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M. Rahimnejad, Anal. Methods, 2019, DOI: 10.1039/C9AY01352K.
Volume 10
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Analytical
Number 10
14 March 2018
Pages 1091-1288
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TECHNICAL NOTE
Kássio M. G. Lima et al.
ATR-FTIR spectroscopy with chemometric algorithms of multi-
shall the Royal Society of Chemistry be held responsible for any errors
variate classifi cation in the discrimination between healthy vs.
dengue vs. chikungunya vs. zika clinical samples
or omissions in this Accepted Manuscript or any consequences arising
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 Page 1 of 12 Analytical Methods
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DOI: 10.1039/C9AY01352K

1
2
3
4 Investigation of New Electrochemical Sensors for Curcumin
5
6
Detection: A Mini Review
7
8 Rosan Zokhtareh a and Mostafa Rahimnejad *a
9 Curcumin (CM) is a natural pigment with a crystalline structure and the most important curcuminoid in turmeric. CM is
10
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effective in treating a wide range of diseases, especially cancers, due to its antioxidant, anti-proliferative, anti-bacterial and
11 anti-inflammatory properties. Electrochemical techniques are among powerful and widely used analytical methods that

Analytical Methods Accepted Manuscript

12 provide valuable information for electrochemical systems. Their dedicated performance as well as their ability to provide
13 very low detection limits are the most important benefits of these methods. Electrochemical sensors have been used as
14 good tools for detection of CM due to their simplicity, accuracy, high sensitivity and selectivity, and proper price. However,
due to the poor response of this compound, it is difficult to detect it directly at the surface of the bare electrodes. Various
15
modifiers have been used to overcome this problem and to increase the sensitivity and selectivity of CM detection sensors.
16
In this research, various types of bare and modified electrodes used in the detection of CM are briefly investigated and their
17 performance is compared with each other scrupulously.
18
19
20
21 1. Introduction
22
23 Nowadays, improving food safety and quality has become a major
24
global issue in food science and industry. Therefore, it seems necessary
25
to enjoy appropriate tools for monitoring the production process and
26
controlling the quality of products 1, 2. Electrochemical sensors are
27
known as strict and portable instruments for food samples analyses
28
29 since they can prepare fast, precise, sensitive, and reliable responses.
30 Moreover, these sensors benefit from the ability of simultaneous
31 detection of multiple analytes. Consequently, electrochemical sensors
32 have the ability to overcome the limitations of conventional analytical
33 techniques 3-6.
34
35 Curcuma longa L, known as turmeric, belongs to the Zingiberaceae
36 distributed throughout South and Southeast Asian countries, especially
37 India and China 7. Turmeric is a spice with many therapeutic effects.
38 Some applications of this substance are the use as an additive,
39 preservative and coloring agent 8, 9. Also, this has been used for many
40 years in traditional medicine for the treatment of various diseases,
Fig. 1 The structure of curcuminoids.
41 such as fever, nephrotoxicity, jaundice, peptic ulcer, arthritis, skin
42 diseases, liver disorders, blood purification and lung diseases 10, 11. The Extensive researches on the therapeutic effects of CM have
43 edible and therapeutic properties of turmeric are found in the rhizome, shown that the presence of hydroxyl and methoxy groups in
44 most of which consists of polyphenols such as CM, its structure causes the antioxidant, anti-proliferative and
45 demethoxycurcumin (DMCM), and bisdemethoxycurcumin (BDMCM). anti-inflammatory activity 17. In addition, antifungal 18 and
46 These polyphenols are generally called curcuminoids and this spice is antibacterial 19 effects are other properties of CM and it has
47 yellow because of their presence in its structure (fig 1) 12-14. CM is the
48 the ability to cope with diseases such as allergies, psoriasis,
most important and active natural pigment in turmeric, which has been depression, Alzheimer, multiple sclerosis (MS), diabetes, AIDS,
49
50 colitis and arthritis 20, 21. Avoiding the formation of cancer cells
51 and inhibiting their growth using different cellular
a. Biofuel
& Renewable Energy Research Center, Department of Biotechnology,
52 mechanisms and interaction between different molecules are
Faculty of Chemical Engineering, Babol Noshirvani University of Technology,
53 Babol, Mazandaran, Iran. of the most important therapeutic effects of CM 22, 23. The
54 E-mail: Rahimnejad@nit.ac.ir antioxidant activity of this compound is more than vitamins E
See DOI: 10.1039/x0xx00000x
55 and C and it is able to prevent the synthesis and spread of free
56 given special attention due to its several therapeutic effects 15, 16.
radicals 24, 25. Clinical studies have shown that several
57
58 1
59
60
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1
2
3 mechanisms, including inducing apoptosis, stopping the cell In one study, electrochemical characteristics, reduction and
4 cycles, inhibiting inflammatory pathways, angiogenesis, and oxidation processes, and optimization of the effective
5 metastasis of cancer cells, contribute to the creating parameters for detection of this compound were investigated
6 anticancer activity of CM 26, 27. This natural compound is using CPE and cyclic voltammetry (CV) and differential pulse
7 effective in the prevention and treatment of various types of adsorptive stripping voltammetry (DPAdSV) techniques 39.
8 cancers, such as prostate, lungs, uterus, liver, pancreas, Also, in another research the electrochemical behavior of CM
9
ovarian, kidney, and skin, and reduces the complications of at CPE surface was investigated using CV under acidic and
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chemotherapy and radiation therapy 28-30. basic conditions. The results showed that CM forms complex
11

Analytical Methods Accepted Manuscript

with Fe (II) and Fe (III) ions in both acidic and basic conditions.
12 The benefits of CM utilization and its ability to prevent,
13 However, a chemical reaction occurs between CM and Fe (II)
control and treat various diseases, are the reasons for the and Fe (III) in basic medium before complex formation 40.
14
development of different analytical methods to identify and Utilizing GCE for recognition of various combinations has
15
determine its amount. The methods are high performance some advantages such as low background current, chemical
16
liquid chromatography (HPLC) 31, high performance liquid stability, desirable mechanical properties, and wide potential
17
18 chromatography-mass spectrometry (HPLC-MS) 32, ultraviolet range 45. The electrochemical behavior of CM at GCE surface
19 visible spectroscopy (UV-Vis) 33, capillary electrophoresis (CE) was investigated in 0.1 M LiClO4 in ethanol. In this study, the
34, resonance light scattering (RLS) 35, and spectrofluorimetry
20 response of the sensor was linear in the range of 1.07×10-4 M
21 (SF) 36.These methods possess great accuracy, sensitivity and to 9.9×10-6 M and the detection limit was 4.1×10-6 M.
22 selectivity, and create quite valid and reliable results, but they Moreover, the results indicated that this electrode was
23 are time consuming, costly, and require complex equipment applicable to determine the amount of extracted CM from
24 and expert personnel in comparison to the electrochemical spices 41. Three combinations of CM, DMCM and BDMCM
25 methods. Therefore, the electrochemical methods are were easily identified and separated from turmeric by HPLC
26 considered as favorable alternatives for other analytical coupled with electrochemical detection using GCE as working
27 techniques since they enjoy advantages such as high accuracy, electrode. Simplicity, quickness, accuracy, suitable selectivity,
28 proper selectivity and sensitivity, simplicity, rapid response and wide linear range were the most important advantages of
29 and low cost. Moreover, by employing electrochemical this method 32. The electrochemical behavior of CM was
30 methods, it is possible to achieve useful information about the investigated at the surface of an anodically activated glassy
31 mechanisms and kinetics of CM reactions. The CM detection carbon electrode in non-aqueous environment using CV and
32 electrochemical sensors have been considered by researchers
33 differential pulse voltammetry (DPV) methods. The results
recently 35, 37, 38. However, due to the poor CM response, showed that this electrode has higher current oxidation peaks
34
modified electrodes are usually used to detect it, therefore, and reduction peaks than bare GCE. Also, CM cooperated
35
challenges continue to find suitable electrodes and modifiers most as diffusional species and it was weak as adsorbed
36
with desirable stability, conductivity, and catalytic activity. species in electron transfer reaction 46. In another study,
37
38 investigation of the CM electrochemical behavior utilizing GCE
Various electrodes and voltammetric techniques have been
39 and DPV technique in 0.1 M phosphate buffer solution (PBS)
used to identify CM. The aim of this study is investigating the
40 (pH 3) as medium showed a pair of oxidation and reduction
performance of various bare and modified electrodes used to
41 reversible picks. In this study, the detection limit of CM was
42 identify and quantify the amount of CM and comparing the
estimated to be 4.0×10-9 M in linear range of 2.50×10-7 M to
43 results.
1.0×10-8 M 47. The CM was identified using HMDE and CV and
44 DPAdSV techniques, then the effective parameters of CM
45 2. Unmodified electrodes determination were optimized. Furthermore, the
46 electrochemical behavior and oxidation and reduction
47 The electrodes used to detect CM are generally divided into
processes of this compound were investigated 39. Utilizing
48 two groups of bare and modified electrodes. Carbon paste
HMDE and differential pulse adsorptive cathodic stripping
49 electrode (CPE) 39, 40, glassy carbon electrode (GCE) 39, 41,
voltammetry (DP-ACSV) technique resulted in an accurate,
50 platinum electrode 38, and hanging mercury drop electrode
fast, simple and reliable method for detecting CM in human
51 (HMDE) 42 are among the bare electrodes that have been used
serum and turmeric. In this study, the Britton–Robinson (BR)
52 to detection of CM. Simple design, low cost, low background
53 buffer (pH 9.5) has been used as an electrolyte and the
current, low recovery time, low ohmic resistance, and wide
54 detection limit was estimated to be 1.5×10-9 M in linear range
potential range are among the advantages of the CPE 43, 44.
55 of 2.80×10-7 M to 5.0×10-9 M. Also, good agreement between
56 electrochemical and HPLC results was observed 42. Using CV
57
58 2
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1
2
3 and DPV methods indicated that the oxidation reaction of CM stability, flat two-dimensional structure, large surface area,
4 on the surface of platinum electrode in 0.1 M (C4H9)4NClO4 in desirable thermal and electrical conductivity, low cell toxicity
5 acetonitrile is an irreversible, two-step, and adsorption- and suitable biocompatibility make graphene a unique
6 controlled process. Rate constant, anodic transfer coefficient material for electrochemical applications 60, 61.
7 and diffusion coefficient were estimated to be (2.92 ± 0.05)
8 ×10-4 cm s−1, 0.29, and 4.52×10−6 cm2 s−1 respectively 38. As it Modifying the GCE by graphene has led to the construction
9 a simple but accurate, sensitive, stable, and very selective
can be observed, GCE is the most used electrode that has been
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applied to detect CM in various solutions without surface voltammetric sensor to detection of small amounts of CM in
11 turmeric. Electrochemical characteristic of GR/GCE was

Analytical Methods Accepted Manuscript

modification, and according to the reported detection limits,
12 investigated using CV and electrochemical impedance
13 the best performance of GCE is in the PBS. But, generally, the
lowest detection limit is obtained in the BR buffer using HMDE. spectroscopy (EIS) techniques. The results showed modifying
14
the electrode surface decreases electron transfer resistance.
15
16 3. Modified electrodes This reduction could be due to electroactive nature and large
surface of graphene. The CV and liner sweep voltammetry
17
18 Bare electrodes have some disadvantages such as non- (LSV) methods were used to study the electrochemical
19 repeatability of surface behavior, slow kinetics of behavior of CM on the surface of GR/GCE and indicated that
20 electrochemical reactions of some compounds on the the high catalytic ability of graphene increases the current and
21 electrode surface and over potential requirement. These decreases the potential of CM oxidation and reduction peaks
22 parameters limit their ability and application to analytical compared to the bare electrode. A mechanism was also
23 objectives. Elimination of these problems is possible by presented for the electrochemical reaction of CM on the
24 physical and chemical changes in the surface of the electrodes surface of GR/GCE 62. Utilizing electrochemically reduced
25 and their modification. Electrode modifying is a process in graphene oxide modified glassy carbon electrode (ERGO/GCE)
26 which the surface of a bare electrode is covered by a chemical as a CM detection voltammetric sensor showed excellent
27 or biological compound called the modifier or this compound activity to oxidizing this compound, and it was found that
28 enters the electrode matrix and changes its electrochemical ERGO/GCE has a better performance compared to bare GCE
29 properties 48-51. Organic, inorganic, and organic-metal and graphene oxide modified glassy carbon electrode
30 (GO/GCE). Electrochemical characterization of ERGO/GCE was
electroactive compounds, surfactants, biomaterials, polymer
31 done via CV and EIS. The results indicated that the GCE surface
films, nanocomposites, and metal and semi-metallic
32 modification by ERGO, decreases electron transfer resistance
nanoparticles can be used for modifying the surface of
33
electrodes. Increase in stability, sensitivity and selectivity of and increases the current of oxidation and reduction peaks of
34
electrode, improvement of electrocatalytic properties, CM distinctly. The electrochemical reaction mechanism of CM
35
preventing undesirable reactions, increasing electron transfer at ERGO/ GCE was also discussed 63.
36
37 rate, increasing current and reducing over potential are some
advantages of modified electrodes 52-55. 3.1.2. CNTs-modified electrodes
38
39 Indeed, CNTs are sheets of graphite with tube
40 3.1. Carbon-based modified electrodes
nanostructure. Generally, CNTs are categorized as multi-
41
Carbon- based electrodes are very popular because of the walled nanotubes (MWNTs) and single-walled nanotubes
42
benefits of suitable price, chemical inertness, low background (SWNTs). Unique atomic structure and morphology,
43
current, biocompatibility and wide potential range 56. mechanical and chemical stability, flexibility, thermal
44
Graphene and carbon nanotubes (CNTs) are examples of conductivity, the high ability to electron transfer and high
45
46 carbon-based modifiers that, due to their highly desirable and surface area are some properties of CNTs, which are valuable
47 unique characteristics, are widely used to modify the surface for biotechnology, biomedical, micro/nano electronics,
48 of the types of electrodes and identify different analytes 57, 58. metallurgy, spintronics and optics scopes 64-68.
49
50 3.1.1. Graphene-modified electrodes Surface modification of GCE by MWCNTs produced a
51 sensitive, accurate, resistant, repeatable and selective sensor
52 Graphene is one of the carbon allotropes that has two to CM detection. CV, adsorptive stripping voltammetry (AdSV)
53 dimensional structure and hexagonal configuration and fast fourier transform square wave voltammetry
54 (honeycomb configuration). Carbon atoms in graphene are (FFTSWV) were used and the results showed that CNT/GCE
55 arranged in form of layers with sp2 orbital hybridization 59. has more increase in stability, sensitivity and repeatability of
56 Unique features such as high mechanical and chemical sensor than bare electrode and it increased current and
57
58 3
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1
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3 decreased over potential of peaks. Moreover, CNT/GCE was applying different types of nanoparticles with various sizes
4 effective in the determination of CM in a milk solution. The and structures and unique physical, chemical and electronic
5 large surface area, desirable conductivity and MWCNTs' ability properties. Particularly metallic nanoparticles play a
6 to facilitate electron transfer rate were among the most significant role in increasing the sensitivity and selectivity of
7 important factors of excellent performance of CNT/GCE in CM sensors due to their desirable catalytic activity 75-78. The
8 detection 69. In another study, a facile, fast, and sensitive combination of nanoparticles with different materials, such as
9
electrochemical sensor was designed for CM quantification in graphene and polymer films, has created new highly capable
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turmeric using a MWCNTs modified basal plane pyrolytic nanocomposite sensors for detecting CM.
11

Analytical Methods Accepted Manuscript

graphite electrode (MWCNT/BPPGE). AdSV was used to
12 A nanocomposite sensor was designed via graphite
13 investigate electrochemical behavior of CM, and the detection
limit of CM was calculated to be 4.5×10-7 M in linear range of electrode surface modification with palladium nanoparticles
14
2.0×10-6 M to 1.0×10-4 M. Moreover, a mechanism was and Al3+ ion physical deposition on the modified electrode
15
proposed for the electrochemical reaction of CM at surface to detection of CM (fig 2). This sensor was
16
MWCNT/BPPGE. The large surface area of BPPGE was one of characterized through CV, square wave voltammetry (SWV)
17
18 the reasons for the favorable performance of this and EIS techniques. Then, dopamine was used for
19 electrochemical sensor 70. Using MWCNT modified GCE for investigation of the sensor sensitivity. Al3+/PdNp/GE had
20 voltammetric measurement of surfactant stabilized CM excellent electrocatalytic activity for CM oxidation and the
21 resulted in construction of a simple, selective and sensitive sensor was applicable for identification of CM in marketed
22 quantification system. Various solvent systems were used to turmeric powder. Electrode surface modification led to an
23 study the electrochemical behavior and stability of CM. Thus, increase in electron transfer rate, increase in sensitivity,
24 a comparative investigation in diverse surfactant media was repeatability, and increase in current and decrease in
25 performed using SWV and the surfactant concentration was potential of oxidation peak. Remarkable surface structure,
26 also optimized. Based on results, 0.01 % concentration of great stability, attractive mechanical features, suitable
27 cetyltrimethylammonium bromide (CTAB) exhibited the best electrical properties, and desirable surface-to-volume ratio of
28 PdNps were among the characteristics that had improved
current response for CM. Additionally, in the concentration
29 electrocatalytic activity of Al3+/PdNp/GE. The use of Al3+ ions
range of 1.08 × 10-6 M to 5.43 × 10-6 M the proposed sensor
30 in the fabricated sensor structure also exhibited a
displayed a linear response with the detection limit of 8.9 ×
31 recognizable enhancement in electron transfer rate in
10-7 M 71.
32 comparison to GE and PdNp/GE. In addition, due to the
33
As expected, using Graphene-modified and CNTs-modified presence of oxygen atoms in β-diketone group, Al3+ and Pd2+
34
electrodes for CM detection showed satisfactory results, and ions possessed the ability to bind to CM 79.
35
made an improvement in electrochemical properties of bare
36
electrodes. In addition, utilizing these modified electrodes led
37
38 to an increase in electron transfer rate and electrode
39 sensitivity. The conductivity and large surface area of
40 graphene and CNTs are the most important reasons for the
41 successful performance of these CM detection sensors.
42 Among these electrodes, the lowest detection limit was
43 obtained using CNT/GCE.
44
45 3.2. Nanocomposite-based modified electrodes
46
47 Nanoparticles are a wide range of materials that their size
48 is less than 100 nm at least at one of the dimensions and they Fig. 2 Al3+/PdNp/GE preparation steps.
49 are zero, one, two or three dimensional 72. The important
50 point is that the physical, chemical and magnetic properties of Utilizing a nanocomposite of polypropylene and palladium
51 nanoparticles depend on the size of them. The nanoparticles nanoparticles for modifying the surface of graphite electrode,
52 are generally classified into six groups of carbon-based, lipid- provided a chance to make a sensitive and selective sensor of
53 based, metal, ceramic, polymer, and semiconductor CM detection (fig 3). CV, EIS, fourier transform infrared
54 nanoparticles. Nanoparticles are not simple molecules and spectroscopy (FTIR) and scanning electron microscopy (SEM)
55 consist of three layers of core, shell, and surface 72-74. techniques were used to investigate electrochemical
56 Performance of electrochemical sensors has improved by properties of PdNps/Poly(Pr)/GE. The results showed that
57
58 4
59
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1
2
3 catalytic activity of electrode increased by its surface in an increase in its surface and improves the electron transfer
4 modification in CM oxidation. Furthermore, electron transfer rate and electrocatalytic activity. To study the electrochemical
5 rate and current of oxidation and reduction peaks increased, behavior of CM, CV and SWV were used 82.
6 and potential of peaks decreased by modifying the surface of
7 electrode. Also, the detection limit was reached 1.20×10-9 M Among the nanocomposite electrodes used to detect CM,
8 by SWV. The simultaneous employment of a conductive NSrGO/Ru@AuNPs/GCE had the best performance, also the
9 lowest detection limit was obtained by this electrode. This can
polymer and PdNps in the structure of this electrochemical
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sensor was the reason of its magnificent electrocatalytic be due to the small size of NSrGO/Ru@AuNPs and the increase
11 in effective surface of the modified electrode.

Analytical Methods Accepted Manuscript

capability. Since Poly(Pr) has a porous structure, PdNps can
12
13 easily be dispersed into the polymer matrix and improve its
3.3. Nanowire-based modified electrodes
14 electrocatalytic ability 80.
15 The nanowires are a group of nanostructured materials that
16 attracted the attention of many researchers due to their
17 special physical, optical, electrical and magnetic properties.
18 Metallic, oxide, nitride, carbide, polymer and composite
19 nanowires are among the most important available nanowires
20 used in mechanical, electronic, optoelectronic, and designing
21
a variety of chemical and biochemical sensors. The advantages
22
of high surface to volume ratio, the ability to facilitate electron
23
transfer and the improvement of catalytic activity are some of
24
the most important reasons for using nanowires in
25 Fig. 3 PdNps/Poly(Pr)/GE preparation steps.
26 electrochemical sensors 69, 83, 84.
27 The surface of GCE electrode was modified by a
nanocomposit consist of reduced graphene oxide (rGO), A sensor with high accuracy and sensitivity was developed
28
functionalized L-cysteine and Ru@Au nanoparticles. The EIS via modification of CPE surface with dysprosium nanowire to
29
30 electrochemical characterization technique of voltammetric detect CM. Applying CV, AdSV and FFTSWV techniques
31 sensor indicated an increase in electron transfer rate indicated that DyNW/CPE is a stable, resistant, repeatable and
32 compared to GCE. Moreover, NSrGO/Ru@AuNPs/GCE had selective sensor. As other result, modifying the surface of
33 high rate, stability, accuracy and selectivity, and was entirely electrode increases the current of oxidation and reduction
34 efficient in the CM detection which added to the plasma peaks and decreases their potential. Also, DyNW/CPE was
35 samples. SWV was used to study on electrochemical behavior successfully used to detect CM in the milk solution. It seems
36 of CM and detection limit was obtained 2.0×10-13 M (fig 4) 81. that using DyNW in this electrochemical sensor and exploiting
37 its large surface area led to increasing CM adsorption and
38 oxidation 69.
39
40 3.4. Polymer-based modified electrodes
41
42 Coating the electrodes by an organic, inorganic or
43 organometallic polymer film is one of the methods to modify
44 surface of electrode 85. Modifying polymers are classified in
45 electroactive, coordinating, polyelectrolyte and biological
46 Fig. 4 (A) SWVs of the NSrGO/Ru@AuNPs/GCE in sodium acetate types. Polymers are among the most valuable materials for
47 buffer solution (pH 5.0), (B) The calibration curve of CM. modifying the surface of the electrodes due to the number of
48 "Reproduced from ref. 81 with permission from [Royal Society of suitable active sites, increasing the effective surface of
49 Chemistry], copyright [2019]." electrode, decreasing electrode fouling and high chemical
50 stability. It is easy to dope the polymer on the surface of the
51 Another sensor which was made to detect CM in urine and electrode and polymers have more electroactive sites than
52 turmeric includes the modified CPE by a composite of covalent bonded monolayers. Dip coating, solvent
53 polyvinylpyrrolidone nanofibers and zinc oxide nanoparticles evaporation, electrochemical polymerization, electrochemical
54 mixed with ferrocene. SEM, infrared spectroscopy (IR) and X deposition, radio-frequency plasma discharge, spin coating
55 ray diffraction (XRD) techniques were used to characterize and cross linking are among the conventional methods in
56 FCNFCPE and it was found that modifying the electrode results
57
58 5
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1
2
3 modifying the surface of electrodes by a thin film of polymer
4 56, 86.

5
6 A voltammetric sensor for detection of CM in urine was
7 designed through electropolymerization of acid chrome blue
8 k (ACBK) on the surface of GCE. Investigating the
9 electrochemical characteristics of GCE and Poly-ACBK/GCE by
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CV and EIS techniques have shown an increase in electron

11 transfer resistance after surface modification, which indicates

Analytical Methods Accepted Manuscript

12 an accumulation of polymer film on the surface of GCE.
13
However, Poly-ACBK/GCE showed excellent electrocatalytic
14
activity in the oxidation of CM, and had high stability,
15
repeatability, and selectivity. According to the results, the
16 Fig. 5 NiCl2/GCE preparation method.
electrode's great ability to CM oxidation originates from the
17
18 desired stability and conductivity of the Poly-ACBK 35. The electrochemical characterization of NiCl2/GCE was
19 carried out by atomic force microscopy (AFM), CV and EIS
3.5. Ionic liquid-based modified electrodes techniques and it was determined that modifying the GCE
20
21 surface increased the specific surface area and facilitated the
Ionic liquids (ILs), which are classified as green chemical
22 transfer of electrons and significantly increased its
compounds, have been widely used in the chemical industry
23 effectiveness in the detection of CM. The high conductivity of
and in various research fields due to their unique
24 NiCl2 solution and the ability of nickel ions to establish a
characteristics such as low volatility, solubility, chemical and
25 specific bond with CM diketone group were the main causes
26 thermal stability, desirable ion conductivity, biodegradability
of reducing the electrode's resistance and consequently,
27 and non-flammability. ILs are composed of organic cations and
increasing the electron transfer rate (fig 6). CV and DPV
28 inorganic anions and are found in liquid form at room
techniques were used to evaluate the electrochemical
29 temperature 87, 88. ILs have higher electrical conductivity than
behavior of CM at NiCl2/GCE surface and the results showed
30 conductive organic compounds, and various compounds such
that the designed sensor had excellent catalytic efficiency in
31 as amino acids, proteins, enzymes, and DNA are easily
the oxidation of CM. Suitable selectivity, sustainability and
32 dissolved in them. The total of these features has led to the
recoverability were some of the advantages of NiCl2/GCE in
33 widespread use of ILs in the design of a variety of
the detection of CM 92.
34 electrochemical sensors and biosensors 89, 90.
35
36 The cadmium oxide nanoparticles-ionic liquid was used to
37 modify the CPE surface and a fast and sensitive voltammetric
38 sensor was developed to detect CM and vitamin B9
39 simultaneously. CV and SWV techniques were used to
40 examine the electrochemical behavior and the detection of
41 CM and it was found that CdO-IL/MCPE has higher selectivity
42 for CM detection compared to CPE. Also, CdO-IL/MCPE was
43 stable and repeatable, and it was effective in detection of CM
44 in spice samples. As both ILs and CdONps enjoyed proper
45
conductivity, their usage facilitated charge transfer and
46
enhanced the sensor's efficiency in CM detection 91. In
47
addition to all of the above-mentioned modifiers, nickel
48
chloride solution was used to modify the GCE surface and
49
50 NiCl2/GCE was used to CM measurement in blood serum (fig
51 5).
52
53
54
55
56
57
58 6
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2
3 Fig. 6 (a) and (b) CVs and EIS of a) bare GCE and b) NiCl2/GCE in 0.1 M
4 PBS (pH 4) including [Fe(CN)6]3-/ [Fe(CN)6]4- (1.0 mM) and KCl (0.1 M)
5 at the scan rate of 100 mV s-1 92.
6
7 A list of electrodes, methods and results of some studies
8 have been summarized in table 1.
9
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11

Analytical Methods Accepted Manuscript

12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
Table 1: Comparison of the performance of CM electrochemical sensors.
28
29 Electrochemical
Electrode Matrix Linear range (µM) LOD (µM) Reference
30 technique
31 0.0576-4.83 (for the
oxidation peak at 0.3
32 V)
33
34 0.2 M sodium acetate buffer
0.96-10.80 (for the
35 CPE DPAdSV oxidation peak at 0.6 - 39
(pH 5.0)
V)
36
37 0.0576-2.7418 (for
38 the reduction peak at
39 0.3 V)
40 0.495-27.6 (for the
reduction peak at -
41 1.1 V)
42 50 mM sodium phosphate
HMDE DPAdSV - 39
buffer (pH 8.5)
43 0.96-48.4 (for the
44 reduction peak at -
1.6 V)
45
Acidic media (pH 3)
46 CPE CV
Basic media (pH 10)
- - 40

47
GCE CV 0.1 M LiClO4 9.9-107 4.1 41
48
49 GCE CV - 0.208–41.6 0.0416 32

50
51 GCE DPV DMSO [a] - - 46

52 GCE DPV 0.1 M PBS (pH 3) 0.01-0.25 0.004 47

53
54 HMDE DP-ACSV BR buffer (pH 9.5) 0.005-0.28 0.0015 42

55 Pt DPV 0.1 M (C4H9)4NClO4 - - 38

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GR/GCE LSV 0.1 M H2SO4 0.05-3.0 0.03 62
4
5 ERGO/GCE DPV 10.0 mM PBS (PH 7.4) 0.2-60.0 0.1 63

6
CNT/GCE FFTSWV 0.05 M PBS (PH 4) 0.002-1.0 0.005 69
7
8 MWCNT/BPPGE AdSV 0.05 M BR buffer (pH 1.8) 2-100 0.45 70

9
MWCNT/GCE SWV PBS (PH 2.5) 1.08-5.43 0.89 71
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11 DyNW/CPE FFTSWV 0.05 M PBS (PH 4) 0.01-1.0 0.0005 69

Analytical Methods Accepted Manuscript

12
Al3+/PdNp/GE SWV 0.1 M PBS (PH 2) 0.03-0.6 0.022 79
13
14 PdNps/Poly(Pr)/G
SWV 0.1 M PBS (PH 2) 0.005-0.1 0.0012 80
E
15
NSrGO/Ru@AuNP acetate/acetic acid buffer
16 s/GCE
SWV
solution (pH 5)
1.0×10-6-1.0×10-4 2.0 × 10–7 81

17
FCNFCPE SWV 0.1 M PBS (PH 8) 0.1-500.0 0.024 82
18
19 poly-ACBK/GCE DPV 0.2 M PBS (pH 6.4) 0.1-70.0 0.041 35

20
CdO-IL/MCPE SWV 0.1 M PBS (PH 7) 0.2-320.0 0.08 91
21
22 NiCl2/GCE DPV 0.1 M PBS (PH 4) 10-600.0 0.109 92

23 [a] Dimethyl sulfoxide

24
25 4. Conclusions significantly. Among CM detection electrochemical sensors,
26 NSrGO/Ru@AuNPs/GCE showed a very successful
27 A comprehensive investigation has been carried out performance, also the lowest detection limit was obtained
28 by this electrode. The reason of this brilliant performance
about the types of electrochemical sensors and
29 could be the simultaneous use of graphene oxide and metal
voltammetric techniques used to CM determination. Also,
30 nanoparticles in the electrode structure and gaining
the function of these sensors and their ability to detect and
31
determine the amount of CM were studied. Generally, an benefits from their unique properties. Large surface area is
32
ideal electrochemical sensor is simple, portable, precise, one of the great properties of graphene. Furthermore,
33
sensitive, selective, repeatable, and has low cost. A nanoparticles due to their small size provide a larger surface
34
desirable electrochemical sensor has a short response and area. Additionally, graphene oxide and metal nanoparticles
35
36 recovery time, and enjoys good mechanical and chemical are conductive compounds and have a proper catalytic
37 stability. Moreover, it has the ability to detect several capacity. Due to the undeniable and countless therapeutic
38 analytes simultaneously with low detection limit. effects of CM and the outstanding performance of
39 Modification of the surface of electrodes by suitable electrochemical sensors in its determination, studies in this
40 modifiers leads to an increase in the effective surface and field seem to be very limited. By a variety of chemical and
41 the rate of electron transfer reactions and thus improves biological modifiers and different methods of modifying the
42 the electrocatalytic properties and performance of the surface of electrodes, new sensors and biosensors can be
43 electrodes. CM is the most important pigment in turmeric designed to detect this important compound.
44 and is the main factor of this plant in the ability of
45 prevention and treatment of various diseases. Conflict of interest
46 Electrochemical sensors are powerful tools for accurate and
47 rapid detection of CM at low concentrations. Graphene, We wish to draw the attention of the Editor to the
48 following facts which may be considered as potential
carbon nanotubes, dysprosium nanowire, nanocomposites,
49 conflicts of interest and to significant financial contributions
polymeric films and ionic liquids are among the modifiers
50 to this work.
that have been successfully applied to the design of CM
51
detection voltammetric sensors to date, and it has been
52 We confirm that the manuscript has been read and
53 made clear that they have a significant effect on sensitivity,
approved by all named authors and that there are no other
54 selectivity, accuracy and repeatability of these sensors. In
persons who satisfied the criteria for authorship but are not
55 addition, the use of these modifiers in most cases increased
56 the electrocatalytic ability of sensors to oxidize CM
57
58 8
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3 listed. We further confirm that the order of authors listed about progress, submissions of revisions and final approval
4 in the manuscript has been approved by all of us. of proofs. We confirm that we have provided a current,
5 correct email address which is accessible by the
6 We confirm that we have given due consideration to the Corresponding Author and which has been configured to
7 protection of intellectual property associated with this work accept email from rahimnejad_mostafa@yahoo.com
8 and that there are no impediments to publication, including
9 the timing of publication, with respect to intellectual Acknowledgments
10
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property. In so doing we confirm that we have followed the

11 regulations of our institutions concerning intellectual

Analytical Methods Accepted Manuscript

The authors appreciate the Biofuel & Renewable Energy
12 property. Research Center at Babol Noshirvani University of
13
Technology (BNUT) for laboratory equipment, technology
14 We understand that the Corresponding Author is the sole
15 and scientific guidance. This work was supported by BNUT
contact for the Editorial process (including Editorial (GRANT NUMBER: BNUT/975115006/1397).
16 Manager and direct communications with the office). He is
17
responsible for communicating with the other authors
18
19
20
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