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Sensors & Actuators: B.

Chemical 305 (2020) 127433

Contents lists available at ScienceDirect

Sensors and Actuators B: Chemical


journal homepage: www.elsevier.com/locate/snb

Glass varnish-based carbon conductive ink: A new way to produce T


disposable electrochemical sensors
Lauro A. Pradela-Filhoa,b, Isabela A.A. Andreottic, Jefferson H.S. Carvalhoc, Diele A.G. Araújoa,b,
Luiz O. Orzaric, Alexandre Gattic, Regina M. Takeuchia,b, André L. Santosa,b, Bruno C. Janegitzc,*
a
Institute of Chemistry, Federal University of Uberlandia, 38400-902, Uberlandia, Minas Gerais, Brazil
b
Institute of Exact and Natural Sciences of Pontal, Federal University of Uberlandia, 38304-402, Ituiutaba, Minas Gerais, Brazil
c
Department of Nature Sciences, Mathematics and Education, Federal University of São Carlos, 13600-970, Araras, São Paulo, Brazil

ARTICLE INFO ABSTRACT

Keywords: Nowadays, there is growing interest in portable and disposable electrochemical sensors due to the low-cost,
Alkyd resin simplicity, and excellent analytical performance associated with these devices. Despite recent advances, how-
Paper-based electrode ever, there remains a need to create cheap, high-performance electrode materials. Thus, this study evaluated the
Screen-printed electrode suitability of carbon conductive inks prepared by the mixture of glass varnish and graphite powder to produce
Carbon conductive ink
disposable electrochemical sensors. Two different ink manufacturing processes and compositions were studied to
Estriol
produce different disposable electrodes, each providing high electrical conductivity and adhesion on paper and
polyethylene terephthalate (PET) substrates. Electrochemical impedance spectroscopy, scanning electron mi-
croscopy, and Fourier-transform infrared spectroscopy were used for the characterization of inks. The electrodes
were applied for the electrochemical determination of some compounds. For the paper electrode, the electro-
chemical detection of dopamine was performed, ranging from 15 μmol to 100 μmol L−1, with a detection limit of
4.1 μmol L−1; the individual electrochemical detection of catechol was performed ranging from 10 μmol L−1 to
1000 μmol L−1, with a detection limit of 9.0 μmol L−1. The detection of hydroquinone was performed, ranging
from 10 μmol L−1 to 1000 μmol L−1, with a detection limit of 5.3 μmol L−1. Also, the screen-printed electrode
was applied for estriol electrochemical determination in the linear range from 0.1 μmol L−1 to 8.0 μmol L−1 with
a detection limit of 0.08 μmol L−1. The glass varnish is an alternative to creating carbon composite electrodes,
and the new devices are inexpensive and simple to prepare, with attractive analytical performance.

1. Introduction electrodes for solar cells [8]. Since then, this technique has been widely
employed in electroanalysis, allowing the development of new high-
The development of compact and disposable electrochemical sen- performance sensing platforms. Screen-printing is an extremely versatile
sors has received growing attention in recent decades. The attractive and efficient technique to produce electrodes with several geometries
features of these devices include their low-cost, combined with the and different materials in a fast and inexpensive way [2].
minimal chemical consumption and waste generation [1]. Moreover, The screen-printing technique can be used to produce disposable elec-
disposable electrochemical sensors minimize the problems associated trodes, which can be inexpensive, easy to produce, compatible with min-
with electrode surface fouling since they can be designed for single-use iaturized systems [9], and extremely versatile, as several chemical modifiers
[2]. Thus, the development of new disposable electrochemical sensors can be immobilized on the substrate. In the literature, it is possible to find
is of interest, as they can provide reliable, inexpensive, and fast ana- several recent works that use screen-printing techniques to make new de-
lytical responses for crucial measurements in different fields such as vices, such as the gold nanoparticle-modified disposable biosensors devel-
biomedical, environmental, and industrial sensing. oped by Zouari et al. [10], the gold screen-printed biomarker stacked with
Screen-printed electrodes (SPE) were the first devices designed as carbon nanotubes by Premaratne et al. [11], and the electrochemical device
disposable sensors and have been successfully used for analytical mea- developed by Lamas-Ardisana et al. [12] for detecting multiple redox pairs.
surements since the late 1980s [3–6]. The screen-printing technique was Due to their adhesion characteristics on various substrates, paper,
introduced in the early 20th century to produce electronic circuits [7] and and polyethylene terephthalate (PET)-based electrodes have had a


Corresponding author.
E-mail address: brunocj@ufscar.br (B.C. Janegitz).

https://doi.org/10.1016/j.snb.2019.127433
Received 11 June 2019; Received in revised form 14 November 2019; Accepted 15 November 2019
Available online 17 November 2019
0925-4005/ © 2019 Elsevier B.V. All rights reserved.
L.A. Pradela-Filho, et al. Sensors & Actuators: B. Chemical 305 (2020) 127433

significant impact on the field. The pioneering paper-based electro- Suzano Report® Premium (Pernambuco, Brazil) were used to prepare
analytical device was described by Dungchai et al. [13] in 2009; since the paper electrodes. The screen-printed electrodes were made by using
then, paper electrodes have continuously evolved, with new fabrication PET sheets reused from beverage bottles. Estriol pharmaceutical sam-
methods introduced [14–17]. In this context, paper electrodes have ples used for the analytical performance tests were the Ovestrion® pill
been successfully used in the electrochemical determination of ascorbic (Laboratories Eurofarma, Itapevi, Brazil) and the Stele® vaginal cream
acid [18,19], catechol [20], dopamine [21], nerve agents [22], and (Biolab Sanus pharmaceutical, Taboão da Serra, Brazil).
metal ions [23]. On the other hand, the use of PET stands out due to its
excellent properties, such as chemical and biological inertness, flex- 2.2. Apparatus
ibility, dimensional stability, low toxicity, and safe handling [24,25].
Due to the large consumption of this material over the years producing The electrochemical studies were performed with a potentiostat/
an increase in the amount of waste, which accumulates in landfills and galvanostat μAUTOLAB type III or AUTOLAB PGSTAT204, both from
oceans as the final destination, this great product has turned into a Metrohm Autolab (Utrecht, Netherlands). Both instruments were in-
great problem given its high degradation resistance. The literature terfaced to a personal computer and managed by NOVA 2.1 software. A
contains some examples of sensors [26–29] and biosensors [30,31] three-electrode system was used to perform the electrochemical mea-
made from PET, which are significant initiatives for the recycling and surements using paper electrodes as the working electrode, a platinum
reuse of this material. wire as the auxiliary electrode, and an Ag/AgCl/KClsat as the reference
Regardless of the substrate, the production of efficient disposable electrode. The working, auxiliary, and pseudo-reference electrodes of
electrochemical sensors is highly dependent on the formulation of con- the screen-printed PET electrode were made of graphite.
ductive ink, which is also a real challenge to the large scale production of Scanning electron microscopy (SEM) analyses were performed with a
analytical devices and flexible electronics [32]. Besides a hydrophobic Vega 3 LMU (TESCAN, Brno-Kohoutovice, Czech Republic) system oper-
binder agent that is able to properly aggregate the conductive particles, ating at 30 kV; the electrodes were covered by carbon tape. Fourier trans-
conductive inks must present high chemical stability and excellent adhe- form infrared spectroscopy (FTIR) measurements were carried out with a
sion to a variety of substrate materials. Commercial conductive inks fulfill Tensor II spectrophotometer (Bruker, Germany) with a resolution of
most of these requirements [13,17]. However, their high cost is a limita- 4.0 cm−1 in the absorbance mode. FTIR spectra were acquired in the range
tion regarding the preparation of disposable electrochemical sensors. This from 400 to 4000 cm−1, and samples were prepared in KBr at a ratio of
limitation has encouraged researchers to produce conductive inks with 1:100. X-ray diffraction (XRD) measurements were performed by a Miniflex
different conductive materials, such as Cu [33] and Ag [16] nanoparticles II X-ray diffractometer (Rigaku), with a radiation source of CuKa, ranging
and Pt-decorated graphite [34]. The variety of conductive materials fa- from 4° to 90°, with a step of 0.02° and 10° per minute of analysis time.
cilitates the creation of new inks, especially carbon-based inks. In this The carbon conductive ink used to prepare the screen-printed
context, Metters and Banks et al. stand out as modern pioneers of this electrodes was blended with a double asymmetric centrifuge
technique, for their work with disposable carbon electrodes, using dif- SpeedMixer™ Dac 150.1 FVZ-K (FlackTec Inc., Landrum, USA) with 2
ferent allotropes, such as graphite [35–37], graphene [38,39] and carbon repeating cycles at 3500 rpm for 180 s. The electrodes were constructed
nanotubes [40]. Alternative binder agents, such as polystyrene [33], cel- with the same design as that described by Orzari et al. [20], and the
lulose acetate [41], and nail polish [21], have also been used. masks were prepared by using a cutting printer (Silhouette model
The glass varnish is an alkyd resin intended for decorative purposes, Cameo 3, Belo Horizonte, Minas Gerais) managed by Silhouette Studio®
which is suitable for glass, ceramics, and porcelain due to its transparent software. The electrical contact with the potentiostat was achieved
and shiny finish. The alkyd resin is widely used as a binder agent for the using a lab-made connector, as also proposed by Orzari et al. [20].
manufacture of different kinds of inks since it presents excellent chemical
and mechanical properties such as film hardness, durability, abrasion 2.3. Preparation of the paper electrodes
resistance, self-oxidative cure, and compatibility with various polymers
[42,43]. It is mainly composed of glycerol, pentaerythritol, phthalic acid, The paper electrodes were produced according to the procedure
glycerides and fatty acids, all of which are compounds that give it described by Pradela-Filho et al. [21]. The carbon conductive ink was
characteristics such as flexibility, fast-drying, and exceptional adhesion prepared by hand-mixing the graphite and glass varnish in the ratio of
[44]. Therefore, due to these properties, this resin has great potential to 1:1 (m:m). For each batch of electrodes, 150 mg of the conductive ink
be used in the preparation of cheap and efficient conductive inks. was prepared, and 500 μL of acetone was added to provide suitable
In this context, the objective of this study was to evaluate the suit- viscosity. The freshly prepared carbon conductive ink was spread onto a
ability of a conductive carbon ink prepared with graphite powder and piece (5.0 × 1.0 cm) of sulfite or quantitative filter paper using a paint-
glass varnish to develop disposable electrochemical sensors. Aiming to brush. The piece of paper containing the carbon conductive ink was
evaluate the versatility of this conductive ink, two kinds of disposable dried for 12 h at room temperature and cut into pieces of 0.5 × 1.0 cm.
sensors, a single-electrode PE and a three-electrode SPE were studied; the The area of the proposed electrode was delimited to a diameter of 3 mm
electroanalytical performance of these devices was evaluated using with a circular adhesive. An insulating layer had to be assembled on the
phenolic compounds and the hormone estriol as model analytes. back of the electrodes to minimize water absorption via capillary action,
as described by Metters et al. [45]. The assembly process and a re-
2. Experimental presentative image of the paper electrode are shown in Fig. 1A–B.
The average cost of each conductive ink component and the paper
2.1. Reagents substrate was computed, and the cost to prepare 150 mg of the con-
ductive ink was estimated. Considering a loss of 20 %, this amount of
The chemicals used to prepare the solutions were of analytical grade conductive ink provided 8 electrodes, leading to a value of approxi-
and were used as received. All of the solutions were prepared with mately U$ 0.05 per electrode. However, in this configuration, only the
ultrapure water (resistivity ≥18 MΩ cm). Graphite from Fisher working electrode was constructed. On the other hand, the costs of the
Chemical™ (New Jersey, USA) or Sigma-Aldrich® (São Paulo, Brazil) auxiliary and reference electrodes were not computed.
with a particle diameter < 20 μm and glass varnish (ACRILEX®, São
Paulo, Brazil) were used to prepare carbon conductive inks. 2.4. Preparation of screen-printed electrodes
Quantitative filter paper (model C42, 9.0 cm diameter and particles
retention of 1−2 μm) from Unifil® (Alvorada, Rio Grande do Sul, A double asymmetric centrifuge was employed to produce screen-
Brazil) and sulfite A4 size commercial paper (density = 75 gm−2) from printed electrode conductive ink, so that an improved and complete

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L.A. Pradela-Filho, et al. Sensors & Actuators: B. Chemical 305 (2020) 127433

Fig. 1. A) Schematic representation of the assembling process. B) Image of the paper electrode.

homogenization could be achieved. As a result, this ink composition the conductive ink that was effectively impregnated was determined by
consisted of 2:1 (m:m) of graphite and glass varnish. However, as the calculating the difference. Following this procedure, it was observed that
process required a certain viscosity, 20 % (m:m) of a proper glass var- the amount of the ink effectively impregnated on the paper substrate was
nish solvent was added. Then, beverage bottles were cut to improve 7.5 ± 0.7 mg cm−2 (N = 4) when 100 mg of the conductive ink was
their handling and pre-treated with a 70 % ethanol solution to clean spread. The electrodes prepared according to this procedure gave low
their surface and enhance wettability [46]. After that, PET pieces were background currents and showed well-defined voltammetric peaks for
sanded with conventional sandpaper (nº 220 from 3 M) to produce the electrochemical probe [Fe(CN)6]4− with peak potential separation
more adherent substrates. To spread the ink, an adhesive label mask (ΔEp) of approximately 150 mV, which is significantly lower than the
(27.94 × 21.59 cm) containing the cutout of the three-electrode system observed for other paper-based electrodes proposed in the literature
was glued to the PET surface. The ink was deposited on the adhesive [14,40–42]. Fig. S1 (presented as Supplementary Information) shows the
masks and spread in one direction only. Immediately after the ink ap- cyclic voltammograms recorded in the presence and absence of 1.0 mmol
plication, the masks were removed, and the device was left to dry for L−1 [Fe(CN)6]4− at a scan rate of 100 mV s−1.
24 h at room temperature. After that, the screen-printed electrodes The composition of conductive ink strongly affects the electro-
were finished, and the electrochemical studies were performed chemical performance of the electrodes, and the effect of this parameter
(Fig. 2A). The developed device was ∼2.0 cm long (Fig. 2B1), which is on both the voltammetry of [Fe(CN)6]4− and stability was evaluated.
an adequate size that allows the analysis of micro-volumes with low Stability was assessed through 100 potential cycles in the presence of
chemical consumption and waste generation, presenting a geometric 1.0 mmol L−1 [Fe(CN)6]4− (in 1.0 mol L−1 KCl) using paper electrodes
radius of ∼2.4 mm and an area of ∼18 mm in the working electrode. prepared with inks at different compositions. The 100th cyclic vol-
After raising the average values of each conductive ink component, the tammograms for the different carbon ink compositions are shown in
relative costs of each component for the production of 5 g of ink were Fig. 3A. The influence of the number of cycles over the cathodic vol-
calculated. With the amount produced, it was possible to make a total of tammetric charge is shown in Fig. 3B.
50 electrodes with a loss percentage of 20 %, and an estimated total As shown in Fig. 3A, the paper electrode prepared with 60 % of glass
value of ∼U$ 0.59, with each unit having an aggregate value of ∼U$ varnish provided a poor voltammetric profile with low peak currents
0.01. Several folds and hand manipulation of the dried ink/device were and ΔEp =340 mV. This behavior is indicative of an electrode with high
performed to evaluate its mechanical resistance (Fig. 2B2). No de- electrical resistance, which is expected for this electrode, regarding the
formation or conductivity loss was observed during these handling high amount of binder agent (an electrical isolating) used to prepare it.
tests, indicating that the conductive ink produced was able to provide The electrodes containing 20 and 40 % of glass varnish showed higher
both electrical conductivity and some flexibility to the final screen- peak currents, but exhibited some variation in their voltammetric
printed electrode device. charge which was higher than 10 % after 100 successive potential cy-
cles, indicating that these electrodes were less stable than the other
2.5. Estriol sample analyses compositions. This behavior can be ascribed to a swelling effect, which
increases the electrochemical area and, therefore, the voltammetric
Three distinct samples were analyzed: water collected in the city of charge. The swelling effect is favored when the paper substrate is not
Araras − Brazil (22º18'22.6" S 47º22'52.1" W) and two commercial efficiently covered by the conductive ink, which allows penetration of
pharmaceutical samples, the first being a vaginal cream and the second, a the supporting electrolyte into the paper by capillarity action [45]. The
pill. The water sample was fortified with known concentrations of estriol results from Fig. 3B show that the conductive inks prepared with 20 and
before analysis by square wave voltammetry (SWV). The pharmaceutical 40 % of glass varnish have a low covering ability and were not ap-
samples had different treatments. The vaginal cream contained 1 mg g−1 propriate for the construction of disposable electrochemical sensors.
estriol in its formulation; therefore, to obtain a stock solution of 1.0 mmol The best combination of voltammetric profile for [Fe(CN)6]4−/3− redox
L−1 estriol, 0.29 g of cream was dispersed in deionized water, given that couple and electrode stability was obtained with the paper electrode
this cream mass contains ∼2.9 × 10−4 g of estriol (MM =288.38 g prepared with 50 % glass varnish and 50 % graphite (m:m). Therefore,
mol−1). For preparation of the tablet, units were macerated and dispersed this composition was adopted in all subsequent experiments.
in ethanol to obtain a stock solution of 1.0 mmol L−1 estriol. From these The effect of the paper substrate used to produce paper electrodes
stocks, solutions of known concentrations were prepared for analysis. was studied using quantitative filter paper and office sulfite paper (Fig.
S2). The office paper electrode was observed to have a poor voltam-
3. Results and discussion metric profile (ΔEp =340 mV) compared with the quantitative filter
paper (ΔEp = 105 mV), which is in good agreement with the previous
3.1. Paper electrodes report by Adkins et al. [1]. Based on this result, the quantitative filter
paper was selected as the best substrate.
3.1.1. Optimization of paper electrode preparation The next step in this study was to evaluate the effect of the amount
The paper electrodes were initially prepared by spreading 100 mg of of carbon ink spread on the quantitative filter paper piece
the conductive ink on the filter paper pieces (5.0 × 1.0 cm). These paper (5.0 × 1.0 cm). In this study, electrodes were prepared with 100 and
pieces were weighed before and after the ink application, and the mass of 150 mg of carbon ink total mass. These results are presented in Figs. S3

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L.A. Pradela-Filho, et al. Sensors & Actuators: B. Chemical 305 (2020) 127433

Fig. 2. (A) Schematic representation of the conductive ink and screen-printed electrode preparation. (1) Mixing of glass varnish, solvent, and graphite. (2)
Preparation of PET substrate and ink application. (3) Finished disposable electrochemical sensor ready for the (4) electrochemical measurements. (B) Representation
of the dimensions of the proposed electrode. (1) Electrode length and geometric area of the working electrode. (2) Image of the screen-printed electrode and folded
device demonstrating the electrode flexibility.

Fig. 3. A) 100th cyclic voltammograms of paper electrodes


prepared with different contents of glass varnish. (―) 20 %; (
) 40 %; ( ) 50 %; and ( ) 60 % of glass varnish. Cyclic vol-
tammograms recorded in 1.0 mol L−1 KCl + 1.0 mmol L−1 [Fe
(CN)6]4−. ʋ =100 mV s−1. B) Normalized cathodic voltam-
metric charge as a function of the number of voltammetric
cycles. The voltammetric charge was normalized against the
voltammetric charge observed for the first voltammetric cycle
(taken as 100%).

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L.A. Pradela-Filho, et al. Sensors & Actuators: B. Chemical 305 (2020) 127433

and S4. Fig. S3 shows that paper electrodes produced with 150 mg of Fig. S7 shows the electrochemical impedance spectroscopy (EIS)
carbon ink had better reproducibility, with relative standard deviation response for paper electrode and GCE in the presence of the [Fe
(RSD) for the cathodic peak current (Ipc) for [Fe(CN)6]4−/3− redox (CN)6]3−/4− redox couple. As can be observed, the GCE had the lowest
couple of 6.5% (N = 4). RSD for paper electrodes prepared with 100 mg charge transfer resistance of ∼1.1 kΩ, and the paper electrode pre-
of carbon conductive ink was 21% (N = 4), indicating that this ex- sented a charge transfer resistance of ∼4 kΩ. The better performance of
perimental condition is unsuitable. By weighing the paper before and GCE was expected regarding its higher electrical conductivity compared
after the carbon ink application, we found that electrodes prepared with to the carbon ink. Although the performance of paper electrodes was
150 mg of carbon ink had 10 ± 1.0 mg cm−2 (N = 4) of carbon con- inferior to GCE, they can be inexpensively prepared as disposable
ductive ink effectively impregnated onto the paper piece. This value is electrodes, which remarkably decreases the cost per experiment.
higher than that observed when 100 mg of the ink was used, which was The proposed paper electrodes were also compared with GCE, and
7.5 mg cm−2. Therefore, the amount of the conductive ink effectively the voltammetric profiles are observed in Fig. 5A. For the [Fe(CN)6]3−/
4−
impregnated onto paper substrate depends on the total amount of ink redox couple, GCE presented ΔEp of 89 mV, and the paper electrode
that was initially spread on the paper substrate. exhibited ΔEp of 149 mV. The value of the paper electrode is acceptable
Considering that 150 mg of conductive ink was spread on 5.0 cm2 as ΔEp values higher than 200 mV are frequently observed in the lit-
paper pieces, the total mass of the conductive ink impregnated was erature [17,49–51]. Therefore, the mixture of glass varnish and gra-
50 mg. This result shows that about 33% of the total amount of carbon phite has excellent potential to produce disposable electrochemical
ink spread on the paper piece was forcefully impregnated, while the sensors with high performance and low cost. To confirm the stability of
remaining ink was lost to the paintbrush. Fig. 3A shows that even after the electrodes for analytical applications in neutral media, a whole
100 successive voltammetric cycles, the paper electrodes still show the analytical curve for [Fe(CN)6]4− was constructed using the same paper
voltammetric peaks for the electrochemical probe [Fe(CN)6]4−/3−. This electrode (Fig. 5B−C). The plots of Ipa and Ipc vs. the concentration of
result indicates that even though the paper electrodes were designed for [Fe(CN)6]4− were linear from 0.1 mmol L−1 to 1.0 mmol L−1, ac-
single-use, they can also be used for multiple experiments if necessary. cording to the equations: Ipa (μA) = 7.57 C [Fe(CN)6]4− (mmol L−1),
Based on these results, 150 mg of the conductive ink was adopted to R2 = 0.9998 and Ipc(μA) = −7.34 C [Fe(CN)6]4− (mmol L−1), and
prepare paper electrodes for further analyses. The reproducibility of the R2 = 0.9996. This study indicates that the paper electrodes are stable
fabrication method was evaluated with five electrodes made in different over the time scale of this experiment, since Ipa and Ipc showed an ex-
batches (Fig. S5). An RSD of 9% (N = 5) for Ipc values for the [Fe cellent linear correlation with the [Fe(CN)6]4− concentration. There-
(CN)6]4−/3− redox couple was obtained, indicating satisfactory re- fore, even though paper electrodes were designed as disposable devices,
producibility. The RSD value found with paper electrodes prepared in they can be used for multiple measurements if needed.
the same batch was 4% (N = 4). The conductive ink was spread onto a The stability of the paper electrodes was also evaluated in neutral,
5.0 cm2 paper piece, cut in smaller pieces of 0.5 × 1.0 cm, which were acidic, and alkaline aqueous solutions (Fig. S8A–B). The electrodes
used as the electrodes. As four electrodes have shown almost the same were stable in neutral and acidic aqueous solutions over 100 con-
response for the [Fe(CN)6]4−/3− redox couple (RSD = 4%), it can be secutive cycles of potential, with a voltammetric charge variation below
concluded that the conductive ink was spread onto the paper piece with 5%. Despite the lower stability in alkaline solution, the electrode can
an acceptable uniformity despite its manual spreading. still be successfully employed for analytical applications in alkaline
solutions if it is designed as a disposable electrochemical sensor
3.1.2. Characterization of the paper electrodes
Scanning electron microscopy (SEM) images of the filter paper 3.1.3. Analytical performance for phenolic compounds
substrate before and after spreading 150 mg carbon conductive ink are The paper electrodes were evaluated for measuring the phenolic
shown in Fig. 4. In Fig. 4A, it is possible to observe the cellulose fibers compounds dopamine, catechol, and hydroquinone as proof of concept.
of the paper. On the other hand, in Fig. 4B we can observe the con- Dopamine is an essential human neurotransmitter, and dopamine defi-
ductive ink spread uniformly on the paper piece, indicating that the ciency causes many problems to human health, among them Parkinson’s
substrate was entirely covered with the proposed carbon conductive disease [52]. Therefore, the reliable determination of dopamine in bio-
ink. Also, Fig. 4B shows graphite agglomerates smaller than 100 μm logical fluid samples is important for diagnosis and treatment monitoring
uniformly distributed along the paper substrate. This is a highly ad- purposes. Catechol and hydroquinone are phenolic compounds that are
vantageous morphology since it can produce paper electrodes with a widely used in the textile, cosmetics, and dye industries [53]. These
high active electrochemical area. compounds are very harmful to the environment, and there is growing
The active electrochemical area of the paper electrodes was determined concern about their spread into the environment as pollutants. Therefore,
by using chronoamperometry and Cottrell’s equation (Eq. (1)) [47]. the development of analytical methods for the quantification of dopa-
mine, catechol, and hydroquinone is highly relevant. These three phe-
nFAD1/2C
i (t ) = nolic compounds are electroactive, and are often chosen as model ana-
1/2t 1/2 (1)
lytes to evaluate the analytical performance of new electrochemical
Where i(t) is the current in a specific time in Ampere, n is the number of sensors [54]. In order to better observe the standard deviations of each
electrons transferred in the electrochemical reaction, F is Faraday constant, sample concentration in their respective analytical curves, Fig. S9 de-
A is the electroactive area in cm2, D is the diffusion coefficient of the monstrates a maximized shape of each point. The voltammetric re-
electrochemical probe in cm2 s−1, C is the redox probe concentration in sponses of these analytes are presented in Fig. 6A−C (dopamine, ca-
mol cm−3, and t is the time in s. The measured areas were compared to the techol, and hydroquinone, respectively), and the oxidation reactions for
active area of a conventional 3 mm diameter glassy carbon electrode these three phenolic compounds are shown in Fig. S10. The analytical
(GCE). The parameters used to calculate the electrochemical active area parameters obtained for each analyte are presented in Table 1.
values were: concentration of [Fe(CN)6]4− = 1.0 × 10−5 mol cm−3, Table 1 shows that wide linear ranges, excellent linearity, and good
Faraday constant = 96,485 C mol−1; number of electrons transferred = 1; limits of detection (LOD) were obtained for the analytes, indicating that
an average diffusion coefficient of the ferrocyanide ion in 0.5 mol L−1 the paper electrodes prepared with glass varnish and graphite are pro-
KCl = 6.39 × 10−6 cm2 s−1 [48]. Fig. S6 shows the chronoamperometric mising as disposable electrochemical sensors. LOD values were calcu-
curves and the I vs. t−1/2 plots; the results are summarized in Table S1. As lated using three times the standard deviation of the blank signal (N = 5)
expected, the paper electrode gave a higher electrochemical active area due divided by the slope from the analytical curve (LOD = 3.0 × SDblank/
to its granular morphology (Fig. 4B), when compared with the smooth slope). As can be seen in Table S2, the analytical performance of elec-
surface of GCEs. trodes is acceptable when compared with other reported electrochemical

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Fig. 4. SEM images of the filter paper substrate before (A) and after (B) spreading the carbon conductive ink.

sensors. Also, paper electrodes are simple to make, disposable and in- components. Fig. 7A presents the SEM images of the screen-printed
expensive, which are the additional advantages of these devices. electrode device. In Fig. 7A1−3, the polymeric PET substrate can be
observed to present a relatively homogeneous and smooth surface with
3.2. Screen-printed electrodes a slight roughness induced by the sanding process. When the con-
ductive ink is coated on the substrate, a completely different mor-
3.2.1. Morphological and electrochemical characterization phology is observed (Fig. 7A1, A4, and A5), demonstrating that the PET
To achieve the desired electrical conductivity in ink, not only must substrate was efficiently covered by the conductive ink. For the ink
the conductive species be dispersed in the polymeric vehicle, but the layer scattered on the PET surface, a rough and porous topography (50
structure must also allow free bands for the electrons to go through. μm) was observed, in addition to the graphite blades exposed on the
Such architecture can be reached by diminishing the conductive par- surface (10 μm), characteristics that increase the geometric area. This
ticle size and/or adjusting the total material percentage, as poor con- result may be related to the manual screen-printing technique for
ductivities were provided by less than 50 % of the conductive compo- making the devices. This graphite-glass varnish ink was also char-
nent [55]. Therefore, the composition used in this study can produce a acterized by using FTIR technique, which provides information about
highly conductive material, which is strongly desirable for the pre- the functional groups present in the conductive ink. By knowing these
paration of disposable electrochemical sensors. functional groups, it is possible to discern, or even expect, different
Alkyd resin has a high number of functional groups, such as esters, electrochemical behaviors, especially in the presence of the analyte.
ketones, and ethers, which increases the interaction between the resin Fig. 7B shows the FTIR spectra of the graphite (A), graphite-glass var-
and the graphite particles, providing an efficient dispersion. To achieve nish composite (B), and glass varnish (C). Spectrum C has the char-
a better understanding of the ink, morphological and spectroscopic acteristic alkyd resin bands, such as the presence of ester in the COO−
characterizations were carried out for the final conductive ink and its asymmetric and symmetrical vibration at 1730 and 1450 cm−1,

Fig. 5. A) Cyclic voltammograms recorded in 1.0 mol L−1 KCl in presence of 1.0/1.0 mmol L−1 [Fe(CN)6]3−/[Fe(CN)6]4− for GCE (a) and paper electrode (b), ʋ
=100 mV s−1. B) Cyclic voltammograms recorded with a same paper electrode in 1.0 mol L−1 KCl in the presence of different concentrations of [Fe(CN)6]4− at
100 mV s−1. a) 0.1; b) 0.2; c) 0.3; d) 0.4; e) 0.5; f) 0.6; g) 0.7; h) 0.8; i) 0.9; j) 1.0 mmol L−1 [Fe(CN)6]4−. C) The respective analytical curves.

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Fig. 6. A1) Baseline-corrected SWV voltammograms recorded with paper electrode in 0.1 mol L−1 phosphate buffer (pH 6.8) at different concentrations of dopamine.
a) 15; b) 25; c) 35; d) 45; e) 55; f) 65; g) 75; h) 85 and i) 100 μmol L−1 dopamine. Voltammetric conditions: f =75 Hz; ΔE =50 mV; ΔEs =2 mV; A2) Analytical curve
for dopamine. B1) LSV voltammograms recorded with paper electrode in 0.1 mol L−1 phosphate buffer (pH 6.8) at different concentrations of catechol. a) 10; b) 20;
c) 40; d) 60; e) 80; f) 100; g) 200; h) 400; i) 600; j) 800 and l) 1000 μmol L−1 catechol. ʋ =100 mV s−1; B2) Analytical curve for catechol. C1) LSV voltammograms
recorded with paper electrode in 0.1 mol L−1 phosphate buffer (pH 6.8) at different concentrations of hydroquinone. a) 10; b) 20; c) 40; d) 60; e) 80; f) 100; g) 200; h)
400; i) 600; j) 800 and l) 1000 μmol L−1 hydroquinone. ʋ =100 mV s−1; C2) Analytical curve for hydroquinone.

Table 1
Analytical parameters obtained for the phenolic analytes using the paper electrodes.
Analyte Technique Linear range/ μmol L−1 R2 LOD/ μmol L−1 Sensitivity/ μA μmol−1 L

Dopamine SWV 15 - 100 0.9998 4.1 0.109


Catechol LSV 10 - 1000 0.9995 9.0 0.021
Hydroquinone LSV 10 - 1000 0.9999 5.3 0.020

respectively [56]; CeO–C and CeO stretch vibrations at 1240 and As shown in Fig. 7C, XRD analyses were carried out for the graphite
1150 cm−1 [57,58]. In spectrum B, we observed a decrease in the resin powder (a), the graphite-glass varnish composite (b), and the varnish (c),
ester band by 1730 cm−1 and an increase in the vibration CeC com- in order to better understand the crystallinity of the materials. The ob-
pared to spectrum A. The decrease in C=O bands may be related to the tained alkyd resin profile (inset) is in agreement with that found in the
high amount of graphite exposed on the electrode surface, partially literature [59], in which the authors used the amorphous alkyd resin
blocking the exposure of the varnish, since the band remains in the profile to determine changes in the object structure. The expected (002)
spectrum but at a smaller intensity. The spectra of the other char- plane for graphite [60–62] was found at 2θ = 26.4° (crystal size:
acterizations corroborate this explanation, demonstrating the decrease 13.9 nm; layer spacing: 1.74 Å). For the composite, the noted graphite
in bands after the joining of the compounds. Also, it is possible to ob- plane slightly shifted to 26.2°, with a crystal size of 26.9 nm, and no
serve similar bands in the spectra obtained for the three materials: at significant difference to the layer spacing.
3421 cm−1N–H vibration and OeH bands, attributed to hydrogen As this device uses a carbon reference electrode, it is of great in-
bonds; C]C bands at 1636 cm−1 referring to alkenes; CeC bands at terest to investigate the differences that this could bring. In order to
1386 cm−1, referring to alkanes; and CeH bands at 613 cm−1, referring observe the redox response, different electrodes were used with dif-
to aromatics (out-of-plane bend). Therefore, the FTIR results suggest ferent references: carbon, Ag/AgCl (KClsat) and Ag ink was evaluated (v
the existence of interactions between the graphite and glass varnish, =100 mV s−1). The obtained results are present in Fig. S11. The
which is consistent with the formation of the conductive carbon ink. pseudo-reference of carbon was expected to present a shift in the Ep,

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Fig. 7. (A) SEM images of the screen-printed electrode device: 1−3 the PET substrate. 4 and 5 the PET substrate covered by the conductive ink. (B) FTIR spectra of
graphite (a), graphite-glass varnish (b) and glass varnish (c). (C) XRD spectra of graphite powder (a), graphite-glass varnish composite (b) and varnish (c and inset
with zoom). (D) Cyclic voltammograms recorded in 0.1 mol L−1 KCl in the presence of 1.0 mmol L−1 [Fe(CN)6]3−/4− for the screen-printed electrode at different
scan rates. (E) Plots of anodic (◼) and cathodic ( ) peak currents vs. the square root of the scan rate (v1/2).

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L.A. Pradela-Filho, et al. Sensors & Actuators: B. Chemical 305 (2020) 127433

due to the different specific conditions required by this type of electrode human and environmental health [67,68]. Among the endocrine dis-
[63,64]. Therefore, a shift of −210 mV from the conventional Ag/AgCl ruptors, estriol (E3; 1,3,5,(10)-estratriene-3,16α, 17β-triol) has re-
(KClsat), and of −145 mV from the Ag inked electrode was observed. ceived attention due to its inherent association with the human re-
The difference between the current magnitudes could be due to the production cycle and pregnancy health. Moreover, some studies have
conventional Ag/AgCl electrode being too big and deforming the so- reported that high levels of estriol may be related to premature births,
lution drop, thus producing an unavoidable charge concentration. In which is one of the main causes of perinatal morbidity and mortality
the literature, it is possible to find works that bring new ideas for dis- [69–72]. Therefore, as a proof of concept, the screen-printed electrode
posable devices using a carbon electrode as a pseudo-reference, which devices were employed for estriol determination in environmental and
has been applied with success in other works already present in the pharmaceutical samples.
literature [26,65,66]. The electrochemical behavior of the hormone was studied by cyclic
Several tests were performed to evaluate the device flexibility. Firstly, voltammetry in a 0.1 mol L−1 phosphate buffer solution (pH 7.0) in the
the same electrode system was bent 5, 10, 20, 40, and 80 times, followed presence of 100 μmol L−1 estriol at the scan rate (v) of 50 mV
by subsequent analysis, as previously described, at v =100 mV s−1 (Fig. s−1 (Fig. 8A). It is possible to observe that the estriol electrooxidation
S12A). In these voltammograms, it can be observed that the current re- gives an anodic peak at 0.53 V with Ipa =3.0 μA. The redox mechanism
mains mostly the same (deviation of 1.2 %) following bending 20 times. for estriol is shown in Fig. S14, following the behavior of other estro-
Around 40 bends, the current starts to decrease, and the device is no gens such as estrone and 17-β-estradiol [73,74]. Then, the pulse vol-
longer useful. However, as a disposable device with a short life span, it is tammetric technique that demonstrated the best behavior for analyte
unlikely that these many bends will occur to incapacitate the measure- detection was determined. As shown in Fig. 8B, square wave voltam-
ment. The following test aimed to evaluate the current response of a flexed metry (SWV) and differential pulse voltammetry (DPV) were tested
device, with the results shown in Fig. S12B It is of interest to note that no using 0.1 mol L−1 phosphate buffer (pH = 5.7) in the presence of 10
current or potential impairment was obtained under these conditions. μmol L−1 estriol. The SWV technique showed an anodic peak current of
Also, the voltammetric response was analyzed with completely flat and 0.7 μA at 0.51 V. The parameters used for the SWV and DPV tests were:
electrodes bent to 90°, as presented in Fig. S12C. It can be seen that the step =5 mV, frequency =25 Hz, modulation amplitude =20 mV, v
peak potentials also remained the same, but with a slight loss of current =125 mV s−1; and modulation amplitude =25 mV, modulation
magnitude: 27.0 μAflat, and 22.8 μAbend. This behavior may have been due time = 0.05 s, v=10 mV s−1, respectively. Considering the fast char-
to some noticeable deformation in the working or counter electrode. acteristic of SWV, the higher current was obtained. In addition, the
The device stability was estimated by cyclic voltammetry at v differential pulse technique, which is known to be slow, hardly had a
=50 mV s−1, using 20 different electrodes, aiming to reveal the current distortion-free voltammogram at scan rates greater than 30 mV s−1.
deviation between them. Therefore, a relative standard error (RSD) of Therefore, the SWV technique was chosen for estriol detection.
3.5 % was obtained (n = 20) (Fig. S12D). Another test, targeting the The SWV parameters were optimized, and the best values found
electrode endurance, was performed by repeating the same measure- were frequency =90 Hz, modulation amplitude =80 mV, and step
ment 10 times with the same electrode. In these, the obtained RSD potential =9 mV. The effect of pH on the voltammetric response for
equals 5.6 % (n = 10) (Fig. S12E). Both of these results demonstrate estriol was also studied (data not shown), and the best response was
that, despite the devices being manually made, they were stable and obtained at pH = 6.4.
similar results were achieved for many devices. Under the optimized experimental conditions, analytical curves
The active electrochemical area of the working electrode of the were constructed (Fig. 8C). The analytical curve (Fig. 8D) was linear
screen-printed electrode device was estimated based on the from 0.1 to 8.0 μmol L−1, according to the equation, Ip (μA) =
Randles–Sevcik equation (Eq (2)): 2.244 × 10−7 + 0.1971 CE3 (μmol L−1). The LOD, obtained by the
equation (LOD = 3.0 × SDblank/slope) was 0.08 μmol L−1. Reprodu-
Ip = ± 2.69 × 105 n3/2ACD3/2v1/2 (2) cibility studies were performed in the presence of 8.0 μmol L−1 of es-
triol, and the calculated RSD for Ipa values was 3.4 % (N = 7).
Where Ip is the peak current, n is the number of electrons in the reac-
The proposed screen-printed devices were applied for the quantifi-
tion, A the electroactive area, C the redox probe concentration, D the
cation of estriol in commercial pharmaceutical samples and spiked tap
diffusion coefficient of the probe, and v the scan rate. The slope of the
water samples. The results from these studies are presented in Table 2.
plot Ipa vs. ν1/2 from the cyclic voltammograms recorded at different
Table 2 shows that recovery percentages ranging from 85.6–95 %
scan rates in the presence of the electrochemical probe [Fe(CN)6]3−/4−
were obtained, which is a good indicator of the accuracy of the ana-
(Fig. 7D, E) was used to estimate A. The diffusion coefficient of [Fe
lyses. Table 2 indicates that the devices can successfully be used for the
(CN)6]4− in 0.1 mol L−1 KCl used in this calculation was 7.60 × 10−6
determination of estriol in tap water and pharmaceutical samples. The
cm2 s−1 [63]. The obtained active electrochemical area was
analytical performance of the screen-printed electrodes for estriol de-
0.186 ± 0.001 cm2 which was higher than that obtained for paper
termination was compared with other electroanalytical methods pro-
electrodes, indicating that the use of the double asymmetric centrifuge
posed in the literature (Table 3).
promotes a more efficient dispersion of the graphite, leading to a higher
As shown in Table 3, the electrodes present satisfactory analytical
electrochemical area.
performance for estriol determination, showing an even better linear
The electrochemical characterization of the electrode was per-
range and LOD than other carbon-based electrodes described in the
formed by EIS and cyclic voltammetry in the presence of an equimolar
literature. The additional advantages of screen-printed electrodes in-
solution of 1.0 mmol L−1 [Fe(CN)6]3−/4− as the electrochemical probe.
clude the simplicity and low-cost preparation and their miniaturized
These studies were conducted using a 0.1 mol L–1 KCl solution as the
size, which allows analyses with micro-volumes, and minimal sample
supporting electrolyte. The charge transfer resistance (Rct) obtained for
consumption and waste generation.
the electrode was 39 kΩ (Fig. S13). The ΔEp obtained for the redox
couple was 560 mV (Fig. 7D), which is comparable with other dis-
4. Conclusions
posable electrochemical sensors proposed in the literature [17,49–51].
This study showed that glass varnish is a promising binder to produce
3.2.2. Analytical performance of screen-printed electrodes for Estriol conductive carbon inks with high electrical conductivity and excellent
determination adhesion to paper and PET substrates. For both compositions, it was
The detection of endocrine-disrupting compounds in water and ef- possible to evaluate their electrochemical behaviors, stability, and mor-
fluents is of emerging importance because of their potential to impact phology, obtaining results that support their use for electrochemical

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L.A. Pradela-Filho, et al. Sensors & Actuators: B. Chemical 305 (2020) 127433

Fig. 8. – (A) Cyclic voltammograms of screen-


printed electrodes recorded in 0.1 mol L−1
phosphate buffer solution (pH 7.0) in absence
of estriol (black) and presence of 100 μmol L−1
estriol (red), v =50 mV s−1. (B) DP (black)
and SW (red) voltammograms of screen-
printed electrode recorded in 0.1 mol L−1
phosphate buffer solution (pH 5.7) in the pre-
sence of 10 μmol L−1 estriol. (C) SW voltam-
mograms of screen-printed electrode recorded
in 0.1 mol L−1 phosphate buffer solution (pH
6.4) in the presence of different estriol con-
centrations. (D) The analytical curve for estriol.

Table 2
Results of estriol determination in tap water and pharmaceutical formulation samples using the devices.
Sample Labeled/mg g−1 Added/μmol L−1 Found Recovered/%

Tap water — 0.80 0.74 ± 0.03 μmol L−1 93.1


— 5.00 4.30 ± 0.08 μmol L−1 85.6
Vaginal cream A 1.0 — 0.90 ± 0.09 mg g−1 90.0
Vaginal cream B 1.0 — 0.91 ± 0.06 mg g−1 91.0
Tablet 2.0 — 1.90 ± 0.07 mg g−1 95.0

Table 3 conductive inks prepared by hand-mixing graphite and glass varnish, the
Comparison between the analytical parameters for estriol determination by reproducibility of the fabrication method was satisfactory, with RSD
using the screen-printed electrode and other carbon-based electrodes proposed values of 9 % (N = 5) for the [Fe(CN)6]3−/4−. To prepare the electrode
in the literature. devices printed on canvas, glass varnish and graphite were mixed and
Electrode Linear range (μmol L−1) LOD (μmol L−1) Reference ground using the asymmetric double centrifugation technique, which in
turn allowed a more conductive material in the ink formulation. This
CNB/AgNP 0.7–3.0 0.16 [73] approach provided an excellent dispersion, improving the electro-
μTED 1.0–1000 0.053 [75]
chemical area of the working electrode and giving a consequent higher
rGO-AgNps 0.1–3.0 0.021 [76]
RGO-GNPs-PS/GCE 0.22–1.5 0.48 [68] current response. In addition, these devices have been successfully em-
GP-GV/PET 0.1–8.0 0.080 This work ployed for the quantification of estriol in water and dispensing phar-
maceutical samples, proving electrode functionality. Therefore, this
CNB/AgNP: glassy carbon electrodes carbon black nanoballs decorated with study has shown that glass-varnish-prepared carbon conductive inks are
silver nanoparticles; μTED: thread-based electroanalytical devices constructed suitable for developing low cost, miniaturized disposable electrochemical
using a cotton thread as the solution channel and screen-printed electrodes
sensors that can be used for micro-volume analysis with minimal waste
surface modified with carbon nanotubes; rGO-AgNPs: reduced griaphene oxide
generation and reagent and sample consumption.
modified with silver nanoparticles; RGO-GNPs-PS/GCE: glassy carbon elec-
trode with reduced graphene oxide, gold nanoparticles, and potato starch.
Declaration of Competing Interest
analysis. SEM images of the electrochemical sensors showed that the
paper and PET substrates were coated with the conductive ink and The authors declare that they have no known competing financial
showed evenly distributed graphite agglomerates on the substrates. The interests or personal relationships that could have appeared to influ-
FTIR spectra show the expected bands for the alkyd resin and its inter- ence the work reported in this paper.
action with the other paint components, reinforcing the homogeneity of
the final product. The paper electrodes showed stability in acid and Acknowledgments
neutral medium; good voltammetric profiles in the presence of [Fe
(CN)6]3−/4− redox pairs and sensitivity in determining phenolic com- The authors are grateful to FINEP (MCT/Finep/CT-INFRA01/2010),
pounds. Although these devices have been produced with carbon FAPEMIG (APQ-02905-15 and APQ-02078-15), CAPES (1687539),

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L.A. Pradela-Filho, et al. Sensors & Actuators: B. Chemical 305 (2020) 127433

FAPESP (2019/04085-7, 2017/21097-3, 2016/12697-4, 2017/21898- cutter printer to create wax barrier and screen-printed electrodes, Talanta 195
6) and CNPq (447668/2014-5 and 443315/2014-0) for the financial (2019) 480–489, https://doi.org/10.1016/j.talanta.2018.11.047.
[20] L.O. Orzari, I.A. de Araujo Andreotti, M.F. Bergamini, L.H. Marcolino, B.C. Janegitz,
support. D. A. G. Araújo and L. A. Pradela-Filho are grateful to CAPES Disposable electrode obtained by pencil drawing on corrugated fiberboard sub-
for the scholarships (finance code 001). The authors would also like to strate, Sens. Actuators B Chem. 264 (2018) 20–26, https://doi.org/10.1016/j.snb.
acknowledge the Multiuser Laboratory of Chemistry Institute at the 2018.02.162.
[21] L.A. Pradela-Filho, D.A.G. Araújo, R.M. Takeuchi, A.L. Santos, Nail polish and
Universidade Federal de Uberlândia for providing the equipment and carbon powder: an attractive mixture to prepare paper-based electrodes,
technical support for experiments involving scanning electron micro- Electrochim. Acta 258 (2017) 786–792, https://doi.org/10.1016/j.electacta.2017.
scopy. The authors are grateful to Prof. Dr. Charles S. Henry from 11.127.
[22] S. Cinti, C. Minotti, D. Moscone, G. Palleschi, F. Arduini, Fully integrated ready-to-
Colorado State University for his revision of the English and scientific use paper-based electrochemical biosensor to detect nerve agents, Biosens.
content. Bioelectron. 93 (2017) 46–51, https://doi.org/10.1016/j.bios.2016.10.091.
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electrode for the voltammetric determination of Cd (II) and Zn (II), Sens. Actuators
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termination of dopamine with an amperometric biosensor using electrochemically Lauro A. Pradela-Filho received his Bachelor's and Master's degrees in Chemistry
pretreated and activated carbon/tyrosinase/Nafion®-modified glassy carbon elec- (Analytical Chemistry) from the Federal University of Uberlândia (UFU), Ituiutaba - MG,
trode, Biotechnol. Bioprocess Eng. 21 (2016) 627–633, https://doi.org/10.1007/ Brazil, in 2014 and 2016, respectively. Currently, he is a Ph.D. student in Chemistry from
s12257-016-0382-3. UFU. He was a visiting scholar, as part of his Ph.D., in the laboratory of Charles S. Henry
[53] J. Ahmed, M.M. Rahman, I.A. Siddiquey, A.M. Asiri, M.A. Hasnat, Efficient hy- at Colorado State University. His research involves the development of disposable elec-
droquinone sensor based on zinc, strontium and nickel based ternary metal oxide trochemical sensors and microfluidics devices for the determination of drugs and en-
(TMO) composites by differential pulse voltammetry, Sens. Actuators B Chem. 256 vironmental pollutants.
(2018) 383–392, https://doi.org/10.1016/j.snb.2017.10.076.
[54] D.P. Rocha, R.M. Dornellas, R.M. Cardoso, L.C.D. Narciso, M.N.T. Silva, E. Nossol,
E.M. Richter, R.A.A. Munoz, Chemically versus electrochemically reduced graphene Isabela Aparecida de A. Andreotti received the Bachelor degree in Biotechnology
(environmental emphasis) from Federal University of São Carlos (UFSCar), Araras - SP,
oxide: improved amperometric and voltammetric sensors of phenolic compounds
on higher roughness surfaces, Sens. Actuators B Chem. 254 (2018) 701–708, Brazil, in 2014. She received the M.S. degree in Genetics and Biology Molecular from
https://doi.org/10.1016/j.snb.2017.07.070. University of Campinas (UNICAMP), Campinas - SP, Brazil, in 2016. At present, is PhD
[55] A. Pekarovicova, P.D. Fleming, Innovations in Ink on Paper Technology to Improve student in Biotechnology at Federal University of São Carlos (UFSCar), São Carlos - SP.
Printability, Pira International Ltd, 2005. Her project of research aims the development of disposable sensors for the detection of
compounds of environmental interest.
[56] D. Işeri-Çaǧlar, E. Baştürk, B. Oktay, M.V. Kahraman, Preparation and evaluation of
linseed oil based alkyd paints, Prog. Org. Coat. 77 (2014) 81–86, https://doi.org/
10.1016/j.porgcoat.2013.08.005. Jefferson Henrique de Souza Carvalho is undergraduate in Chemistry at the Federal
[57] M.E. Elba, E.M. Abdel Rehim, R.E. Ashery, Synthesis and characterization of alkyd University of São Carlos since 2016. His current research interests include electro-
resin based on soybean oil and glycerin using zirconium octoate as catalyst, Int. J. chemistry, electroanalytical chemistry, nanostructured materials, disposable electro-
Chem. Technol. 2 (2018) 34–43, https://doi.org/10.32571/ijct.347670. chemical sensors and development of conductive inks.
[58] N. Akartasse, E. Mejdoubi, B. Razzouki, K. Azzaoui, S. Jodeh, O. Hamed,
M. Ramdani, A. Lamhamdi, M. Berrabah, I. Lahmass, W. Jodeh, S. El Hajjaji, Diele A. G. Araújo graduated at Federal University of Uberlandia (UFU), Ituiutaba – MG,
Natural product based composite for extraction of arsenic (III) from waste water, Brazil, in 2015. She received her Master’s degree in Chemistry (Analytical Chemistry)
Chem. Cent. J. 11 (2017) 1–13, https://doi.org/10.1186/s13065-017-0261-9. from the UFU in 2018. She currently is a Ph.D. student from UFU and her research ex-
[59] G. Lin, X. Zhang, Y. Li, W. Allen, I. Noda, J.E. Mark, Some nanocomposites based on periences include the development of carbon paste electrodes and disposable screen-
a glycerol-derived alkyd resin and layered silicates, Mol. Cryst. Liq. Cryst. 483 printing electrodes for the voltammetric determination of metal ions and organic and
(2008) 33–48, https://doi.org/10.1080/15421400801898066. inorganic species of environmental interest.
[60] Z.Q. Li, C.J. Lu, Z.P. Xia, Y. Zhou, Z. Luo, X-ray diffraction patterns of graphite and
turbostratic carbon, Carbon N. Y. 45 (2007) 1686–1695, https://doi.org/10.1016/j.
Luiz Otávio Orzari is undergraduate in Chemistry at the Federal University of São Carlos
carbon.2007.03.038.
since 2015. His current research interests include electrochemistry, eletroanalytical
[61] A.N. Popova, Crystallographic analysis of graphite by X-ray diffraction, Coke Chem.
chemistry, nanostructured materials, electrochemical sensors and biosensors.
60 (2017) 361–365, https://doi.org/10.3103/S1068364X17090058.
[62] B. Kartick, S.K. Srivastava, I. Srivastava, Green synthesis of graphene, J. Nanosci.
Nanotechnol. 13 (2013) 4320–4324, https://doi.org/10.1166/jnn.2013.7461. Regina M. Takeuchi received her Ph.D. in Analytical Chemistry in 2007 from São Paulo
[63] L.R. Bard, J. Allen, Falkner, Electrochemical Methods Fundamentals and State University (UNESP), Araraquara-SP, Brazil. Currently, she is Associate Professor of
Applications, 2nd ed., John Wiley & Sons, Inc., New York, 2001. Chemistry at UFU, Ituiutaba-MG, Brazil. Her current researches are focused on the
[64] G. Inzelt, A. Lewenstam, F. Scholz (Eds.), Handbook of Reference Electrodes, electroanalytical determination of inorganic and organic compounds in pharmaceutical,
Springer, Berlin Heidelberg, Berlin, Heidelberg, 2013, , https://doi.org/10.1007/ biological, and environmental samples.
978-3-642-36188-3.
[65] L.O. Orzari, R.C. de Freitas, I.A. de A. Andreotti, A. Gatti, B.C. Janegitz, A novel André L. Santos received his Ph.D. in Analytical Chemistry in 2007 from São Paulo State
disposable self-adhesive inked paper device for electrochemical sensing of dopa- University (UNESP), Araraquara-SP, Brazil. He is currently Associate Professor of
mine and serotonin neurotransmitters and biosensing of glucose, Biosens. Chemistry at UFU, Ituiutaba-MG, Brazil. His principal research interest is the develop-
Bioelectron. 138 (2019) 111310, , https://doi.org/10.1016/j.bios.2019.05.015. ment of new electrochemical sensors using alternative and low-cost materials.
[66] D. Agustini, M.F. Bergamini, L.H. Marcolino-Junior, Low cost microfluidic device
based on cotton threads for electroanalytical application, Lab Chip 16 (2016) Bruno Campos Janegitz received Ph.D. degree from Federal University of São Carlos, in
345–352, https://doi.org/10.1039/c5lc01348h. 2012. He was a postdoctoral researcher at University of São Paulo between 2012 and
[67] I. Cesarino, F.H. Cincotto, S.A.S. Machado, A synergistic combination of reduced
2014. At present, he is Professor at Federal University of São Carlos. His research interests
graphene oxide and antimony nanoparticles for estriol hormone detection, Sens. include electroanalytical chemistry, nanostructured electrode materials and modified
Actuators B Chem. 210 (2015) 453–459, https://doi.org/10.1016/j.snb.2015.01.
electrode surfaces, electrochemical sensors and biosensors for medical and environmental
013. analysis.
[68] L.V. Jodar, F.A. Santos, V. Zucolotto, B.C. Janegitz, Electrochemical sensor for

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