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CHEMOMETRICS
Abstract: In the study of voltammetric electronic tongues, a key point is the preproces-
sing of the departure information, the voltammograms which form the response of the
sensor array, prior to classification or modeling with advanced chemometric tools. This
work demonstrates the use of the discrete wavelet transform (DWT) for compacting
these voltammograms prior to modeling. After compression, a system based on
artificial neural networks (ANNs) was used for the quantification of the electroactive
substances present, using the obtained wavelet decomposition coefficients as their
inputs. The Daubechies wavelet of fourth order permitted an effective compression
2189
2190 L. Moreno-Barón et al.
up to 16 coefficients, reducing the original dimension by ca. 10 times. The case studied
is a mixture of three oxidizable amino acids:tryptophan, cysteine, and tyrosine. With
the reduced information, one ANN per specie was trained using the Bayesian regular-
ization algorithm. The proposed procedure was compared with the more conventional
treatments of downsampling the voltammogram, or its feature extraction employing
principal component analysis prior to ANNs.
INTRODUCTION
We have been attending during recent years to the success of the concept
of electronic tongues in the field of chemical sensors. This case is one of
the more clear benefits accounted for in the combination of chemometrics
and electrochemical sensors (Pravdová 2002), which was foreseen as an
excellent way to improve sensor performance (Lavine 2002). An accepted
definition of electronic tongue (Holmberg 2004) entails an analytical instru-
ment comprising an array of nonspecific, poorly selective, chemical sensors
with cross-sensitivity to different compounds in a solution, and an appropriate
chemometric tool for the data processing. For the analysis of liquid samples,
there are two main kinds of electronic tongues, those employing potentio-
metric sensors (Gallardo 2003) and those employing voltammetric sensors
(Winquist 1997). The latter usually employ arrays of voltammetric electrodes,
for example, a number of different metallic electrodes, or a number of
modified electrodes (Apetrei 2004). From the conceptual point of view, a vol-
tammetric system with a single electrode can also be considered an electronic
tongue, as the dominating point here is the high order measuring information
fed to the computer-processing tool.
Moreover, regarding this feature, the complexity of the input information,
it makes enormously cumbersome any chemometrical stage, becoming a cri-
tical issue in voltammetric electronic tongues. In this way, a crucial point in
this field is the reduction of the data, prior to classification or calibration.
The use of artificial neural networks (ANNs) is widely accepted to build the
calibration model of electronic tongues (Krantz-Rülcker 2001). When the
input information is of the voltammetric type, it becomes difficult to
correctly build and adjust a network with hundreds of input nodes, as needed
by these voltammograms. Again, the way to solve this bottleneck is through
the preprocessing of the original signal in order to reduce its dimensions.
In addition to size reduction, compression is intended to extract signi-
ficant features from the departure information, besides the elimination of
irrelevant content, such as noise or redundancies (Simons 1995; Despagne
1998). Further advantages of such pretreatment can be an increased training
speed, a reduction of memory needs, better generalization ability of the
Data Compression for Voltammetric Electronic Tongue 2191
EXPERIMENTAL
All chemicals for electrolyte and the stock of amino acid solutions, tryptophan
(Trp), cysteine (Cys), and tyrosine (Tyr), were purchased from Merck as pro-
analysis grade. The support electrolyte solution consisted of 0.1 M potassium
chloride þ 0.1 M phosphate solution (pH was adjusted to 7.5). Synthetic
mixtures for the evaluation of the voltammetric method were prepared from
0.1 M stock solutions of each amino acid.
Apparatus
Procedure
Three series of synthetic solutions were prepared for Trp, Cys, and Tyr
analysis. For each analyte, six concentration levels were considered as
follows: 5.0, 10, 20, 25, 30, and 35 mM for Cys and Tyr, and 2.0, 6.0, 10,
14, 17, and 21 mM for Trp. Interferences were studied at two levels: 10 and
25 mM for Trp and Cys; 5.0 and 34 mM for Tyr. As a result, each analyte
series was composed of 24 mixture solutions, and the set of voltammograms
processed 72.
Software
The procedures for data reduction employing DWT, PCA, and downsampling
were set up and fine-tuned before the voltammograms were coupled to the
modeling system based on ANNs. The performances of the three alternatives
were compared after training, using the input training data and an external test
subset. The analytical case studied was the simultaneous direct determination
of oxidizable amino acids, a common application in animal feed analysis.
Figure 1 shows a typical voltammogram, corresponding to one of the
original input data. As can be observed, a degree of overlapping, together
with background oxidation, makes the estimation of the components an inter-
esting issue.
The departure universe of data used for building the calibration model
consisted of an input matrix, formed by 72 samples (columns) with 164
current values (rows) for each one, plus the corresponding output matrix,
formed by 72 samples with three concentration values (rows) for each one.
The first preprocessing was done with the DWT using the Daubechies
mother wavelet of fourth order and taking the decomposition to a fourth
level. The mother wavelet, order, and decomposition level were chosen
based on a compromise between the number of approximation coefficients
obtained at each decomposition level and the degree of similarity between
the original voltammogram and the one recovered with these coefficients, as
was done in a previous work (Moreno-Barón 2005). The fewest number of
coefficients and the highest similarity were the goals. With this processing,
the size of the input information was reduced from 164 points per voltammo-
gram to only 16; therefore, the information was compressed by a factor
slightly larger than 10.
To reduce the input information employing PCA, the analysis showed that
more than 95% of input variance could be explained with just the first three
PCs; nevertheless, in order to compare the efficiency with the DWT com-
pression, the first 16 PCs were taken, including in this way more information
than strictly necessary.
Lastly, in the downsampling scheme, the input matrix was reduced by a
factor of 10, following the decimation procedure (Mitra 2001), in which
a signal is resampled at a lower rate after lowpass filtering. The filter has a
cutoff frequency of p/D, where p is a normalized frequency and D is the
downsampling factor. In this way, all three compression techniques yielded
16 rows. No change was needed to the output matrix in any case.
After the three compression alternatives were done, the data were split
into two subsets for training and testing the neural networks. For the
training process, 75% of the total number of columns was taken, while
for testing, the remaining columns were used. All data were normalized
to the interval [21,1] to facilitate the convergence of the learning
algorithm. No internal validation subset was needed, due to the nature of
the used algorithm, as explained below.
ANNs
The goal for convergence training was a sum of squared error (SSE) of
0.001 in 200 or less training epochs. SSE was calculated as follows:
X
N
SSE ¼ ðcexpected ccalculated Þ2 ð1Þ
j¼1
The programming for the ANN training was devised to improve the general-
ization performance of the network, i.e., to correctly predict outputs related to
testing data. The Matlab program starts with the loading of the compressed
information for training and testing, then the network is initialized, and the
training is performed with the selected learning strategy. The network is
trained until it reaches the previously fixed SSE goal. After convergence
state is reached, the external test data are interpolated to check the
modeling ability for the considered chemical component. From the output
values, a prediction error using the absolute values of the residuals is
calculated. This error is a percentile relative absolute error (PRAE) defined
by Eq. (2):
M c
1X expectedi ccalculatedi
PRAE ¼ 100 ð2Þ
M i¼1 cexpected
i
The alternative that showed better generalization ability to data test was that
of ANNs employing DWT preprocessed voltammograms. Training for
each network lasted approximately 96 h to reach a minimum PRAE, and as
Data Compression for Voltammetric Electronic Tongue 2197
Figure 2. Flowchart of the training process used for each artificial neural network
model.
Figure 3. Comparison of the obtained vs. expected results for the three considered
amino acids for DWT preprocessed input data. The dashed line corresponds to ideality
(y ¼ x), and the solid line is the regression of the comparison data. Graphs on the left
correspond to training and those on the right to external testing.
Data Compression for Voltammetric Electronic Tongue 2199
Table 1. Linear regression parameters for the line (y ¼ m . x þ b) that best fits the
plots of obtained vs. expected results for the networks trained with the three data
sets obtained with the WT, PCA, and downsampling processing techniques. The sets
were split into two subsets for training and testing. Uncertainty intervals were calcu-
lated at 95% of confidence level
Training Testing
Amino
acid m b m b
DWT
Trp 0.998 + 0.0023 1.1E-5 + 2.6E-05 1.012 + 0.0086 2.3E-4 + 1.1E-03
Cys 1.002 + 0.0018 8.9E-6 + 3.7E-05 1.043 + 0.0761 26.4E-4 + 1.7E-03
Tyr 0.994 + 0.0061 3.6E-5 + 1.2E-04 0.980 + 0.126 1.7E-4 + 2.7E-03
PCA
Trp 0.999 + 0.0019 5.7E-6 + 2.2E-05 0.897 + 0.128 7.7E-4 + 1.6E-03
Cys 0.987 + 0.014 2.4E-4 + 3.0E-04 0.865 + 0.395 4. 9E-3 + 8.9E-03
Tyr 0.999 + 0.0016 1.5E-5 + 3.2E-05 0.970 + 0.194 24.2E-4 + 4.4E-03
Downsampling
Trp 0.998 + 0.0021 0.028 + 2.5E-05 1.060 + 0.0130 20.96 + 1.7E-03
Cys 0.999 + 0.0012 0.020 + 2.5E-05 1.112 + 0.077 21.4 + 1.7E-03
Tyr 0.998 + 0.0014 0.031 + 2.8E-05 0.938 + 0.121 21.1 + 2.8E-03
Although some works in the literature achieved correct results (de Carvalho
2000; Ensafi 2002), networks trained with PCA compressed data did not
show good responses with the data test, which must be due to the difficulty
of the case studied. With exception of the network for Trp, which obtained
a PRAE value of 9.33%, the networks modeling Cys and Tyr yielded values
larger than the 10% limit, being 32.73% and 14.23%, respectively. Figure 4
shows the comparison graphs between obtained and expected concentration
2200 L. Moreno-Barón et al.
Figure 4. Comparison of the obtained vs. expected results for the three considered
amino acids for PCA preprocessed input data. The dashed line corresponds to ideality
(y ¼ x), and the solid line is the regression of the comparison data. Column at left
corresponds to training and column at right to testing.
Data Compression for Voltammetric Electronic Tongue 2201
values, for both training and testing sets. Corresponding data on Table 1
summarize the regression lines shown on the graphs, which are clearly
worse than those for the DWT case, specially when observing the modeling
ability for the external test.
Figure 5. Comparison of the obtained vs. expected results for the three considered
amino acids for downsampled preprocessed input data. The dashed line corresponds
to ideality (y ¼ x), and the solid line is the regression of the comparison data. Column
at left corresponds to training and column at right to testing.
Data Compression for Voltammetric Electronic Tongue 2203
Preprocessing
technique PRAE1 PRAE2 PRAE3
resolve in frequency domain, and thus, finer frequency resolution is desirable for
the processed voltammograms in this work.
The determination of Tyr amino acid from voltammograms is better when
the compacted signal presented at the input of the ANN carries spectral and
temporal information about the original signal. The upper graph in Fig. 6
shows one raw voltammogram, and the lower graph shows the same voltam-
mogram reconstructed from the 16 approximation coefficients obtained by
DWT using Daubechies wavelet of fourth order. Notice the smoothing
effect on the reconstructed signal. Correlation between original and recon-
structed signals was 0.98. The downsampled voltammogram is also plotted
in the lower graph over the reconstructed signal, and some points of it lie
outside the recovered voltammogram, mainly at the end of the signal.
Figure 6. (Upper) One raw voltammogram of the oxidizable amino acids. (Lower)
The previous signal reconstructed after wavelet processing (solid line) and downsam-
pling (asterisks). Note that differences in postprocessed signals are more manifest for
the lower current values.
2204 L. Moreno-Barón et al.
CONCLUSIONS
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