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These results convey that the NiO nanoparticles modi fied electrode can act as a novel non-enzymatic sensor in trace level quanti fication of nitrite.. 3.9.[r]

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Original Article

Photocatalytic, nitrite sensing and antibacterial studies of facile

bio-synthesized nickel oxide nanoparticles

C.R Rajith Kumara, Virupaxappa S Betageria, G Nagarajub, G.H Pujarc, B.P Sumad,

M.S Lathaa,*

a Research Centre, Department of Chemistry, G M Institute of Technology, Davangere, Karnataka, 577006, India

b Energy Materials Research Laboratory, Department of Chemistry, SIT, Tumakuru, Karnataka, 572103, India

c Research Centre, Department of Physics, G M Institute of Technology, Davangere, Karnataka, 577006, India

d Department of Chemistry, Bangalore University, Central College Campus, Bengaluru, 560001, India

a r t i c l e i n f o

Article history:

Received 15 October 2019

Received in revised form

5 February 2020

Accepted 11 February 2020

Available online xxx

Keywords:

NiO nanoparticles

Calotropis gigantea

Dye degradation

Antibacterial activity

Nitrite sensing

a b s t r a c t

In the present work, Nickel oxide nanoparticles (NiO NPs) were synthesized using leaves extract of

C gigantea through a solution combustion method The NiO NPs were characterized through analytical techniques such as X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and Fourier transform infrared spectroscopy (FT-IR) The XRD results revealed rhombohedral structured crystallites with average size of 31 nm SEM and TEM images indicate that the nanoparticles are agglomerated with an asymmetrical shape The optical energy bandgap of 3.45 eV was estimated using UV-diffused reflectance spectroscopy (UV-DRS) The synthesized NiO NPs have shown superior photodegradation for methylene blue (MB) dye Further, the antibacterial activity of the pre-pared nanoparticles was tested against E.coli and S.aureus bacterial strains In addition, nanoparticles were utilized for electroanalytical applicability as a novel non-enzymatic sensor in the trace level quantification of nitrite The proposed nitrite sensor showed wide linearity in the range 8e1700mM and good stability with a lower detection limit of 1.2mM

© 2020 The Authors Publishing services by Elsevier B.V on behalf of Vietnam National University, Hanoi This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/)

1 Introduction

Nanoscience and nanotechnology have acquired an excellent

impetus in the rapidly growing technological era by covering the

basic understanding of physicochemical and biological properties

in atomic/sub-atomic levels with promising applications in various

fields [1] In the last few years, various researchers investigated on

transition metal oxide nanoparticles due to their increasing

importance and potential applications [2] Among all, NiO an

interesting p-type, wide direct bandgap semiconductor

(3.4e4.0 eV), has caught more attention owing to its key

applica-tions Indeed, nano-sized NiO materials have gained great interest

with respect to bulk NiO because of their size quantization and

large surface-area ratio [3] Due to their unique and remarkable

properties NiO NPs gained significant importance in various fields,

as battery cathodes/anodes [4], catalysis [5], solar cells [6], mate-rials for sensors [7], electrochemical super capacitors [8] Various plants have been increasingly employed in the synthesis of nano-particles due to their ample advantages in elimination of elaborate processes of maintaining cell cultures, cost-effectiveness and easy scale up for large-scale synthesis During the bioproduction of NPs, plant extracts act as both reducing and stabilizing agents [9] Kumar

et al [10], and Vidya et al [11], have reported about the synthesis of

Ag NPs, and ZnO NPs using leaf extract of Calotropis gigantea In the present study, NiO NPs have been synthesized using leaves extracts

of C gigantea plant The C gigantea, also called as Arka, Madara, etc., belongs to the family of Apocynaceae and is available throughout India, especially in the dry and vast land Various phytochemical constituents are present in different parts of the Calotropis plant, mainly in the leaves, which acts as a reducing and stabilizing agents during the synthesis of NPs

Highly toxic dyes play a major role in polluting water These, are frequently being used in the industries like textile, food, cosmetics, paper, plastics, etc., [12] The natural degradation of such dyes is very difficult due to their complex structure However, recently,

* Corresponding author GM Institute of Technology Davangere, Karnataka,

577006, India.

E-mail address: lathamschem97@gmail.com (M.S Latha).

Peer review under responsibility of Vietnam National University, Hanoi.

Contents lists available atScienceDirect Journal of Science: Advanced Materials and Devices

j o u r n a l h o m e p a g e : w w w e l s e v i e r c o m / l o c a t e / j s a m d

https://doi.org/10.1016/j.jsamd.2020.02.002

2468-2179/© 2020 The Authors Publishing services by Elsevier B.V on behalf of Vietnam National University, Hanoi This is an open access article under the CC BY license ( http://creativecommons.org/licenses/by/4.0/ ).

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various semiconductor photocatalysts NiO, Cu2O, FeO, etc., have

been developed to degrade the organic pollutants [13,14] In the

present study, the synthesized NiO NPs have been used to study the

photocatalytic degradation of methylene blue dye Various

nano-structure materials have shown good antibacterial activity against

human pathogens [15] Earlier reports have demonstrated the

possibility of utilization of metal oxide NPs, in particular, NiO NPs in

biomedicines due to their unique therapeutic and biological

prop-erties such as adsorbing and metal ion releasing ability, cytotoxic

effects and surface-area ratio [16] Hence, the antibacterial activity

of NiO NPs has been demonstrated in the present study

In the past decades, the highly sensitive detection of‘nitrite’ has

caught increasing interest because of its harmful effect on both

human health and global environment Further, ground water

pollution is rapidly increasing by‘nitrates’ due to the anthropogenic

activities [17] The World Health Organization (WHO) recommends,

the maximum limit of‘nitrite’ should be 3 mg/L in drinking water

[18], hence, it is an important task of chemists to monitor the

existing levels/limits of nitrite in water and environment Generally,

the analysis of nitrites can be quantified by using various

tech-niques such as chromatography,

spectrophotometry/spectro-fluorimetry, electroluminescent and capillary electrophoresis

techniques However, some of the above quantitative techniques

lack sensitivity and, high detection limits and do require extensive

instrumentation In contrast, electrochemical methods give better

precision quantification over all these methods in terms of

sensi-tivity/selectivity [19] In a quantitative analysis, the thorough

exploitation of CMEs within thefield of electrochemistry and

sur-face manipulation with selective indicator moieties is desirable to

achieve the tailored properties Such CMEs have found to be very

sensitive, easy to fabricate and target specific in electrochemical

applications [20] Here, the synthesized NiO NPs have been used as

a modifier molecule in the fabrication of electrode The modifier

electrode has been explored for its electroanalytical applicability as

a novel non-enzymatic sensor in trace level quantification of nitrite

2 Experimental section

2.1 Materials

All the chemicals (analytical grade) were purchased from

SDeFine Chemicals Pvt Ltd and Hiemedia and used without any

further purification

2.2 Instrumentation and experimental methods

The Crystalline nature and phase purity was identified with the

aid of the X-ray diffractometer (Rigaku Smart Lab) The morphology

and elemental composition of the material was examined using

SEM and EDAX (Hitachi S3400n), respectively The HR-TEM with

SAED (Jeol/JEM 2100) was used to measure shape and size of the

nanoparticles, respectively The FT-IR spectrometer (Bruker

alpha-P) was used to examine the functional groups Absorption spectra

were recorded with the UVeVisible spectrophotometer (Agilent

technology cary-60 spectrophotometer) The diffuse reflectance

spectrum was measured using the Lab India UV 3092, UV-VIS

spectrophotometer Electrochemical measurements were

ach-ieved using the CH instrument

2.3 Synthesis of NiO NPs

Freshly collected leaves of C gigantea were washed, dried and

grinded well The Soxhlet extractor with water as solvent was used

for the extraction for 5 h and the obtained extract was dried using a

rotary evaporator The combustion synthesis method was used to

synthesize NiO NPs using Nickel nitrate hexahydrate (Ni (NO3)26H2O) as an oxidizer and C gigantea leaves extract as a fuel

In this process, 2 gm of the extract dissolved in 100 mL of double distilled water was, constantly stirred for 10 min to get a homog-enous solution Ni (NO3)26H2O of 0.5 M was dissolved in 10 mL of

C gigantea extract and was placed in a preheated muffle furnace (400± 10C) A smouldering reaction takes place and the entire

process was completed within 10 min The obtained NiO NPs were subjected for calcinations at 500C for 3 h to eliminate the impu-rities Until further use, the obtained product was stored in an airtight container

2.4 Photo catalytic studies The photocatalytic studies of NiO NPs were assessed by the degradation of cationic methylene blue (MB) dye in aqueous media using a 250 W UV-light irradiation source For the photocatalytic experiments, a visible annular photoreactor was used, which con-sists of cylindrical tubes with transparent interior to employ com-plete radiation In this process, 50 mg of NiO NPs as a photocatalyst was added to quartz tubes of 100 mL capacity, which contains

100 mL MB solution of concentration 5 ppm The solution was continuously air bubbled for complete mixing of the MB dye and the photocatalyst Then, 2 mL was taken out from the above solu-tion, thefirst time after 15 min and then at regular intervals of

30 min The percentage of degradation of the cationic MB dye has been calculated using the BeereLambert law as follows [21]:

% of degradation¼Ci Cf

where, Ciand Cfare the initial andfinal concentration of the dye solution, respectively

2.5 Antibacterial studies The antibacterial activity of NiO NPs was screened against Gram positive bacteria NCIM-5022 and Gram negative

bacteriaNCIM-5051 through the Agar well diffusion method [22] The bacteri-cidal activity of NiO NPs was tested in Nutrient Agar (NA) media, the

NA plates were prepared using 28 gm of NA media Then, it was dissolved in 1000 mL of double distilled water and subjected to pasteurization at 121C with pressure of 15 lbs during 15e20 min

NA plates with 100ml of 24 h mature broth culture of each indi-vidual bacterial strains were prepared and swabbed using a sterile L-shaped glass rod In each petri - plate 6 mm wells were made using a sterile cork bore The NiO NPs were dispersed in sterile double distilled water and loaded onto the well The zone of inhi-bition (ZOI) was measured after the incubation of NA plates for 24 h

at 37C [23,24]

2.6 Fabrication of the electrode for electrochemical sensing Prior to fabrication, the glassy carbon electrode was uniformly polished using an alumina slurry on polishing pads to get a mirror like shiny surface To remove physically adhered impurities on the surface of the electrode, it was washed and ultrasonicated with double distilled water and ethanol respectively for 15 min Modi fi-cation of the surface of the bare glassy carbon electrode was carried out by drop coating 10mL of a NiO NPs dispersed solution (1 mg/mL) The modified electrode was dried at room temperature and used as it

is in further experiments The electrocatalytic behaviour of the NiO modified glassy carbon electrode was evaluated by using the CH Instrument with a three electrode configuration comprising of the NiO particles modified glassy carbon electrode as the working

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electrode, a platinum disc electrode as a counter electrode and

saturated Ag/AgCl electrode as a reference electrode [25]

3 Results and discussion

3.1 Structural and morphological analysis

The diffractogram of green synthesized NiO NPs is depicted in

Fig 1 (a)The XRD peaks coincide with the rhombohedral structure

and match well with the standard value of JCPDS (No 22e1189),

with lattice parameters (a¼ 2.954, c ¼ 7.236) and Space group R-3m

166 From the XRD pattern, it was confirmed that NiO NPs exhibited

a crystalline nature with no impurity peaks The crystallite size of NiO NPs was estimated using the Debye-Scherer's formula [32]:

D¼0:9l

where, ‘D’ is the crystallite size of synthesized NPs, ‘l’ is the wavelength of X-ray radiation (1.54 Å),‘b’ is the full width at half maximum (FWHM) of the diffraction peak and ‘q’ is Bragg's

Fig 1 (a) XRD pattern (b) EDAX spectrum (c, d) SEM images of synthesized NiO NPs.

Fig 2 (a) TEM, (b) HR-TEM images, (c) Interplanar spacing (d) SAED pattern of synthesized NiO NPs.

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diffraction angle The average crystallite size of NiO NPs was found

to be 31 nm

InfigFig 1 (b)EDAX report confirms the elemental composition

of Ni and O The SEM micrographs (Fig 1(c and d) show the

agglomeration with irregularly shaped nanoparticles The TEM

micrograph (Fig 2 (a)) confirms that sizes of crystallites are in the

range of about 10e30 nm which is in good agreement with the

estimated value of XRD the analysis.Fig 2(b and c) represent the

HR-TEM micrographs that show particles in hexagonal and

rhom-bohedral shape with interplanar spacing of 0.21 nm The SAED

pattern depicted inFig 2(d) indicates the presence of (111) (200)

and (220) planes of the synthesized rhombohedral NiO NPs

3.2 Fourier transform infrared spectroscopy analysis

The FT-IR spectrum of NiO NPs is shown inFig 3 The spectrum

is scanned in the range 400e4000 cm1 to analyse the various

functional groups The absorption band that appeared at

3410 cm1corresponds to (OeH) stretching of water and at

1632 cm1 to (HeOeH) bending vibrations The band at

1114 cm1is due to (CeO) bonds of carbon dioxide adsorbed on the NPs surface The bands corresponding to stretching and bending vibrations of (CeH) were observed at 2912 and 1381 cm1, respectively In addition, the significant absorption band at

430 cm1is attributed to metaleoxygen (NieO) stretching vibra-tions [37].Thus, the expected structure and functional groups are confirmed by the above results

3.3 Diffuse reflectance spectroscopic (DRS) analysis Fig 4 (a)shows the DRS spectrum of green synthesized NiO NPs

A blue shifted strong absorption peak is observed at 305 nm DRS Spectral data can be used to estimate the optical energy bandgap of biosynthesised NiO NPs as shown inFig 4 (b) The optical energy bandgap was determined using the KubelkaeMunk equation [22]:

Fig 3 FT-IR spectrum of synthesized NiO NPs.

Fig 4 (a) Diffuse reflectance spectrum (DRS) (b) Optical energy band gap (Eg) of synthesized NiO NPs.

Fig 5 Time dependent absorbance spectrum of synthesized NiO NPs against Methy-lene blue dye.

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FðRÞ ¼ð1  RÞ2

where, R is the reflection coefficient of the sample From eq.(3),

plot of F(R)2 vs the photon energy (eV) gives an optical energy

bandgap (Eg) of 3.45 eV Thus, nanoscale NiO exhibits directly a

wide bandgap semiconductor nature

3.4 Photocatalytic studies

The photocatalytic behavior of green synthesized NiO NPs is

assessed through the photo-degradation of the MB dye with the aid

of visible annular type photoreactor under UV light irradiation The

actual trail starts when the light is irradiated and, the photon of

energy is consumed by the semiconducting NiO in which the band

gap is higher Electrons and hole pairs are generated in the

con-duction and valence bands If the charge carriers are not put

together again, then the migration of free electrons on the surface

leads to the oxygen reduction and formation of peroxides and

su-peroxides The newly generated holes can oxidizes water and forms

OH free radicals Such radicals are unstable and highly reactive in

nature, which eventually leads to the organic dye degradation The

photocatalytic action on dyes is enhanced by factors like particle

size, morphology, composition, size distribution, surface area, band

gap, etc The steady decrease in the absorption peak intensity at

663 nm by the time exposed to UV light indicates the dye

degra-dation as shown in Fig 5 The degradation efficiency has been

calculated using eq (1) The calculated efficiency is found to be 97.76% at 180 min against MB dye [21] The degradation mechanism

in dye solution is stated in the following equations(4e11) Com-parable results of the degradation efficiency of MB dye with other metal oxide nanoparticles are tabulated inTable 1

NiOþ hv / NiO (e

3.5 Antibacterial studies The antibacterial study of the synthesized NiO NPs was tested against the human pathogenic bacteria's Staphylococcus aureus and Escherichia coli, employing the Agar well diffusion method Generally, the antibacterial activity depends upon the reactive ox-ygen species (ROS), surface area, particle size, etc NiO NPs produce ROS (hydroxyl, superoxide radical, singlet oxygen, and

alpha-Table 1

Comparison of results with published data: photocatalytic activity (MB dye) with

different metal oxide NPs.

Sl.

No

Photocatalyst Synthesis method average

crystal size (nm)

% of dye degradation

references

1 ZnO NPs Sol gel 30 81 [ 32 ]

2 Co-precipitation 23 90 [ 33 ]

3 Solution combustion 20 81 [ 25 ]

4 Ag 2 O NPs Solution combustion 11 84 [ 34 ]

5 MgO NPs Microwave assisted 14 88 [ 35 ]

Hydrothermal 20 92

6 NiO NPs Green Synthesis 20 97 [ 36 ]

7 precipitation 2e3 97 [ 37 ]

8 Solution combustion 31 98 Present

work Bold signifies the current work details/data compared to published data.

Fig 6 Antibacterial activity of NiO NPs against E.coli and S.aureus bacterial strains (S) Standard antibiotic (C) control (a) 500mg/mL (b) 1000mg/mL.

Table 2 Antibacterial activity of synthesized NiO NPs.

Treatment Bacterial strains Sample Concentration Escherichia coli

(mean ± SE)

Staphylococcus aureus (mean ± SE) Ciprofloxacin 10mg/mL 9.26 ± 0.28 14.13 ± 0.67 NiO NPs 500mg/mL 2.95 ± 0.48 4.63 ± 0.41

1000mg/mL 6.14 ± 0.37 7.86 ± 0.52 Values are the mean ± SE of inhibition zone in mm.

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oxygen) through the Fenton reaction, which leads to lipid

peroxi-dation, DNA damage and protein oxidation which can eliminate the

bacteria The zone of inhibition formed by the NiO NPs of known

concentrations (500 and 1000mg/mL) with reference to the positive

control (Ciprofloxacin) is shown inFig 6and corresponding data

are tabulated inTable 2 The antibacterial activity of NiO NPs shows

a significant inhibition to both bacterial strains compared to

stan-dard antibiotic Ciprofloxacin [25,26]

3.6 Electrochemical investigation of NiO nanoparticles

The initial electrochemical characterization of the NiO

nano-particles modified glassy carbon electrode surface was carried out

by using the most powerful electrochemical techniques such as

cyclic voltammetry (CV) The redox activity of the NiO

nano-particles modified electrode was studied in the presence of a

standard redox standard potassium ferricyanide solution From the voltammogram inFig 7, it is observed that theDE value of 136 mV for NiO NPs modified electrode (peak b) shows a better redox ac-tivity with increased current density than the bare glassy carbon electrode withDE value of 263 mV (peak a) The decrease in peak potentials has increased effect on conductivity This increased ac-tivity might be attributed to the high surface area provided by the nanoparticles in comparison to the bare glassy carbon electrode [27e30]

The NiO NPs modified electrode was utilized to investigate its electrocatalytic property in the electro oxidation of nitrite The voltammograms at modified interface were recorded in the pres-ence of a nitrite in acetate buffer of pH 4 at the scan rate of 50 mV/

s From Fig 8, it is clear that the NiO nanoparticles modified electrode in the absence of nitrite did not show any redox signa-ture (peak c) suggesting that the modified electrode is inactive in absence of nitrite under the potential window studied However,

in the presence of nitrite the modified electrode showed an enhanced current response responsible for the electro oxidation of nitrite with potential at 0.93 V (peak a) in comparison to the unmodified electrode at 1.03 V (peak b) The observed results illustrate the electrocatalytic behaviour of the modified electrode towards the electro oxidation process Hence, the NiO NPs modi-fied electrode can be used in the electrochemical quantification of nitrite at trace level

As presentedFig.S1 (a) (in ESI), with increasing scan rate from 10

to 300 mV/s the anodic peaks were shifting towards more positive potentials with increase in peak current response with R2¼ 0.98 showing that the process of nitrite oxidation at NiO NPs modified electrode is a diffusion controlled process

3.7 Optimization of experimental parameters Owing to the excellent analytical sensitivity and resolved re-sponses of the differential pulse voltammetry (DPV) technique over cyclic voltammetry, the experimental parameters were optimized The factors which affect the analytical responses such as pH, deposition potential, deposition time and the concentration were varied and their effect on the current responses were studied The optimized parameters are as follows-pH:4, deposition

Fig 7 Overlaid Cyclic voltammograms at (a) bare (b) NiO NPs modified electrode in

presence of a potassium ferricyanide solution and 0.1 M KCl as supporting electrolyte.

Scan rate: 50 mV/s.

Fig 8 Overlaid Cyclic voltammograms at a) bare, b) NiO NPs modified electrode in

presence and c) absence of nitrite in acetate buffer and 0.1 M KCl.

Fig 9 Overlaid differential pulse voltammograms at NiO NPs modified electrode with increasing nitrite concentration in an acetate buffer under optimized conditions Insetecalibration plot of the peak current versus concentration.

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potential:0.4 V and deposition time:15 s All the graphs are

depic-ted inFig.S1 (b-d) (in ESI)

3.8 Calibration plot and linearity

The determination of nitrite has been done using differential

pulse voltammetry (DPV) due to its high current sensitivity and

better resolution compared to cyclic voltammetry Hence, under

the optimized experimental conditions, the performance of the

NiO NPs modified electrode on increasing nitrite concentration

has been studied as shown in Fig 9 The anodic peak currents

linearly increase with the successive addition of nitrite in the

concentration range 8e1700mM with linear regression co-efficient

of 0.998 The detection limit (3s) was found to be 1.2mM These

results convey that the NiO nanoparticles modified electrode can

act as a novel non-enzymatic sensor in trace level quantification of

nitrite

3.9 Stability of the modified electrode

The stability of the modified electrode was studied by

contin-uously recording the responses at the modified electrode up to 10

cycles as depicted inFig.S5 and S6 (ESI) The modified electrode

showed significant analytical responses responsible for the electro

oxidation of nitrite even after 10 cycles However, the peak current

density decreased which might be due to an oxide layer formation

on the electrode surface [31] This reveals that the modified

elec-trode is very stable and can be used in the continuous monitoring of

nitrite The modified electrode showed excellent analytical

per-formance in comparison to other reported nitrite sensors and is

given inTable 3

4 Conclusion

In this study, NiO NPs have been synthesised through a

so-lution combustion method using C gigantea leaves extract as a

fuel NiO NPs and were characterised using X-RD, SEM with

EDAX, HR-TEM with SAED and FT-IR spectroscopy The

syn-thesised NiO NPs were utilized to study their diversified

appli-cations in dye degradation, anti-bacterial activity and in

electrochemical sensing The X-RD pattern confirms the

rhom-bohedral structure of NiO NPs with a particle size in the range

10e30 nm The EDAX spectrum confirms the presence of Ni and

O as major elements in its elemental composition The NiO NPs

exhibited very good photocatalytic activity in the degradation of

methylene blue dye The anti bacterial activity studies revealed

that the nanoparticles have good ability to inhibit the growth of

E.coli and S.aureus pathogens The electrochemical investigation

of the NiO NPs modified electrode depicts an excellent electro

catalytic behaviour in the quantification of nitrite at trace level in

comparison to the bare electrode The modified electrode showed

wide linearity in the concentration range 8e1700 mM with a

detection limit of 1.2 mM, which allows the exploration of NiO NPs as a novel non-enzymatic nitrite sensor for biological applications

Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper

Acknowledgments

Dr G Nagaraju thanks the DST-Nano mission (SR/NM/NS-1262/ 2013) Govt of India, New Delhi for providing characterization techniques and also the VGST, Govt of Karnataka (CISEE-VGST/GRD-531/2016e17) for UV-DRS studies Rajith Kumar C R thanks the Department of Biotechnology, GM Institute of Technology, Davan-gere and Siddaganga Institute of Technology, Tumakuru for providing lab facility

Appendix A Supplementary data Supplementary data to this article can be found online at https://doi.org/10.1016/j.jsamd.2020.02.002

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Table 3

Comparison of reported values with other modified electrodes.

Modifier Technique Linearity range (mM) Limit of detection (mM) Reference

SPCE/anodized/CuAgNP Hydrodynamic chronoamperometry 20e370 11.1 [ 39 ]

poly (4-aminobenzoic acid/o-toluidine) (4-AB/OT)/CPE Amperometry 6e600 3.5 [ 40 ]

Bold signifies the current work details/data compared to published data.

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