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1 Chapter 9
2 Materials for Electronic Tongues: Smart

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3 Sensor Combining Different Materials
and Chemometric Tools

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4

5 Manel del Valle

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6 9.1 Introduction

In recent years, we have been promulgating the concept of electronic tongues in the
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field of chemical sensors. This case has proved to be one of the most striking AQ1

9 benefits of the combination of chemical sensors with data processing tools [1].
10 Electronic tongues have been defined as an instrument devised for chemical anal-
11 ysis formed by an array of sensors having non-specific or partial overlapped
responses plus advanced mathematical procedures for signal processing based on
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12

13 the pattern recognition (PARC) and/or multivariate analysis, viz. artificial neural
14 networks (ANNs), principal component analysis (PCA), etc. [2]. Variants can be a
15 classical quantitative determination, where a number of substances may be deter-
16 mined in a single, direct operation, or the determination of a substance in the
17 presence of its interferents, provided their separation is not needed [3–5]. Also, the
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18 concept can provide more interesting applications, such as identification of varieties


19 or establishing the membership to a group or class, when pattern recognition pro-
20 cedures are applied. The latter qualitative applications are of great interest, as they
21 can be the basis of automated detection principles in fields such as food, beverages,
22 or pharmaceutics, where alternatives to the human expert are in demand [6]. It is
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23 also possible to correlate a characteristic or property, for example, a perception,


24 with the contribution of the different species sensed. In our studies, the preferred
25 chemometric tool for the processing of data has been ANN. These are known to be
26 powerful nonlinear modelers, applicable for quantitative and also qualitative
27 applications. In this sense, our approach is doubly biomimetic; firstly, the use of
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28 groups of sensors with cross-response is the sensing scheme in the taste buds of
29 animals and, secondly, employing ANNs which are parallel information processing
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M. del Valle (&)


Sensors and Biosensors Group, Chemistry Department,
Universitat Autònoma de Barcelona, Bellaterra, 08193 Barcelona, Spain
e-mail: manel.delvalle@uab.es

© Springer International Publishing AG 2017 1


T.R.L. Cesar Paixão and S.M. Reddy (eds.), Materials for Chemical Sensing,
DOI 10.1007/978-3-319-47835-7_9
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2 M. del Valle
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30 tools inspired in the animal nervous system, whose maximum expression is the
31 human brain [7].
32 There is no doubt that main stream research in the sensor field is the improvement

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33 of selectivity, the foremost analytical property if one needs to integrate sensor use in a
34 stand-alone operation, without any sample pretreatment or elimination of interfering

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35 species. The novel complementary, bioinspired way to do this is by the use of an array
36 of non-specific sensors, responding to primary ions and interferents, coupled with the
37 multivariate chemometric treatment of the complex data to extract the different
38 components present [8]. The purpose of the processing tool differs depending on the
39 application; it can be to identify a chemical species or to determine its concentration
40 without having to eliminate interferences or to quantify them at all. Key points are that

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41 the multidimensional generated data have to comprise the required information about
42 the system and that the high-order data have no co-linearity (thanks to the
43 cross-sensitivity assumption). Since all sensors used in the array may respond to all
44 analytes, a great amount of complex data are generated, which must be processed
45 using a multivariate calibration approach. Chemometrics is in charge then for the
46 extraction of significant features and for the transformation into the sought infor-
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47 mation. This coupling of chemometrics and electrochemical sensors, already iden-
48 tified as one of the recommended ways to improve the sensor performance, is
49 representing also a consolidated line of research in the electroanalysis field [9, 10].
50 If a literature search is performed with the terms “electronic tongue,” it can be
51 observed that the number of articles has been growing steadily since the initial
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52 works dated in 1997, although it seems to stabilize in the last years. These trends
53 are summarized in Fig. 9.1. The number of articles in the most recent years is ca.
54 46 per year—an additional observation is that nearly all the records documented per
55 year correspond to the use of electrochemical sensors; apart from those mentioned
56 above, very few electronic tongues have been proposed employing optical sensors
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57 and piezoelectric mass sensors. Lastly, it can be commented that at the very
58 beginning, most of the works related to electronic tongues employed potentiometric
59 sensors, while more recently, this variant accounts only for around the half of the
60 contributions. That is, as more research groups have entered the field, the different
61 variants are more equally distributed than at the beginning and the more diverse
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62 applications are covered. In brief, one may conclude that the research field of
63 electronic tongues is now mature.
64 In practice, then, there are essentially two main types of electronic tongue
65 systems, distinguishing the nature of the chemical sensors used. These may be
66 potentiometric, when an ion-selective electrode (ISE) array is used or voltammetric,
using, for example, a number of metal electrodes of different nature or a number of
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68 modified electrodes. There is also the possibility of using both types of sensors, and
69 then, a hybrid electronic tongue is the proper name.
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70 A second interesting insight from the literature is to visualize how the research
71 on electronic tongues is distributed geographically. This can be easily grasped by
72 using Springer’s author mapper tool, an Internet application that creates a world
73 map according to the incidence of certain keywords on each country (see Fig. 9.2).
74 After this database search, the tool visualizes where the groups are with
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2015

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2010
Year

2005

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2000
Potentiometric
Voltammetric
ED Impedimetric
Non electrochemical

0 10 20 30 40 50 60
N. research papers

Fig. 9.1 Share of the transduction technique used for the sensors forming ET systems. Data
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obtained from the literature search for the period 1996–2014 using SCOPUS database (Elsevier B.
V.), October 2015
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Fig. 9.2 Visualization of the research groups doing contribution to the topic “electronic tongue”
according to Springer’s author mapper tool (http://www.authormapper.com), October 2015
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75 publications containing that keyword, and also indicates with color intensity their
76 research activity, the most intense the hottest color. Although coverage is limited to
77 publications appearing in Springer’s products, it serves as a first attempt visual-

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78 ization tool on how the authors are distributed. From the generated map, it is
79 curious how the topic has been cultivated mainly from Europe and Asia, with scarce

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80 intervention from North and Latin America, and only occasional appearance by
81 Africa and Oceania. The hottest groups, the ones in orange, correspond to Spain
82 (accounting for active groups in Valladolid, Valencia, and Barcelona) or the
83 Russian federation (pointing to the founder group from St. Petersburg). Other
84 regions especially active are Sweden (with pioneering work in voltammetric elec-
85 tronic tongues in Linköping), France (that accounts for interesting groups plus the

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86 company Alpha MOS, manufacturer of one of the commercial electronic tongues),
87 China, and Japan (in this case with the works from Kyushu University related to
88 artificial taste, i.e., human taste mimicking).
89 On one additional inquiry, inspecting the journals that concentrate the publica- AQ2

90 tions on electronic tongues, the major one is Sensors and Actuators B: Chemical that
91 stands out with more papers related to voltammetric, acoustic or impedimetric sen-
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92 sors; a second place is headed by Analytica Chimica Acta, showing high number on
93 works related to potentiometry, but also other sensor types; a third placement can be
94 shared by Talanta, Analytical Chemistry, and Electroanalysis, also devoted to mainly
95 electrochemical sensors; as observed, mainly journals are from the field Analytical
96 Chemistry, whereas also other journals from the food field or the nanoscience field
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97 are also participants on the share of publications, but to a lesser extent.


98 An arrangement of appropriate sensors, which provides the information related
99 to the problem to be addressed, is the first requirement for the development of an
100 electronic tongue. This chapter will focus on how the different technologies and
101 materials existing for the development of electrochemical sensors have been uti-
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102 lized in the development of electronic tongues. On one side, for the potentiometric
103 subtype, the different variants in obtaining potentiometric transduction, with the
104 usage of different materials for developing the ion-selective membranes, will be
105 commented. On the other side, the different materials and options to achieve dif-
106 ferentiated current response when experimenting electrode configurations in a redox
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107 system (i.e., metallic electrodes and modified electrodes) will be also reviewed.
108 The information generated by the sensors must be related to the chemical species
109 involved in the problem, either to the exact species considered or to the range of the
110 significant concentrations in which they may appear. This information will be the
111 starting point to create an intelligent system. Thus, assembly can correctly inter-
polate or classify unknown samples and identify similar to our brain. The trans-
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113 formation required needs to perform the correspondence between 1 and k sensors,
114 n-dimensional vectors to another m-dimensional vector, which describes the char-
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115 acteristics of interest of the sample. An ANN is an example of chemometric tool


116 that easily processes situations where the size of the input information is given by
117 k  n; here, it is also contained the simpler case of the potentiometric electronic
118 tongue, in which k sensors that provide the instant information of complexity n = 1
119 are used. However, this departing scenario can be much more complex (i.e.,
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120 high-dimensional), if vector info is supplied by each sensor, for example, the case
121 in voltammetric electronic tongues (where n can be on the order of several hundred
122 measures).

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123 9.1.1 Strategies for Signal Processing

124 In applications of electronic tongues, it is common to use sensor arrays; however, due to
125 the poor selectivity of these, the answer is a complex signal containing information
126 about the item of interest, but also information from other interfering elements. This

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127 scenario proves more complex when voltammetric techniques are employed; the signals
128 obtained are of a higher dimension, being constituted of a large number of points.
129 The second component of an electronic tongue is the stage of signal processing.
130 For this purpose, multivariate analysis techniques are normally used to determine the
131 contribution of various factors to an event or outcome. These factors are related to the
132 explanatory variables of the system; in electronic tongues, usually they are deter-
133

134

135
D
mined experimentally and are related to the signals from each sensor. The response
variable, in turn, is related to the concentration value determined, the identification of
a chemical or a specific event, or alternatively the perception modeling.
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136 In any case, there are usually high levels of interference that result in a poor
137 signal-to-noise ratio, in addition to nonlinear behavior character data relating to the
138 analytes to be determined. Extracting relevant information from these situations
139 where it is not easy to extract and interpret the data, so that they can be used in
140 useful models for prediction, has become a complex task that makes use of mul-
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141 tivariate processing tools. Figure 9.3 shows the most frequent chemometric tools
142 employed in conjunction with electronic tongues.

PCA/LDA
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ANN

PLS
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PCR

k-NN

MCR

Other
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0 10 20 30 40 50
% of publications
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Fig. 9.3 Main chemometric tools applied in the studies with electronic tongues. PCA principal
component analysis; LDA linear discrimination analysis; ANN artificial neural network; PLS partial
least squares; PCR principal component regression; k-NN k-nearest neighbor; MCR multiple
component regression. Data obtained from the literature search on the period 1996–2015 using
SCOPUS database (Elsevier)
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143 The chemometric knowledge area has been proposing and developing various
144 methods based on mathematical, statistical, and formal logic calculations, aiming to
145 establish or select procedures that may perform tasks to discriminate, measure,

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146 classify, and model systems and use the maximum relevant information from the
147 available analytical data [1, 11]. For this purpose, approaches mainly used are PCA,

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148 partial least squares (PLS) regression, or ANNs. The choice of the processing tool
149 for a particular case depends on the particular task to be addressed, but also the
150 structure of the input data (nonlinear components, autocorrelation, etc.).
151 PCA is a matrix transformation technique, in which multivariate departure data
152 are linearly reorganized through a change in the visualization axis; the new access is
153 determined in a way so that they are orthogonal and they contain as much infor-

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154 mation as possible, i.e., they are calculated to contain a maximum variance from the
155 original data. In this way, highly multivariate data can be concentrated in a few axes
156 containing the relevant (differentiated from noise) information, and just from the
157 first axis components, one can predict the pertinence to a class. In order to perform
158 this pattern recognition task, one must provide a classifier rule, that is, an additional
159 chemometric tool that will accomplish the identification/classification.
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160 Another important chemometric tool used in electronic tongues are ANNs; these
161 are attractive alternatives as they are logical operations that reproduce the human
162 brain. The ANNs get this functionality through the use of an entity, artificial
163 neuron, or perceptron, which process the input stimuli in a bioinspired form, i.e., as
164 our neural system does. ANNs are especially interesting because of its adaptability
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165 to almost any mathematical transform. The models obtained can be linear or AQ3

166 nonlinear, allowing them to adapt to different types of sensors, making them useful
167 not only multivariate calibration of electronic tongues, but typical of many other
168 tasks Analytical Chemistry [12].
169 The other important chemometric tool is PLS. PLS is a linear statistical model in
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170 which a similar processing is applied to PCA both responses (data set) of the
171 sensors, as to the values of the concentrations of the chemical elements that are
172 being predicted. Then, a linear regression is applied to each main component to
173 obtain a regression model between data and concentrations. Its application is
174 usually related to problems where there are a large number of variables and rela-
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175 tively few samples, a situation that causes the models obtained unfit for predicting
176 new samples and obtained good results when the relationship between measurement
177 and concentration is linear.
178 Even so, in some cases, the initial information is too complex to be handled with
179 the tools mentioned, for example, when a full (or various) voltammogram needs to
be processed using ANNs. Normally, the starting signal is so complex that the
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180

181 network performance is not adequate. For example, this occurs for network
182 architectures with hundreds of input neurons, as it would be required for a regular
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183 voltammogram, and therefore, it becomes impracticable. In these situations, it is


184 necessary somehow to preprocess the starting signal in order to extract the mean-
185 ingful information components and allow for the processing.
186 One of the most common methods is using data reduction methods, capable of
187 reducing the volume of information so that this amount is contained, without
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188 significant losses, in fewer variables. Techniques such as PCA can be used to
189 reduce the complexity of initial data trying to preserve the significant information;
190 the methodology is to observe the variance in the experimental data in the lesser

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191 number of new coordinate axes grouping information [13, 14]. Other techniques
192 used are Legendre polynomial fitting where the responses of the sensors are

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193 approximated to a power series [15, 16], the Fourier transform used to decompose
194 the signal into a series of coefficients corresponding to the frequency content of the
195 original signal [17], and recently the wavelet decomposition [18, 19], consisting of
196 decomposing the signal into different frequency components, so that each has a
197 resolution according to a scale [20]. But whatever the approach made, it must meet
198 two objectives, reducing the complexity of the departure information and retaining

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199 its meaningful content.
200 In short, from the techniques listed, it is possible to obtain the relevant infor-
201 mation and enable us to build suitable calibration models. To obtain a model from a
202 set of calibration data, we may use different tools, but the preferred ones will be
203 PLS regression and ANNs.
204 Next, we will present the two main types of electronic tongues in relation to the
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205 type of sensors that form the array: potentiometric electronic tongues and
206 voltammetric electronic tongues.
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207 9.2 Potentiometric Electronic Tongues

208 There are two main variants in the development of electronic tongues when the type
209 of sensors used is the main feature to distinguish them [7]. These may be poten-
210 tiometric, when the sensor array is formed by ISEs (or related sensors), or they may
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211 be voltammetric, using, for example, a number of different metal electrodes or a


212 number of catalyst-modified carbon electrodes. A third variant, of minor use, is to
213 employ equivalent recognition elements as above, but adopting the electrochemical
214 impedance spectroscopy as the transduction technique.
215 Just with the use of commercial ISEs, sufficiently interesting seminal works can
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216 be found in the literature. For example, there is the founding work of Van der
217 Linden [21] in which an array of commercial ISE responses were modeled
218 employing neural network software. Two cases were described, a simultaneous
219 determination of calcium and copper(II) ions and the simultaneous determination of
220 potassium, calcium, nitrate, and chloride. The measurements for the Ca2+/Cu2+
determinations were done with a pH glass electrode plus calcium and copper
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222 ion-selective electrodes equipped with PVC membranes; for the K+/Ca2+/NO3−/Cl−
223 determinations, the measurements were made with the relevant four ion-selective
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224 electrodes (made of commercial PVC membrane type) plus a glass electrode; mean
225 relative errors were in the ±6 and ±8 % range. In a second example [22], a mixture
226 of halide ions (Cl−, Br−, F−, and OH−) was estimated simultaneously using an
227 experimental design and multivariate calibration methods. The sensor array
228 employed commercial ISEs, particularly two different chloride selective, one
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229 bromide selective and one thiocyanate selective, of the polycrystalline type, a
230 fluoride ISE of the monocrystalline type, plus a glass pH electrode. PLS regression
231 and principal component analysis did slightly worse than multivariate linear

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232 regression. In the case of very slight or no interference on the ISE, each ion can be
233 determined using the corresponding ISE and univariate calibration methods, but the

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234 use of multivariate methods did not degrade the overall results. In a third case study
235 worth mentioning [23], an expert system strategy (case-based reasoning) was
236 applied for multicomponent analysis in water from the data obtained by an ISE
237 sensor array. The latter was comprised of six commercial ISEs, a glass pH electrode
238 plus calcium, sodium, potassium, nitrate, and chloride PVC membrane electrodes.
239 One of the groups more active in this research, and normally employing

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240 potentiometric electronic tongues, is that of Andrey Legin, in St. Petersburg
241 (Russia). With their pioneering work in collaboration with the group of d’Amico in
242 Rome, they practically initiated the field [24], also coining the terminology elec-
243 tronic tongue. In their studies, they normally use an array of PVC membrane ISEs
244 [25], with large number of sensors and with membranes custom-formulated, more
245 with components from the ligand and ion-exchange chemistry than with commer-
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246 cial ionophores [26].
247 Also, a significant research group doing research with electronic tongues is that
248 of Ciosek and Wróblewski, in Warsaw [3]. They essentially use custom-formulated
249 potentiometric PVC membranes, with the goal of optimizing the variability of the
250 response in a custom way for the application studied. For this purpose, they adapt
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251 the classical formulations of the PVC membranes; for example, in order to get
252 generic response to alkaline ions, they can prepare ISEs equipped with membranes
253 having mixture of ionophores in order to get sensors with partial selectivity. For
254 example, to get mixed response to alkaline ions, they report the use of the mixture
255 of valinomycin plus commercial sodium ionophore X, or to get generic response to
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256 anions, they formulate a membrane with a mixture of hydrogen phosphate plus
257 fluoride ionophore of the uranyl salophen family [27]. Their preferred configuration
258 has been to glue a previously casted PVC membrane on a Philips body, achieving a
259 final symmetric membrane configuration design, in which the potentiometric
260 membrane separates the sample solution and an internal reference solution [28].
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261 Although of a bit more complex design, it is recognized that this is the most stable
262 and reproducible setup for potentiometric sensing.
263 In our laboratory, we started research with electronic tongues taking profit of our
264 experience in the development of solid-contact ISEs, equipped with
265 custom-purpose PVC liquid membranes. Just opting with different formulations
from the ion-selective membranes’ literature, rather specific response ISEs or other
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267 with more generic response to groups of substances could be arranged in arrays, in
268 order to explore the specific applications. The goal pursued in these preliminary
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269 works was the multicomponent determination of certain species in the presence of
270 usual secondary ions that can act normally as interferents. This type of application
271 showed an important advantage, in determining simultaneously the ions of interest
272 and the different interferents present at no extra cost. As an example, the work
273 described in [29] performed the determination of ammonium using the well-known
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274 ISE based on the nonactin electrode. As it is known, this sensor is affected by the
275 significant interference of sodium and potassium, and the aim was to obtain a
276 procedure for NH4+ determination without the need of eliminating alkaline ions.

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277 The sensor array incorporated sensors with response to ammonium, potassium, and
278 sodium, plus others with generic response to alkaline ions. Multivariate calibration

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279 was implemented using an ANN model, and the final application was successful in
280 the analysis of water samples from river waters and wastewaters. Figure 9.4 depicts
281 the construction procedure of one of these ISEs, in which a solid contact made from
282 an epoxy–graphite composite formed the base for the deposition of the PVC
283 membrane by solvent casting. These membranes were of standard use in ISE
284 methodology and were prepared using tetrahydrofuran as the volatile solvent.

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285 Figure 9.5 shows the typical formulation of one of these membranes, where the

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Fig. 9.4 Fabrication process of a potentiometric sensor by depositing the liquid membrane onto a
solid contact based on epoxy–graphite composite. Reprinted from [29], with permission from
Taylor & Francis

Fig. 9.5 Typical


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composition of a
potentiometric PVC
membrane
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286 coupling of ionophore and plasticizer is important for the exact pattern of selectivity
287 response displayed by the device; the 33 % PVC share constitutes the inert polymer
288 matrix for support of the recognition chemistry. Table 9.1 summarizes the formu-

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289 lation of the sensors used for a more elaborated example, in this case to monitor the
290 nutrients and interferents for the nutrient solution in a hydroponic cultivation

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291 facility. Ions determined were from two groups, cations including ammonium, AQ4

292 sodium, potassium, plus cations nitrate and chloride; to complement the response
293 by the rather specific ISEs used, three sensors with generic responses to cations
294 (two of them), and a third to anions were included as departure information [30].
295 The system used an ANN model to predict the concentrations of the considered
296 nutrients (ammonium, potassium, and nitrate) plus the undesired species sodium

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297 and chloride that accumulate in the recirculated solution. The scheme of the pro-
298 posed procedure is shown in Fig. 9.6. The new monitoring system represented a
299 clear improvement in front of the classical replenishing systems in hydroponic
300 cultivations that just operate from a pH plus conductivity signals.
301 Multichannel sensor measurement combined with advanced treatment is the
302 departure point for a new concept in sensorics, the electronic tongue, a sensor
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303 monitoring principle that has shown special suitability in the environmental field
304 [31]. In a further research work from our laboratory, an enlarged setup worked with
305 an array of 20 ISEs plus an ANN used as a pattern recognition method applied to
306 soil analysis [32]. Formulated membranes included sensors sensitive to cations
307 (alkaline and alkaline earth), anions, heavy metals, and sensors with generic
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308 response. With this design, we got a versatile tool which was able to perform
309 qualitative and quantitative determinations. Figure 9.7 displays the experimental
310 setup during measurement for one of this soil extract.
311 As the first application, the qualitative discrimination between six distinct soil
312 types based on their extractable components was attempted. The procedure was
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Table 9.1 Formulation of different potentiometric PVC membranes used in the environmental
monitoring of ammonia with correction of the presence of alkaline interferent ions
Sensor PVC (%) Plasticizer (%) Recognition element (%)
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NH4+ 33 BPA (66) Nonactin (1)


K+ 30 DOS (66) Valinomycin (3)a
Na+ 22 NPOE (70) CMDMM (6)a
+
H 32.8 DOS (65.6) TDDA (1)a

NO3 30 DBP (67) TOAN (3)
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Generic 1 29 DOS (67) Dibenzo (18-crown-6) (4)


Generic 2 27 DBS (70) Lasalocide (3)
Generic 3 29 DBP (65) TOAB (4)
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a
Indicated sensors incorporate the lipophilic salt potassium tetrakis-p-chlorophenyl borate
BPA bis(1-butylpentyl) adipate; NPOE o-nitrophenyloctyl ether; DOS dioctylsebacate; DBS
dibutyl sebacate; DBP dibutyl phthalate; CMDMM bis[(12-crown-4) methyl]-
2-dodecyl-2-methylmalonate; TDDA tridodecylamine; TOAN tetraoctylammonium nitrate; TOAB
tetraoctylammonium bromide
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Fig. 9.6 Artificial neural network used as a quantitative model for predicting a number of
concentrations from the readings of a potentiometric sensor array

Fig. 9.7 Conventional setup


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of a potentiometric electronic
tongue made from an array of
ISEs, measuring one sample
with all sensors in parallel
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313 simplified to a single extraction step before measurements. Water, a BaCl2 saline
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314 solution, and an acetic acid extract were evaluated as extracting agents. The best
315 performance was reached with the acetic acid extraction method with a correct
classification rate and sensitivity both of 94 %, and a specificity of 100 %, as it is
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316

317 presented in Fig. 9.8. In addition, a quantitative determination of several physic-


318 ochemical properties of agricultural interest, such as organic carbon content and
319 selected cations (like K+ or Mg2+) and anions (like NO3− or Cl−), was also
320 demonstrated, showing satisfactory agreement with the reference methods.
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Fig. 9.8 3D PCA score plot in the identification/analysis of soils, in this case just from a simple
extraction in acetic acid, and a sensor array formed by 20 ISEs, selective to specific cations,
anions, and also of generic response. The grouping regions correspond to Vallgorguina (I),
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Bellmunt (II), Montesquiu (III), Taradell (IV), Bellaterra (V), and Delta de l’Ebre (VI) soils. Each
class formed by six separate subsamples. Adapted from [32], with permission from Wiley

321 Miniaturized electrochemical cell integrated on epoxy–glass laminate support is


322 an alternative sensor design reported [33, 34], essentially with the goal of inte-
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323 gration of the sensors and miniaturization of the setup. Potassium-selective


324 microelectrodes based on valinomycin and two polymeric matrices [plasticized poly
325 (vinyl chloride) and polyurethane] were fabricated on planar Au or Ag/AgCl
326 transducers. Polymeric layers containing ionic liquid were cast on the surface of
327 Ag/AgCl microelectrodes to form the reference half cells. Performances of the
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328 ion-sensitive and reference microelectrodes (i.e., ion selectivity, slopes of calibra-
329 tion curves, signal stability and repeatability, and long-term stability) were studied.
330 The influence of the method of membrane deposition on sensor characteristics was
331 not significant; however, the microelectrodes with polyurethane membranes
332 exhibited better durability. Theoretical calibration curves were obtained when K+
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333 ISEs and reference electrodes were integrated on a single substrate. The designed
334 electrochemical cell was subsequently applied in further studies devoted to the
335 development of miniaturized electrode arrays for multicomponent analysis or
336 electronic tongue purpose (Fig. 9.9), in this case [35] for the classification of milk
337 originating from various producers.
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338 In a similar attempt, in this case by our laboratory, we attempted the integration
339 of the potentiometric sensor array in a polymeric substrate and with the use of the
340 screen-printing technology [36]. The conductive and insulating materials needed for
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341 the development of the devices are available from specific suppliers centered on the
342 electronic industry, and the potentiometric membranes are essentially the same as
343 the ones described up to this point, only that they are deposited onto solid-contact
344 microwells, previously defined by screen-printing.
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Fig. 9.9 Integrated array of solid-state microelectrodes. Array of integrated ion-selective


microelectrodes (a), schematic top view (b), cross section of a single sensor transducer through
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the A–A0 line (c), and cross section of the coated wire-type microelectrode (d). 1 Au or Ag/AgCl
electrode, 2 Au or Ag contact pad, 3 sealing epoxy layer, 4 epoxy–glass substrate, and 5
ion-selective polymeric membrane. Reprinted from [33], with permission from Elsevier
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345 Figure 9.10 shows a scheme of the different stages in the preparation of a
346 disposable all-solid-state planar-type potentiometric electronic tongue, developed
347 with a five-sensor array screen-printed on a polymeric substrate. The fabrication

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348 method enabled the simple and reproducible mass production of low-cost electronic
349 tongue systems, since the sensors showed good reproducibility (0.96 % RSD),

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350 repeatability (0.58 % RSD), and lifetime (8 % decrease of sensitivity after 37 days
351 in solution). The system was used for the simultaneous determination of NH4+, K+,
352 and Na+ ions in synthetic and natural surface water samples. The signals were
353 processed by using a multilayer ANN which was optimized for that purpose.
354 Correct results were obtained for the three ions in synthetic samples. In natural
355 surface waters, ammonium and potassium ions could be determined, while sodium

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356 ions showed some biased results due to the effect of the complex matrix.
357 Figure 9.11 illustrates the performance of operation, in this case displaying the
358 calculated versus expected concentrations of the three species considered in the
359 response model. Fitted comparison lines can be contrasted against the ideal
360 expected behavior, with highly precise results for ammonium, satisfactory for
361 potassium, and slightly worse for sodium. Slopes of the fitted lines were
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362 1.02 ± 0.27 for ammonium, 1.05 ± 0.26 for potassium, and 0.90 ± 0.28 for
363 sodium (theoretical value, 1.00).
364 Different attempts have been recorded in the effort to obtain integrated electronic
365 tongue devices by microfabrication technologies. The group of Prof. Schöning in
366 Jülich, Germany, produced a microfabricated potentiometric thin-film sensor array
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367 for the simultaneous detection of Pb2+, Cd2+, and Cu2+ [37]. The sensitive layers
368 used were formed on the basis of chalcogenide glass materials. These thin-film
369 chalcogenide glass materials consisted of mixtures of Pb–Ag–As–I–S, Cd–Ag–As–
370 I–S, or Cu–Ag–As–Se and were prepared by pulsed laser deposition technique,
371 with advantages as the short preparation time and the compatibility with silicon
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372 planar technology microfabrication procedures. The developed sensor array, as


373 observed in Fig. 9.12, was physically characterized by microscopy and spectrom-
374 etry and next further evaluated through its potentiometric measurements. The
375 developed devices were employed in the simultaneous multicomponent analysis of
376 complex liquid media based on the principles of the electronic tongue.
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377 Multicomponent analysis of heavy metal ion species Pb2+, Cd2+, and Zn2+ were
378 determined simultaneously [38] by direct potentiometric measurements using a
379 sensor array formed by the different chalcogenide microsensors, overcoming the
380 problem of the insufficient selectivity by use of single sensors.
381 Verrelli in the University of Rome “Tor Vergata” [39] described a miniaturized
potentiometric electronic tongue system used standard PVC membranes placed in
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382

383 this case onto microfabricated silicon structures, as it is shown in Fig. 9.13.
384 Membranes used as ionophores different metal complexes of porphyrins and cor-
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385 roles, therefore originating response mainly to different anions. The developed
386 system was applied for the qualitative and quantitative analyses of different artificial
387 wine samples, characterized by the presence of polluting agents such as SO2, H2S,
388 and acetate in a wide concentration range. The developed system was able to
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Fig. 9.10 The fabrication


process for screen-printed
five-sensor potentiometric

F
sensor array: a polycarbonate
substrate (50  75 mm),
b silver ink printing,

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c graphite ink printing,
d insulator layer printing,
e cavities for the sensors, and
f deposition of different PVC
membranes. Reprinted from
[36], with permission from
Springer

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Fig. 9.11 Modeling performance achieved for the optimized ANN with the samples of the

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external test set: a ammonium, b potassium, and c sodium. The dashed line corresponds to
ideality, and the solid one is the regression of the comparison data. Reprinted from [36] with
permission from Springer

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Fig. 9.12 Thin-film sensor array after wire bonding and encapsulation of thin-film sensor array
with three different chalcogenide glass thin films. Reproduced from [38], with permission from
Springer
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389 distinguish wines with different defects and polluting agents and also to predict the
390 amount of each one, also at low concentrations.
391 In another variant to prepare electronic tongue devices from materials and
392 techniques used in the electronics industry, there are the works by Gil et al., which
393 were conceived in thick-film technology, i.e., with the use of conductive and
394 resistive pastes [40]. Different conducting surfaces deposited using thick-film
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395 technology were used as potentiometric electrodes, and the emf of each electrode in
396 contact with a certain aqueous solution was used as input signal for a PCA. An
array containing the electrodes RuO2 (with resistivities of 10 X/sq and 1 M X/sq),
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397

398 C, Ag, Ni, Cu, Au, Pt, Al, Sn, Pb, and C (graphite) was used in a first approach as it
399 is shown in the photograph in Fig. 9.14. To test this “electronic tongue” design, a
400 family of different natural waters was studied. These include seven mineral waters,
401 tap water, and osmotized (reverse osmosis) water. Figure 9.15 displays the obtained
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Fig. 9.13 Sensor


miniaturization can be
reached by the integration of

F
potentiometric sensors with
silicon technology which can
allow the construction of

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microdimensioned sensors
with different geometries for
deposition area. Silicon
fabrication technique will
allow the implementation of
different structural layer and
metal thin films, to investigate

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the influence of different
materials. Reprinted from
[39], with permission from
Elsevier

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Fig. 9.14 Electronic tongue developed in thick-film technology. Reproduced from [40], with
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permission from Elsevier B.V.


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402 PCA plot, where the power to differentiate the waters assayed is clearly demon-
403 strated. Additionally, a qualitative analysis of the different waters was performed
404 using fuzzy ARTMAP neural networks. The final system was successfully
405 employed for the differentiation of the above-mentioned waters with a success rate
406 higher than 93 %.
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Fig. 9.15 Principal


component analysis
(PCA) score plot for different

F
waters (different commercial
brands plus tap waters and
osmotized distilled water).

OO
Data show from five different
trials. PC axes are calculated
to lie along the lines of
diminishing levels of variance
in the data set. Reproduced
from [40], with permission
from Elsevier B.V.

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407

408
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A special type of potentiometric sensors that needs to be included in this section
is that of ISFETs, or ion-selective field-effect transistors. These devices are
409 microfabricated transistors, in which the control region (the gate) has been devised
410 as a potentiometric membrane, in this case inorganic polycrystalline nature. The
411 presence/absence of ions in this zone can be translated, by the effect of the electric
field, to the intrinsic operation features of the transistor, thereby modulating the
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412

413 transistor current, which is the generic signal monitored. Given that the interaction
414 of the ions in the gate area is of potentiometric nature, these sensors are taken of the
415 potentiometric type. Research groups with the availability of these devices have
416 prepared then ISFET sensor arrays [41] and have used them with the electronic
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417 tongue principles. Additional potentiometric membranes can be deposited on top of


418 the initially inorganic prepared gate areas, exchanging the sensitivity from pH (the
419 usual chemical primary chemical sensitivity provided to these devices) to any
420 standard cation or anion, depending on the ionophores used. As the adherence of
421 standard PVC membranes to silicon substrates is poor, the polymeric matrix of
these modified devices is changed to polysiloxane or to acrylate photocured nature.
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422

423 Figure 9.16 shows the “electronic tongue” device based on the multisensor
424 ion-selective field-effect transistor (ISFET) array, which is subsequently inserted in
425 a sequential injection analysis (SIA) flow system for automated operation. The
426 system was used for the analysis of mineral waters and their components (sodium,
427 potassium, and chloride). The precision of the ion determination in samples was
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428 typical for potentiometric method with a standard deviation of about 3–5 %. The
429 proposed approach could be used for automatic analysis of waters.
To finish this section, it is important to mention the latest technology suggested
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430

431 for the development of disposable electronic tongues, in this case using paper as the
432 cheapest substrate. These devices define contact elements with base of carbon in the
433 paper substrate, onto which standard potentiometric membranes (e.g., based on
434 PVC matrix) can be deposited, and the proper potentiometric reading can be
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Fig. 9.16 ISFET sensor array chip with different ion-selective membranes. Reproduced from
[41], with permission from Elsevier B.V.

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Fig. 9.17 Paper-based ion-selective electrodes, anticipating what shortly will be a paper
electronic tongue. Reproduced from [42], with permission from Wiley

435 developed [42]. The main goal of this variant is the low cost of the disposable
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436 paper-based device. This case study is comprised of 4 paper-based potentiometric


437 sensors, sensitive to chloride, alkaline ions (Na+/K+), alkaline earth ions (Ca2+/
Mg2+), plus NO3−, with a similar design to that shown in Fig. 9.17, displaying one
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438

439 of the potentiometric channels. The developed electronic tongue was able to dis-
440 tinguish tap and lake waters from mineral water samples using chemometric
441 treatments PCA and KNN (k-nearest neighbor) pattern recognition.
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442 9.3 Voltammetric Electronic Tongues

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443 Voltammetric electronic tongues are the second variant of importance in this novel
444 concept in sensory analysis, in which computer data processing is required to
improve the overall performance of the sensing approach. In this section, definitions

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445

446 and a general review of the different subvariants reported up to this moment will be
447 provided; these will include the nature of sensors used, methods more widely used
448 for the data processing, and the more recurrent application fields.

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449 9.3.1 Using a Single Voltammetric Sensor

450 From a conceptual point of view, a voltammetric system with a single electrode
451 may be also considered an electronic tongue, provided that the voltammogram, the
452 multicomponent departure information as the key point, is also characterized by a
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453 high dimensionality of the signal supplied to the processing tool. Depending on the
454 particular electrochemical technique, the information may be slightly different,
455 because we have, for example, simple linear sweep, cyclic voltammetry, differential
456 pulse voltammetry, chronoamperometry, etc.
457 Some of the worked examples have been resolving mixtures of compounds with
electrochemical activity from a voltammogram with superimposed signals, for
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458

459 example, oxidizable amino acids, phenols, or heavy metals. The conventional
460 identification/classification application of different varieties or classes, especially of
461 foods or beverages, has been also reported.
462 As representative application of these simple voltammetric electronic tongues,
we may cite the resolution of complex signals, superimposed or overlapping type,
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463

464 where it is possible to identify which compounds are present and even its con-
465 centration. This software approach is typically described for signals from a single
466 voltammetric sensor, where the vector of currents is processed to correlate the
467 information sought, as illustrated in Fig. 9.18. This case has been studied for sit-
468 uations mixtures of heavy metals [43], oxidizable amino acid [19], or phenols [44,
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469 45].

470 9.3.2 Using Voltammetric Sensor Arrays


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471 The first voltammetric electronic tongue described as such was that reported by the
472 Winquist laboratory in Linköping (Sweden) [46]. This used just two metal elec-
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473 trodes, platinum and gold, and the voltammetric technique applied was normal
474 pulse voltammetry. With it, it was possible to discriminate different drinks such as
475 fruit juices, milk, and buffers (pH), in an application of purely qualitative identi-
476 fication. After this assembly, an improved style multielectrode, consisting of a
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Fig. 9.18 Electronic tongue


developed in thick-film
technology. Reproduced from

F
[45], with permission from
Elsevier B.V.

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477 number of different metal electrodes (or conductors) on one body fixed by an
478 insulating resin, was designed. Some element materials considered were gold,
479 platinum, palladium, iridium, rhodium, vitreous carbon, etc. [47]; the recorded
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480 redox signal is dependent on the metallic electrode used. With a setup like this, it is
481 possible to increase the information available, provided that this is not correlated
482 with any of the other channels, because in that case would be superfluous
483 (Fig. 9.19). AQ5

484 A second way to achieve a similar effect can be to use a large number of
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485 identical electrodes, such as platinum, and biasing each at a different voltage; thus,
486 it is possible to obtain information equivalent to a potential sweep without the need
487 to perform it, thus eliminating downtime. With this simplification of the voltam-
488 metric electronic tongue, the array can be incorporated in a flow system, and the
489 equivalent voltammogram can be acquired with the help of a multichannel mea-
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490 suring device, eliminating therefore the potential scan and facilitating the use.
491 Precisely with these principles, a system to evaluate astringency in tea was
492 described, which used six platinum electrodes inserted in a flow injection
493 (FIA) system [48].
494 A very interesting application of a voltammetric electronic tongue was made in
the environmental field, where they could correctly predict the nature, burden
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495

496 organic (expressed as chemical oxygen demand) conductivity, and pH of the


497 wastewater from a paper mill [49]. A metallic multielectrode array—formed by
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498 platinum, gold, and rhodium electrodes—was employed as the detection system,
499 while the measurements were based on large amplitude pulse voltammetry (LAPV).
500 LAPV consisted of scans of pulses from 0 to 1.8 V at 0.2 V steps. Five current
501 values were recorded for each pulse, so a set of 300 current values (three
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Fig. 9.19 Configuration of


the voltammetric electronic
tongue, consisting of five

F
metal working electrodes, a
reference electrode, and an
auxiliary electrode of stainless

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steel. This setup realizes the
sequential measuring through
the use of a relay box to
multiplex the used working
electrode. Reproduced from
[47], with permission from
Springer

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ED
CT

502 electrodes  20 pulses  five values) was recorded for each sample. Samples were
503 first discriminated using PCA, while ANNs were used for the characterization and
504 prediction of chemical parameters. One potential problem of such devices, which is
505 fouling or degradation of electrode response by deposition of insoluble oxidized
506 residues, or even growth of biofilm, has been corrected recently by the use of
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507 automated periodic polishing of the sensing surfaces, always exposing a more
508 reproducible, clean surface for each analysis [50].
509 In a similar approach to this typical arrangement in the Swedish laboratory, we
510 devised in Barcelona an array comprising of three conductive elements, platinum,
511 gold, and graphite–epoxy (the multielectrode device can be seen in the photograph
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512 in Fig. 9.20), which was assayed for the multidetermination of three oxidizable
513 species in the pharmaceutical field: ascorbic acid, uric acid, and acetaminophen
514 [51]. Signals, merged into a single vector, were processed directly by ANNs, as
515 outlined in Fig. 9.21. Figure 9.22 shows the final performance of the developed
516 system, where the predicted concentration values can be seen versus the expected
517 ones, both for the training subset and for the external test subset, the one that does
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518 not intervene at all in the building of the response model.


519 More recently, research in the field of electronic tongues has focused not only on
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520 the development of new measurement techniques and the application of new pro-
521 cessing methods, but also on the finding of new chemosensitive materials in order
522 to develop greater variability response sensor arrays.
523 Aside from using pure metallic elements, various alternative materials have been
524 used to modify the surfaces of the electrode, especially when this departs from
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Fig. 9.20 Photograph of the working 4-electrode array. Au, Pt, and epoxy–graphite disks act as
working electrodes. Setup is derived from the enclosure of the four preconnected electrode
elements, inserted as 1-mm-diameter wires in epoxy resin. The Ag electrode is previously oxidized
into an Ag/AgCl disk acting as pseudoreference electrode, once in contact with a predefined
chloride concentration (added to each measured sample)
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OR

Fig. 9.21 Fusion of the signals from an array of three voltammetric sensors to develop a
multicomponent quantification application using an ANN model. The components determined are
ascorbic acid, uric acid, and paracetamol

525 carbon materials; for example, conductive polymers or certain metalloporphyrins


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526 that may act as catalysts or also certain metal phthalocyanines that may be incor-
527 porated with the carbon conductive part. In our laboratories, from a traditional AQ6

528 graphite–epoxy configuration, useful to prepare base electrodes [52], and later
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529 modified to many variants in chemical sensing and biosensing, the incorporation of
530 specific catalysts and modifiers has meant a quick and convenient way to generate
531 an array formed by a number of sensors and with differentiated response, as an ideal
532 departure point to develop electronic tongue applications. In essence, the chemistry
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Fig. 9.22 Prediction of the developed voltammetric electronic tongue, for the determination of the
three oxidizable compounds, a ascorbic acid, b paracetamol, and c uric acid. Filled circles
correspond to the training subset, and white circles correspond to the external test subset of
samples
OR

533 of these carbon electrodes, modified with additional electroactive elements, follows
534 the know-how of the previously developed carbon–paste configuration, in which
535 fine graphite was simply agglutinated in a confined space with the use of a mineral
536 oil (or wax), to obtain an easily reconfigurable, repolishable, and regenerable
537 electrode material, in use for decades [53]. Figure 9.23 shows the preparation of
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538 one of these sensing devices. From a plastic cylinder, in which an electrical con-
539 nector and a copper disk are placed to assure the electrical contact, a portion of the
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540 polymer mixture (resin + hardener) plus conductive material (graphite or other
541 carbon allotropes) and modifiers are placed and then cured at proper temperature to
542 obtain a conducting solid, with the catalytic modifiers embedded in its body.
543 A proper polishing, with emery paper of increasing grade, permits to end in a mirror
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Fig. 9.23 Graphite–epoxy


composite electrode
construction scheme.

F
a Copper disk soldered to the
connector and assembled into
the PVC tube. b Preparation

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of the graphite–epoxy mixture
and incorporation of the
modifier. c Final look after
hardening and polishing.
Electronic tongue developed
in thick-film technology.
Reproduced from [54], with

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permission from Wiley

544 finish conductive surface, where many modifiers can be tested as potential elements
545 for the voltammetric electronic tongues.
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546 Table 9.2 summarizes some of the modifiers that have been historically used in
547 our laboratories and the formulation details for the constructed electrodes. Apart,
548 currently in the nanotechnology era, specific forms of carbon like nanotubes or
549 graphene might be employed, also in search of improved or modified response. An
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550 application study of such an electronic tongue system is the work in [54], where a
551 voltammetric sensor array formed by five modified graphite–epoxy electrodes was
552 applied in the qualitative and quantitative analyses of cava wines. The electrodes
553 used were those modified with copper nanoparticles, with platinum nanoparticles,
554 or with conducting polymer in powder forms like polyaniline and polypyrrole, plus
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555 a control, non-modified graphite–epoxy electrode. The different samples were


556 analyzed using cyclic voltammetry without any sample pretreatment. Recorded data
557 were evaluated by PCA and discrete wavelet transform in order to compress and
558 extract significant features from the voltammetric signals. Preliminary visualization
559 from the PCA treatment permitted to observe the clustering of the different cava
OR

560 types, according to the added sugar elaboration (see Fig. 9.24): brut nature, brut,
561 semi-dry, etc. Two outliers, a French champagne wine and a cava wine from a

Table 9.2 Some formulations used to obtain a number of voltammetric sensors with differentiated
response, in order to develop electronic tongue applications
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Resin (%) Hardener (%) Graphite (%) Modifier (%)


81.7 1.23 17 –
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81.7 1.23 15 Cu nanoparticles (2 %)


81.7 1.23 15 Pt nanoparticles (2 %)
81.7 1.23 15 Polypyrrole (2 %)
81.7 1.23 15 Polyaniline (2 %)
81.7 1.23 15 Cobalt phthalocyanine (2 %)
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Fig. 9.24 Principal component analysis plot of the first three components. A total of 21 samples
were analyzed. As can be observed, clear discrimination is obtained for the different types of cava
ED
wines: (1) brut nature, (2) brut, (3) medium dry from Penedés region, (4) medium dry from
Extremadura region, and (5) French champagne wine (the outliers). Reproduced from [54], with
permission from Wiley

562 different Spanish region, were incorporated in the study and were separated (i.e.,
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563 were not confounded) with the trained specimens. To accomplish the pattern
564 recognition, the preprocessed information was evaluated by an ANN that did the
565 qualitative classification. Moreover, a preliminary study related to the quantification
566 of sugar amount present was assessed by second-order standard addition method;
567 for this, the score from the first PC and each sample was correlated with sugar
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568 content, analyzed by conventional method. Figure 9.25 illustrates the experimental
569 setup adopted in this study, accounting for the 6-channel multipotentiostat con-
570 trolled by computer and a voltammetric cell formed by the epoxy–graphite working
571 electrodes, plus a platinum auxiliary electrode and a double-junction Ag/AgCl
572 reference electrode.
OR

573 Other modifiers that have been incorporated with success in the bulk of carbon AQ7

574 electrodes with the goal of altering their sensitivity to target compounds and then
575 may be postulated to be used in voltammetric electronic tongues are among others:
576 molecularly imprinted enrichment agents, either in electropolymerized form, or
577 incorporated as microbeads, cyclodextrins as complexing agents for specific
578 organics, complexing ligands (essentially for metals), and semiconducting or
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579 metallic oxides incorporated as nanopowder. Surely, in future, we will notice


580 reporting electronic tongue systems using these variants, especially for specific
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581 applications with specific target chemicals involved.


582 In a final reflection mode, it is noteworthy that the right choice of sensitive
583 materials, i.e., the selection of sensors that will form the array, is of fundamental
584 importance in the results. Without taking into account the chemical nature of the
585 samples or analytes sought, and if the sensors used do not complement them, it is
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Fig. 9.25 Photograph of the six-sensor composite epoxy–graphite electrode array, together with
the multichannel potentiostat used to perform the voltammetric electronic tongue experimentation
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586 clear that not in any case, the electronic tongue biomimetic approach will achieve
587 the transmutation of junk in precious gems—only a sensible and correct choice of
588 sensors and measurement techniques will be the determining factor in the success of
589 any application of this nature. Much of the voltammetric electronic tongue key
OR

590 work is to use an array of sensors and to check whether their voltammetric signals
591 correlate with the information needed, for the type of samples under study. For AQ8

592 example, the group of Winquist used an array formed by noble metal electrodes [46,
593 55] for a variety of applications, for example to identify and classify water and
594 beverages (fruit juices, teas), identify solutions industrial washing [56], correlating
595 aging of dairy products and juices [57], identifying the growth of microorganisms
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596 or assisting in the control of wastewater treatment plants. Also, there are more
597 elaborate applications, like that describing the identification of microbiologic
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598 samples [58], i.e., in differentiating between various types of microorganisms,


599 particularly the identification of yeasts, fungi, and bacteria, or the recognition of
600 two fungal species growing in three nutrient media (glucose, sugar, and malt
601 extract). Detection by the sensor array of electroactive metabolites in the stage of
602 growth of these microorganisms is the basis of the developed application, allowing
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603 differentiation between species, type of the culture medium, or the incubation
604 period.
605 The examples above correspond mainly to the use of metallic electrodes or

F
606 conductors. There have also been described electronic tongues with the use of
607 modified sensors, i.e., with the electroactive surface coated with selective films.

OO
608 Thus, the information generated is much more rich and varied, for example, by
609 interference effect minimization or catalysis, manifesting in increased signal, or
610 shifts its characteristic potential. This significantly improves selectivity and
611 detection power of the substances that provide weaker signals. In this mode, the
612 work group of Mari Luz Rodriguez Mendez in Valladolid [59] used a sensor array
613 consisting of carbon paste electrodes modified with phthalocyanines, polypyrrole

PR
614 doped with different agents, or perylene derivatives. Many of his works have been
615 applied to the world of wine, for example, to detect adulterants, or determine certain
616 organoleptic characteristics of a wine, such as alcohol, total acidity, astringency
617 (tannic acid), preservatives (sulfites), sugar, and flavorings (ethanal) [60, 61]. In
618 Fig. 9.26, the preparation of an integrated sensor array card, with thick-film tech-
619 nology using an alumina substrate, can be visualized.ED
620 Analogous to the case with potentiometric sensors, also voltammetric devices
621 have been microfabricated in silicon substrates, with the goal of obtaining a
622 voltammetric electronic tongue device [62]. Direct translation of principles men-
623 tioned up to now is to produce a number of thin-film metal electrodes, with upper
624 finishing from different materials, such as gold, platinum, and palladium, in order to
CT

625 get differentiated response. Figure 9.27 displays one of such devices, equipped with
626 four different metal working electrodes (on the corners, made of gold, platinum,
627 rhodium, and iridium), plus a gold central electrode with larger area.
RE
C OR
UN

Fig. 9.26 Lithographed gold electrodes onto an alumina substrate. Polymeric sensors have been
obtained by electrodeposition of pyrrole in the presence of different doping agents. Phthalocyanine
and perylene-based electrodes have been prepared using the carbon paste. Reprinted from [59],
with permission from Elsevier
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9 Materials for Electronic Tongues: Smart Sensor Combining … 29


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F
OO
Fig. 9.27 Microfabricated miniaturized planar voltammetric sensor array for use in an electronic

PR
tongue. Reprinted from [62], with permission from Elsevier

628 A new approach to fabricate a disposable voltammetric electronic tongue is


629 reported [63]. The fabrication of the disposable sensor is aimed to integrate all
630 electrodes necessary for measurement in the same device. The disposable device
ED
631 was constructed with gold CD-R and copper sheet substrates, and the sensing
632 elements were gold, copper, and a gold surface modified with a layer of Prussian
633 blue. Figure 9.28 depicts the procedure, departing from a gold-finished CD-R
634 surface. Modification of the gold working electrode surface with a Prussian blue
635 (PB) film was accomplished by electrodepositing the insoluble layer by cyclic
CT

636 voltammetry. Copper working electrodes were obtained from the equivalent pro- AQ9

637 cedure but departing from a Cu plated printed circuit board. Reproducibility of the
638 disposable devices showed a relative standard deviation for signals obtained from
639 20 different disposable gold and 10 different disposable copper electrodes below
640 3.5 %. The performance, electrode materials, and the capability of the device to
differentiate samples were evaluated for taste substances model, milk with different
RE

641

642 pasteurization processes (homogenized/pasteurized, ultrahigh temperature


643 (UHT) pasteurized, and UHT pasteurized with low-fat content), and that adulterated
644 with hydrogen peroxide. In all analyzed cases, a good separation between different
645 samples was noticed in the score plots obtained from the PCA. The performance,
low cost, reproducibility, and simplicity of the fabricated electronic tongue devices
OR

646

647 demonstrated the advantages of modifying electrode surfaces with specific films
648 toward a more selective recognition strategy.
649 Finally, we should mention the efforts being made to improve the coupling of the
650 complex signals of the voltammetric electronic tongues with processing tools. In
651 these cases, extracting significant information is sought in order to enable the
C

652 efficient use of computational methods. Examples are the use of PCA for com-
653 pacting the starting information [13], the signal modeling using a polynomial fit or
654 using wavelet transform [43]. In a classic study [19], the principles of voltammetric
UN

655 electronic tongue to resolve a mixture of three components from direct voltam-
656 metric signal are applied. The overlapping signal is obtained from the differential
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30 M. del Valle
Author Proof

Fig. 9.28 Obtention of


disposable voltammetric
electronic tongues by using
Prussian blue films

F
electrodeposited onto CD-R
gold surfaces. Adapted from

OO
[63], with permission from
Elsevier

PR
ED
CT
RE
C OR

657 pulse voltammetry response to mixtures of the three oxidizable amino acids tryp-
UN

658 tophan, cysteine, and tyrosine. The signal was first compressed by wavelet trans-
659 form, removing both of meaningful information. Extensive comparison studies
660 were later performed by Cetó et al. [64], also in a contribution from our
661 laboratories.
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9 Materials for Electronic Tongues: Smart Sensor Combining … 31


Author Proof

662 This operation was necessary to optimize, for that mother function type and level
663 of compression and its effect on the degree of reconstruction of the original signal
664 are studied. Then, the compressed information was used as input for a calibration

F
665 model based on ANNs, as shown as a successful combination of the chemometric
666 techniques with the use of complex voltammetric signals.

OO
667 9.3.3 Use of Biosensors

668 A progress field just beginning to be investigated is the use of arrays of biosensors

PR
669 for generating starting information of the electronic tongue. Here, the requirements
670 are known, and one needs to generate cross-selective biosensor information used for
671 the different species present in a sample; therefore, not very high selectivity of
672 biosensors is chosen. The topic has received the name bioelectronic tongue by
673 different researchers in the field [6, 65].
674 A worked example in our laboratory was to an electronic tongue formed by three
ED
675 enzymatic amperometric biosensors using the enzyme glucose oxidase (GOx) with
676 three different formulations [66], and the target was the simultaneous determination
677 of glucose in the presence of two typically interfering species, ascorbic acid and
678 uric acid. Figure 9.29 illustrates the three-electrode system, each of them incor-
679 porating enzyme plus different catalysts, as Pt microparticles, or mixture of Pt/Au
CT

680 microparticles, as the way to induce a differentiated response. The different


681 catalysts/modifiers will introduce the differentiated response of each electrode; in
682 this case, all of them will present signal for the primary substrate, only with dif-
683 ferent shapes or appearing at different potentials, depending on the catalyst or
684 modification of the electroanalytical signal. The device was tested in the joint
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685 determination of glucose and its common interferents in biologic fluids, namely
686 ascorbic acid and uric acid, with the usage integrated in an automated SIA system
687 for proper automation of operation. This idea with GOx was retaken recently by
688 Al-Issa et al. [67]; in their work, they prepared a bioelectronic tongue immobilizing
689 the enzyme over Au or Pt disk electrodes. The determination of glucose in the
OR

690 presence of their common interferents ascorbic acid and uric acid could be

Fig. 9.29 Photograph of the


C

three-biosensor integrated
array. In this case,
modifiers/catalysts are the
agents causing the
UN

differentiation of the response.


Reproduced from [66], with
permission from Wiley
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32 M. del Valle
Author Proof

691 successfully determined at the 1 mM level, while interfering species were quanti-
692 fied at no extra effort.
693 A second example worth mentioning is the inhibition electronic tongue, in which

F
694 three amperometric biosensors were used with three varieties of the acetyl-
695 cholinesterase enzyme, wild electric eel, and genetically engineered B1 and B394

OO
696 [68]. As the degree of inhibition of dichlorvos and carbofuran insecticides is
697 slightly different for each enzyme, this cross-information allowed the resolution of
698 mixtures containing both substances, at a level below 1 nmol L−1. Table 9.3
699 summarizes how the two considered pesticides are resolved by the three enzymes
700 considered; given the response profile (inhibition constant) is different for each
701 pesticide and each enzyme variant, this demonstrates the correct departure point for

PR
702 attempting the inhibition electronic tongue study. One point to comment is that
703 given the nature of the inhibition is irreversible, the application had to be developed
704 with disposable screen-printed electrodes, where each inhibition assay used a new,
705 unused electrode.
706 In the more recent work in our laboratories dealing with bioelectronic tongues,
707 that is, in voltammetric electronic tongues equipped with enzyme-modified elec-
ED
708 trodes, we have been using phenol-degrading enzymes (tyrosinase and laccase) and
709 applying their differentiated response to the wine field [69]. In these works, the
710 proposed bioelectronic tongue has been used for the estimation of global
711 polyphenol content in wine and alternatively to differentiate and to quantify indi-
712 vidual (and majoritary) polyphenolic compounds present in wine [70]; later, AQ10
CT

713 equivalent work was repeated, in this case with the more specific polyphenols
714 present in beer [71]. In the more advanced cases, the proposed bioelectronic tongue
715 was formed by an array of four voltammetric enzymatic biosensors based on
716 epoxy–graphite composites, one blank electrode and the other three bulk-modified
717 with tyrosinase and laccase on one side and copper nanoparticles on the other; these
RE

718 modifiers were used in order to incorporate differentiated or catalytic response to


719 different polyphenols present in wine and aimed to the determination of its total
720 polyphenol content value. The obtained voltammetric responses were preprocessed
721 employing the fast Fourier transform (FFT); this was used to compress the relevant
722 information, whereas the obtained coefficients fed an ANN model that accom-
OR

723 plished the quantification of total polyphenol content. This strategy is shown in
724 Fig. 9.30. For comparison purposes, the obtained polyphenol content was com-
725 pared against the ones assessed by two different reference methods: Folin–Ciocalteu
C

Table 9.3 Degree of inhibition shown by the three acetylcholinesterases employed in the
bioelectronic tongue for the determination of pesticides
Ki (μM−1 min−1)/acetylcholinesterase subtype
UN

Wild (electric eel) B1 B394


Dichlorvos 0.026 1.9 224
Carbofuran 4 6 1.08
Adapted from the data shown in [68], with permission from Wiley
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9 Materials for Electronic Tongues: Smart Sensor Combining … 33


Author Proof

F
OO
PR
Fig. 9.30 Strategy used with the high-dimensionality voltammetric electronic tongue. Reprinted
from [69], with permission from Elsevier

ED
CT
RE

Fig. 9.31 Results in the prediction of the global index indicating the total polyphenolic
compounds, Folin–Ciocalteu index, from the voltammetric bioelectronic tongue; the figure
OR

distinguishes results from the training subset of data (left) and from the external validation subset
(right). Reprinted from [69], with permission from Elsevier

726 and UV polyphenol index (I280); good prediction ability was attained with cor-
727 relation coefficients higher than 0.949 when compared against the reference
C

728 methods; for example, Fig. 9.31 displays the satisfactory agreement obtained versus
729 the Folin–Ciocalteu reference method.
730 The modified electronic tongue has also been used for the determination of the
UN

731 vintage year or origin/variety of grapes used in winemaking. Some of these works
732 have also been extended to the field of vegetable oils, to estimate their quality and
733 polyphenol content. The possibility of using enzymatic amperometric biosensors
734 has been previously discussed [66, 68]; again, using a greater amount of
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34 M. del Valle
Author Proof

Fig. 9.32 Photograph of the


screen-printed eight-sensor
composite epoxy–graphite

F
electrode array

OO
PR
735 information, or of better quality, as provided use of an array of biosensors, can
736 improve the performance of the classical concepts, improving discrimination
737 against interference or resolution of mixtures that otherwise would provide only a
ED
738 global content.
739 In the purpose of integration, the use of commercial multielectrode platforms has
740 been described that once modified might be usable for (bio)electronic tongue
741 applications; the firm DropSens supplies, for example, the multielectrode device
742 shown in Fig. 9.32. On the other hand, as the disposable paper-based potentio-
CT

743 metric electronic tongue has been already described [42], the voltammetric elec-
744 tronic tongue, also using the paper substrate, is surely very close to appear and
745 offers an interesting alternative to low-cost, disposable devices.
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746 9.4 Concluding Remarks

747 This chapter has provided a review of technological aspects of (bio)electronic


748 tongue development, especially from the point of view of more chemical nature,
OR

749 i.e., from the involved materials in their construction. Potentiometric electronic
750 tongues were the first to be proposed and quickly progressed from existing tech-
751 nology related to conventional potentiometric sensors, i.e., ISEs. Later, these could
752 be made more complex, when specific technologies were called for, as in the
753 development of ISFET-based electronic tongues.
Not much separated in time, voltammetric electronic tongues also started and
C

754 AQ11

755 developed, and here the possibilities offered to researchers to prepare different
756 electrodes, and to modify them, either in bulk or in surface has enlarged consid-
UN

757 erably the types of systems described up to now. Although scientific communica-
758 tions with the involvement of voltammetric electronic tongues do not exceed in
759 number those using potentiometric sensors, they have advantages in which sensors
760 of very different nature can be used, to which the variants of chemical and biologic
761 modification must be added and also the possibility of using various modes of
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9 Materials for Electronic Tongues: Smart Sensor Combining … 35


Author Proof

762 electrochemical technique particularly used (i.e., cyclic voltammetry, linear sweep,
763 differential pulse, and square wave). Therefore, it is obvious they represent a very
764 interesting field of work in order to develop tools for control in industrial, food,

F
765 clinical, or environmental fields.
766 Voltammetric electronic tongues have shown to be much more complex in use,

OO
767 given the high-dimensionality signals involved, or given their complexity, for
768 example with overlapping shapes or interaction or cross-response. These signals
769 are, in turn, chemically rich in useful information and therefore represent very
770 interesting alternatives for classification tasks, identification, or discrimination
771 component. It becomes obvious only with powerful chemometric treatment that
772 successful applications can be developed. Even, for the more complex situations,

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773 there are no clearly established processing protocols able to develop application
774 systems with bilinear or trilinear data; for that reason, this area is identified as one
775 of the crossroads of time where the interdisciplinary collaboration of mathemati-
776 cians, engineers, physicists, and/or chemists is needed.
777 About what can be the limits of electronic tongues of one type, or the other, very
778 little comparison studies have been made. One of the few appeared very recently in
ED
779 which different electronic tongue technologies were compared when applied to the
780 pharmaceutical field [72].
781 Apart from the variants sketched in this chapter, it has to be mentioned that it is
782 also possible to mix the ideas, and hybrid electronic tongues already exist in which
783 the sensor array used sensors from the potentiometric and from the voltammetric
CT

784 type. In this case, special efforts have to be placed in making compatible the
785 different dimensionality of the information provided by the two sensor types.
786 Feature extraction from data and aspects of data fusion are then necessary to cope
787 with the demanding data processing aspects in the case [73].
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788 Acknowledgments Financial support from the Spanish Ministry of Economy and Innovation,
789 MINECO (Madrid), through project CTQ2013-41577-P is gratefully acknowledged. M. del Valle
790 thanks the support from program ICREA Academia. Many thanks are also debt to PhD students
791 that completed their formation in our laboratories in the research line of (bio)electronic tongues:
792 Jordi Gallardo, Albert Gutés, Montserrat Cortina, Manuel Gutiérrez Capitán, Juan Manuel
793 Gutiérrez, Xavier Cetó, Andrea Cipri, and Andreu González-Calabuig.
OR

794 References

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796 sensors. Anal Lett 35:2389–2399


797 2. Vlasov Y, Legin A, Rudnitskaya A, Di Natale C, D’Amico A (2005) Nonspecific sensor
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UN

799 Appl Chem 77(11):1965–1983


800 3. Ciosek P, Wroblewski W (2007) Sensor arrays for liquid sensing—electronic tongue systems.
801 Analyst 132(10):963–978
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F
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OO
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CT

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831 18. Moreno-Barón L, Cartas R, Merkoçi A, Alegret S, Gutiérrez JM, Leija L, Hernandez PR,
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836 for quantification purposes in a voltammetric electronic tongue. Sens Actuators, B: Chem 113
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OR

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844 23. Colilla M, Fernández CJ, Ruiz-Hitzky E (2002) Case-based reasoning (CBR) for multicom-
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UN

852 26. Rudnitskaya A, Legin A, Seleznev B, Kirsanov D, Vlasov Y (2008) Detection of ultra-low
853 activities of heavy metal ions by an array of potentiometric chemical sensors. Microchim Acta
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856 cross-sensitive electrode-based electronic tongue for qualitative analysis of beverages.
857 Analyst 129(7):639–644
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858 28. Ciosek P, Brzózka Z, Wróblewski W (2004) Classification of beverages using a reduced
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860 29. Gallardo J, Alegret S, De Román MA, Muñoz R, Hernández PR, Leija L, del Valle M (2003)

F
861 Determination of ammonium ion employing an electronic tongue based on potentiometric
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OO
864 a potentiometric electronic tongue to fertigation strategy in greenhouse cultivation. Comput
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867 (2008) Remote environmental monitoring employing a potentiometric electronic tongue. Int J
868 Environ Anal Chem 88(2):103–117
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870 assessment of soil fertility using information from an ion selective electrodes array and

PR
871 artificial neural networks. CLEAN—Soil, Air Water 42(12):1808–1815
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874 34. Toczyłowska-Mamińska R, Ciosek P, Ciok K, Wróblewski W (2008) Development of a
875 miniaturised electrochemical cell integrated on epoxy-glass laminate. Microchim Acta 163(1–
876 2):89–95
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878 microelectrode for the recognition of milk samples. Talanta 76(3):548–556
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880 Electronic tongue for the determination of alkaline ions using a screen-printed potentiometric
881 sensor array. Microchim Acta 163(1–2):81–88
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890 tongue. Sens Actuators B: Chem 123(1):191–197


891
́
40. Martınez-Máñez R, Soto J, Garcia-Breijo E, Gil L, Ibáñez J, Llobet E (2005) An “electronic
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896 Chem 131(1):48–52
OR

897 42. Witkowska Nery E, Guimarães JA, Kubota LT (2015) Paper-based electronic tongue.
898 Electroanalysis 27(10):2357–2362
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901 domain. Talanta 59(4):735–749
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903 of phenolic compounds by means of an automated voltammetric “electronic tongue”. Anal


904 Bioanal Chem 382(2):471–476
905 45. Gutes A, Cespedes F, Alegret S, del Valle M (2005) Determination of phenolic compounds by
UN

906 a polyphenol oxidase amperometric biosensor and artificial neural network analysis. Biosens
907 Bioelectron 20(8):1668–1673
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911 Microchim Acta 163(1–2):3–10
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38 M. del Valle
Author Proof

912 48. Scampicchio M, Benedetti S, Brunetti B, Mannino S (2006) Amperometric electronic tongue
913 for the evaluation of the tea astringency. Electroanalysis 18(17):1643–1648
914 49. Gutés A, Cespedes F, del Valle M, Louthander D, Krantz-Rülcker C, Winquist F (2006) A
flow injection voltammetric electronic tongue applied to paper mill industrial waters. Sens

F
915
916 Actuators, B: Chem 115(1):390–395
917 50. Cavanillas S, Winquist F, Eriksson M (2015) A self-polishing platinum ring voltammetric

OO
918 sensor and its application to complex media. Anal Chim Acta 859:29–36
919 51. Gutés A, Calvo D, Céspedes F, del Valle M (2007) Automatic sequential injection analysis
920 electronic tongue with integrated reference electrode for the determination of ascorbic acid,
921 uric acid and paracetamol. Microchim Acta 157(1–2):1–6
922 52. Alegret S, Alonso J, Bartroli J, Cespedes F, MartinezFabregas E, del Valle M (1996)
923 Amperometric biosensors based on bulk-modified epoxy graphite biocomposites. Sens Mater
924 8(3):147–153

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925 53. Kalcher K (1990) Electroanalysis 2:419
926 54. Cetó X, Gutiérrez JM, Moreno-Barón L, Alegret S, del Valle M (2011) Voltammetric
927 electronic tongue in the analysis of cava wines. Electroanalysis 23(1):72–78
928 55. Holmin S, Björefors F, Eriksson M, Krantz-Rülcker C, Winquist F (2002) Investigation of
929 electrode materials as sensors in a voltammetric electronic tongue. Electroanalysis 14
930 (12):839–847
931 56. Ivarsson P, Johansson M, Höjer NE, Krantz-Rülcker C, Winquist F, Lundström I (2005)
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932 Supervision of rinses in a washing machine by a voltammetric electronic tongue. Sens
933 Actuators, B: Chem 108(1–2 SPEC. ISS.):851–857
934 57. Winquist F, Krantz-Rülcker C, Wide P, Lundström I (1998) Monitoring of freshness of milk
935 by an electronic tongue on the basis of voltammetry. Meas Sci Technol 9(12):1937–1946
936 58. Söderström C, Winquist F, Krantz-Rülcker C (2003) Recognition of six microbial species
937 with an electronic tongue. Sens Actuators, B: Chem 89(3):248–255
59. Parra V, Arrieta ÁA, Fernández-Escudero JA, García H, Apetrei C, Rodríguez-Méndez ML,
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938

939 Saja JAd (2006) E-tongue based on a hybrid array of voltammetric sensors based on
940 phthalocyanines, perylene derivatives and conducting polymers: discrimination capability
941 towards red wines elaborated with different varieties of grapes. Sens Actuators B: Chem 115
942 (1):54–61
943 60. Parra V, Arrieta AA, Fernández-Escudero JA, Rodríguez-Méndez ML, De Saja JA (2006)
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944 Electronic tongue based on chemically modified electrodes and voltammetry for the detection
945 of adulterations in wines. Sens Actuators, B: Chem 118(1–2):448–453
946 61. Rodríguez-Méndez ML, Parra V, Apetrei C, Villanueva S, Gay M, Prieto N, Martinez J, De
947 Saja JA (2008) Electronic tongue based on voltammetric electrodes modified with materials
948 showing complementary electroactive properties. Appl Microchim Acta 163(1–2):23–31
949 62. Twomey K, de Eulate EA, Alderman J, Arrigan DWM (2009) Fabrication and character-
950 ization of a miniaturized planar voltammetric sensor array for use in an electronic tongue.
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951 Sens Actuators, B: Chem 140(2):532–541


952 63. Paixão TRLC, Bertotti M (2009) Fabrication of disposable voltammetric electronic tongues
953 by using Prussian Blue films electrodeposited onto CD-R gold surfaces and recognition of
954 milk adulteration. Sens Actuators B: Chem 137(1):266–273
955 64. Cetó X, Céspedes F, del Valle M (2013) Comparison of Methods for the processing of
956 voltammetric electronic tongues data. Microchim Acta 180(5–6):319–330 (in press)
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957 65. Gutiérrez M, Alegret S, del Valle M (2008) Bioelectronic tongue for the simultaneous
958 determination of urea, creatinine and alkaline ions in clinical samples. Biosens Bioelectron 23
959 (6):795–802
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960 66. Gutés A, Ibáñez AB, del Valle M, Céspedes F (2006) Automated SIA e-tongue employing a
961 voltammetric biosensor array for the simultaneous determination of glucose and ascorbic acid.
962 Electroanalysis 18(1):82–88
963 67. Al-Issa Y, Njagi J, Schuckers SC, Suni II (2015) Amperometric bioelectronic tongue for
964 glucose determination. Sens Bio-Sens Res 3:31–37
Layout: T1_Standard Book ID: 334670_1_En Book ISBN: 978-3-319-47833-3
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9 Materials for Electronic Tongues: Smart Sensor Combining … 39


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965 68. Cortina M, del Valle M, Marty JL (2008) Electronic tongue using an enzyme inhibition
966 biosensor array for the resolution of pesticide mixtures. Electroanalysis 20(1):54–60
967 69. Cetó X, Céspedes F, del Valle M (2012) BioElectronic tongue for the quantification of total

F
968 polyphenol content in wine. Talanta 99:544–551
969 70. Ceto X, Cespedes F, Isabel Pividori M, Manuel Gutierrez J, del Valle M (2012) Resolution of
970 phenolic antioxidant mixtures employing a voltammetric bio-electronic tongue. Analyst 137

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971 (2):349–356
972 71. Ceto X, Cespedes F, del Valle M (2013) Assessment of individual polyphenol content in beer
973 by means of a voltammetric bioelectronic tongue. Electroanalysis 25(1):68–76
974 72. Pein M, Kirsanov D, Ciosek P, del Valle M, Yaroshenko I, Wesoły M, Zabadaj M,
975 Gonzalez-Calabuig A, Wróblewski W, Legin A (2015) Independent comparison study of six
976 different electronic tongues applied for pharmaceutical analysis. J Pharm Biomed Anal
977 114:321–329

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978 73. Gutiérrez JM, Haddi Z, Amari A, Bouchikhi B, Mimendia A, Cetó X, del Valle M (2013)
979 Hybrid electronic tongue based on multisensor data fusion for discrimination of beers. Sens
980 Actuators, B: Chem 177:989–996

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