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Sensors and Actuators B 241 (2017) 182–189

Contents lists available at ScienceDirect

Sensors and Actuators B: Chemical

journa l homepage: www.e lsev ier .com/ locate /snb

new droplet-based polymeric banana electrochemical biosensor fornalysis of one microliter solution of paracetamol

azam Aliabadi, Gholam Hossein Rounaghi ∗, Mohhamad Hossein Arbab Zavarepartment of Chemistry, Faculty of Sciences, Ferdowsi University of Mashhad, Mashhad, Iran

r t i c l e i n f o

rticle history:eceived 14 August 2016eceived in revised form 3 October 2016ccepted 14 October 2016vailable online 17 October 2016

eywords:anana biosensorarbon pasteolyphenol oxidase

a b s t r a c t

Modern researches and also the laboratories increasingly need the methods to measure the small volumesas microliter of analytical samples for determination of various analytes with a high accuracy. An electro-chemical biosensor based on a modified carbon paste electrode with hydrogel as an absorbent polymericmatrix and banana as a source of polyphenol oxidase was constructed and it was used for determinationthe concentration of paracetamol in one microliter volume of solution. The electrochemical oxidationof paracetamol was studied by cyclic voltammetry and square wave voltammetry. The effective param-eters on the voltammetric response of the constructed biosensor were optimized. The results obtainedby cyclic voltammetry revealed that the banana-hydrogel carbon paste electrode shows a higher currentresponse compared to a banana carbon paste electrode and hydrogel carbon paste electrode. Because of

ydrogelaracetamolow sample volume consumption sensor

high absorption property of hydrogel, the proposed electrode has the capability to measure only one �Lof sample solution, which is very important and considerable property for limited volumes of samplesolutions. The modified electrode also exhibits a low detection limit (1.6 �M) with a good linear range(10–250 �M) and it has a good reproducibility and stability in both basic and acidic environments even inthe presence of the enzyme and a long life time (20 days) for measurement of paracetamol in solutions.

© 2016 Elsevier B.V. All rights reserved.

. Introduction

Plant tissues have received considerable interest in biosensoronstruction. For construction an enzyme biosensor, two sources ofnzyme: the pure enzyme and plant tissue can be employed. Plantissue biosensors use thin slices of plant as a source of the enzyme.he plant tissue has low cost, high stability, long life time but poorelectivity and a long response time. The diversity and availability oflants, no need sample preparation steps, the presence of necessaryofactors, are other advantages of the plant tissue for constructionf biosensors [1–9].

The procedures most commonly used for the construction ofhe electrochemical biosensors, are the retention of a thin slicef plant, directly fixed on the surface of the electrode and mixinghe tissue with a carbon paste matrix [3]. Other methods, are the

mmobilization of plant tissue in alginate and hydrogels [10].

The hydrogels are hydrophile, porous, insoluble, cross-linkedolymers, containing ionic functional groups. These polymers can

∗ Corresponding author.E-mail addresses: a.aliabadi92@gmail.com (A. Aliabadi),

hrounaghi@yahoo.com, ronaghi@um.ac.ir (G.H. Rounaghi), arbab@um.ac.irM.H. Arbab Zavar).

ttp://dx.doi.org/10.1016/j.snb.2016.10.070925-4005/© 2016 Elsevier B.V. All rights reserved.

absorb and retain fluids, such as water, biological fluids such asblood and urine. Hydrogels are also smart materials that respond tosome stimuli such as pH, temperature and light. The pH responsivehydrogels have acidic or basic side groups that are ionizable andtheir charge will be a function of the pH value of the solutions.The main advantages of these hydrogels in the biosensor field, arebiocompatibility and their ability to be responsive to physiologicalstimuli [10–17].

Banana, potato, apple, avocado, coconut, mushroom and otherspecies of plants have the tyrosinase or polyphenol oxidase (PPO)enzyme. PPO catalyses two different reactions, the o-hydroxylationof monophenols to o-diphenols and the subsequent oxidation of theo-diphenols to o-quinones [18,19].

Acetaminophenol or paracetamol (PA), is a common analgesicand antipyretic drug that is used for the alleviation of fever,backaches, headaches and pains. Because of the exigent roles ofparacetamol, its determination is important in drugs and biologi-cal fluids [20–28]. Many analytical methodologies such as opticalmethods [29,30], chromatographic methods [31–34], electroan-alytical methods [35,36] and capillary electrophoretic methods

[37,38] have been proposed for the determination of paracetamolin solutions.

Low sample volume consumption is an important aspect of tech-nical analysis. For samples that are restricted in volume, we need

A. Aliabadi et al. / Sensors and Actuators B 241 (2017) 182–189 183

linker

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Fig. 1. Chemical structure of monomers (Acrylamide, Acrylic acid), cross

he methods that consume a low volume of sample solution foretection process.

In this paper, we describe the determination of paracetamolith a new droplet based banana- hydrogel carbon paste electrode.

t offers interesting advantages, such as: good selectivity because ofhe presence of the enzyme, rapidity, good stability in both acidicnd basic media, ease of preparation, low cost and also it needs aery low volume of sample solution. The method for fabricationf the electrochemical biosensor and its characterization are alsoeported.

. Material and methods

.1. Apparatus

All experiments were carried out in a 15 ml glass cell at 25 ◦C. Theoltammetric measurements were performed using a �Autolablectrochemical system (Metrohm) equipped with NOVA software.he electrochemical cell was assembled with a three electrodeystem; an Ag/AgCl reference electrode, a platinum counter elec-rode (both from Azar electrode Co, Urmia Iran) and a constructedanana-hydrogel carbon paste electrode (BH-CPE) as a workinglectrode.

.2. Reagents and solutions

All chemical reagents were of analytical-reagent grade and dion-zed distilled water was used for preparation of the solutions.crylamide (AM) and acrylic acid (AA) monomers, ammoniumersulfate (APS), N,N’-methylenebisacrylamide (MBA), sodiumydroxide and hydrochloric acid (37%w/w) were purchased

rom Merck chemical company. Chitosan, molecular weight:00,000–300,000 was purchased from Across organics. Paraceta-ol (PA) was purchased from Sigma and a 2.5 × 10−2 mol l−1 stock

olution of this drug in 0.10 mol l−1 phosphate buffer solution wasrepared. For preparation of the standard solutions, the stock solu-ion was diluted with adequate phosphate buffer solution.

.3. Preparation of the hydrogel

The hydrogel [39–41] used in this work, was synthesized accord-ng to the following procedure [39]: 150 ml solution of acrylamideAM) and neutralized acrylic acid (AA) monomers (AA/AM molatio: 0.8) with total concentration of 5% wt, was prepared inionized distilled water in a volumetric flask. Before prepara-ion of the solution, the AA monomer was neutralized at 5 ◦C

ith sodium hydroxide solution (2 M). Then, 8.8 mg of N,N’-ethylenebisacrylamide (MBA) as a cross linker was added to the

bove monomers solution. After purging the solution with N2 for0 min, the solution was heated at 50 ◦C and 35.2 mg of ammo-

(N,N-methylen bisacrylamide) and reaction path for hydrogel synthesis.

nium persulfate (APS) as an initiator was added into the flask. Thesolution was stirred vigorously for 3 h to complete the polymeriza-tion process. The prepared hydrogel was washed with water andethanol respectively, and then dried in an oven at 70 ◦C. Finally,the dried sample was milled with a mortar and it was used forfurther characterization. Fig. 1, shows the chemical structures ofacrylamide, acrylic acid, N,N’-methylenebisacrylamide and the syn-thesized hydrogel [42]. A typical FT-IR pattern of the hydrogel(Fig. 2) confirmed the presence of the functional groups in syn-thesized hydrogel.

2.4. Construction of the electrochemical biosensors

0.1 g of the banana tissue was ground in a mortar and mixedwith 0.2125 g of graphite powder and 0.0375 g of hydrogel, and then0.05 g of paraffin oil was added and mixed thoroughly for prepa-ration of banana-hydrogel carbon paste electrode (BH-CPE). Alsoa hydrogel carbon paste electrode (H-CPE) without banana tissueand banana carbon paste electrode (B-CPE) without hydrogel, wereprepared for investigation of the performance of the modified elec-trode. A portion of each paste was packed into the tip of a 1 mlinsulin plastic syringe and a copper wire was inserted to obtainthe electrical contact. Prior to use, the surface of the electrode waspolished with a weighing paper.

3. Results and discussion

3.1. Electrode characterization

The scanning electron microscopy (SEM) is a type of electronmicroscopy that routinely used to generate high-resolution imagesof the surface of the solid samples. The surface morphologies ofthe banana-hydrogel modified electrode were investigated usingSEM. As is evident in Fig. 3, the surface topography for the banana-hydrogel electrode shows a homogeneous surface.

3.2. Principle of the electrochemical measurements

The polyphenol oxidase at the electrode surface, catalyses theoxidation of paracetamol (PA) to n-acetyl-p-benzoquinoneimine(NAPQI) and this product is electrochemically reduced to parac-etamol [6]. The oxidation of PA, is a two-electron transfer process(Fig. 4). All measurements were carried out in a 15 ml glass cell in5 ml of phosphate buffer solution (0.1 mol l−1). The cyclic voltam-

mograms were obtained by cycling the potential between −0.35and +1 V at scan rate of 100 mV s−1. The square-wave voltammetric(SWV) measurements were performed at the potentials between−0.1 and +1 V.

184 A. Aliabadi et al. / Sensors and Actuators B 241 (2017) 182–189

Fig. 2. FT-IR spectrum of hydrogel.

Fig. 3. Scanning electron microscopy image of bana

Fig. 4. Schematic representation of the enzymatic process between paracetamola

nd polyphenol oxidase.

na- hydrogel carbon paste electrode surface.

3.3. Cyclic voltammetric study of PA

The cyclic voltammograms for 125 �M paracetamol in 0.1 Mphosphate buffer solution are shown in Fig. 5. As can be seen fromthis Figure, the electrochemical behavior of paracetamol moleculesis a quasi-reversible redox process. The oxidation peak current ofparacetamol on B-CPE (dotted line), H-CPE (dashed line) and BH-CPE (solid line) electrochemical sensors, show that the highest peakcurrent is obtained at BH-CPE modify electrode with respect tothe other constructed electrodes. This improvement in electrontransfer kinetics can be attributed to the following factors: (1)The excellent absorption of paracetamol molecules on the surface

of this electrode, due to their entrapment in porous structure ofthe hydrogel and hydrogen bond formation. (2) The semi wet andthree-dimensional environment of the hydrogel for enzyme immo-

A. Aliabadi et al. / Sensors and Actu

Fig. 5. Cyclic voltammograms of 125 �M of PA at B-CPE (dotted line), H-CPE (dashedline) and BH-CPE (solid line) in 0.1 M phosphate buffer (pH 7). In the all cases, thescan rate is 100 mV s−1.

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ig. 6. Influence of pH on cyclic voltammograms of 125 �M PA at BH-CPE with acan rate of 100 mV s−1 (pH 3, 5, 7, 9, and 11, respectively).

ilization. (3) The hydrogel biocompatibility and enzyme friendlynvironment.

.4. Effect of tissue and hydrogel composition

The effect of the amounts of the banana tissue (0.05 to 0.15 g)nd hydrogel (0.025 to 0.05 g) on the electrode response for 125 �Maracetamol in 0.10 mol l−1 phosphate buffer solution (pH 7.0),as investigated. The experimental results showed that the elec-

rode which contains 25% of tissue (0.1 g) and 9.375% of hydrogel0.0375 g) has the best response. Therefore, this composition wassed in the construction of the banana hydrogel carbon paste elec-rode.

.5. Effect of pH

The electrochemical behavior of paracetamol is dependent onhe pH value of the solution, due to the presence of two protonransfer in its redox reaction. Therfore, the effect of pH (from 3 to 11)as investigated using cyclic voltammetry technique. The result-

ng pH profiles in Fig. 6 reveal that this electrochemical biosensoras a maximum sensitivity at pH 11. As can be seen from this Fig-

re, the peak potential for the paracetamol oxidation varies overhe pH range of 3–11and it is shifted to more negative potentialsith increasing of the pH values. We choose pH 11 as an optimum

H value in further investigations. The enzyme molecules can be

ators B 241 (2017) 182–189 185

denatured (unfolded) in extra pH values, but in the case of our pHresponsive hydrogel matrix, the enzyme can be active in both acidicand basic pH media with low variation in response of the elec-trode. Our pH −responsive hydrogel, contains both acidic (COOH)and basic (NH2) groups that they can be changed to NH3

+ and COO−

upon changing the pH of the solution and it seems that the enzymemolecules are not denatured and their conformation is not changedupon a wide pH range of the solutions [43].The schematic presen-tation of the hydrogel structure in acidic and basic pH is shown inFig. 7.

3.6. Effect of scan rate

The effect of scan rate (v) on the electrochemical behavior of PAat the BH-CPE electrochemical sensor was studied by cyclic voltam-metry. As is evident in Fig. 8A, there is a linear relationship betweenthe peak current (Ip) and the square root of the scan rate (v 1/2). Thislinear relationship, indicates that the kinetics of the oxidation ofPA molecules at the surface of the modified electrode is controlledby diffusion process. The depicted graph in Fig. 8 B shows that theoxidation peak current of paracetamol molecules increases withincreasing the scan rate because of heterogeneous kinetics.

3.7. The calibration plot and limit of detection

The measurement of paracetamol concentration at BH-CPE wascarried out in 0.1 M buffer solution (pH 11) by square wave voltam-metry (SWV) at a scan rate of 50 mVs−1. The ability of the hydrogelto absorb and retain the liquids, allows us to insert only 1 �l ofstandard paracetamol solution into the surface of the electrodeand in fact we measure the concentration of paracetamol whichis absorbed in the surface of the electrode, not in solution. Afterabsorption of paracetamol in hydrogel matrix, one �L of chitosan(0.5 g in 2% acetic acid) as a gum, was added on the surface of theelectrode to prevent falling apart the paste from the electrode sur-face. Chitosan is a biocompatible linear polysaccharide that acts as aliquid adhesive [44]. Then the electrode was dried and it was dippedin a voltammetric cell containing 5 ml of buffer solution (pH 11) andthe square wave voltamograms were recorded. The scheme of theprocedure is shown in Fig. 9. The exprimental results, demonstratethat with this low volume of PA solution (only one �L) and using thisprocedure, a better performance is achieved, compared to the tra-ditional analytical methods. This procedure shows a reproducibleresponse to PA molecules and only need one �L of sample, whichis a very considerable property for limited samples in volume. Itseems to us the disadvantage of this biosensor is only its dryingtime (10 min) for each measurement.

Fig. 10, shows the calibration graph for oxidation of one micro-liter of paracetamol over a concentration range of 10 to 250 �M.The detection limit (3Sb/m) was found to be: 1.6 �M. The per-formance of the constructed tissue electrode for determination ofparacetamol, with the other electrochemical carbon paste elec-trodes and some screen printed electrodes, which are reported inthe literature, is compared in Table 1. As is evident in this Table, theelectroanalytical data of the proposed novel biosensor are com-parable and in some cases, are better than the other constructedelectrochemical sensors for determination of paracetamol in solu-tions. Besides, this electrode needs only one microliter of samplesolution for analysis.

The relative standard deviation (RSD) of 50 �M solution of PA,was found to be: 3.2% (n = 5). When the electrode was not in use,it was stored at 4 ◦C. No considerable change was observed in theoxidation peak current after storage for 20 days.

186 A. Aliabadi et al. / Sensors and Actuators B 241 (2017) 182–189

Fig. 7. The schematic presentation of the pH influence on the hydrogel structure.

Fig. 8. (A) Plot of Ip versus �1/2 for the oxidation of PA at BH-CPE. (B) Cyclic voltammograms of PA (125 �M) at different scan rates of 10, 50, 100, 150 and 200 mV s−1,Electrolyte; 0.1 M phosphate buffer; pH 11.

Table 1Comparison of electroanalytical data for paracetamol determination.

Electrode Linear range (�M) Detection limit (�M) Reference

CNT-PCPE 10–100 1.1 [25]CS-CPE 0.8–200 0.5 [26]Zucchini-CPE 120–2500 69 [27]Avacado-CPE 120–5800 88 [6]EIGPU-SPE 1–100 0.8 [45]EIGPU-SPE 1–40 0.84 [46]SPCE 5–30 0.1 [47]BH-CPE 10–250 1.6 This work

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Table 2Interference study for the determination of paracetamol, with Bannana- hydrogelcarbon paste electrode.

Substance (50 �M) Current ratios(I/I◦ )a

Lactose 1.08Fructose 1.36Ascorbic acid 1.04Ascorbic acidb 1.35Glucose 1.05Urea 1.18

a Current ratios for mixtures of 1:1 of interfering substance and paracetamol (I)in comparison to that of paracetamol alone.

b Current ratios for mixture of 2:1 of Ascorbic acid and paracetamol (I) in com-

NT-P: Carbon nanotube and Poly(3-Aminophenol), CPE: Carbon paste electrode,S: Chitosan, EIGPU: Graphite and polyurethane composite, SPE: Screen printedlectrode, SPCE:Screen printed carbon electrode.

.8. Study the effect of interferences

Some of the interferences which are present in some of the bio-ogical fluids, can interfere with determination of PA in solutions.

herfore, investigation of the influence of these interferences onhe response of the electrode is important issue. This effect wastudied for a 50 �M standard solution of PA and the interferenceubstances. The experiments were carried out according to the cal-

parison to that of paracetamol alone.

ibration procedure, with using only one �L of sample solution. Theexperimental results are summarized in Table 2. According to thedata which are summarized in this Table, it can be concluded thatthe selected materials do not interfere with determination of PA in

solutions because the oxidation peak current of the paracetamol,shows no considerable variation in the presence of this material.Therefore, due to the high selectivity of the enzyme which is present

A. Aliabadi et al. / Sensors and Actuators B 241 (2017) 182–189 187

Fig. 9. The schematic presentation of the calibration procedure: (1) Inserting of 1 �l of paracetamol and chitosan gum in the surface of the electrode, respectively. (2) Insertingof the electrode in the voltammetric cell containing 5 ml buffer solution, counter electrode and reference electrode.

Fig. 10. Plot of the oxidation peak current of PA as a function of PA concentrations. Inset: square wave voltammograms of PA in 0.1 M buffer solution (pH 11) containingdifferent concentrations: (1) 10, (2) 12.5, (3) 25.0, (4) 50.0 (5) 83.0 (6) 250.0 �M.

188 A. Aliabadi et al. / Sensors and Actu

Table 3Voltammetric determination of paracetamol in urine samples.

Urine sample Added(�M) found(�M) recovery

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[37] S. Zhao, W. Bai, H. Yuan, D. Xiao, Detection of paracetamol by capillary

Sample 1 50 52.2 104.4Sample 2 83 83.9 101.08

n the banana tissue, the fabricated electrochemical biosensor, isighly selective for recognition of PA in solutions.

.9. Determination of paracetamol in urine samples

In order to evaluate the practical performance of the BH-CPElectrode, healthy human urine samples were analyzed. Prior tonalysis, the urine samples were centrifuged and diluted 10 timesith phosphate buffer solution (pH 11). Then a known concentra-

ion of standard paracetamol was spiked into the prepared urineamples and one microliter of the resulted urine solution was ana-yzed for paracetamol determination. As shown in Table 3, thebtained results are in good agreement with the known paraceta-ol concentration spiked in the urine samples. The good recovery

esults, suggests that the BH-CPE electrode could be used for theetermination of parecetamol in urine samples.

. Conclusions

In the present paper, for the first time, a novel polymeric (hydro-el) tissue sensor was fabricated and it was used for determinationf paracetamol (PA). The oxidation current of PA molecules on theroposed electrode (BH-CPE) increased 7.5 folds in compared with-CPE and 2.2 folds in compared with H-CPE. It was found that theresence of the hydrogel with excellent properties, results in a highnhance in the oxidation peak current of paracetamol molecules.he constructed electrode showed a high current sensitivity, highelectivity, low detection limit, good reproducibility and good sta-ility in both acidic and basic media, for measurement of this drug inolutions. Furthermore, the electrode successfully used for deter-ination of PA in urine samples with good recovery results. The

esults obtained in this study, show a major potential in construc-ion of low-consumption biosensors in the field of droplet basedlectrochemical sensors. The main advantages of this biosensor arets analytical potentiality for determination the concentration ofaracetamol in one microliter of solution, low cost because of thesage of banana tissue instead of expensive pure enzyme, the sim-le and easy renewal of the surface of the carbon paste electrode,

ast response, high sensitivity, enzyme stability of the electrode inH ranges (3 to 11), high reproducibility of the electrode and highelectivity.

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Department of Chemistry, Faculty of Sciences Ferdowsi University of Mashhad,Mashhad, Iran.

Mohhamad Hossein Arbab Zavar (Third author) is a Professor of Department ofChemistry, Faculty of Sciences Ferdowsi University of Mashhad, Mashhad, Iran.

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Biographies

Aazam Aliabadi (First author) is a Ph.D student of Department of Chemistry, Facultyof Sciences Ferdowsi University of Mashhad, Mashhad, Iran and also a guest teacherof Sabzevar Payamnoor University, Sabzevar, Iran.

Gholam Hossein Rounaghi (Second and corresponding author) is a Professor of