1-s2.0-S0925400515004669-main Electrochemical sensor

Sensors and Actuators B 215(2015)445–450

Contents lists available at ScienceDirect

Sensors and Actuators B:

Chemical

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 /s n

b

Electrochemical sensor based on graphene doped gold nanoparticles modi?ed electrode for detection of diethylstilboestrol

Xinying Ma,Meifeng Chen ?

Department of Chemistry and Chemical Engineering,Heze University,Heze 274015,People’s Republic of China

a r t i c l e

i n f o

Article history:

Received 27January 2015

Received in revised form 22March 2015Accepted 2April 2015

Available online 15April 2015

Keywords:

Diethylstilbestrol Modi?ed electrode Gold nanoparticle Graphene

Cyclic voltammetry

a b s t r a c t

An electrochemical sensor for detection of diethylstilboestrol (DES)was successfully developed.At ?rst,graphene-modi?ed glassy carbon electrode (Gr/GCE)was fabricated by casting graphene (Gr)on the surface of the pretreated glassy carbon electrode (GCE).Then,gold nanoparticles (Nano-Au)were produced by reducing gold chloride tetrahydrate (HAuCl 4)employing cyclic voltammetry (CV).Electrochemical behavior of DES at the graphene doped gold nanoparticle modi?ed glassy electrodes (Gr/Nano-Au/GCE)was studied and a new method was developed for the electrochemical analysis of DES.Gr/Nano-Au/GCE showed a good catalytic performance for the electrochemical oxidation of DES in pH =6.0phosphate buffer solution (PBS).The oxidation peak currents of DES showed a linear relationship with their concentrations in the ranges of 1.20×10?8–1.20×10?5mol L ?1.The estimated detection limit is 9.80×10?9mol L ?1.When the relative error is less than ±5%,no interference was found when detec-tion was performed in the presence of some common ions,estradiol,estriol,estrone and folic acid.The modi?ed electrode has good selectivity and stability and has been successfully applied to the detection of DES in food samples.

?2015Elsevier B.V.All rights reserved.

1.Introduction

Diethylstilbestrol (DES)is a kind of synthetic estrogens.It is used widely as a growth stimulant in animals for food and as a treatment for estrogen-de?ciency disorders in veterinary medicine [1,2].It was also prescribed to pregnant women to prevent miscarriage,premature labor,and related complications of pregnancy.But the unfortunate side-effects of such treatment are well known [3].Its presence as a residue in meat and its proven carcinogenic nature for human beings and laboratory animals has led to the regulation of its use.Therefore,it is of great importance to develop a fast and ef?cient method for its detection to prevent illegal usage.

Various methods such as gas chromatography–mass spectrom-etry [4–6],liquid chromatography–mass spectrometry [7–10],electrochemical immunoassay [11]or chemiluminescence [12]have been reported for the detection of DES.However,the above noted techniques usually require expensive instruments and/or materials,large amount of highly puri?ed solvents,and are time-consuming.

?Corresponding author.Tel.:+86135********.

E-mail address:maxinying5966@https://www.360docs.net/doc/6b2064643.html, (M.Chen).

Recently,chemically modi?ed electrodes have been used widely in analytical chemistry.Electrochemical methods provide a simple,convenient,and fast means for detecting biological and environ-mental molecules.DES has the property of electrochemical activity because of hydroxyl groups in its molecule.In the past few years,electrochemical detection of DES has been reported [13–15].How-ever,there is no report on detection of DES using Gr/Nano-Au/GCE by electrochemical method,to our best knowledge.

Due to its extraordinary structure and properties,graphene exhibits excellent electronic,optical,mechanical and thermal properties [16–18].It has been used to modify electrodes for elec-trochemical studies [19–26].Metal nanoparticles also have been used widely as sensing material to modi?ed electrode because of its excellent conductivity,good electrocatalytic activity and chem-ical stability [27–31].Among various metal nanoparticles,gold nanoparticles have been extensively studied in electroanalytical chemistry because of their unique properties [32–34],such as good biological compatibility and conductivity.They have synergistic effects on the chemical and physical properties,which can enhance the sensitivity and the stability of the graphene modi?ed electrode.

In this work,a Gr/Nano-Au/GCE was prepared.The electro-chemical behavior of DES was studied and a new method for the detection of DES was developed.The results showed that the oxida-tive peaks increased linearly with DES concentration in the range

https://www.360docs.net/doc/6b2064643.html,/10.1016/j.snb.2015.04.016

0925-4005/?2015Elsevier B.V.All rights reserved.

446

X.Ma,M.Chen /Sensors and Actuators B 215(2015)

445–450

Fig.1.(a)SEM image of Gr/GCE.(b)SEM image of Gr/Nano-Au/GCE.(c)EDS spectrum of Gr/Nano-Au/GCE ?lm.

of 1.20×10?8and 1.20×10?5mol L ?1,with a detection limit of 9.80×10?9mol L ?1.The method was successfully applied to the quick detection of DES in food samples with good results.

2.Experimental

2.1.Apparatus and chemicals

Electrochemical measurements were performed on a CHI 660C Workstation (CH Instruments,Shanghai,China)with a conven-tional three-electrode system,which composed of a bare or modi?ed GCE as the working electrode,and a saturated calomel electrode and a platinum wire electrode as the reference and counter electrodes,respectively.Ultrasonic cleaning was per-formed using a KQ-100ultrasonic cleaner (Kunshan,China)and solution pH was measured using a pHS-3B pH meter (Shanghai,China).SYZ-550Quartz Sub-Boiling High-puri?ed Water Distiller (Jiangsu,China)and MT Infrared lamp (Guangzhou,China)were used.

DES was purchased from Chengdu Aikeda Chemical Reagent Co.,Ltd (Chengdu,China).Food samples (beef,?sh,and milk pow-der)were obtained from the local markets (Heze,China).The concentration of 1.00×10?3mol L ?1standard solution of DES was prepared in alcohol.Graphene was synthesized from graphite pow-der according to our previously reported method [35];0.3mg suspension graphene was dispersed in 10mL water after son-ication to prepare a suspension solution of 0.3mg mL ?1.Buffer solution was obtained by mixing the stock solutions of 0.20mol L ?1sodium phosphate dibasic (Na 2HPO 4)and 0.10mol L ?1citric acid.All reagents were obtained as analytical grade and used without further puri?cation.Double distilled water was used throughout the experiments.All experiments were performed at room tem-perature.

2.2.Preparation of Gr/Nano-Au/GCE

A glassy carbon electrode (?=3.8mm)was polished before each experiment with gold sand paper (2000-Grit)and Al 2O 3slurry,respectively,and was then rinsed with distilled water between each polishing step.Next,it was sonicated successively with 50%nitric acid,absolute alcohol and doubly distilled water,and dried in air.The Gr/GCE was prepared by casting 5?L of graphene sus-pension (0.3mg ml ?1)on the electrode surface and dried under an infrared lamp.A Gr/Nano-Au/GCE was prepared by immersing the Gr/GCE into an aqueous solution containing 0.1mol L ?1KNO 3and 5mmol L ?1HAuCl 4with a scan rate of 50mV s ?1in the potential range of ?0.2V to 1.0V for two cycles.A Nano-Au/GCE was prepared for comparison studies by immersing the pre-treated GCE into

Table 1

Content of C,O and Au elements.

Element

Weight/5

Atom/%C 42.4254.65O 45.9544.44Au 11.630.91Total

100.00

100.00

an aqueous solution containing 0.1mol L ?1KNO 3and 5mmol L ?1HAuCl 4under the same conditions.

The morphology and chemical composition of the Gr/GCE and Gr/Nano-Au/GCE surface were investigated and veri?ed by SEM and EDS,as shown in Fig.1.From the Fig.1b,it can be observed that large amounts of gold nanoparticles were well-dispersed on the surface of the Gr/GCE.At the same time,EDS spectrum of Gr/Nano-Au/GCE ?lm was carried out,as shown in Fig.1c.The content of C,O and Au are lasted in the Table 1.The EDS image con?rmed the presence of Au elements on the surface of Gr/GCE.

2.3.Analytical procedure

Certain amounts of pH 6.0PBS and DES standard solutions were pipetted into a 50mL electrolytic cell.Electrochemical measure-ments were performed with a CHI 660C Workstation having a three-electrode cell con?guration comprising a bare GCE,a Gr/GCE,a Nano-Au/GCE or a Gr/Nano-Au/GCE as the working electrode,an Ag/AgCl electrode as the reference electrode,and a platinum as the counter electrode.After stirring for 90s,cyclic voltammograms (CVs)were obtained by scanning in the potential range from ?0.2V to 0.8V.Scan rate was 100mV s ?1.The modi?ed electrode was placed in pH =6.0PBS and scanned until no peak for reuse.

3.Results and discussion

3.1.The choice of graphene volume

The redox peak current of DES was affected by the volume of graphene.Therefore,we investigated the effect of the volume of graphene casted on GCE.At the graphene concentration of 0.3mg mL ?1,the current peak of DES increased as the volume of graphene increased from 1to 5?L,and then decreased while the amount of graphene suspension exceeded 5?L.This may be due to high loading of graphene increased the thickness of the mod-i?ed layer on GCE,then the catalyst on the surface cannot be utilized effectively and catalytic substrates have been hampered to spread to the electrode surface.Thus,we used 5?L of a 0.3mg mL ?1graphene suspension to prepare the modi?ed electrodes in our experiments .

X.Ma,M.Chen/Sensors and Actuators B215(2015)445–450

447

Fig.2.CVs(CVs)of5.00×10?6mol L?1DES at a bare GCE(a),a Gr/GCE(b),a Nano-Au/GCE(c)and a Gr/Nano-Au/GCE(d).Scan rate:100mV s?1.

3.2.Optimization of Gr/Nano-Au/GCE

The Gr/Nano-Au/GCE was prepared at different scan rate and cycle by immersing the Gr/GCE into an aqueous solution contain-ing0.1mol L?1KNO3and5mmol L?1HAuCl4through the cyclic sweeping of the potential from?0.2to1.0V.The results showed that aggregation of the gold nanoparticles occurred at a low scan rate for many cycles.Meanwhile,the catalytic ability of nano-Au to DES was decreased.Under optimal conditions,the Gr/Nano-Au/GCE was prepared for2cycles with a scan rate of50mV s?1.

3.3.Electrochemical behavior of DES

The electrochemical behaviors of DES at a GCE,a Gr/GCE,a Nano-Au/GCE and a Gr/Nano-Au/GCE were investigated by CV.As shown in Fig.3that the value of the oxidation peak current of DES at the Gr/Nano-Au/GCE(32.4?A;Fig.3,curve d)was sig-ni?cantly increased in contrast to the poor response at the GCE (2.7?A;Fig.3,curve a),the Gr/GCE(11.0?A;Fig.2,curve b), and a nano-Au/GCE(10.7?A;Fig.3,curve c),which suggested that the Gr/Nano-Au?lm on the electrode has a high electro-catalytic activity toward the oxidation of DES.The remarkable signal enlargements indicated that the gold nanoparticles and graphene have synergistic electrocatalytic effect for the electro-

chemical detection of DES.The redox peak currents and peak at

the

Fig.3.CVs of5.00×10?6mol L?1DES at a Gr/Nano-Au/GCE at different pH(from a to g):2.2,3.0,4.0,5.0,6.0,7.0,and8.0,respectively.Inset A is the plot of oxidation peak currents versus pH.Inset B is the plot of oxidation peak potentials versus pH. Scan rate:100mV s?1

.Fig.4.CVs of5.00×10?6mol L?1DES at a Gr/Nano-Au/GCE at different scan rate. Each of the numbers from a to j corresponds to a scan rate of20,60,100,140,180, 220,260,300,340,and380mV s?1,respectively.Inset A is the plot of redox peak currents of DES versus scan rates.Inset B Plots of the peak potentials versus the logarithms of the scan rates.

Gr/Nano-Au/GCE were i pa=32.4?A,i pc=40.6?A,E pa=0.255V, E pc=0.225V,i pa/i pc=0.8<1and E=E pa?E pc=0.03,suggesting that the redox performs a half-reversible process.

3.4.Optimization of conditions for DES detection

3.4.1.Effect of medium’s pH

The effect of the medium’s pH on the electrochemical signal was analyzed.A variety of pH supporting electrolyte(pH2.2–8.0)were investigated,respectively(Fig.4).The oxidation peak current of DES reached its maximum peak value in the pH=6.0PBS.Thus, pH=6.0PBS was chosen as the supporting electrolyte(Fig.4,Insert A).Furthermore,the relationship between the peak potential(E pa) and the solution pH can be described by the following equation (Fig.3,Insert B):E pa=0.66–0.058pH,R=0.9982.The slope is0.058, which indicates that the number of electrons and protons involves in the reaction is equal according to Nernst Equation.

We investigated the effects of scan rates on the oxidation peak current of DES.Fig.4shows the CVs of DES at the Gr/Nano-Au/GCE at different scan rates.The oxidation peak potentials of DES were observed to shift positively with an increase in the scan rate.In addition,there are linear relationships between the peak current of DES and the scan rates(Fig.4,Insert A).The linear regression equa-tions are:i pa=3.29×10?6?2.32×10?7v(mV s?1),R=?0.9996, i pc=4.12×10?6+2.99×10?7v(mV s?1),R=0.9989.These show that it is an adsorption process of electrochemical behaviors of DES at the Gr/Nano-Au/GCE.Experimental results also show that the limit of detection becomes lower when the scan rate is higher than100mV s?1than other peaks.Therefore,100mV s?1was used as the scan rate in our work.

Insert B of Fig.4shows the plots of the peak potentials versus the logarithms of the scan rates.The linear regression equations of the E pa and E pc versus the scan rates are expressed as:E pa=?0.09+0.18 lg (mV s?1),R=0.9942;E pc=0.75?0.22lg (mV s?1),R=0.9935.

Laviron’s equation can be expressed as[36]:

E pa=a+(2.303RT/(1??)n?F)lg v(1) E pc=b?(2.303RT/?n?F)lg v(2) where a and b are all constant,

F the Faraday constant(96,487C),R the universal gas constant(8.314J K?1mol?1),T the Kelvin temper-ature(K),n the number of electron transferred and?the electron transfer coef?cient.By combining Eqs.(1)and(2),we obtained n?=0.60and?=0.45.It can be seen that the value of?is quite close to its theoretical value.

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Fig.5.Cvs of DES at the Gr/Nano-Au/GCE at different concentrations.Each of the letters from a to l corresponds to a concentration of:0.012,0.050,0.12,0.24,0.50, 0.75,1.2,2.5,5.0,7.5,10and12respectively(in?mol L?1).Inset is the plot of the oxidation peak current versus concentration of DES.Scan rate:100mV s?1.

3.4.2.Effect of accumulation time

Because of the adsorption-controlled process of DES at the Gr/Nano-Au/GCE,accumulation time may exert great in?uence on the detection sensitivity and the intensity of peak current. To investigate the effect,various accumulation times were stud-ied.Experimental results showed that the oxidation peak current increased as accumulation time increased from0to90s and kept almost unchanged when the accumulation time was further increased.Therefore,a stirring time of90s was chosen in our exper-iment.

3.5.Linear range and the detection limit

The relationship between the oxidation peak current and the concentration of DES was examined by CV under the optimal con-ditions and the results are shown in Fig.5.A linear relationship between the oxidation peak current and the concentration of DES was obtained from1.20×10?8to1.20×10?5mol L?1.The linear regression equations is i pa=3.73×10?6+2.49c(mol L?1),with a correlation coef?cient of0.9994.The detection limit was estimated to be9.80×10?9mol L?1.The limit of detection was estimated by gradually decreasing the concentration levels of DES.When the concentration of DES was decreased to9.80×10?9mol L?1,the oxi-dation peak of DES can still be observed,but the oxidation peak of DES almost disappeared when the concentration was further decreased.Therefore,the limit of detection was evaluated to be 9.80×10?9mol L?1.

3.6.Stability,reproducibility and robustness

When the electrodes were stored in air for30days for detec-tion of5.00×10?6mol L?1DES,98.4%of its initial responses were kept after storage,indicating that the Gr/Nano-Au/GCE has good stability.

Under optimal conditions,reproducibility of the Gr/Nano-Au/GCE was evaluated.A series of six electrodes were prepared for detection of5.00×10?6mol L?1DES.The relative standard devia-tion(RSD)of the measurements was2.2%(Fig.6),indicating that the Gr/Nano-Au/GCE has good reproducibility.

The robustness of the proposed method was evaluated by study-ing the effect of small variations in electrolyte pH(5.8–6.2),scan rate(98–102mV s?1),and accumulation time(88–92s)on the recovery of DES.Recovery for DES under all variable conditions was in the range of96.8–99.5%.No signi?cant changes were

observed

Fig.6.CVs of5.00×10?6mol L?1DES using six electrodes.

when these critical parameters were slightly varied,indicating that the Gr/Nano-Au/GCE had good robustness.

3.7.Interference studies

Potential interference in the detection of5.00×10?6mol L?1 DES has been studied.If peak current change is no more than±5% when a species is added,we assume that no interference occurs. Experimental results showed that there was no oxidation peak in presence of100-fold of K+,Na+,Mg2+,Ca2+,Al3+,Cl?,NO3?,SO42?, folic acid,glucose and vitamin E in a potential range of?0.2and 0.8V in PBS6.0.The CVs of10-fold of dopamine(DA),ascorbic acid (AA),uric acid(UA),estradiol(E2),estriol(E3)and estrone(E1)were obtained in a potential range of?0.2and0.8V in PBS6.0,as shown in Fig.7.These results indicated good selectivity of the method for the detection of DES

3.8.Recovery measurements of the DES

3.8.1.Pretreatment of samples

At?rst,suf?cient of fresh meat(beef or?sh meat)was chopped rapidly in a meat grinder.Next,?ve grams of each sample(beef,?sh, and milk powder)was translated to a sample tube and extracted ultrasonically for30min with3mL of acetonitrile and acetone(4:1, v/v).The supernatants were taken out from the sample tube and ?ltered through0.45?m membrane?lter.The solution was then diluted with4mL pH6.0PBS and1mL

ethanol.

Fig.7.CVs of DES,DA,AA,UA,E1,E2and E3.

X.Ma,M.Chen/Sensors and Actuators B215(2015)445–450449 Table2

Recovery measurements of the DES in food samples(n=6).

Samples DES added(×10?6mol L?1)Average found

(×10?6mol L?1)

Recovery(%)RSD(%)

Beef– 1.71a,1.67b– 2.5a,2.8b

1.50 3.23a,3.15b101.3a,98.7b 3.3a,3.6b

2.50 4.24a,4.27b101.2a,104.0b 2.8a,

3.1b

3.50 5.16a,5.09b98.6a,97.7b 2.9a,2.8b Fish meat––a,–b

1.50 1.48a,1.46b98.6a,97.3b 1.9a,

2.7b

2.50 2.44a,2.46b97.6a,98.4b 2.3a,

3.1b

3.50 3.45a,3.42b98.5.1a,97.7b 2.5a,3.1b Powdered milk––a,–b

1.50 1.45a,1.47b96.7a,98.0b

2.1a,2.9b

2.50 2.51a,2.43b100.4a,97.2b 2.5a,

3.1b

3.50 3.54a,3.47b101.1a,99.1b 2.9a,2.7b

a Results obtained by the proposed method.

b Results obtained by HPLC method.

3.8.2.Recovery measurements of the DES

Under our best conditions,DES in the food samples was deter-mined using this method and the results of DES were shown in Table2.

4.Conclusions

In this paper,a new,rapid and simple method was developed for the detection of DES,with high sensitivity and selectivity as well as a wide linear range.The Gr/Nano-Au/GCE has high electro-catalytic activity toward the oxidation of DES.The remarkable signal enlargements indicated that the nano-Au and graphene have a synergistic effect in the electrocatalytic oxidation of DES on the Gr/Nano-Au/GCE.The method was successfully applied to food samples’detection with the recovery in the range from97.2%to 104.0%.The modi?ed electrode exhibited good stability and repro-ducibility.

Acknowledgements

We are grateful to the?nancial support of A Project of Shan-dong Province Higher Educational Science and Technology Program (J14LC55),Natural Science Foundation of Shandong Province,China (ZR2014BL020),and Scienti?c Research Foundation of Heze Univer-sity(XY14KJ02).

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Biographies

Xinying Ma,an associate professor of the Department of Chemistry and Engineer-ing of Heze University,Heze,China.Her research interests include electroanalytical chemistry,biosensors,immunoassay and detection of the electroactive materials in food.

Meifeng Chen is an associate professor.Now she works in the Department of Chem-istry and Engineering,Heze University,Heze,China.Her research interests include electroanalytical chemistry,biosensors and synthesis of material.

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