ISSN 10619348, Journal of Analytical Chemistry, 2015, Vol. 70, No. 6, pp. 718–724. © Pleiades Publishing, Ltd., 2015.

Original Russian Text © D.M. Bikmeev, A.V. Sidelnikov, F.Kh. Kudasheva, V.N. Maistrenko, 2015, published in Zhurna Analiticheskoi Khimii, 2015, Vol. 70, No. 6, pp. 624–630.

ARTICLES

Development of Chemometric Methods for Signal Processing

in Voltammetric Systems of the Electronic Tongue Type
D. M. Bikmeev, A. V. Sidelnikov, F. Kh. Kudasheva, and V. N. Maistrenko
Department of Chemistry, Bashkir State University, ul. Zaki Validi 32, Ufa, Republic of Bashkortostan, 450076 Russia
email: bikmeev@gmail.com
Received March 19, 2014; in final form, June 25, 2014

Abstract—The main approaches and methods of the chemometric processing of analytical signals for the
quality control and identification of engine oils are considered on an example of electronic tongues based on
carbon paste electrodes containing substances to be identified in the paste. The analytical characteristics of
the sensors are assessed in various modes of recording voltammograms using multicomponent marker mix
tures under the conditions of linear, differential, and squarewave voltammetry; the accuracy of the identifi
cation of engine oils is estimated.

Keywords: voltammetry, chemometrics, carbon paste electrode, principal component analysis, electronic
tongue, engine oil
DOI: 10.1134/S1061934815060052

Measurement systems of the electronic tongue
type, i.e., devices consisting of different electrodes,
have received wide use in electroanalytical chemistry.
Multidimensional data obtained by such devices are
processed using chemometrics [1, 2]. Electronic
tongues are used to fulfill various analytical tasks, such
as the quality control of foodstuffs, fruit juices, oils,
wines, medicines, and process liquids [3, 4].
The available sensors and methods of signal pro
cessing usually cannot fulfill the specified tasks for
objects consisting of nonelectroactive components.
We have shown previously [5–7] that such objects can
be identified using voltammograms of standard marker
substances recorded on electrodes modified with car
bon pastes containing compounds to be determined.
In this case, the nature of the studied object affects not
only the value of the recorded marker signal but also
the shape of the voltammogram. A multidimensional
image of an analyte is formed by the chemometric pro
cessing of the voltammogram of the electroreduction
of markers on carbon paste electrodes containing
compounds to be determined, for example, engine oil,
in the paste. The arrangement of the voltammogram
along the axis of potentials and the shapes and heights
of the peaks depend on the nature of engine oil. The
availability of a set of markers (aromatic nitrocom
pounds; Cu(II), Cd(II), Pb(II), etc. ions) ensures the
necessary crosssensitivity of electrodes for the opera
tion of electronic tongue systems [8].
The values of analytical signals and the shapes of
voltammogram recorded in different modes (cyclic,
squarewave, and alternatingcurrent voltammetry;
pulse options; etc.) differently depend on the concen
tration and nature of the identified substances. Mea
surements of the ratio of capacitive and Faraday cur
rents in the voltammograms and the use of marker
mixtures can significantly improve the reliability of
identification.
Such voltammetric electronic tongues have poorly
been studied, and virtually no works were found on
their applications in combination with the chemomet
ric processing of the results measurements for the
identification of samples containing electroactive and
nonelectroactive components.
In this work, the main approaches and methods of
the chemometric processing of analytical signals for
the quality control and identification of engine oils are
considered on an example of carbon paste electrodes
(CPE) bearing identified substances in the paste.
EXPERIMENTAL
We used a standard temperaturecontrolled three
electrode cell with a carbon paste indicator electrode
containing engine oil as a binding component (the
ratio of graphite to engine oil was 6 : 1 by weight). The
auxiliary electrode was a glassy carbon electrode and
the reference electrode was a silver–silver chloride
electrode. Squarewave and differentialpulse voltam
mograms of the markers were recorded for aqueous
solutions against 0.1 M HCl using a voltammetric
IVA5M analyzer and a P8nano potentsiostat
at the potential scan rate 0.1–5 V/s in the range 0.0–
(–1.5) V after the accumulation of a marker on a CPE
surface for 15 s under intense stirring.

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 DEVELOPMENT OF CHEMOMETRIC METHODS FOR SIGNAL PROCESSING
The electroactive markers were standard 1 × 10–4 M
solutions of оnitroaniline (oNA), mnitroaniline
(mNA), pnitroaniline (pNA), onitrophenol
(oNP), 2,4dinitrophenol (αdinitrophenol,
αDNP), 2,5dinitrophenol (γdinitrophenol,
γDNP), and оnitrobenzoic acid (оNB) and 1 × 10–3 M
solutions of CuSO4, Pb(NO3)2, and Cd(NO3)2. Syn
thetic, semisynthetic, and mineral engine oils from
various producers were studied. The physical and
chemical properties of oils were provided in [6].
A voltammetric data array for each oil was formed
by 15 replicate measurements (voltammograms) and
included more than 300 current values at different
potentials.
The chemometric processing of the voltammo
grams was done using the principal component analy
sis [8–10], which allowed the subdivision of the matrix
of experimental data into two parts, informative and
noise. In this case, each voltammogram in a multidi
mensional potential space after transformation was
presented by a point, which was projected onto the
first principal component (PC1), built along the max
imum change of the experimental data. Then the next
principal component was built; it was orthogonal to
the first component and directed along the next
change of multidimensional data in magnitude, etc.
Using the specified chemometric operation, the
experimental data were compressed: of 300 values of
currents and potentials in each voltammogram we
obtained a set of generalized coordinates x, y, z, etc.
(PC1, PC2, PC3).
Using the principal component analysis, multidi
mensional voltammetric data were contracted and
transferred to a new coordinate system, the system of
principal components; the origin or coordinates in this
system lied in the center of the data area and the direc
tions of the principal components were determined by
hidden regularities typical for the experimental data
obtained. By the relative positions of point clusters on
the plane of principal components, the scores plot, we
estimated data structure and revealed the similarity
and distinctions between the samples. The optimum
number of principal components (from 3 to 5) was
selected based on the specified value of the explained
variance, 90%.
Engine oils were identified using the soft indepen
dent modeling of class analogies (SIMCA) [8–10].
For this purpose, each class from a training set, which
consisted of samples of engine oils, was independently
simulated using the principal component analysis.
Then distances from an identified sample to each class
were calculated and compared with the standard ones
calculated for each PCAmodel from the training set.
The results of identification were presented as num
bers of test samples assigned to one or another class. A
version of SIMCA classification implemented into the
Chemometrics AddIn software for Microsoft Excel
[11] was used.
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RESULTS AND DISCUSSION
As was shown previously [5–7], all of the studied
markers were reduced on a CPE containing engine oils
in the paste in the same region of potentials, but their
voltammograms exhibited different shapes and heights
and differed in the positions of peaks along the axis of
potentials, depending on the nature of oil and marker
and on the shape of polarization voltage.
In the identification of engine oils using threefac
torial patterns (variation of the potential scan rate and
marker nature), we could not identify individual sam
ples if big sets of test samples similar in composition
and properties were used [6]. However, the range of
analytical tasks fulfilled with voltammetric electronic
tongues is quite diverse and can also include specific
identification tasks, such as a comparison of two sam
ples of the same oil, i.e., the revelation of a correspon
dence between the quality of the studied oil and stan
dard requirements. In this case, the percentage of cor
rectly identified engine oils increased and the
electronic tongue allowed the analyst to find a corre
spondence between the oils and standard samples
(Table 1).
Another method of recording signals exhibiting
crosssensitivity can be implemented using marker
mixtures (for example, ternary) competing on the
CPE, i.e., accumulated and reduced on the electrode
surface depending on the marker nature and also on
the CPE properties. The results of the SIMCA classi
fication of engine oils based on the proposed approach
demonstrate that almost all possible pairs of engine
oils could be distinguished using ternary marker mix
tures [5, 7]. Thus the percentage of correctly recog
nized samples was not lower than 67% and as high as
100% for the majority of samples (Table 2). In using
binary marker mixtures, the results of identification
were more ambiguous.
From the scores plots of PCA models of square
wave voltammograms of the reduction of pNA
(marker) on the studied CPE (see figure), one can see
that the voltammograms of engine oil samples are
grouped into clusters on the plane of the principal
components, depending on the oil nature. One can
observe both closely lying clusters superimposing each
other, for example, P9 and P11, S1 and M14, etc., and
those differing by their positions in the scores plots.
These were samples lying against each other along the
axes of the principal components, for example, P10
and M15 and also P17 and M13 along the first princi
pal component; P17 and S5, S6 and S8, along the sec
ond principal component; and S3 and S5, M12 and
P11, along the third principal component. The dis
tinctions between the clusters can be used for gaining
information about the nature of engine oils.
The oils were identified by the SIMCA method of
multidimensional classification using the obtained
PCA models (Table 3). When comparing the results of
SIMCA classification with the data of oil identifica
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