the intensity of sensor 3 of RCX,
Dujiangyan (N8) is –1.481. Therefore sensor 6 (T30/1)
can not have strong influence on the discrimination of
the CMM from Umbelliferae.
Fi gure 1 . A typi cal res pons e of 18 sensors during the meas-
urement of RCX (N8).
Figure 2. CA dendrogram based on the response intensity of
the 18 sensors to the 11 CMM from Umbelliferae.
3.3. The Similarity of the Fingerprint of the 11
CMM from Umbelliferae
The inuence of different odors of the 11 CMM from
Umbelliferae on the responses of the E-nose was ana-
lyzed by dynamic headspace methods. As it is illustrated
in Figure 3, the odors of the 11 CMM from Umbelliferae
samples did not show any significant differences, indi-
cating the composition of the samples in the performance
being of the similar odor. The results showed that it was
impractical to use a radar map to distinguish the odors of
the 11 CMM directly.
The bar chart of the 11 CMM from Umbelliferae (Fig-
ure 4) are similar to the radar fingerprint. This result is
reasonable because the same volatiles have the same odor.
As we can find in Table 1 that some of the 11 CMM
from Umbelliferae contain many common components,
for example, sample 1, 2, 3, 4, 8, 10 contain α-pinene;
sample 1, 2, 3, 4, 7, 8 contain bergapten, etc.
Figure 3. Radar fingerprint of 11 CMM from Umbelliferae.
Figure 4. Bar fingerprint of 18 sensors during the meas-
urement of the 11 CMM from Umbelliferae.
Copyright © 2011 SciRes. CM
Q. M. FANG ET AL.
150
f the property,
in Table 1, Radix peucedani, qianhu (N5)
ha
aditional CMM (Daodiyaocai) is
a
3.4. The Comparison between the 11 CMM from
Diriminant function analysis is a supervised classifica-
mbelli-
fe
And this result is fitted with the records o
functions and usages of the 11 CMM from Umbelliferae,
too [5]. Maybe there exists relationship between the
similarity of the odor fingerprint with the some of the
same property, function and the usages among some of
the CMM.
As shown
s a property (yaoxing) of a little cold in nature, but
there has no apparent difference between N5 and other
CMM samples in the radar map and in the bar fingerprint
(Figure 3 and Figure 4), which has a property (yaoxing)
of balmy or a little balmy in nature. That means the odor
captured by the electric nose can not reflect the differ-
ence between CMM with different property (cold, cool,
warm or hot in nature).
In China, Genuine Tr
most important concept of the TCM theory. In another
word, a CMM produced from a special area is better than
the CMM produced from other areas. For example, RCX
produced from Dujiangyan county (Sample 8) is a Gen-
uine Traditional CMM, its quality is generally accepted
by the TCM doctors as the best, while RCX produced
from other areas, such as Penshan county (Sample 12
and 13) and Penzhou county is not as better as the one
produced from Dujiangyan county. The comparison of
18 sensors’ intensity of the three samples of RCX, pro-
duced from Dujiangyan county and Penshan county is
shown in Figure 5. The fingerprints of the 3 samples are
similar to each other. The coefficient between N8 and
N13 is 73%, the coefficient between N8 and N14 is
89.8% and the coefficient between N13 and N14 is
80.7%. The intensity of all the 18 sensors of Dujiangyan
county (N8) is weak than that of Penshan county (N13,
N14). This result is conflict with the traditional knowl-
edge: RCX produced in Dujianyan is better in quality
and RCX with strong aroma is superior in quality [7].
Further research is needed to reveal the genuineness of
RCX. Based on the intensity of the E-nose, a fingerprint
of the Genuine Traditional CMM (Daodiyaocai), such as
RCX can be set up.
Umbelliferae
sc
tion method aimed at finding a formal decision boundary
between classes. The idea is to find linear discriminant
functions

S1, S2,, Sn, which are linear combina-
tions of thles. The classification model
(DFA) was built on the first four PC, which normally
account for over 90% of the variance (information) of the
original data matrix. In each case, the DFA model was
cross- validated as follows. Data from individual samples
(culture or sputum) were withheld, and a DFA model
was built on the remaining data set (training set). The
data from the withheld samples (testing set) were then
inserted into the discriminant functions and subsequently
assigned to the class for which the centroid had the
smallest Euclidean distance to the unknown sample. The
result could be visualized by plotting the individual dis-
criminant functions against each other [18]. Figure 6
shows the DFA results of the 11 CMM from Um-
belliferae data projected onto their rst four PCs.
In Figure 6, all the 11 CMM samples from U
e original variab
rae can be isolated from each other by the electronic
nose. That means there has difference between the odors
of the CMM samples from Umbelliferae. The electronic
nose can be used as method to identify the 11 CMM
from Umbelliferae. Although the 11 CMM samples from
Umbelliferae contain some common components, but
most of the components of them are different and fur-
thermore, the contents of the common components is not
Figure 5. Bar fingerprint of 18 sensors during the measure-
ment of three samples of RCX from different production
areas.
Figure 6. DFA results of the 15 samples of the 11 CMM
from Umbelliferae.
Copyright © 2011 SciRes. CM
Q. M. FANG ET AL. 151
lt is fitted with the TCM records of
mbelliferae which are produced from
di
nt in the TCM the-
or
nis violacei, chuanmingshen, pro-
du
ce
ta description in
te
rent groups could be
se
e
se
the same. This resu
the 11 CMM from Umbelliferae. For example, there ex-
ists difference between their characteristics, such as, pro-
perty (yaoxing), channel tropism, functions and usages,
etc, as shown in Table 1. Consequently, it is scientific
that the TCM doctor uses the smell (odor) as a standard
to discriminate the CMM from Umbelliferae. The E-nose
can reflect the holistic characteristics of the odor of the
CMM from Umbelliferae, it is more scientific and is
more relevant to the practical identification method used
by the TCM doctor.
The CMM from U
fferent areas can easily be discriminated from each other
by E-nose, as shown in Figure 6. RCX, produced from
Dujiangyan county (N8) and Penshan county (N13) can
be discriminated with each other in Figure 6, Radix chuan-
mingshinis violacei, chuanmingshen, produced from Lang-
zhong county (N6) and Qingbaijian county (N12) can be
discriminated with each other, too.
Processing method is very importa
y. By using different processing methods, the odor of a
CMM is changed, consequently the property, function
and usage of a CMM is changed, too. In fact, processing
method has some effects on the quality of a CMM. The
CMM from Umbelliferae which are processed with dif-
ferent methods can easily be discriminated from each
other by E-nose. RCX, produced from Penshan county, are
processed with two methods, sun-dried (N13) and coa-
led-heated (N14) can be discriminated with each other in
Figure 6. Therefore the processing method has some
effects on the quality of CMM. Sample 14 is coal-heated
RCX from Penshan county, its intensity of 18 sensors is
decreased than the sun-dried RCX (N13) from Penshan
county. As RCX is concerned, the quality of sun-dried
one is better than the coal-heated one, as shown in Fig-
ure 5. It is coherent with the traditional processing me-
thod, sun-drying.
Radix chuanmingshi
ced from Qingbaijian county, which are processed with
two different methods, cuticle-peeled (N12) and cuticle-
keeping (N15) can be discriminated with each other, too.
The difference between the samples with different pro-
ssing methods (N8, N14 and N6, N15) is more signify-
cant than the difference between the samples from dif-
ferent production areas (N8, N13; N6, N12).This result
indicates that the processing method has more influence
on the quality of the CMM from Umbelliferae than the
production areas, as shown in Figure 7.
Generally speaking, CA can yield a da
rms of clusters or groups of data points that possess str-
ong internal similarities. CA is a more direct tool to nd
subclasses than PCA. We used CA analysis to study the
relationships and the scale of each affecting factor, such
as production areas, Genus, processing method, when the
CMM from Umbelliferae were surveyed by the elec-
tronic nose. The Euclidean metric was used in the CA
with an “average between groups” method of linkage.
Considering the large amount of the measurements, the
average responses of four measurements to each of 15
CMM samples were applied to CA analysis and the CA
dendrogram is shown in Figure 7.
As shown in Figure 7, two diffe
en in the dendrogram, the rst group included samples 1,
5, 7, 10, 8, 13, 14. The three samples of RCX (N8, N13,
N14), can be found in this group. The Euclidean distance
between the two sun-dried and coal-heated chuanxiong
(N8 and N14) was close and satised. The Euclidean dis-
tance between N8 and N14 is near than the distance be-
tween N8 and N13. This result is contrary with the DFA
result. Radix peucedani, Qianhu (N5) was misplaced in the
first group with N8 and N14 in Figure 7. And sample 2, 4,
9, 6, 12, 15 formed the second group. It is shown that the
Radix chuanmingshinis violace, Chuanmingshen with
cuticle, Qingbaijiang were more similar to each other and
the Euclidean distance between them (N6, N12) was close
and satisfied, this result is similar with the DFA result.
Sample 4 and sample 6, 12, 15 are clustered as in th
cond group. This result is relevant to the TCM theory.
Sample 4 (Radix Glehniae) is also called beishashen in
China, and sample 6 (Radix chuanmingshinis violacei) is
called chuanmingshen in China [8]. When a CMM is
called “shen”, like renshen (Radix ginseng), it has a func-
tion to nourish yin of the body. Radix chuanmingshinis
violacei and Radix glehniae have the functions to nourish
yin of the body, as shown in Table 1.
Figure7. CA dendrogram based on the average responses of
18 sensors to the 11 CMM samples from Umbelliferae.
Copyright © 2011 SciRes. CM
Q. M. FANG ET AL.
152
s of
Sttica1 quality control (SQC) is a set of statistical tools
Th odor of the CMM is a holistic reflection of all the
3.5. The Comparison between the Two Specie
Radix Chuanmingshinis Violacei, and
Rhizoma Chuanxiong
atis
used by quality professionals to evaluate organizational
quality. Descriptive statistics are used to describe quality
characteristics and relationships between the samples.
Statistical process control (SPC) involves inspecting a
random sample of the output from a process and deciding
whether the process is producing products with characte-
ristics that fall within a predetermined range. Acceptance
sampling is the process of randomly inspecting a sample
of goods and deciding whether to accept the entire lot
based on the results. As shown in Figure 8, the 3 sam-
ples of Radix Chuanmingshinis violacei, chuanmingshen
(N6, N12, N15) and the 3 samples of RCX (N8, N13,
N14) can be easily classified into two types. RCX (N8,
N13, N14) formed a group which is up the average line
(1.3). On the contrary, the three samples of Radix chuan-
mingshinis violacei, chuanmingshen (N6, N12, N15)
formed a group which is below the average line (1.3).
Therefore, SQC is a very useful tool to classify the sam-
ples of the CMM and find the differences between the
CMM.
4. Conclusions
e
volatile components which can be smelled by nose and
E-nose. The E-nose is a technology that can reflect the
holistic odor of a CMM and is relevant to the TCM doc-
tor’s practical identification. The odor of CMM can be
expressed by objective data instead of subjective sense.
Figure 8. SQC of Radix chuanmingshinis violacei, chuan-
CM re-
co
M without preju-
di
tively used to discrinimate the
CM
o many advantages, only use
E-
] T. G. Kang, “Authentication of Chinese Medicines,”
Zhao, Z. T. Liang and P. Guo, “Macroscopic
mingshen (N6, N12, N15) and RCX (N8, N13, N14).
The results of the E-nose are fitted with the T
rds about the property (yaoxing), channel tropism (gui-
jing), function and usage of the CMM.
The E-nose can discriminate the CM
ce, and has been demonstrated as a sensitive, fast and
non-invasive technology. Moreover, the other advantages
of E-nose are like sample is analyzed without reference
compound and requiring no pretreatment, etc. These ad-
vantages of E-nose show its further application in the
quality control of CMM.
The E-nose can be effec
M from different production areas, different proc-
essing methods, storage time, etc. After further research,
it maybe a useful tool to reveal the connotation of the
Genuine Traditional CMM (Daodiyaocai). Based on the
sensor`s intensity of E-nose, the fingerprint of a CMM
can be established, too.
Although the E-nose has s
nose technology is not enough to evaluate the property
(yaoxing) and to control the quality of CMM, it must be
combined with the other macroscopic technology, such
as the E-tongue, the E-eye [19], to have a holistic analy-
sis of a CMM.
5. References
[1
China Press of Traditional Chinese Medicine, Beijing,
2003.
[2] Z. Z.
Identication of Chinese Medicinal Materials: Traditional
Experiences and Modern Understanding,” Journal of Eth-
nopharmacology, Vol. 134, No. 3, 2011, pp. 556-564.
doi:10.1016/j.jep.2011.01.018
[3] X. Q. Chang and L. X. Ding, “Handbook of Analysis of
ng, “Strategies for Quality
the Active Components of Chinese Marteria Medcia,”
School Press, Beijing, 2002.
[4] S. P. Li, J. Zhao and B. Ya
Control of Chinese Medicines,” Journal of Pharmaceuti-
cal and Biomedical Analysis, Vol. 55, No. 4, 2011, pp.
802-809. doi:10.1016/j.jpba.2010.12.011
[5] Chinese Pharmacopoeia Commission, “Pharmacopoeia of
nd Y. L. Zheng,
ration of the Chinese Herbs in the Place
J. W. Gardner, “Electronic
the People’s Republic of China,” China Medical Science
and Technology Press, Beijing, 2010.
[6] C. X. Zhang , J. C. Bao, X. G. Li a
“HPLC Determination of the Amount of Ginsenosides in
Different Part of Panax Ginseng C. A. Mey and P. Quin-
quefolius L. and P. Notoginseng (Burk) F.H. Chen,” Chi-
nese Journal of Pharmaceutical Analysis, Vol. 10, 2005,
pp. 1190-1194.
[7] S. L. Hu, “Illust
of the Genuine,” Shandong Publishing House of Science
and Technology, Jinan, 1998.
[8] P. N. Burtlett, J. M. Elliott and
Copyright © 2011 SciRes. CM
Q. M. FANG ET AL.
Copyright © 2011 SciRes. CM
153
Borgonovo and E.
Noses and Their Application in the Food Industry,” Food
Technology, Vol. 51, 1997, pp. 44-48.
[9] M. Laureati, S. Buratti, A. Bassoli, G.
Pagliarini, “Discrimination and Characterization of Three
Cultivars of Perilla Frutescens by Means of Sensory De-
scriptors and Electronic Nose and Tongue Analysis,”
Food Research International, Vol. 43, No. 4, 2010, pp.
959-964. doi:10.1016/j.foodres.2010.01.024
[10] R. Baby, M. Cabezas, E. Castro, R. Filip and N. E. Wal-
söe de Reca, “Quality Control of Medicinal Plants with
an Electronic Nose,” Sensors and Actuators B: Chemical,
Vol. 106, No. 1, 2005, pp. 24-28.
doi:10.1016/j.snb.2004.05.049
[11] H. S. Peng, M. E. Cheng, L. Zhang, Y. Yao and B. X.
. H. Xiao, “Can Odors of TCM Be
Han, “Analysis Odor of Rhizoma Aatractylodis Macro-
cephalae Based on Electronic Nose,” Journal of Chinese
Medicinal Materials, Vol. 33, 2010, pp. 503-506.
[12] A. D. Daurat, “Application Note of Alpha M.O.S-20 at
04: QC of Chinese Medicine via Fingerprint Analysis,”
2004. http://www.insung.net/cgi/pdf-new/21/AT04
[13] B. X. Han, N. F. Chen, X. K. Zhou and S. Wang, “Elec-
tronic Nose for Odor Analysis of Radix Peucedani with
Different Growth Time,” Food Science, Vol. 31, No. 4,
2010, pp. 132-134
[14] T. Ye, C. Jin and X
Captured by Electronic Nose? The Novel Quality Control
Method for Musk by Electronic Nose Coupled with
Chemometrics,” Journal of Pharmaceutical and Bio-
medical Analysis, Vol. 55, No. 5, 2011, pp. 1239-1244.
doi:10.1016/j.jpba.2011.03.018
[15] A. H. Gomez, J. Wang, G. Hu and A. G. Pereira, “Elec-
tronic Nose Technique Potential Monitoring Mandarin
Maturity,” Sensors and Actuators B: Chemical, Vol. 113,
No. 1, 2006, pp. 347-353. doi:10.1016/j.snb.2005.03.090
[16] J. H. Fu, S. C. Li, Y. Dong, W. Z. Wang, Y. Y. Wang and
Z. X. Yu, “The Four Classic of Traditional Chinese
Medicine,” Ancient China Medical Material Press, Bei-
jing, 1996.
[17] Q. Y. Zhang, S. P. Zhang, C. S. Xie, D. W. Zeng, C. Q.
Fan, D. F. Li and Z. K. Bai, “Characterization of Chinese
Vinegars by Electronic Nose,” Sensors and Actuators B:
Chemical, Vol. 119, No. 2, 2006, pp. 538-546.
doi:10.1016/j.snb.2006.01.007
[18] M. Otto, “Chemometrics: Statistics and Computer Appli-
cation in Analytical Chemistry,” John Wiley and Sons,
New York, 1999.
[19] C. Apetrei, I. M. Apetrei, S. Villanueva, J. A. de Saja, F.
Gutierrez-Rosales and M. L. Rodriguez-Mendez, “Com-
bination of an E-Nose, an E-Tongue and an E-Eye for the
Characterisation of Olive Oils with Different Degree of
Bitterness,” Analytica Chimica Acta, Vol. 663, No. 1,
2010, pp. 91-97. doi:10.1016/j.aca.2010.01.034