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2019 International Conference on Sensing and Instrumentation in IoT Era (ISSI)

Mobile Potentiostat IoT Compatible


João Monge1 , Octavian Postolache 1,2 ,
Alexandru Trandabat3,4 , Stefan Macovei4 and Ramona Burlacu4
1 ISCTE-IUL, Lisbon, Portugal
Email: jpdme@iscte-iul.pt
2 Instituto de Telecomunicações IT-IUL, Lisbon, Portugal

Email: opostolache@lx.it.pt
3 ”Gh. Asachi” Technical University of Iasi, Romania
4 S.C Intelectro Iasi SRL, Iasi, Romania

Abstract—Electrochemical analysis has great importance in and eighty million people are at risk of consuming too much
several areas, such as Healthcare and Agriculture. This paper arsenic from well water, which might have already caused one
presents the development details of mobile potentiostat IoT hundred thousand cancer cases and thousands of death [5].
compatible characterized by AI to be used for accurate charac-
terization of chemical compounds with embedded hardware in a Like arsenic there are other heavy metals such as cadmium,
small portable package. A printed circuit board was designed and lead, mercury and chromium considered highly dangerous
manufactured as a shield for coupling with computation board. for human health [6]. Thus scientific community have been
Several laboratory tests were carried out with the developed contributing with potentistat systems and bio-sensors to per-
system. Thus, 0.1 M solution of TBABF4 (tetrabutylammonium form certain chemical and organic compounds analysis. In
tetrafluoroborate) in acetonitrile containing 0.05 mM Ferrocene
and another solution 0.01 M AA (Ascorbic Acid) in 0.5 M H2SO4 [7], [8] a Low-Cost Inkjet-Printed Paper-Based Potentiostat
were used to test the developed system. was developed for water quality monitoring, although the
A Web GUI interface for the system was developed using results obtained was using 0.1M KCL solution containing
3−
Firebase as a service provider. 5mM [F e(CN )6] 4− and not water samples as a result there is
Index Terms—IoT, Potentiostat, Electrochemistry, Bluetooth no prove that this system would be able to assess water qual-
Low Energy, AI
ity analysis,thereby the low-cost design and implementation
provide a low-cost solution that could be improved in future.
I. I NTRODUCTION
In addition another system to detect water contaminants is
Electrochemical analysis have proven to successful identify presented in [9] as a point-of-use portable potentiostat solution
and analyze certain types of chemical compounds. Further- to detect the presence of arsenic in water. The scientific
more a potentiostat is a device that can perform electrochemi- community had also contributed for creating systems capable
cal analysis using a set of three electrodes: working electrode of analyzing sweat using bio-sensors and a potentiostat as pre-
(WE), reference electrode (RE) and counter electrode (CE). Its sented in [10]–[12]. The developed system aims to be capable
working principle is to make potential changes between the of analyzing sweat in a a wearable solution but also to detect
WE and RE allowing the chemical species to be measured, presence of substances like drugs in human organism through
reduced or oxidized on the surface of the working electrode sweat analysis. Another aim of the presented system is to use
and generate current between the WE and the CE [1].The AI to automatic find the best potentiostat parameter setup,
current is measured usually with a transimpedance ampli- potential range and scan rate. Using AI with the data provided
fier that perform current to voltage conversion.The obtained by a potentiostat as reported in [13] could identify tea samples
voltage is applied to the ADC input. Potentiostats have been using Support Vector Machine Algorithms. In the proposed
applied in several different areas. Water quality monitoring, system a cloud IoT architecture is used providing increased
food quality monitoring and healthcare. The challenge is to computing capabilities, taking into account the computation
develop a mobile potentiostat IoT compatible to be used on resources needed for AI algorithms implementation. Cloud
water quality field measurement or for biosensors. architecture are scalable and imply less cost for the user side
The quality of water have a big impact on the human being versus the cost of the hardware needed to run such algorithms.
life. The presence of heavy metals in water can negatively This paper is organized as follows. Section II describes the
influence the health of the human being consequently asso- architecture of the presented system referencing the hardware
ciated with a wide range of serious pathologies [2]. On the and software components. Section III introduces the design
other hand, soil pollution through heavy metals causes negative and development of the system. Finally Section IV presents
effects as C. Micó et al reported in [3] consequently induced the results and its discussion.
toxic agricultural cultivation’s.
Arsenic is a type of Heavy Metal (HV) that is found in II. S YSTEM D ESCRIPTION
water in India and Bangladesh above the 10 µg/L current The purposed system included a computation platform con-
limit of arsenic in drinking-water recommended by the World nected to a LMP91000 potentiostat and Bluetooth wireless
Health Organization (WHO) [4].Furthermore between forty communication interface. The IoT compatibility is also assured

978-1-7281-1022-6/19/$31.00
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2019 International Conference on Sensing and Instrumentation in IoT Era (ISSI)

through the additional advanced processing and communica- 2) LMP91000 AFE Potentiostat: The LMP91000 is a pro-
tion unit expressed by a smartphone, laptop or tablet. grammable potentiostat for chemical sensing applications. The
LMP91000 is designed for 3-lead single sensors and for 2-
lead galvanic cell sensors. This device provides all of the
functionality for detecting changes in gas concentration based
on a delta current at the working electrode. The LMP91000
generates an output voltage proportional to the cell current.
Transimpedance gain is user programmable through an I2C
compatible interface from 2.75 kΩ to 350 kΩ making it easy
to convert current ranges from 5 µA to 750 µA full scale.
Optimized for micro-power applications, the LMP91000 AFE
works over a voltage range of 2.7 V to 5.25 V. The cell voltage
is user selectable using the on board programmability. In
addition, it is possible to connect an external transimpedance
gain resistor. Depending on the configuration, total current
consumption for the device can be less than 10 µA. For
power savings, the transimpedance amplifier can be turned off
and instead a load impedance equivalent to the TIA’s inputs
impedance is switched in [14].

Fig. 1. System Layer Diagram

The architecture of the potentiostat presented in this paper


is described in Figure 1. A Web App was developed for
the acquisition control and GUI assuring maximum compat-
ibility with different types of devices (Laptops, Tablets and
Smartphones). The proposed design allows the user to control
the potentiostat using his own device without having to buy
additional hardware minimizing the costs of the final system. Fig. 2. LMP91000 Block Diagram.
The communication protocol used to establish connection from
potentiostat to application is Bluetooth Low Energy also know Presented in Fig. 2 includes a differential input amplifier
as Bluetooth 4.0. The Web Application is hosted on Firebase that is used to compare the potential between the working and
hosting service as well as the database for this system. The reference electrodes to a required working bias potential (set
database is a relational database that enables remote access at by the Variable Bias circuitry). The error signal is amplified
real-time. and applied to the counter electrode (through the Control
Amplifier - A1). Any changes in the impedance between
A. Hardware the working and reference electrodes will cause a change
in the voltage applied to the counter electrode, in order to
The hardware components of the proposed system are an
maintain the constant voltage between working and reference
MCU, Potentiostat IC, power regulation and battery man-
electrodes. A Transimpedance Amplifier connected to the
agement. The microcontroller has embedded Bluetooth low
working electrode, is used to provide an output voltage that
energy tranceiver, that is used to communicate with the com-
is proportional to the cell current. The working electrode is
putation unit. An a LMP91000 chip from Texas Instruments
held at virtual ground (Internal ground) by the transimpedance
is used as the potentiostat unit.
amplifier. The potentiostat will compare the reference voltage
1) RFduino microcontroller: An arduino with wireless ca- to the desired bias potential and adjust the voltage at the
pabilities and with the size of a fingerprint. This microcon- counter electrode to maintain the proper working-to-reference
troller has bluetooth embedded and a cortex M0 processor. voltage [14].
I2C and SPI protocols are also present in this microcontroller
enabling it to configure Texas Instruments LMP91000 IC used B. System Software
as a potentiostat [14] and the embedded ADC allows the mcu The developed Acquisition and GUI Software is based on
to read the output of LMP91000 sensor. Cloud Application Architecture. The Cloud service provider

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2019 International Conference on Sensing and Instrumentation in IoT Era (ISSI)

is Firebase by Google, inc. and assures hosting and real-time is also reusable since a a new disposable electrode can be
interrogation database. As a result of using both services from plug-in in the socket. For the final prototype a complete PCB
same provider comes a easy integration between application was designed and manufactured ensuring maximum quality of
and database. The selected database for this system allows the the end system. The board can be adapted to other type of
user to receive data updates in real-time [15]. micro-controller although the design was for an RFDuino.
1) Web Application: The web application is the com-
bination of GUI and Acquisition software that allows the
user to control the system and analyze the data through an
interface easily. This application as responsive Web App is III. D ESIGN AND D EVELOPMENT
compatible with various types of devices (Laptop, Tablets and
smartphones). As the bluetooth protocol is used to transmit
data from the potentiostat to the application is necessary The work done for developing the presented potentiostat had
to implement the bluetooth protocol application side too. several phases. The first phase was tests with the LMP91000
Therefore Chrome Web Bluetooth API is a recent feature that evaluation board available by Texas Instruments 4.
allows connecting via bluetooth directly to the browser without
requiring native application. Thus, the system developed is
compatible with Android, Chrome OS, Windows 10 (Chrome
70) and Mac (Chrome 56) which are the current versions that
support this API [16].
2) Real-time Database: A relational database was used in
this system is scalable and flexible and allows real-time data
transmission [17].

Fig. 4. Adapted LMP91000EVM evaluation board.

Fig. 3. Firebase Web Application.


Figure 4 presents the developed board coupled with and
Figure 3 describes the system work diagram. The system battery shield and RFDuino. This was used to evaluate the
is composed by a shield for RFDuino that communicates performance and limitations for this type of application of
via Bluetooth to a device that contains a compatible Chrome LMP91000 AFE Potentiostat. The results were successful
Browser and Bluetooth. The Software allows easy configu- with the modified LMP91000EVM board in order to work
ration of the potentiostat and also real time graph while in with RFDuino and other microcontrollers. After successful
background this application is sending the data to a cloud testing the LMP91000 integration with RFDuino a PCB was
database as part of IoT architecture. The presented model designed to produce a mobile and wearable system. The final
shows the simplicity of the potentiostat enabling it to work system was designed in Altium Sofware and then a PCB
with any device. Software updates are also assured as the was manufactured resulting in a final prototype. This PCB
application is on server side there is no need to realize update integrates voltage regulators, battery charger circuit and micro
on user side. The small size makes it easier to transport and usb charging port completing the system in order that it can
final prototype is small enough move anywhere. This system act as standalone device

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2019 International Conference on Sensing and Instrumentation in IoT Era (ISSI)

be able to perform an analysis using the presented system


without the necessary knowledge.

Fig. 5. Stackable parts of the system.

To ensure easy integration and use taken in consideration


RFDigital stackable RFDuino design and the developed po-
tentiostat was created as a shield that could be stacked with
other components such as FTDI programer board (left board)
or battery AA board second in right (Fig. 5). It is also to couple
more sensors, for example humidity and temperature, creating Fig. 7. Potentiostat web GUI.
a more complete solution by simply placing a sensor with a
compatible shield on top of each other, thus interconnecting
all the shields between them and creating a bridge to the
microcontroller RFDuino. After successfully apply the configuration another page will
show up see figure 8 were the resulting graph will show mean-
while in background data is being transmitted to the database
in real-time. The user is able to return to configuration menu
at any time to a perform a new or adjust the current analysis.

Fig. 6. Final prototype coupled with battery and RFDuino.

In figure 6 is presented the potentiostat shield coupled with


RFduino powered using a lithium battery. The board also has
microusb that is used to charge the battery. This system is
very low consumption and a small lithium battery can provide
sufficient autonomy for several analysis. Fig. 8. Application GUI Graph representation.
In order to use this potentiostat a Chrome Browser com-
patible with the Bluetooth Web API should be used. As
this app is hosted on Firebase is possible to access it with
internet(Wifi, 3G or 4G depending on the device used), the To achieve accurate and fast measurements the embedded
user should then connect the potentiostat and a configuration AI will be considered. The main characteristics of presented
menu will appear as showed in Figure 7. In this menu is system are described in table I. As is possible to observe the
possible to configure several parameters of the potentiostat maximum voltage reference is 3.3V because a ic for reference
making it able to be used in different types of applications for was integrated on the pcb of the final prototype, although
example cyclic voltammetry, linear voltammetry and square the real reference voltage maximum rating for the LMP91000
wave voltammetry. The parameters that can be configured are would be 5.25V. The reference voltage allows to to increase
TIA gain, RLoad, Reference source, Internal Zero, FET short, BIAS Potential range that for this system is -0.8V to 0.8V.
Operation Mode, Begin potential, lower and higher potential. It also possible to perform several different techniques of
This options allow different experiments with low effort from voltammetry with the presented system in table I there are
the end user. In Future development we aim to make the some techniques that were already tested. Finally the presented
parameter selection automatic this means that any user should system allows Galvanic or amperometric operation modes.

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2019 International Conference on Sensing and Instrumentation in IoT Era (ISSI)

TABLE I LMP91000 outputs a analog signal that correspond to TIA


M AIN CHARACTERISTICS TABLE converted current obtained at Working Electrode which the
Voltage Reference Min Max RFDuino ADC reads and then using equation (1) is possible to
2.5V 3.3V convert this ADC analog value to µA. The results obtained are
Bias potential range Min Max presented in the next graph. In the equation Vout corresponds
-0.8V 0.8V
-24%*VRef 24%*Vref to sensor output, Vref correspond to 2.5V, Internal Zero is
Linear Sweep Voltammetry 20% and finally RTia is 35KΩ
Type of techniques supported Cyclic Voltammetry
Square Wave Voltammetry
Amperometric (V out − V ref ∗ InternalZero)
Operation Modes
Galvanic
Iout = (1)
RT ia

With the equation applied to the voltage output the value is


IV. R ESULTS AND DISCUSSION
converted to µA and transmitted to the web application that
The results were obtained using the developed system and display the evolution of current. The graph presented in figure
a commercial potentiostat. Similar configuration was used and 10 presents the results for the same substance and in similar
the results compared and the experienments were conducted conditions.
with a three electrode with WE - disc of platinum CE -
platinum wire and RE - Ag/AgCl as represented in figure 9.
The solution used was 0.1M TBABF4 (tetrabuthyl ammonium
tetrafluorborate) in acetonitrile containing 0.05 mM Ferrocene.

Fig. 10. Comparative results obtained with commercial and designed poten-
tiostat

Based on cyclic voltammetry the main values associated


with the experiments are presented in Table II. The redox and
oxidation peak and the difference between them is as the table
II shows the difference value is the same although the graphs
are slightly different the developed system proved to perform
a similar result at a fraction of the price. One important
metric is to achieve a similar difference between peaks that
as demonstrated in table as a minor difference between two
devices.

TABLE II
Fig. 9. Electrodes WE, CE and RE. OXIDATION AND R EDOX P EAKS TABLE

Oxidation Peak Redox Peak Difference


The technique used was cyclic voltammetry. To perform this Developed system 46,095 -32,814 78,909
technique the registers were written using the RFDuino via I2C Solartron 1285 49,542 -28,559 78,101
and the web application inputs. The Reference Control Regis-
ter(REFCN), allocates the input waveform biasing and level,
the internal zero and voltage source selection. A biasing point Using Cyclic Voltammetry further tests were realized. Some
of 20% was selected. The trans-impedance amplifier resistance of experimental results were carried out to compare the cyclic
Rtia was setted at (35KΩ) and a load impedance resistance at voltammetries for different values of pH associated with
10Ω in TIACN control register. Then the potentiostats stepped experimental solutions (0.01 M AA in 0.5 M H2SO4 which
from 0V to 0.6V and then back to 0V creating a cycle. The is used to change the pH of the AA).

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2019 International Conference on Sensing and Instrumentation in IoT Era (ISSI)

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ACKNOWLEDGMENT
To all team colleagues who helped making this project
possible. A special thank to Instituto de Telecomunicações
Organic laboratory and Senior Researcher Ana Charas for
the help and knowledge sharing during the test phase of the
purposed system. This work was supported by a grant of
the Romanian National Authority for Scientific Research and
Innovation, NANO-IMUNELCHIM-PLAT Project/ Competi-
tiveness Operational Programme 2014-2020, under grant P 37
766, cod my smis103847, nr. 68/08.09.2016.

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