Documents - Tips Application of Chemometrics For Data Processing of The Electronic Tongue

APPLICATION OF CHEMOMETRICS FOR DATA
PROCESSING OF THE ELECTRONIC TONGUE
Alisa Rudnitskaya, Andrey Legin, Kirill Legin, Andrey

Ipatov, Yuri Vlasov
Laboratory of Chemical Sensors, Chemistry Department, St. Petersburg
University, St. Petersburg, Russia
http://www.electronictongue.com
CHEMISTRY FACULTY
RADIOCHEMISTRY DEPARTMENT
LABORATORY OF CHEMICAL SENSORS
Head of the Laboratory prof. Yuri Vlasov
ELECTRONIC TONGUE RESEARCH GROUP

Project leader
Dr. Andrey Legin
Permanent
Dr. Alisa Rudnitskaya
staff
Dr. Andrey Ipatov
M.Sc. Boris Seleznev
Associated researchers, currently 3 Ph.D. students, several students a year
WSC 3, Pushkinskie Gory, Russia, February 16-20,
Research directions
1. New sensing materials
Solid-state materials (chalcogenide glasses)

Organic polymers
Thin films
2. Chemical sensors
3. Sensor systems electronic tongue
Electrochemical characteristics
Cross-sensitivity study
Sensing mechanism
Multisensor arrays
Chemometrics tools
Recognition & Analysis
4. Application of chemical sensors and sensor systems
Industrial analysis
Environmental control
Medical analysis
Foodstuff analysis
3
Advantages and drawbacks of potentiometric chemical

sensors
Advantages
1.
2.
3.
4.
5.
6.
7.
A wide range of available sensing materials and sensors.

Wide variations of sensor properties, some unique features.
A wide knowledge about composition/properties relationship.
Simple installation. Easy, direct measurements.
Different configuration (static, flow) and size (bulk, micro).
Easy applicability for automatic routine analysis.
Low cost.
Drawbacks
1. Insufficient selectivity of many sensors.

2. The number of available sensors is far smaller than the variety of analytes.
Electronic tongue
Electronic tongue is an analytical instrument comprising an array of nonspecific, poorly selective, chemical sensors with partial specificity (crosssensitivity) to different components in solution, and an appropriate
chemometrics tool (method of pattern recognition and/or multivariate
calibration) for the data processing. Of primary importance is stability of
sensor behaviour and enhanced cross-sensitivity, which is understood as
reproducible response of a sensor to as many species as possible. If properly
configured and trained (calibrated), the electronic tongue" is capable to
recognise quantitative and qualitative composition of multicomponent
solutions of different nature.
Potentiometric electronic tongue
multiplexor
sensor
array
measuring device
V
reference
electrode
computer
analysed
solution
Electronic tongue laboratory version
Composition of chemical sensor array for electronic

tongue
Chalcogenide glass sensors

As2S3, GeS2, AsSe with various additives
Polymer based
PVC, plastisizer and active substances
Chrystalline based
Ag2S with different additives, LaF3
Totally: up to 40 sensors
Methods for the ET data processing
Quantitative analysis (concentrations/parameters prediction)

Modeling using MLR, PLS-regression, artificial neural
networks, N-PLS
Data exploration, recognition
PCA
Classification
SIMCA, LDA, PLS-regression
Electronic tongue applications

Types of analysis
Classification and discrimination (identification, recognition)
Quantitative analysis of multiple components simultaneously
Process control
Taste assessment and correlation with human perception
Objects
Food fruit juices, coffee, soft drinks, milk, mineral
water, wine, vodka, cognac, meat, fish, onion
Medical analysis - dialyses solution for artificial kidney,
pharmaceuticals, urine
Environmental groundwater, seawater, dirty water from farms
Industrial analysis - galvanic baths, waste purification systems,
control of biotechnology processes
10
Selected applications of the electronic tongue
Discrimination of substances eliciting different taste and different

substances eliciting the same taste
Determination of ultra low activity of transition metals in seawater
Determination of ammonium and organic acids content in the model

growth media
New approach to the data for flow-injection electronic tongue determination of zinc and lead concentration in mixed solutions
11
Discrimination of taste substances
Objective
Discrimination of substances eliciting different tastes (i.e. bitter, sweet
and salty) and substances eliciting the same taste
Samples: 10mmolL-1 individual solutions of substances

bitter: quinine, caffeine, drugs A and B
sweet: acesulfam K, aspartame, sucrose
salty: sodium chloride, sodium benzoate, drug D
Measurements
ET comprising 20 sensors
at least 3 replicas of each sample in random order
Data processing
discrimination
LDA
PCA
12
Discrimination of taste substances

5
bitter
sweet
salty
4
3
120
80
PC2 (26%)
Root2 (8%)
NaCl
1
0
40
0
-1
-40
-2
Na benzoate
Drug D
-80
-3
-6
-4
-2
10
12
-200 -150 -100
14
Root1 (92%)
150
-50
50
Drug B
20
200
10
Quinine
PC2 (2%)
50
PC2 (11%)
150
Aspartame
100
100
PC1 (73%)
Drug A
-50
ASK
-10
-100
-150
-250 -200 -150 -100
Sugar
-20
Caffeine
-50
0
50
PC1 (81%)
100
150
200
250
-250
-200
-150
-100
-50
50
100
150
PC1 (98%)
13
Determination of ultra low activities of transition

metals
Objective
Determination of ultra low activities of transition metals in waste waters
and seawater
Solutions
Individual and mixed binary buffered solutions of Cu, Zn, Cd and Pb
Total concentration of metals 1 M to 0.3mM, activity - 1nM to 0.1M
Background of 0.01M of NaCl and 0.01M citrate, pH 8
Measurements
Data processing
Calibration and activity prediction of transition metals
PLS-regression
14

metals
Measurements in individual buffered solutions
320
240
-240
200
-280
160
-320
120
-360
E, mV
Ch2 june
Ch2 august
Ch3 june
Ch3 august
-10.0 -9.5 -9.0 -8.5 -8.0 -7.5 -7.0 -6.5

-400 -6.0 -5.5 -5.0 -4.5
-240
2+
loga(Zn )
-440
-280
-480
-320
-11
-10
-9
-8
E, mV
E, mV
280
P1
P2
-7
-6
loga(Cd)-360
-5
Ch3 june
Ch3 august
Ch2 june
Ch2 august
-400
-440
-480
-9.5
-9.0
-8.5
-8.0
-7.5
-7.0
-6.5
-6.0
-5.5
-5.0
loga(Pb)
15

metals
Ion
Copper
Zinc
Cadmium
Lead
Copper
Lead
Added, nM
1.48
8.13
107
5.01
11.7
19.1
2.6
15.1
52.5
2.0
12.0
53.7
3.2
10
85
3
11
66
79
Found, nM
St. Deviation Average relative error, %
Binary Cu-Zn solutions
1.7
0.2
23
8
4
110
30
5.4
0.2
11
11
1
17
2
Binary Cd-Pb solutions
3.0
0.7
24
15
6
49
16
2.3
0.5
25
10
4
50
14
Binary Cu-Pb solutions
3.3
1.3
22
10
2
97
22
2.3
0.5
13
4
26
56
12
69
16
16
Determination of ammonium and organic acids content

in the model growth media
Objective
Quantification of main substances consumed / produced during
microorganisms growth monitoring of the fermentation processes
Samples
Set of 22 solutions modeling growth media
Components: MgSO4, KCl, KH2PO4, citrate, pyruvate, oxalate, glucose,
glycerol, mannitol, erythritol, NH4Cl
Measurements
At least 3 replicas of each solution
Data processing
Calibration and concentration prediction w.r.t. ammonium, oxalate and
citrate
Artificial neural network
17
Determination of ammonium and organic acids in the

growth media
Sample Added, mM Predicted, mM St.Deviation Average relative error, %
Ammonium
2
2.0
2.1
0.4
4
2.8
2.5
0.3
6
4.8
4.9
0.1
6
14
6.0
6.01
0.04
16
12.0
11.8
0.3
18
13.2
13.57
0.05
19
14.0
13.59
0.02
Oxalate
6
7.8
7
1
8
13.0
14
1
9
20.7
21.0
0.3
6
10
28.5
28
1
16
33.7
33.8
0.6
18
44.0
43.9
0.4
20
49.2
51
2
Citrate
6
1.7
2.1
0.1
8
2.6
2.5
0.2
10
3.3
2.9
0.2
8
13
3.6
3.11
0.03
16
3.8
4.0
0.1
18
4.3
4.5
0.1
20
5.0
5.0
0.2
18
Determination of zinc and lead concentrations in mixed

solutions using flow-injection electronic tongue
Objectives
Evaluate relevance of different types of signals produced using
flow-injection ET
Evaluate relevance of different multivariate calibration methods
for processing of the flow-injection electronic tongue data
19
Schematic of flow-injection electronic tongue

KNO3
0,1M
20
Flow-through cell
21
Sensor response parameters in FIA
T
ta- time before sample
enters measuring cell
H(mV)
time of sample pass

through the cell
tb peak width
t- recovery time
peak height
tb
ta
t(c )
22
Data produced by flow-injection ET

1. Peak height measured for each sensor:
one signal from each sensor, I x J
2. Time-dependent response for each sensor:
3-dimensional data set, I x J x K
Samples
3. Time-dependent response for each sensor:
Ti
m
e
Unfolded data set, I x JK
Sensors
23
Calibration methods
Data sets 1 and 2:

Partial least square regression
Artificial neural network (back-propagation neural network)
Data set 3
N-way partial least square regression
24
N-PLS regression
PLS-regression:
X = TP + E;
Y = TQ + E
N-PLS regression:
X = TWj(Wk) + E;
Y = TQ + E
25
Experimental set-up
ET 7 sensors with PVC plasticized membranes
Set of mixed solutions containing zinc and lead;

Sample 1 2 3 4
5 6 7 8 9
pZn
5 4 5 4 5.3 5 5.3 4 5.3
pPb
5.3 4 5 5.3 5.3 4 5 5 4
Background solution - 0.1M KNO3
Sensor potentials measured every 4 s for 2 minutes, 30 points for each

solutions
Four replicas of each solutions
Three types of data sets
Data processing using PLS-1 and N-PLS regression
26
Sensors response in the individual solutions of zinc and

lead
Sensor 1
Sensor 1
320
300
310
290
pZn
E, mV
270
6
5
4
3
290
280
E, mV
280
pPb
300
6
5
4
3
260
250
270
260
250
240
240
230
230
220
210
220
0
50
100
150
210
200
50
Time, s
150
200
Time, s
Sensor 4
Sensor 4
380
350
340
pZn
360
6
5
4
3
340
pPb
330
6
5
4
3
320
310
320
300
E, mV
E, mV
100
300
290
280
270
280
260
260
240
250
240
0
50
100
150
200
50
Time, s
100
Time, s
150
200
27
Determination of zinc and lead in individual solutions

using flow-injection ET
Calibration was done using PLS regression with test set
validation, only pick height being used as sensor signals.
Concentration range of both zinc and lead 10-6 10-3 molL-1
28
Sensors response in the mixed solutions of zinc and

lead
Sensor 4
Sensor 1
270
320
pPb = 5
pZn
6
5
4
260
250
pPb = 5
pZn
6
5
4
310
300
240
E, mV
E, mV
290
230
280
270
260
220
250
240
210
-10
10
20
30
40
50
60
70
80
90
100
230
110
Time, s
Sensor 1
10
20
30
40
50
60
70
80
90
100
110
Time, s
Sensor 4
280
310
PZn = 5
pPb
6
5
4
270
260
250
290
280
240
E, mV
E, mV
300
PZn = 5
pPb
6
5
4
230
270
260
220
250
210
240
200
230
0
10
20
30
40
50
60
70
80
90
100
110
20
Time, s
40
60
Time, s
80
100
29
Results of zinc and lead concentrations prediction using

three different types of data sets
30
X-loadings weights
Peak heights
Time dependent response (unfolded data)
0.8
0.30
5
0.6
0.25
0.4
0.20
0.15
-0.2
PC2
0.0
0.10
0.05
0.00
-0.4
-0.05
-0.6
-0.10
-0.8
-0.6
-0.5
-0.4
-0.3
-0.2
-0.1
0.0
-0.16
-0.14
-0.12
-0.10
PC1
-0.08
-0.06
-0.04
-0.02
0.00
0.02
PC 1
0,3
PC1
PC2
0,2
0,1
X-loadings
PC2
0.2
5-32
5-28
5-36
5-40
5-24
5-44
5-48
5-52
4-32
4-28
5-56 4-36
4-40
4-24 5-20
5-60
1-24
4-445-641-32 1-28
1-20
4-48 5-68
1-36
5-16
5-8
5-12
4-52
5-72
4-20
5-4
1-16
7-44 7-407-36 7-32
1-4
1-12
1-8
1-40 5-76
4-12
7-28
4-8
4-16
4-56
4-4
7-48
5-80
4-601-44
7-52
7-24
5-84
4-641-48
1-112
2-8
1-108
1-120 2-20
7-56
2-16
1-104
1-100
2-12
5-88 7-60
1-116
4-681-52
1-88
1-92
2-24
1-96
7-20
2-4
1-84
1-56
7-16
5-92
6-4
1-80
7-8
1-76
4-72
5-96
7-4
1-68
7-12
1-64
6-24
1-72
5-100
2-28
1-60
6-16
7-68
7-64
6-12
2-32
6-8
6-28
6-20
5-104
5-116
5-112
6-32
5-120
5-108
6-120
4-76
6-108
7-108
7-116
2-120
7-112
7-120
6-36
6-96
6-112
7-72
7-104
2-116
7-84
6-104
2-100
2-112
6-116
7-76
2-36
6-100
4-80
7-92
6-40
6-92
7-80
7-100
6-88
2-108
7-96
4-104
2-104
3-20
3-4
4-120
7-88
2-96
3-16
4-84
4-116
4-112
6-80
6-84
3-8
4-108
6-44
6-72
3-24
4-100
3-28
4-96
6-76
6-56
2-92
6-48
3-12
2-40
6-68
2-44
4-88
6-64
6-52
6-60
3-32
2-80
4-92
2-84
3-36
2-88
3-40
3-112
3-120
3-100
3-108
3-96
3-92
3-116
3-104
3-80
3-88
3-72
2-76 3-60
3-64
2-48
2-68
3-52
3-48
3-56
3-76
2-72
3-84
3-44
2-56
3-68
2-52
2-64
2-60
0,0
-0,1
-0,2
1-120
2-120
3-120
4-120
Variables
5-120
6-120
31
7-120
X-loadings weights
Time dependent response (3-d data)
X-loadings in the order of sensors
X-loadings in the order of time

0.8
0.42
0.41
0.40
0.4
0.38
PC2
PC2
0.39
5 4
0.37
0.36
0.33
-0.2
0.370
0.2
0.0
0.35
0.34
76
0.6
0.375
0.380
0.385
0.390
-0.4
0.00
72
60
56
4
108
20
92
16
104
24
40
100
3696 88 120
52
4844
32
0.05
0.10
0.15
PC1
80
8
112
116
28
0.20
12
68
0.25
84
0.30
64
0.35
0.40
PC1
32
Conclusions
Use of time-dependent response of flow-injection ET instead of peak

heights allows higher accuracy of concentrations determination in
mixed solutions
Use of 3-dimensional data set and N-PLS regression for calibration

leads to simpler model and the same prediction errors compared to
unfolded 2-dimensional data set and PLS regression for calibration
33

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APPLICATION OF CHEMOMETRICS FOR DATA

PROCESSING OF THE ELECTRONIC TONGUE

Alisa Rudnitskaya, Andrey Legin, Kirill Legin, Andrey

ELECTRONIC TONGUE RESEARCH GROUP

Dr. Andrey Legin

WSC 3, Pushkinskie Gory, Russia, February 16-20,

1. New sensing materials

Solid-state materials (chalcogenide glasses)

3. Sensor systems electronic tongue

4. Application of chemical sensors and sensor systems

WSC 3, Pushkinskie Gory, Russia, February 16-20,

Advantages and drawbacks of potentiometric chemical

A wide range of available sensing materials and sensors.

1. Insufficient selectivity of many sensors.

WSC 3, Pushkinskie Gory, Russia, February 16-20,

WSC 3, Pushkinskie Gory, Russia, February 16-20,

Potentiometric electronic tongue

WSC 3, Pushkinskie Gory, Russia, February 16-20,

Electronic tongue laboratory version

WSC 3, Pushkinskie Gory, Russia, February 16-20,

Composition of chemical sensor array for electronic

Chalcogenide glass sensors

WSC 3, Pushkinskie Gory, Russia, February 16-20,

Methods for the ET data processing

Quantitative analysis (concentrations/parameters prediction)

WSC 3, Pushkinskie Gory, Russia, February 16-20,

Electronic tongue applications

Selected applications of the electronic tongue

Discrimination of substances eliciting different taste and different

Determination of ultra low activity of transition metals in seawater

Determination of ammonium and organic acids content in the model

WSC 3, Pushkinskie Gory, Russia, February 16-20,

Discrimination of taste substances

Samples: 10mmolL-1 individual solutions of substances

WSC 3, Pushkinskie Gory, Russia, February 16-20,

Discrimination of taste substances

-200 -150 -100

-250 -200 -150 -100

WSC 3, Pushkinskie Gory, Russia, February 16-20,

Determination of ultra low activities of transition

Determination of ultra low activities of transition

-10.0 -9.5 -9.0 -8.5 -8.0 -7.5 -7.0 -6.5

WSC 3, Pushkinskie Gory, Russia, February 16-20,

Determination of ultra low activities of transition

WSC 3, Pushkinskie Gory, Russia, February 16-20,

Determination of ammonium and organic acids content

WSC 3, Pushkinskie Gory, Russia, February 16-20,

Determination of ammonium and organic acids in the

WSC 3, Pushkinskie Gory, Russia, February 16-20,

Determination of zinc and lead concentrations in mixed

WSC 3, Pushkinskie Gory, Russia, February 16-20,

Schematic of flow-injection electronic tongue

WSC 3, Pushkinskie Gory, Russia, February 16-20,

WSC 3, Pushkinskie Gory, Russia, February 16-20,

Sensor response parameters in FIA

time of sample pass

WSC 3, Pushkinskie Gory, Russia, February 16-20,

Data produced by flow-injection ET

2. Time-dependent response for each sensor:

3-dimensional data set, I x J x K

3. Time-dependent response for each sensor:

Unfolded data set, I x JK

WSC 3, Pushkinskie Gory, Russia, February 16-20,