FORM 2

THE PATENTS ACT, 1970

5 (39 of 1970)

&

THE PATENT RULES, 2003

10

COMPLETE SPECIFICATION

15 [See Section 10 and Rule 13]

TITLE:
20
“A LARGE AMPLITUDE PULSE IMPEDIMETRIC
ELECTRONIC DEVICE FOR ELECTROCHEMICAL
ANALYSIS”

25

APPLICANT:

NATIONAL INSTITUTE OF TECHNOLOGY, PATNA

30 An Indian Autonomous body
having address at
Patna-800005, Bihar, India

35 PREAMBLE TO THE DESCRIPTION:

The following specification particularly describes the invention and the

manner in which it is to be performed:
 FIELD OF THE INVENTION

The present invention relates to the field of electrochemical devices. More

particularly, the present invention relates to a large amplitude pulse
impedimetric electronic device for electrochemical analysis for rapid quality
5 screening of electrochemically active food samples.

BACKGROUND OF THE INVENTION

Electronic tongue is an analytical instrument that comprises of the chemical

sensors in it with partial specificity for measuring and comparing taste. It has
10 the ability of recognizing the quantitative and qualitative compositions of
simple and complex solutions. This electronic sensor is capable of screening the
taste attributes of different formulations in a rapid timeframe, when used in
addition with human taste assessment data. These electronic sensors are
developed based on the potentiometry, impedance spectroscopy and
15 voltammetry.

A voltammetric electronic tongue is an array of electrochemical sensors with

the help of which an electrochemical cell is perturbed using a standard voltage
pulse sequence thereby extracting a fair amount of information about the
process descriptors like quality/spoilage of food samples in the form of current
20 waveform signatures. Analysis of such response waveform in time or frequency
domain coupled with statistical and artificial intelligence techniques leads to
the development of computational models for given applications like quality
prediction, classification or process monitoring etc. Quality analysis or process
monitoring applications regarding food samples may be solved in a cost
25 effective and rapid manner using electronic tongue. The development of
hardware circuit and software analysis modules for this type of electronic
tongue are critical and complicated. Also, in this type of electronic tongue,
time domain information and transient characteristics are not considered in a
direct manner. Impedimetric electronic tongue is useful for the analysis of basic

2
 tastes as well as complex matrices. Till date, due to the high sensitivity of the
impedimetric electronic tongue it has been utilized to analyse a variety of food
items.

Until now, a conventional pulse voltammetric electronic tongue response is

5 analyzed mainly from the perspective of time domain information. A pulse
voltammetric electronic tongue has an advantage of high sensitivity and
produces an information rich time domain response with transient as well as
steady state features correlated with process properties. However, frequency
domain response is also known to uncover important characteristics about the
10 process under study.

Cátia Magro et al. 10 October 2018 https://doi.org/10.1139/er-2018-0019

disclose about the electronic tongue sensors having the ability for real-time
environmental monitoring as well as the potential of the electronic tongue
sensor to detect organic contaminants in aqueous environmental matrices.
15 Specifically, the electronic tongue sensor for the detection of the pollutants in
aqueous media as well as the emerging organic contaminants –pharmaceuticals
and personal care products. However, in real-time monitoring of the emerging
organic contaminants, the detection power of the electronic tongue sensor is
still under research. Despite having high sensitivity, low cost and easy to
20 operate properties, there remains a lack of selectivity for electronic tongue
related to the real-time environmental monitoring.

EP1010005A1 discloses about the electronic tongue for use as electronic taste
sensor that is capable of instant quality monitoring of food. It is capable of
classifying various fruit drinks and milk, thereby opening the future
25 applications in food industry. Further, the invention discloses that a tasting cell
can be a part of a simple pump, for instance a rotary vane pump. The
electrodes may be arranged in a wall of the pump body and the vane is
provided with a brush part that serves as some sort of a seal against the wall.
The electrodes will be continuously swept clean by the brush. Moreover, the

3
 vane provided may be a rubber blade that is pre-tensioned against the wall of
the cell.

In view of the above-mentioned problems encountered with known taste

sensors or electronic tongues devices, there is a need to improve feature
5 extraction technique in the impedimetric electronic device for electrochemical
analysis for rapid quality screening of electrochemically active food samples
without hampering the accuracy.

OBJECT OF THE INVENTION

10 The main object of the present invention is to provide a large amplitude pulse
impedimetric electronic device for electrochemical analysis for rapid quality
screening of electrochemically active food samples.

Another object of the present invention is to provide a large amplitude pulse

impedimetric electronic device for the identification of physicochemical nature
15 of solution under test.

Yet another object of the present invention is to provide a large amplitude

pulse impedimetric electronic device supporting an electrochemical sensor
array comprising of up to six working electrodes for applying the electrical
perturbations to the sample.

20 Yet another object of the present invention is to provide a large amplitude

pulse impedimetric electronic device with an in-house data acquisition unit
with user interface for data logging and device control.

Still another object of the present invention is to provide a large amplitude

pulse impedimetric electronic device having a data processing unit that
25 performs sequence control of the electrode array, data recording, processing
and presentation.

4
 SUMMARY OF THE INVENTION

The present invention relates to a large amplitude pulse impedimetric

electronic device for electrochemical analysis of active sample for rapid quality
5 screening of electrochemically active food samples having multiple
electrochemical electrode arrays for applying the electrical perturbations to the
sample along with an in-house data acquisition unit with user interface for data
logging and device control.

In an embodiment, the present invention provides a large amplitude pulse

10 impedimetric electronic device for electrochemical analysis, comprising of a
housing with an electrode array, and an electronic signal conditioning module,
a display platform with inbuilt graphical user interface, wherein, the electrode
array comprise of at least six electrodes for sensing a plurality of
electrochemical response of an active sample, the electronic signal conditioning
15 module comprises of a potentiostat unit, a data acquisition unit, a data
processing unit with a driver unit, the potentiostat unit is a multi-potentiostat
unit for potentiostatic and switching control over the electrode array, the data
acquisition unit is configured with the potentiostat unit for receiving and
sending the plurality of electrochemical response sensed by the electrode array
20 to the data processing unit; the data processing unit performs a rapid pulse
impedimetric analysis on the plurality of electrochemical response via a
plurality of multivariate statistical methods to estimate composition(s)/analyze
the properties of the test sample electrochemical response

In another embodiment of the present invention, the data processing unit is

25 configured to transform the electrochemical response via a network synthesis
approach of feature extraction and a transfer delay block into a set of time
domain and frequency domain features and the display platform presents the
large amplitude pulse voltammetry voltage waveform along with time domain

5
 and frequency domain features in a user understandable format. The data
processing unit is a computing unit.

In another embodiment, the present invention provides a large amplitude pulse

impedimetric electronic device for electrochemical analysis in which the
5 display platform presents said large amplitude pulse voltammetry voltage
waveform.

In another embodiment, the present invention provides a large amplitude pulse

impedimetric electronic device for electrochemical analysis in which
multivariate statistical method has a high compression ratio and is independent
10 of the length of the waveform and rapid pulse impedimetric analysis including
a network synthesis approach that is based on an identified transfer function.

The above objects and advantages of the present invention will become
apparent from the hereinafter set forth brief description of the drawings,
detailed description of the invention, and claims appended herewith.

15 BRIEF DESCRIPTION OF THE DRAWING

An understanding of the large amplitude pulse impedimetric electronic device

for electrochemical analysis of the present invention may be obtained by
reference to the following drawings:

Figure 1 is a block diagram of the large amplitude pulse impedimetric

20 electronic device for electrochemical analysis, according to an embodiment of
the present invention.

Figure 2 is another block diagram of the large amplitude pulse impedimetric

electronic device for electrochemical analysis, according to an embodiment of
the present invention.

25 Figure 3 is a schematic diagram of the large amplitude pulse impedimetric

electronic device according to an embodiment of the present invention.

6
 Figure 4 is a perspective view of the housing with electrode array according to
an embodiment of the present invention.

Figure 5(a) and Figure 5(b) are block diagram and schematic diagram of the
electrode switching unit, respectively according to an embodiment of the
5 present invention.

Figure 6(a) and Figure 6(b) are block diagram and schematic diagram of the
potentiostat unit, respectively according to an embodiment of the present
invention.

Figure 7(a) and Figure 7(b) are block diagram and schematic diagram of the
10 data acquisition unit, respectively according to an embodiment of the present
invention.

Figure 8 is a flow diagram of the large amplitude pulse impedimetric electronic

device according to an embodiment of the present invention.

Figure 9 is a pictorial view of the graphical use interface used in the present
15 invention.

Figure 10 is a perspective view of the large amplitude pulse impedimetric

electronic device according to an embodiment of the present invention.

Figure 11(a) and Figure 11(b) are block diagrams of measurement circuit and
measurement circuit with a RC filter inside the potentiostat unit, respectively
20 according to an embodiment of the present invention.

Figure 12 is a block diagram of the transfer delay block in the large amplitude
pulse impedimetric electronic device according to an embodiment of the
present invention.

Figure 13 is a schematic view of the equivalent circuit of the large amplitude

25 pulse impedimetric electronic device according to an embodiment of the
present invention.

7
 Figure 14 is graphical representation of the normalized root mean square fit
percentage of identified model for different transport delays in the present
invention.

Figure 15 is a graphical representation of comparison of the identified transfer

5 function with the measured response for the tea sample.

Figures 16 and 17 are graphical representations of extracted features matrix

data used for principal component analysis in the present invention.

DETAILED DESCRIPTION OF THE INVENTION

10 The present invention will now be described hereinafter with reference to the
accompanying drawings in which a preferred embodiment of the invention is
shown. This invention may, however, be embodied in many different forms
and should not be construed as being limited to the embodiment set forth
herein. Rather, the embodiment is provided so that this disclosure will be
15 thorough, and will fully convey the scope of the invention to those skilled in
the art.

Many aspects of the invention can be better understood with references made
to the drawings below. The components in the drawings are not necessarily
drawn to scale. Instead, emphasis is placed upon clearly illustrating the
20 components of the present invention. Moreover, like reference numerals
designate corresponding parts through the several views in the drawings.
Before explaining at least one embodiment of the invention, it is to be
understood that the embodiments of the invention are not limited in their
application to the details of construction and to the arrangement of the
25 components set forth in the following description or illustrated in the drawings.
The embodiments of the invention are capable of being practiced and carried
out in various ways. In addition, the phraseology and terminology employed

8
 herein are for the purpose of description and should not be regarded as
limiting.

The present invention relates to a large amplitude pulse impedimetric

5 electronic device for electrochemical analysis for rapid quality screening of
electrochemically active food samples.

In an embodiment, the present invention provides a large amplitude pulse

impedimetric electronic device for electrochemical analysis, comprising of a
housing with an electrode array, and an electronic signal conditioning module,
10 a display platform with inbuilt graphical user interface, wherein, the electrode
array comprises of at least six electrodes for sensing a plurality of
electrochemical response of an active sample, the electronic signal conditioning
module comprises of a potentiostat unit, a data acquisition unit, a data
processing unit with a driver unit, the potentiostat unit is a multi-potentiostat
15 unit for potentiostatic and switching control over the electrode array, the data
acquisition unit is configured with the potentiostat unit for receiving and
sending the plurality of electrochemical response sensed by the electrode array
to the data processing unit; the data processing unit performs a rapid pulse
impedimetric analysis on the plurality of electrochemical response via a
20 plurality of multivariate statistical methods to estimate composition(s)/analyze
the properties of the test sample electrochemical response.

In another embodiment of the present invention, the data processing unit is

configured to transform the electrochemical response via a network synthesis
approach of feature extraction and a transfer delay block into a set of time
25 domain and frequency domain features and the display platform presents the
large amplitude pulse voltammetry voltage waveform along with time domain
and frequency domain features in an user understandable format.

9
 In another embodiment, the present invention provides a large amplitude pulse
impedimetric electronic device for electrochemical analysis in which the
platform presents the said large amplitude pulse voltammetry voltage
waveform.

5 In another embodiment, the present invention provides a large amplitude pulse

impedimetric electronic device for electrochemical analysis in which
multivariate statistical method has a high compression ratio and is independent
of the length of the waveform and rapid pulse impedimetric analysis including
a network synthesis approach that is based on an identified transfer function.

10 Referring to Figure 1, a block diagram of the large amplitude pulse

impedimetric electronic device for electrochemical analysis is depicted. The
device (100) comprises of a housing (1) with an electrode array (2), an
electronic signal conditioning unit (3), a potentiostat unit (8), a data acquisition
unit (4), a data processing unit, a platform with graphical user interface. The
15 data processing unit is a computing unit. The large amplitude pulse
impedimetric electronic device (100) produces output within the range of 18 to
20 seconds.

The large amplitude pulse impedimetric electronic device (100) is for rapid
quality screening of electrochemically active food samples specially the one
20 which shows conductive properties and dissolves in aqueous medium. The
present invention provides the end users with information about the
physicochemical nature of solution under test. This information is provided in
terms of the optimized impedance model and time domain features for the test
solution. Further interpretation about the nature of test solution is derived by
25 the end user of the device (100) after obtaining the optimum equivalent circuit.
This device (100) provides the required set of features or descriptors for the test
sample.

The housing (1) accommodates six electrochemical electrode array (sensors)

(2) comprising up to six working electrodes for applying the electrical

10
 perturbations to the test electrolytes (food samples) along with the in house
data acquisition unit (4) for data logging and device control. Further, the data
acquisition unit includes but is not limited to processor, microcontroller of any
other form of microchip.

5 Referring to Figure 2, another block diagram of the large amplitude pulse

impedimetric electronic device is depicted. The large amplitude pulse
impedimetric electronic device (100) is a biologically inspired sensory-electrical
device wherein the responses from electrode array (2) with overlapping
sensitivities are recorded and interpreted using intelligent multivariate
10 statistical techniques through the data processing unit. The multivariate
statistical techniques are employed to extract the desired quantity of interest
from the electrical signatures obtained from the electrodes.

The large amplitude pulse impedimetric electronic device (100) helps to obtain
large amount of information in the form of transient (capacitive current) and
15 steady state (faradaic current) portions of the response. This information when
properly analyzed yields sufficient indications regarding the chemical nature of
constituents and their contributions to overall quality.

Referring to Figure 3, a schematic diagram of the large amplitude pulse

impedimetric electronic device is depicted. The analysis procedure using large
20 amplitude pulse impedimetric electronic device (100) is rapid and objective. It
not only requires none or very simple sample preparation procedures but also
generates large amount of information characterizing the constitution of a
complex multi-component sample. The onus of feature extraction technique is
to uncover the desired information regarding the parameter or process under
25 study from the complicated electrical spectra obtained from the electrode array
(2).

The working of large amplitude pulse impedimetric electronic device (100)

works by making a contact between the active sample and the electrode array
(2) i.e. working electrode with respect to reference electrode. The pulse

11
 waveform is configured and initiated via the graphical interface from the
platform (7) or embedded display in data processing unit.

The voltage parameters are quantified and sent to a control unit present in the
data acquisition unit (4) that generates the digital voltage sample in a
5 sequential manner to conform to specified large amplitude pulse voltammetry
waveform parameters. Further, a digital to analog converter (5) is configured
within the circuit of data acquisition unit (4) that converts the generated digital
voltage sample into analog voltage sample and applies them to the input of
potentiostat unit (8).

10 The analog large amplitude pulse voltammetry voltage samples are applied to
the input of potentiostat unit (8). The potentiostat unit (8) acts as an interface
between the electrical and electrochemical electrode array (2) arrangement in
the present invention. The potentiostat unit (8) circuit applies the analog large
amplitude pulse voltammetry voltage samples to the working electrode.

15 Further, the present invention includes an electrode switching circuit (3) that
connects one of the working electrodes with the potentiostat unit (8). The
sequence of working electrode to be connected with potentiostat unit (8) is
controlled by the data processing unit as per the order specified in the present
invention.

20 The response current produced due to reduction-oxidation (redox) reaction

occurring on the surface of connected working electrode because of the applied
large amplitude pulse voltammetry waveform is collected by the current
measurement module in potentiostat unit (8), digitized by the analog to digital
converter (6), and forwarded by the control unit to the data processing unit.
25 Further, the shape and amplitude of the response current is the signature of the
test sample. A data analysis module then transforms the response current
waveform into a set of time domain and frequency domain features.

12
 Referring to Figure 4, a perspective view of the housing with electrode array is
depicted. The housing (1) includes six working electrodes i.e. gold (Au),
iridium (Ir), palladium (Pd), platinum (Pt), rhodium (Rh), and glassy carbon
electrode (GC), a stainless steel counter electrode (CE), and reference electrode
5 (RE). The metal electrodes have a purity of above 99%. Each working
electrode is of 1 mm diameter and is exposed by 1 mm into the test electrolyte.
The diameter of stainless-steel counter electrode is 4 mm. The diameter of the
RE tip is 3mm.

The arrangement of each working electrode around the counter electrode is

10 maintained at a uniform separation of 30 mm. The diameter of housing (1) is
45 mm. The housing (1) is made such that a minimum sample volume of 20 ml
is required for analysis. The electrode housing (1) includes the base (made of
polytetrafluoroethylene (PTFE) disk) and a hollow enclosure unit made of
polytetrafluoroethylene tube of thickness 1 mm and inner diameter of 2.5 cm.

15 The disk and hollow tube as press fitted and sealed from fluids with hot melt
adhesive glue. The electrode wires are drilled into the base disk in a circular
fashion. The electrodes are connected to single core conducting wires. The
metal electrodes are solder connected with the conducting wires while the
glassy carbon electrode are crimp fitted with copper ferrule to the terminals.

20 The terminals wires so prepared are then soldered to the solder terminals. An
eight-element insulated wire mesh-screened multicore cable has been used to
connect the electrode array (2) terminals (6-WE+1-CE) with the electronic
signal conditioning unit (3) via a circular connector.

The electrode array (2) cables are detachable from the potentiostat unit (8) by
25 connecting a male-female D connector at the middle total cable length. The
reference electrode terminal is connected to the middle D connector through a
detachable balloon jack. The connections are made detachable to facilitate
cleaning of electrode array (2) after detaching it from the electronic signal
conditioning unit (3). At the same time, it is ensured that all the non-

13
 detachable connection points remain firmly in place by insulating and
immobilizing those junctions by using hot melt adhesive glue. The mesh-screen
of the multicore cable is earth grounded and connected with the metallic body
of the electronic signal conditioning unit (3) housing.

5 The electronic signal conditioning unit (3) creates the necessary interface
between the display device (100) and the response current received from
working electrode. The electronic signal conditioning unit (3) comprise of an
electrode switching unit, a potentiostat unit (8) and a data acquisition unit (4).
Referring to Figure 5(a) and Figure 5(b), a block diagram and schematic
10 diagram of the electrode switching unit are depicted respectively. The electrode
switching unit has six signal level, low current latching relays, powered by +5
V. These relays are non-latching, low current relays with double pole double
throw behavior. The non-latching behavior leads to the alleviation of the
requirement to maintain a steady state control signal to maintain the state of
15 relay. The relay switching signals to connect/disconnect the working electrode
are obtained from the digital output pins in the data acquisition unit (4).

Referring to Figure 6(a) and Figure 6(b), a block diagram and schematic
diagram of the potentiostat unit are depicted, respectively. The potentiostat
unit (8) comprises of a circuit board that is built completely in-house with
20 designated components. The task of potentiostat unit is to apply the analog
large amplitude pulse voltammetry voltage between working electrode and
reference electrode, stabilize the voltage applied. The analog large amplitude
pulse voltammetry voltage is obtained from the output of control unit present
in the data acquisition unit (4) board and is applied at the input of potentiostat
25 circuit. It measures the response current and forwards the current converted
voltage to the input of analog to digital converter present in the data acquisition
unit (4). The potentiostat unit supports current measurement ranges from
10nA-100nA, 100nA- 1µA, 1µA- 1mA, and 1mA – 100 mA.

14
 Referring to Figure 7(a) and Figure 7(b), a block diagram and schematic
diagram of the data acquisition unit are depicted, respectively. The data
acquisition unit (4) is completely built in-house with specific components. The
main purpose of digital to analog converter (5) in the data acquisition unit
5 developed in the present invention is to generate a different signal which be
used to perturb liquid samples in the form of different voltage profiles like
cyclic voltammetry signal (CV), large amplitude pulse voltammetry, staircase
voltammetry (SV) and differential pulse voltammetry (DPV) signals etc. It is
primarily used to collect analog response signal from the potentiostat unit and
10 converts the same into a digital value.

Furthermore, the protocol operating the data processing unit is completely in-
house and for this specific application. The protocol is developed in an event-
driven manner. The commands received via the USB-link from the computer
unit accommodating the front-end application is used to control the behavior of
15 data acquisition task. The protocol initializes all the required modules after
startup. Then it waits for a character-based command to be received from front-
end program in computer unit. The characters and their expected behavior are
ASCII character ‘O’, ASCII character ‘N’, ASCII character ‘E’, Numeric data.

The ASCII character ‘O’ is used for connection test. This character is
20 repeatedly sent by front end protocol to data processing unit via USB link to
test whether the data acquisition unit (4) is connected with the front-end
protocol or not. This embedded protocol echoes this character back to front-
end program to indicate it is ONLINE.

The ASCII character ‘N’, when received by the driver protocol, checks whether
25 an analysis is already running. If an analysis process is already running, it is be
stopped. The stages of stopping an analysis include re-initializing the operating
variables related to an analysis type, stopping the sampling timer, and the
interrupt driven data acquisition process.

15
 The ASCII character ‘E’: To reset the microprocessor in case of problems in
operation. Numeric data are used to specify the type of operation required. 0:
cyclic voltammetry (CV), 1: large amplitude pulse voltammetry (LAPV), 2:
differential pulse voltammetry (DPV).

5 The present invention includes data acquisition routines in which the required
perturbation voltage samples are programmatically synthesized inside the
microprocessor during the measurement stages, each voltage sample is applied
to the potentiostat unit, and immediately response current sample is read from
the output of current measurement unit inside the potentiostat unit. Providing
10 perturbation signal sample through data acquisition unit (4) and reading
response current sample using analog to digital converter are carried out using
synchronous codes to maintain the real-time reading performance.

While the measurement cycle is being continued, it is also required to transmit

the response samples without hampering much the real time aspect of the
15 measurement process. The data transmission and reception modules are thus
interrupt driven so that it will not interfere with measurement process.

Two 1 KB circular buffers are used; one for storing response samples and the
other for storing perturbation voltage samples in order to eliminate data loss.
An interrupt driven producer consumer architecture is used to synchronize the
20 measurement and data transmission process. It was checked that the system
could transmit data at rates up to 20 KHz without sample loss.

The data processing unit driver protocol also implements the logic for
generating necessary switching signals from the five pins of data processing
unit to connect required current measurement relays and electrode switching
25 relays. The sequence and binary patterns corresponding to relay operations are
developed.

Referring to Figure 8, a flow diagram of the large amplitude pulse

impedimetric electronic device is depicted. The front-end user interface

16
 protocol is for the purpose of interacting with the device (100). The user
provides the selectable parameters of the perturbation waveform and specify
the location of data-log file. The user interface protocol is implemented in the
state-machine architecture. The backend of the protocol runs two independent
5 loops in separate threads; data acquisition loop and display loop. The two
separate loops are synchronized by using a queue maintained in producer
consumer pattern. The data received from the data processing unit is pushed in
a queue by the data acquisition loop (producer). The display loop (consumer)
pops the sample value to be displayed from the same queue and renders on the
10 display. The graphical user interface of the present invention is depicted in
Figure 9.

Referring to Figure 10, a perspective view of the large amplitude pulse

impedimetric electronic device is depicted. The present invention includes an
improved equivalent circuit-based feature extraction module with an addition
15 of a delay term in the transfer function significantly enhances the model fit as
compared to conventional devices and systems. The response waveforms
obtained from the device (100) contains around 11,000 data points that makes
it difficult for conventional and existing feature extraction techniques to reduce
features. The present invention has a very high compression ratio and is
20 independent of the length of the waveform unlike a very conventional feature
extraction technique used in this domain i.e., discrete wavelet transforms
(DWT). The present invention is used to rapidly screen the qualitative
properties, and approximately estimate the composition of electrochemically
active liquid food samples.

25 EXAMPLE 1

Experimentation Analysis

The large amplitude pulse impedimetric electronic device (100) produces

current output depending on the chemical characteristics of the electrolyte
under the test for a given input. The network synthesis approach of feature

17
 extraction used by the present invention tries to transform the chemical basis of
an electrolyte solution into a linear circuit.

Referring to Figure 11(a) and 11(b), block diagrams of the measurement circuit
and measurement circuit with a RC filter are depicted, respectively. The block
5 diagram of the measurement circuit is composed of a block of electrochemical
cell E(s) cascaded with the filter block F(s). Before data logging, the output
current is converted into voltage by using a trans-resistance amplifier present in
the potentiostat unit. A small filter capacitor is also added in parallel with the
gain resistance of the measurement circuit for noise rejection. In the trans-
10 resistance amplifier, the current is passed through a filter F(s), which is a
parallel combination of a resistor (Rm) of 10 kΩ and a capacitor (Cs) of 0.1 μF.
The recorded current is therefore multiplied by 10 kΩ to get the corresponding
measured voltage. However, during the data-logging process, the recorded
voltage points were divided by Rm (10 KΩ) to estimate the response current (Ir).

𝑉𝑜 (𝑠)
15 𝐼𝑟 (𝑠) =
10000
The transfer function of the circuit is determined by the input large amplitude
pulse voltammetry (Vi) and output Current response (Ir) of the system. During
the investigation of the best possible model fit (based upon the normalized root
mean square (NRMSE)) for the waveform obtained from the e-tongue, it was
20 observed that the existence of transport delay (d) in-between input and output
is also present in the physical system.

Therefore, a transport delay block is additionally added to the measurement

circuit as depicted in the block diagram of measurement circuit in Figure 12.

The transfer function with one zero and two poles gives a better fit and the
25 identified second order transfer function is depicted in equation (1) below:

𝐼𝑟 (𝑠) 𝑘(1+𝑍1 𝑠)
= 𝑒 −𝑑𝑠 × ..eq. (1)
𝑉𝑖 (𝑠) (1+𝑃1 𝑠)(1+𝑃2 𝑠)

The filter impedance is given by equation (2) below:

18
 10 × 103
𝐹(𝑠) =
(10 × 103 × 0.1 × 10−6 ) 𝑠 + 1
..eq. (2)

5 The overall identified transfer function of the electronic tongue system is given
by, equations 3 and 4 below:

𝑉𝑜 (𝑠)
= 𝐸(𝑠) 𝐹(𝑠) × 𝑒 −𝑑𝑠 = 𝐺(𝑠) - eq. (3)
𝑉𝑖 (𝑠)

10000
10 ⟹ 𝐺(𝑠) = 𝐸(𝑠) × × 𝑒−𝑑 𝑠
0.001 𝑠 + 1
-eq. (4)
The transport delay (d) of the device (100) is assumed to be constant for any
analyte, therefore, the transport delay term has not affected the parameters of
the synthesized network for the different analytes and it can be neglected for
15 the further network synthesis approach.

After neglecting transport delay, the transfer function of the electrochemical

cell E(s) is depicted in equation 5 below:

𝐼𝑜 (𝑠) 0.001 𝑠+1

⟹ 𝐸(𝑠) = = 𝐺(𝑠) × -eq. (5)
𝑉𝑖 (𝑠) 10000
Since, G(s) is a 2 pole- 1 zero system, therefore, E(s) is of the form, (refer to
20 equation (6)) below:

𝐾(𝑠 + 𝑐)(𝑠 + 𝑑)
𝐸(𝑠) =
(𝑠 + 𝑎)(𝑠 + 𝑏)
𝐼𝑜 (𝑠) 𝐾(𝑠 + 𝑐)(𝑠 + 𝑑)
⟹ =
𝑉𝑖 (𝑠) (𝑠 + 𝑎)(𝑠 + 𝑏)
(𝑠+𝑎)(𝑠+𝑏)
⟹ 𝑍(𝑠) = -eq. (6)
𝐾(𝑠+𝑐)(𝑠+𝑑)

25 Dividing both sides by s, we get (refer to equation (7)) mentioned below:

19
 𝑍(𝑠) (𝑠+𝑎)(𝑠+𝑏)
= -eq. (7)
𝑠 𝐾𝑠(𝑠+𝑐 )(𝑠+𝑑)

Applying partial fraction, (refer to equation (8), (9)) below:

𝑍(𝑠) (𝑠+𝑎)(𝑠+𝑏) 𝑃 𝑄 𝑅
= = + + - - eq. (8)
𝑠 𝐾𝑠(𝑠+𝑐)(𝑠+𝑑) 𝑠 𝑠+𝑐 𝑠+𝑑

5
So,
𝑄𝑠 𝑅𝑠
𝑍(𝑠) = 𝑃 + +
𝑠+𝑐 𝑠+𝑑
Solving,
−𝑄𝑐 −𝑅𝑑
⟹ 𝑍(𝑠) = (𝑃 + 𝑄 + 𝑅) + +
𝑠+𝑐 𝑠+𝑑
10

⟹ 𝑍(𝑠) = 𝑍1 (𝑠) + 𝑍2 (𝑠) + 𝑍3 (𝑠) - eq. (9)

The parameters R1, R2, C2, R3, C3 are the obtained parameters those are
considered as features of the test sample for further physico-chemical analysis.

15 Referring to Figure 13, a schematic view of the equivalent circuit of the large
amplitude pulse impedimetric electronic device is depicted, as a part of large
amplitude pulse impedimetric response analysis stages with tea as a test
sample. For other type of test samples, the equivalent circuit and circuit
parameters are changed. The optimized circuit is obtained from the identified
20 transfer function considering the best fit normalized root mean square error
criteria. For tea samples the obtained transfer function in Eq. (6) produced the
best fit. The same technique as illustrated above is adopted to analyze other test
samples.

EXAMPLE 2
25 Another experimentation analysis

20
 Experiments were performed on different concentrations of Potassium
Ferricyanide sample and the response was recorded and analyzed. The present
invention introduced a new delay term and it has been observed that the
transport delay between input and output accidentally comes equal to the delay
5 due to circuit components (=RC=0.001 s) in the current measurement circuit.
A plot of the normalized root mean square fit percentage of identified model
for different transport delays is shown in Figure 14. Therefore, 1 ms transport
delay is identified as optimum transport delay that shows a better model fit
than the old system identification technique. A comparison of the identified
10 transfer function with the measured response for the tea sample is shown in
Figure 15.

An experiment was performed with different concentrations of Potassium

Ferricyanide and response is recorded. Both, conventional discrete wavelet
transforms feature extraction technique and improved equivalent circuit-based
15 feature extraction technique are used to extract features from raw data. The
extracted features matrix data is used for PCA (principal component analysis),
which is shown in Figure 16 and Figure 17 respectively. SI (separability index)
for both plots are calculated as 537 for conventional discrete wavelet
transforms feature extraction method and 1775 for improved equivalent circuit-
20 based feature extraction method. Therefore, the technique of feature extraction
used in the present invention is better than conventional discrete wavelet
transforms method of feature extraction.

Therefore, the present invention provides a large amplitude pulse impedimetric

electronic device for electrochemical analysis allows to consider the parameters
25 of frequency domain, equivalent circuit, as well as time domain features to
produce an information rich feature set, possesses a much rapid operation as
compared to the existing analytical instrumentation techniques like high
performance liquid chromatography (HPLC), spectrophotometry etc. and
further the device has applications in food sample classification from

21
 agricultural sources and process monitoring purposes and classification or
prediction of quality biomarkers of food sample.

Many modifications and other embodiments of the invention set forth herein
will readily occur to one skilled in the art to which the invention pertain having
5 the benefit of the teachings presented in the foregoing descriptions and the
associated drawings. Therefore, it is to be understood that the invention is not
to be limited to the specific embodiments disclosed and that modifications and
other embodiments are intended to be included within the scope of the
appended claims. Although specific terms are employed herein, they are used
10 in a generic and descriptive sense only and not for purposes of limitation.

The foregoing description of embodiments of the invention has been presented

for purposes of illustration and description. It is not intended to be exhaustive
or to limit the invention to the precise form disclosed, and modifications and
variations are possible in light of the above teachings or may be acquired from
15 practice of the invention. The embodiments were chosen and described in
order to explain the principals of the invention and its practical application to
enable one skilled in the art to utilize the invention in various embodiments
and with various modifications as are suited to the particular use contemplated.

20

22
 CLAIMS

We claim:

1. A large amplitude pulse impedimetric electronic device (100) for

5 electrochemical analysis, comprising of:

a housing (1) with an electrode array (2);

an electronic signal conditioning module (3);

a data processing unit; and

a display platform (7) with inbuilt graphical user interface;

10 wherein,

said electrode array (2) comprise of at least six electrodes for sensing a
plurality of electrochemical response of an active sample;

said electronic signal conditioning module (3) comprise of a potentiostat

unit (8), a data acquisition unit (4), a data processing unit;

15 said potentiostat unit (8) is a multi-potentiostat unit for potentiostatic

and switching control over said electrode array (2) and a response
current produced due to reduction-oxidation (redox) reaction occurring
on the surface of connected working electrode because of the applied
large amplitude pulse voltammetry waveform is collected by a current
20 measurement module that is present in potentiostat unit (8) and
digitized by an analog to digital converter (6);

said data acquisition unit (4) is configured with said potentiostat unit (8)
for receiving and sending said plurality of electrochemical responses
sensed by said electrode array to said data processing unit;

23
 said data processing unit perform a rapid pulse impedimetric analysis
on the plurality of electrochemical response via a plurality of
multivariate statistical method to estimate composition(s) of said
electrochemical response and transforms said composition(s) into a
5 large amplitude pulse voltammetry voltage waveform and said data
processing unit is configured to transform said electrochemical response
via a network synthesis approach of feature extraction and a transfer
delay block into a set of time domain and frequency domain features;
and

10 said display platform (7) presents said large amplitude pulse

voltammetry voltage waveform along with time domain and frequency
domain features in an user understandable format.

2. The large amplitude pulse impedimetric electronic device (100) for

15 electrochemical analysis as claimed in claim 1, wherein said electrode
array comprises of at least 6 electrodes that include but are not limited
to gold, iridium, palladium, platinum, rhodium, and glassy carbon
electrode, a stainless steel counter electrode, and reference electrode.

20 3. The large amplitude pulse impedimetric electronic device (100) for

electrochemical analysis as claimed in claim 1, wherein said housing (1)
has a diameter ranging from 40 to 45 mm.

4. The large amplitude pulse impedimetric electronic device (100) for

25 electrochemical analysis as claimed in claim 1, wherein said data
processing unit is a computing unit and said data acquisition unit (4)
includes but is not limited to processor, microcontroller of any other
form of microchip.

24
 5. The large amplitude pulse impedimetric electronic device (100) for
electrochemical analysis as claimed in claim 1, wherein said electronic
signal conditioning unit (3) includes but not limited to six signal levels,
low current latching relays.
5
6. The large amplitude pulse impedimetric electronic device (100) for
electrochemical analysis as claimed in claim 1, wherein said
potentiostat unit (8) supports current measurement ranges from 10nA-
100nA, 100nA- 1µA, 1µA- 1mA, and 1 mA – 100 mA.
10
7. The large amplitude pulse impedimetric electronic device for
electrochemical analysis as claimed in claim 1, wherein said active
sample includes electrochemically active food samples which show
conductive properties and dissolves in aqueous medium.
15
8. The large amplitude pulse impedimetric electronic device (100) for
electrochemical analysis as claimed in claim 1, wherein said data
acquisition unit (4) is connected with a digital to analog converter (5)
and is configured within the circuit of data acquisition unit (4) that
20 converts the generated digital voltage sample into analog voltage sample
and applies them to an input of potentiostat unit (8).

9. The large amplitude pulse impedimetric electronic device (100) for

electrochemical analysis as claimed in claim 1, wherein said
25 multivariate statistical method has a high compression ratio and is
independent of the length of the waveform and rapid pulse
impedimetric analysis includes a network synthesis approach that is
based on an identified transfer function.

30 10. The large amplitude pulse impedimetric electronic device (100) for
electrochemical analysis as claimed in claim 1, wherein said large

25
 amplitude pulse impedimetric electronic device (100) produces output
within the range of 18 to 20 seconds.

Dated this 29th day of October, 2022

SHRUTI KAUSHIK
10 of PATENTWIRE
Agent for the Applicant
[IN/PA 1324]

26
 ABSTRACT

“A LARGE AMPLITUDE PULSE IMPEDIMETRIC ELECTRONIC

DEVICE FOR ELECTROCHEMICAL ANALYSIS”

5 The present invention relates to a large amplitude pulse impedimetric

electronic device (100) for electrochemical analysis, comprising of, a housing
(1) with an electrode array (2) and an electronic signal conditioning module
(3), a display platform (7) with inbuilt graphical user interface, wherein, said
electrode array (2) comprises of at least six electrodes for sensing a plurality of
10 electrochemical response of an active sample, said data processing unit
perform a rapid pulse impedimetric analysis on the plurality of
electrochemical response via a plurality of multivariate statistical method to
estimate composition(s) of said electrochemical response and transforms said
composition(s) into a large amplitude pulse voltammetry voltage waveform
15 and said data processing unit is configured to, transform said electrochemical
response via a network synthesis approach of feature extraction and a transfer
delay block into a set of time domain and frequency domain features.

20

25

Figure 1 on sheet no. 1 of the drawings may accompany the abstract when published.