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Journal of Electroanalytical Chemistry
Electrochemical sensor for simultaneous determination of epinephrine andnorepinephrine based on cetyltrimethylammonium bromide assisted SnO
2
nanoparticles
N. Lavanya, C. Sekar
 Department of Bioelectronics and Biosensors, Alagappa University, Karaikudi 630003, Tamilnadu, India
A R T I C L E I N F O
 Keywords:
Electrochemical sensorNeurotransmittersEpinephrineNorepinephrineSurfactantSnO
2
 nanoparticles
A B S T R A C T
A highly sensitive and selective electrochemical sensor has been developed for simultaneous determination of catecholamine neurotransmitters, epinephrine (EP) and norepinephrine (NEP) using cetyltrimethylammoniumbromide (CTAB) assisted SnO
2
 nanoparticles (NPs) synthesized by microwave irradiation method. The productswere characterized by powder XRD, HRTEM, UV-visible absorption and FTIR spectroscopy and cyclic voltam-metric methods. The CTAB-SnO
2
 NPs modi
󿬁
ed glassy carbon electrode (GCE) exhibited two sharp well de
󿬁
nedreduction peaks for EP and NEP with a signi
󿬁
cant potential di
ff 
erence of 0.354 V in phosphate bu
ff 
er solution(pH 5.0). Under optimum conditions, the calibration curves for EP and NEP were obtained over a wide con-centration range of 0.1
250 and 0.1
300
 μ
M with the lowest detection limits of 10 and 6 nM for EP and NEPrespectively. Interference studies showed that the modi
󿬁
ed electrodes have excellent selectivity towards EP andNEP in the presence of potential biological interferents uric acid and ascorbic acid. The proposed electrode hasbeen successfully applied to the simultaneous determination of EP and NEP in human urine samples with sa-tisfactory recoveries.
1. Introduction
Neurotransmitters control the physiological and behavioural con-ditions in human beings by regulating communication within the neuralnetwork. These molecules are involved in a large variety of neuro-physiological processes including learning, sleep, memory and appetite.Damage in secretion or uptake of neurotransmitters is known to causeneurodegenerative diseases, drug addiction, and depressive syndromes[1]. Among various neurotransmitters, two important catecholaminesepinephrine (EP) and norepinephrine (NEP) play essential roles in themammalian central nervous system (CNS). Excess of EP in the bodya
ff 
ects the regulation of blood pressure and heart rate, lipolysis, im-mune system and glycogen metabolism. On the other hand, de
󿬁
ciencyof EP leads to Parkinson's disease. The EP also serves as a chemicalmediator for conveying the nerve pulse to di
ff 
erent organs. When EP issecreted into the bloodstream, it rapidly prepares the body for action inan emergency. Hence the EP is used as a common healthcare medicinefor emergency treatment in severe allergic reaction, cardiac arrest andsepsis [2,3].NEP is also a signi
󿬁
cant transmitter which regulates blood pressure,emotional arousal, and mood disorders. It promotes the conversion of glycogen to glucose in the liver and helps in converting the fats intofatty acids, resulting in an increment in energy production. The NEP isresponsible for the increased heart rate, dilation of pupils, dilation of airpassages in lungs and narrowing of blood vessels due to which body isable to perform well in stressful situations [4]. Knowledge of the con-centrations of plasma catecholamine and their metabolites is oftenuseful for diagnosis and evaluation of therapeutic and pharmacody-namic e
ff 
ects for neurological, psychiatric and cardiovascular disorders.Considerable e
ff 
orts have been made to develop reliable methods forthe detection of EP and NEP which are structurally similar and oftencoexist in biological samples. The identi
󿬁
cation and simultaneous de-termination of these neurotransmitters using the electrooxidation pro-cess become di
cult due to their interference with each other duringidenti
󿬁
cation. Therefore, the development of an e
cient electro-chemical sensor to monitor and determine catecholamines in realsamples is very important for non-invasive disease diagnosis andpharmaceutical applications.Various analytical methods including liquid chromatography [5],chemiluminescence [6] and electrophoresis [7] have been employed for the determination of catecholamines. These conventional methods aretime consuming, expensive and involve tedious procedures for sample
http://dx.doi.org/10.1016/j.jelechem.2017.08.018Received 11 May 2017; Received in revised form 7 August 2017; Accepted 8 August 2017
Corresponding author.
 E-mail address:
Journal of Electroanalytical Chemistry 801 (2017) 503–510Available online 09 August 20171572-6657/ © 2017 Elsevier B.V. All rights reserved.
 
preparation. As a result, the determination of catecholamines by em-ploying modi
󿬁
ed electrodes using distinct electrochemical techniqueshas attracted more attention, because the approach does not requirepretreatment of samples and it may be performed in situ [8]. Individualdetermination of EP or NEP has been reported by many researchers[9
16]; however, the simultaneous determination of EP and NEP hasbeen rarely reported [8]. In many modi
󿬁
ed electrodes the determina-tion of EP and NEP is impaired when ascorbic acid and uric acid arepresent in the solution, causing overlapping of peaks. To the best of ourknowledge, there is only one report in the literature dealing with thesimultaneous detection of EP and NEP based on MWCNT modi
󿬁
ed edgeplane pyrolytic graphite electrode. In the present work, we report thepreparation of a new non-enzymatic electrochemical sensor based onsurfactant mediated SnO
2
 NPs to catalyze the reduction of EP and NEPat well separated potentials. The fabricated sensor provides a platformfor a simple and sensitive voltammetric determination of the twoneurotransmitters EP and NEP simultaneously.Tin dioxide (SnO
2
), an n type wide band gap semiconductor (3.6 eVat 300 K), has attracted attention in various
 󿬁
elds because of its uniqueproperties which are strongly dependent on the size, shape and or-ientation [17]. Recently, SnO
2
 nanostructures have been used ex-tensively for electrochemical sensing because of its high electro-chemically accessible area, high electrical conductivity, high reactivityand selectivity, as well as excellent chemical stability [18,19]. Nu-merous methods have been developed to synthesize various nanos-tructures that make more e
cient use of the active surfaces by tuningporosity, shapes, sizes, and facets which improve performance of thesensors. In particular, surfactant mediated synthesis is extensively usedto decorate the chosen material for the purpose of enhancing bothphysical and chemical properties. Herein, we have synthesized SnO
2
NPs by microwave irradiation method using cationic cetyl-trimethylammonium bromide (CTAB) and anionic ethylene diaminetetra acetic acid (EDTA) as mediators and fabricated a novel electro-chemical sensor for the selective and simultaneous determination of EPand NEP by electrochemical reduction process. The attractive feature of this method is the fact that the major biological interferents such asascorbic acid (AA) and uric acid (UA) do not undergo reduction andhence their interference is greatly avoided.
2. Experimental
 2.1. Materials
SnCl
2
·2H
2
O, centrimonium bromide (CTAB), ethylenediaminete-traacetic acid (EDTA), Na
2
HPO
4
, NaH
2
PO
4
 and NH
4
OH were purchasedfrom Fischer Scienti
󿬁
c, Mumbai. Epinephrine and norepinephrine werebought from Sigma Aldrich. 0.1 M phosphate bu
ff 
er solutions (PBS) of various pH values were prepared by mixing the stock solutions of Na
2
HPO
4
 and NaH
2
PO
4
 in appropriate ratios. All chemicals were of analytical grade and were used without further puri
󿬁
cation and thesolutions were prepared using deionized water.
 2.2. Surfactant mediated synthesis of SnO
 2
 and fabrication of modi
 󿬁
edelectrodes
Surfactant mediated SnO
2
 nanoparticles were synthesized by mi-crowave irradiation method. 0.1 M solution of SnCl
2
·2H
2
O was mixedwith 0.5 g (~20 wt% of SnO
2
) of CTAB under stirring at room tem-perature [20]. Then, several drops of ammonium hydroxide (NH
4
OH)were added to the above solution to reach a pH value of 8. The colloidalsolution was washed with deionized water and ethanol several times inorder to remove NH
4+
and Cl
ions. The washed precipitate was ex-posed to microwave irradiation at 600 W for 20 min. The
 󿬁
nal productswere annealed at 600 °C for 5 h in ambient atmosphere in order toobtain SnO
2
 nanoparticles with improved crystallinity. The aboveprocess was repeated for preparing EDTA assisted SnO
2
 and pristineSnO
2
 nanoparticles.Glassy carbon electrodes (GCEs) were polished carefully with alu-mina powder (1.0, 0.3 and 0.5
μ
m) on polishing cloth, rinsed withdeionized water and sonicated to remove the physically adsorbedsubstances. SnO
2
 NPs (1.0 mg/1 mL) was dispersed in deionized waterby sonicating for about 20 min. Then, the prepared suspension (10
 μ
L)was dropped onto the GCE surface and dried at room temperature toobtain SnO
2
 modi
󿬁
ed GCEs.
 2.3. Instrumentation
Powder X-ray di
ff 
raction (XRD) patterns of the samples were re-corded using a Bruker AXS D8 advanced di
ff 
ractometer in the range of 20
80° with Cu K
α
 radiation (
λ
= 1.5406 Å). High resolution electronmicroscopy (HRTEM), and selected area electron di
ff 
raction (SAED)studies were carried out using a JEOL JEM 2100 microscope operated at200 kV. Fourier transform infrared (FTIR) spectra were recorded anAVATAR330 FTIR Thermo Nicolet spectrometer using the KBr pellettechnique. The optical spectra measurements were made using a UV
visspectrophotometer (Thermoscienti
󿬁
c-Evolution 201).Electrochemical measurements were performed with a CHI-900electrochemical workstation (CH Instruments, USA) which consists of athree electrode system comprising GCE (3 mm in diameter) as workingelectrode, a platinum wire as auxiliary electrode and an Ag/AgCl (3 MKCl) electrode as reference electrode. Square wave voltammetry (SWV)measurements were performed in PBS (pH 5.0) containing EP and NEPover the potential region from 0.6 to
 −
0.4 V at a frequency of 10 Hz,amplitude of 50 mV and step potential of 5 mV.
3. Results and discussion
3.1. Structural analysis
Fig. 1A shows the powder XRD pattern of SnO
2
 powders synthesizedwith and without mediators. The di
ff 
raction peaks could be indexed tothe tetragonal rutile structure of SnO
2
 (ICDD card No: 41-1445) withspace group
 
42
/
mnm
. No additional peaks corresponding to possibleimpurity phases such as CTAB and EDTA or other tin oxides were ob-served in the XRD pattern up to the resolution limit of the instrument.The average crystallite sizes, calculated using the Scherrer formula,were found to be 13.09, 9.26 and 8.28 nm for pristine SnO
2
, EDTA andCTAB assisted SnO
2
 respectively. It can be noticed that the presence of mediators led to a moderate decrease in the peak intensity, accom-panied by a pronounced broadening of the di
ff 
raction peaks.Optical absorption spectra of surfactant assisted SnO
2
 samplessuggest that the absorption edge shifts to higher wavelengths implyinga red shift in the band gap with respect to bulk SnO
2
 (3.6 eV at 300 K).The wavelength of absorption edge is observed at 483, 533 and 556 nmfor pristine SnO
2
, EDTA and CTAB assisted SnO
2
 (Fig. 1B) with bandgap energy (Eg) values of 2.95, 3.11 and 3.35 eV respectively (insetFig. 1B).Fourier transform infrared spectroscopy (FT-IR) is usually employedas an additional probe to evidence the presence of OH groups as well asother organic and inorganic species. The FT-IR spectra of surfactantassisted SnO
2
 nanoparticles are shown in Fig. 1C. In this spectrum, thebroad band at 3411 cm
1
may be due to
 
OH stretching vibration of surface hydroxyl group or adsorbed water. The peak observed at1636 cm
1
is due to the stretching vibration of OH groups. Anotherstrong peak appeared in the low wave number region of 559 cm
1
corresponding to the vibration of antisymmetric O-Sn-O mode of na-nocrystalline SnO
2
 [21]. The observed increment in O-Sn-O band widthfor surfactant assisted SnO
2
 NPs may be due to the decrement in crys-tallinity, removal of residual organic impurities and increase of oxygencontent. The weak peaks observed at 2345 and 2940 cm
1
for surfac-tant assisted samples belong to the stretching vibrations of 
 e
C
e
Hbonds, which might originate from organic groups absorbed on the
 N. Lavanya, C. Sekar 
 Journal of Electroanalytical Chemistry 801 (2017) 503–510
504
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Fig. 1.
 (A) XRD pattern, (B) UV
Vis absorption and (C) FTIR spectra of (a) pristine SnO
2
, (b) EDTA and (c) CTAB assisted SnO
2
 NPs.
Fig. 2.
 TEM (A&D), HRTEM (B&E) andSEAD pattern (C&F) of pristine and CTAB-SnO
2
 nanoparticles.
 N. Lavanya, C. Sekar 
 Journal of Electroanalytical Chemistry 801 (2017) 503–510
505
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surfaces of SnO
2
 nanoparticles.Surface morphology of the pristine SnO
2
 and CTAB-SnO
2
 sampleswere examined using TEM and HRTEM. As shown in Fig. 2A, pristineSnO
2
 nanoparticles are mostly spherical in shape without any ag-gregation. The average particle size is 15 nm, which is consistent withthe crystallite size calculated from the XRD patterns. The correspondingHRTEM image clearly shows a single crystalline nature with the latticefringe width of 0.34 nm corresponding to a crystal plane of (110) andthe surface is free from any lattice defects (Fig. 2C). However, the ad-dition of CTAB led to the aggregation of SnO
2
 NPs (Fig. 2B) and surfacedefects could be observed in the HRTEM image as shown in Fig. 2D. Thecorresponding selected area electron di
ff 
raction (SAED) pattern(Fig. 2E&F) con
󿬁
rms that the SnO
2
 NPs were of single crystallinenature with lattice planes corresponding to (110), (101) and (200) of SnO
2
 tetragonal phase. The results are in good agreement with the XRDresults.
3.2. Electrochemical behaviour of EP and NEP at CTAB-SnO
 2
/GCE 
The electrochemical behaviour of EP and NEP at di
ff 
erent SnO
2
 NPsmodi
󿬁
ed glassy carbon electrodes was investigated by observing elec-trocatalytic reduction in 0.1 M PBS (pH 5.0) by square wave voltam-metry (SWV) method. Fig. 3 presents SWVs of EP and NEP at (a) bareGCE, (b) SnO
2
/GCE, (c) CTAB-SnO
2
/GCE and (d) EDTA-SnO
2
/GCE. Thetwo neurotransmitters exhibited relatively poor current response atbare GCE (curve a) and SnO
2
/GCE (curve b). Interestingly, when theCTAB-SnO
2
/GCE (curve c) was used, the mixture displayed two well-de
󿬁
ned and sensitive peaks at
 −
0.045 V and 0.309 V corresponding tothe reduction of EP and NEP with a large peak separation of 0.354 V. Itwas also noted that the cathodic peak currents were more than three-fold higher (I
pc
 =
39.9
μ
A for EP and
 
30.6
μ
A for NEP) whencompared to that of bare GCE and pristine SnO
2
/GCE. The enhancedcurrent response clearly indicates that the CTAB-SnO
2
 NPs acceleratethe rate of electron transfer with an excellent electrocatalytic activitytowards the reduction of EP and NEP. The signi
󿬁
cant potential se-paration between EP and NEP (0.354 V) allows simultaneous
Fig. 3.
 SWVs obtained for the mixture of 500
μ
M each EP and NEP in 0.1 M PBS (pH 5.0)at (a) bare GCE, (b) pristine SnO
2
, (c) CTAB-SnO
2
 (d) EDTA-SnO
2
 modi
󿬁
ed GCE.
Fig. 4.
 CVs of 500
μ
M (A) EP and (B) NEP in 0.1 M PBS (pH 5.0) at di
ff 
erent scan rates (50
500 mV s
1
) at CTAB-SnO
2
/GCE; (C)&(D) corresponding plots of log
 υ
 vs. E
p
/V.
 N. Lavanya, C. Sekar 
 Journal of Electroanalytical Chemistry 801 (2017) 503–510
506
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