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Department of Material Science and Engineering, Huazhong University of Science and Technology, Wuhan 430074, China
b Department of Material Science and Engineering, Wuhan University of Technology, Wuhan 430070, China
Received 31 August 2005; received in revised form 30 December 2005; accepted 4 January 2006
Available online 8 February 2006
Abstract
In this paper, 17 commercial Chinese vinegars, acetic acid and 5% diluted acetic acid were analyzed by an electronic nose containing nine nano
ZnO thick film gas sensors, which are doped by 5 wt.% and 10 wt.% TiO2 , 5 and 10 wt.% MnO2 , 1 wt.% V2 O5 , 5 wt.% Bi2 O3 , 0.6 and 2.4 wt.% Ag,
and 5 wt.% W, respectively. Principal component analysis (PCA) and cluster analysis (CA) were employed to investigate the presence of classes
inside the sample population. It was shown that characterizing the Chinese vinegars by the electronic nose was highly related to their type, raw
materials, total acidity, fermentation method and production area and all these influencing factors were not independent. The CA results indicated
that the type and fermentation method were more effective than the other influencing factors when the vinegars were analyzed by the electronic
nose. Finally, the data colleted by the electronic nose were applied to the learning vector quantization (LVQ) neural network performing the role of
recognition and classification of the vinegars. The accuracy in terms of predicting tested vinegar measurements was 72.1%, 76.5%, 77.9%, 94.1%
and 82.4% according to their type, raw materials, total acidity, fermentation method and production area, respectively. This work was the first
step to establish a gas-sensing fingerprint database of Chinese vinegars and develop a commercial electronic nose on the Chinese vinegars quality
control.
2006 Elsevier B.V. All rights reserved.
Keywords: Electronic nose; Chinese vinegar; PCA; CA; LVQ
1. Introduction
Vinegar is defined as a liquid fit for human consumption
and contains a specified amount of acetic acid. China has more
than 5000 years history of producing vinegar. Every year over
26 million hectoliters of vinegar is produced in China. Chinese
people treat the vinegars as favorite condiments, health products
and even medicines. More than 3.2 million liters of vinegar is
consumed every day in China. Because the quality of vinegar
directly affects the peoples health, Chinese governments have
paid more and more attention on the quality control of vinegar.
The China State Bureau of Quality and Technical Supervision
had issued the market allowance policy on vinegar quality and
safety in 2002 in China. From then on, the vinegar enterprises
must take out the vinegar producing license and pass the onthe-spot check of the producing necessary conditions. At the
Corresponding author. Tel.: +86 27 8755 6544; fax: +86 27 8754 3776.
E-mail address: csxie@mail.hust.edu.cn (C. Xie).
0925-4005/$ see front matter 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.snb.2006.01.007
same time, the China State Bureau of Standards has issued the
related standards to specify the classification, requirement, labeling, packaging, storage, transport and inspecting of vinegar to
ensure the quality of vinegar and the peoples health.
In China, studies on Chinese vinegar quality evaluation are
scarce, but in Europe, the quality control of vinegar is widely
investigated by using sensory analysis for the concession of
manufacturers seals of guarantee over the last decade [1,2].
Sensory analysis requires a well trained testing panel and limited vinegar samples are examined at each tasting session, in
order not to excessively tire the assessors [2]. At the same time,
the accuracy and objectivity cannot always be ensured because
the assessors are influenced by their healthy conditions, emotions and environment. So, various chemical analysis methods,
such as ion-selective electrodes [3], atomic absorption spectrum
[4], gas chromatography [58] and pyrolysis-mass spectrometry [9,10], are developed to measure the vinegar compounds and
control the vinegar quality. Since vinegars contain more than
100 compounds, chemical analysis methods are complicated and
expensive. Also, they are not convenient for real-time, on-line
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Table 1
The details of the vinegar samples utilized in the experiment
No.
Sample name
Type
Raw materials
Total acidity
(g/100 ml)a
Fermentation method
Production area
Hengshun Xiangcu
Aromatic vinegar
4.0
Solid fermentation
Jiangsu province
Beigushan Xiangcu
Aromatic vinegar
5.0
Solid fermentation
Jiangsu province
Yanhui Xiangcu
Aromatic vinegar
5.5
Solid fermentation
Jiangsu province
4
5
Jinyou Xiangcu
Zhengjiang Xiangcu
Aromatic vinegar
Aromatic vinegar
6.0
6.0
Solid fermentation
Solid fermentation
Jiangsu province
Jiangsu province
Longmen Xiangcu
Aromatic vinegar
4.4
Solid fermentation
Beijing
Weichunyuan Xiangcu
Aromatic vinegar
5.0
Solid fermentation
Guizhou province
Shuita Chencu
Mature vinegar
4.5
Solid fermentation
Shanxi province
Donghu Chencu
Mature vinegar
6.0
Solid fermentation
Shanxi province
10
Beigushan Chencu
Mature vinegar
4.5
Solid fermentation
Jiangsu province
11
Zhengjiang Chencu
Mature vinegar
5.0
Solid fermentation
Jiangsu province
12
Weichunyuan Chencu
Mature vinegar
5.0
Solid fermentation
Guizhou province
13
14
Jinbiao Micu
Longmen Micu
Rice vinegar
Rice vinegar
5.0
4.4
Liquid fermentation
Solid fermentation
Guangdong province
Beijing
15
16
17
Meiweixian Baicu
Longmen Baicu
Haitian Pingguocu
White vinegar
White vinegar
Fruit vinegar
3.5
3.95
2.5
Liquid fermentation
Liquid fermentation
Liquid fermentation
Guangdong province
Beijing
Guangdong province
540
Table 2
Specification of the sensors utilized in the array
Sensor no.
Dopants (wt.%)
1
2
3
4
5
6
7
8
9
TiO2 (5)
MnO2 (5)
V2 O5 (1)
W (5)
TiO2 (10)
Ag (2.4)
Ag (0.6)
Bi2 O3 (5)
MnO2 (10)
Fig. 1. PCA results of acetic acid, 5% diluted acetic acid and the vinegars data
obtained from sensor array.
Fig. 2. PCA results of the vinegars data obtained from sensor array.
Fig. 3. PCA results of the vinegars data obtained from sensor array; making for
vinegar type.
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Fig. 4. PCA results of the vinegars data obtained from sensor array; making for
total acidity.
Fig. 5. PCA results of the vinegars data obtained from sensor array; making for
fermentation method.
Fig. 6. PCA results of the vinegars data obtained from sensor array; making for
raw materials.
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Fig. 7. PCA results of the vinegars data obtained from sensor array; making for
production area.
areas by the rice vinegars in the PCA plane. The reason will be
discussed later.
Considering acetic acid is the main ingredient in the vinegars,
the PCA data were redrawn according to the total acidity of the
vinegars in Fig. 4. The graph in Fig. 4 shows a sufficient but not
so good separation among clusters. Only the Longmen Baicu,
Meiweixian Baicu, Hengshun Xiangcu and Haitian Pingguocu,
which contain less than or equal to 4.0 g/100 ml total acidity,
can ideally come together in a group. The other groups, which
contain 4.44.5, 5.05.5 and 6.0 g/100 ml total acidity, highly
overlapped either at their edges or inside their groups. It is clearly
evident that acetic acid is an important but not critical factor to
character the Chinese vinegars.
It is indicated that two distinct groups of points, which correspond to solid fermentation and liquid fermentation vinegar,
respectively, are well distinguished in Fig. 5. The vinegars used
in our experiment can be perfectly divided into two classes,
i.e. solid fermentation vinegar and liquid fermentation vinegar,
according to their fermentation methods. We also noticed that
the fermentation method was highly related to the vinegar raw
materials, as will be discussed below. Furthermore, the two rice
vinegar samples, i.e. the Jingbiao Micu and the Longmen Micu,
show a great difference in Fig. 5. The Jingbiao Micu is very
similar to the white vinegars because of the same fermentation
method and the similar raw materials, while the Longmen Micu
is basically the same as the aromatic vinegars, which are all fermented in solid and produced from rice and wheat bran, etc.
This can explain that the aromatic vinegars were divided into
two isolated areas by the rice vinegars in Fig. 3.
Comparing the relationships between the responses of the
electronic nose and the raw materials of the vinegars was a hard
work in our experiment, because the each vinegar used more
than three or four different materials. We noticed that most of
the vinegars used stick rice, rice or sorghum, and/or wheat bran,
sugar and salt as the raw materials, except that the Longmen
Micu and the white vinegars used rice and alcohol as the raw
materials. We also perceived that some vinegar were added with
sodium benzoate or potassium sorbate as antiseptic substances to
prolong the vinegars storage life. Based on our best knowledge,
543
Therefore, the PCA results of the same data were plotted onto the
first three PCs, as shown in Fig. 9, to investigate the difference.
Most of the data points roughly took up similar positions (Fig. 2)
except that the Beigushan Xiangcu data points sharply changed
its position from the bottom to the top (refer to Figs. 2 and 9).
This is the reason why the Beigushan Xiangcu did not enter
any group in Fig. 8 though the Beigushan Xiangcu data points
were very close to mature vinegar data points in Fig. 2. The
Yanhui Xiangcu closed to the mature vinegars and the Shuita
Chencu still attached to the aromatic vinegars in Fig. 9 as well
as in Fig. 3. Though we successfully explained the difference
between the results of PCA and those of CA, there is a limitation to this research in explaining the misclassified samples in
the CA analysis. Further research will be devoted to removing
this limitation. More characteristics of the vinegars are needed
for understanding the gas-sensing properties and eliminating the
misclassifications. Sensory analysis [1,2] and analytical chemistry [310] are expected to be the best accessorial tools to
investigate the vinegars.
Samples 13, 15 and 16 closed together and represented the
group of liquid fermentation except sample 17, Haitian Pingguocu. The reason of misclassification of the Haitian Pingguocu
was discussed before. Classifying the vinegars according to their
total acidity, raw materials or production area was not satisfied
enough in CA analysis. Taken as a whole, these results indicate
that the type and fermentation method are more effective than
the other influencing factors discussed in this paper when the
vinegars are analyzed by the electronic nose.
3.3. LVQ analysis
LVQ networks classify input vectors into target classes by
using a competitive layer to find subclasses of input vectors, and
then combining them into the target classes. An LVQ network
has a first competitive layer and a second linear layer. The competitive layer learns to classify input vectors in much the same
Fig. 9. PCA results of the vinegars data obtained from sensor array; score plot in the PC1, PC2 and PC3.
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Table 3
Classification results for 17 vinegars by using LVQ according to their type
Samples
Aromatic vinegar
Mature vinegar
Rice vinegar
White vinegar
Fruit vinegar
28
20
8
8
4
Classified as
Aromatic vinegar
Mature vinegar
16
4
16
Rice vinegar
White vinegar
3
8
Fruit vinegar
Classified as
4.0 g/100 ml
4.0 g/100 ml
4.44.5 g/100 ml
5.05.5 g/100 ml
6.0 g/100 ml
16
16
24
12
4.44.5 g/100 ml
5.05.5 g/100 ml
6.0 g/100 ml
16
3
1
5
16
16
3
4
4
Classified as
Solid fermentation
Solid fermentation
Liquid fermentation
52
16
Liquid fermentation
48
4
16
Table 6
Classification results for 17 vinegars by using LVQ according to their raw materials
Samples
Classified as
Using alcohol
Using alcohol
Adding sodium benzoate
Adding potassium sorbate
The others
12
8
20
28
The others
16
4
16
12
8
4
4
Classified as
Jiangsu province
Jiangsu province
Shanxi province
Beijing
Guangdong province
Guizhou province
28
8
12
12
8
Shanxi province
16
Beijing
4
Guangdong province
4
Guizhou province
4
8
12
12
8
The accuracy in terms of predicting tested vinegar measurements was 72.1%, 76.5%, 77.9%, 94.1% and 82.4% according to
type, raw materials, total acidity, fermentation method and production area, respectively. It was evident that all the influencing
factors which were chosen to characterize the Chinese vinegars
in this experiment were suitable and effective because of their
relative high accuracies. The LVQ results basically matched the
results of PCA and CA. The accuracy according to the fermentation method was highest and only 4 of 68 testing measurements
were misclassified. There is no significant difference in the accuracy to the rest of influencing factors and all of them were about
80% except the accuracy to the type. The fact that the accuracy
to the vinegar type was not satisfied is attributable to the similarities among the aromatic vinegar, rice vinegar and white vinegar
which have been discussed in the CA analysis.
4. Conclusions
Vinegar is favorite food and a large amount of vinegar is produced and consumed every year in China. There is no effective
method or instrument for real-time, on-line and in situ detecting
the vinegars yet, though Chinese government has paid more and
more attentions on the quality control of vinegar. Sensory analysis and chemical analysis are widely used for vinegar quality
evaluation in Europe, but the electronic nose seems to be the
most promising method for vinegar classification.
In this paper, we analyzed 17 commercial Chinese vinegars,
acetic acid and 5% diluted acetic acid by an electronic nose
under laboratory conditions. The electronic nose contained nine
nano ZnO thick film gas sensors, which were doped with 5
and 10 wt.% TiO2 , 5 and 10 wt.% MnO2 , 1 wt.% V2 O5 , 5 wt.%
Bi2 O3 , 0.6 and 2.4 wt.% Ag, and 5 wt.% W. PCA and CA were
applied to examine the presence of classes inside the sample population and LVQ was used to perform the role of recognition and
classification of the vinegars. The findings of the study indicated
that the gas-sensing properties of acetic acid and 5% diluted
acetic acid were very different from those of vinegars. Though
the main ingredient is acetic acid in vinegars, their total acidity is not a critical element to characterize the Chinese vinegars
because of the lower classification accuracy by LVQ analysis. It
was evident from the experimental data that characterizing the
Chinese vinegars by the electronic nose was highly related to
their type, raw materials, total acidity, fermentation method and
production area, and all these influencing factors were not independent. The CA results indicated that the type and fermentation
method were more effective than other influencing factors when
the vinegars were analyzed by the electronic nose. The accuracy
of LVQ was 72.1%, 76.5%, 77.9%, 94.1% and 82.4% according
to the type, raw materials, total acidity, fermentation method and
production area, respectively. It was shown that the electronic
nose was a very promising tool to vinegar characterization. The
present study was made in order to establish a gas-sensing fingerprint database of Chinese vinegars and develop a commercial
electronic nose on the Chinese vinegars quality control.
A further investigation might explore thorough understanding of the gas-sensing properties and the components of vinegars. Sensory analysis and analytical chemistry can be used as
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[19] B.L. Zhu, C.S. Xie, W.Y. Wang, K.J. Huang, J.H. Hu, Improvement in gas
sensitivity of ZnO thick film to volatile organic compounds (VOCs) by
adding TiO2 , Mater. Lett. 58 (2004) 624629.
[20] Q. Zhang, C. Xie, S. Zhang, A. Wang, B. Zhu, L. Wang, Z. Yang, Identification and pattern recognition analysis of Chinese liquors by doped nano
ZnO gas sensor array, Sens. Actuators B 110 (2005) 370376.
[21] R.E. Shaffer, S.L. Rose-Pehrsson, R.A. McGill, A comparison study of
chemical sensors array pattern recognition algorithms, Anal. Chim. Acta
384 (1999) 305317.
Biographies
Qinyi Zhang received his BSc from Wuhan University of Technology in 1993
on material science and engineering. At present, he is a researcher of Wuhan
University of Technology and a PhD student at the Huazhong University of
Science and Technology. His research interests include application of electronic
noses, neural networks and nanomaterials.
Shunping Zhang received his BSc from Huazhong University of Science and
Technology in 2004 on material science and engineering. Currently he is working
on electronic noses as a PhD student at the Huazhong University of Science and
Technology.
Changsheng Xie received his PhD from Huazhong University of Science and
Technology in 1985 on material science and engineering. He is professor of
material science and engineering at Huazhong University of Science and Technology. His research interests include the synthesizing of nanomaterials and
electronic noses.
Dawen Zeng received his BSc in 1993 from Tsinghua University and PhD in
1998 from Huazhong University of Science and Technology on material science
and engineering. He is an associate professor of material science and engineering at Huazhong University of Science and Technology. His research interests
include the synthesizing of nanomaterials and electronic noses.
Chaoqun Fan received her BSc from Wuhan University of Technology in 2005 on material science and engineering. At present, she is a
graduate student at the Huazhong University of Science and Technology. Her research interests are in the field of applications of electronic
noses.
Dengfeng Li received his BSc from Wuhan University of Technology in 2003
on material science and engineering. At present, he is a graduate student at the
Huazhong University of Science and Technology. His current research interests
involve electronic noses and chemical sensors.
Zikui Bai is graduated from the Huazhong University of Science and Technology on material science and engineering in 2005. At present, he is a PhD
student at the Huazhong University of Science and Technology. His current
research interests involve electronic noses and preparation of chemical sensor
array.