Ultrasensitive determination of ceftizoxime using pencil graphite electrode modified by hollow gold nanoparticles/reduced graphene oxide

F. Azadmehr; K. Zarei

doi:10.1016/j.arabjc.2018.02.004

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Original article

13 (

); 1890-1900

doi:

10.1016/j.arabjc.2018.02.004

Ultrasensitive determination of ceftizoxime using pencil graphite electrode modified by hollow gold nanoparticles/reduced graphene oxide

F. Azadmehr, K. Zarei^⁎

School of Chemistry, Damghan University, Damghan, Iran

⁎Corresponding author. zarei@du.ac.ir (K. Zarei)

Received: 2017-10-17, Accepted: 2018-2-18, Published: 2018-01-01

Disclaimer:
This article was originally published by Elsevier and was migrated to Scientific Scholar after the change of Publisher.

Peer review under responsibility of King Saud University.

Abstract

In this work, a pencil graphite electrode (PGE) was modified using electrochemically reduced graphene oxide (rGO) and then hollow gold nanoparticles (HGNPs) were generated onto rGO/PGE by electrodeposition of cobalt and after that galvanic displacement reaction of cobalt nanoparticles with Au³⁺ ions. In this way, hollow gold nanoparticles/reduced graphene oxide/pencil graphite electrode (HGNPs/rGO/PGE) was constructed and used for sensitive voltammetric determination of ceftizoxime (CFX). The design experiment as a central composite design (CCD) methodology was developed as the experimental strategy for optimization of the influence of variables on the performance of modified electrode. The modified electrode was characterized using electrochemical impedance spectroscopy (EIS), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM) and choronocoulometry. The cyclic voltammetry (CV) and adsorptive differential pulse voltammetry (AdDPV) methods were utilized to survey the electrochemical action of CFX on the modified electrode. The linear dynamic range was $1.0 \times 10^{- 12} M$ to $1.0 \times 10^{- 11} M$ and $1.0 \times 10^{- 11} M$ to $1.0 \times 10^{- 9} M$ with a detection limit of 3.5 × 10⁻¹³ M. The existent method was employed to the determination of CFX in pharmaceutical and biological samples.

Keywords

Hollow gold nanoparticles

Reduced graphene oxide

Graphite pencil electrode

Ceftizoxime

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1 Introduction

Ceftizoxime (CFX) (Fig. 1) is the third descendant cephalosporin antibiotic that is active against aerobic both gram-negative and gram-positive bacteria and reduces the putrefaction by intervening with the wall so that the wall ruptures, resulting in the decay of bacteria. CFX is an active operator against infection, widely used in the therapy of delicate infection including bellows infection, skin and mild texture infection, bone and joint infection and other ventral infections. Quantitative determination of the content of antibiotics and analgesics in biological fluids is necessary for displaying the physiological and biochemical processes involved in the drug metabolism and it is also important for quality control of the drugs so several methods such as spectrophotometry (Sengun and Fedai, 1986; Zhang et al., 2008; Suzuki et al., 1980 ) and chromatography (Suzuki et al., 1980; Sanli et al., 2011) were applied for determination of CFX. The electrochemical methods have the fast response, easiness and high sensitivity in the analysis and they have been prosperous to study pharmaceutically important compounds. However, there are only few reports about the determination of CFX with voltammetric methods (Shahrokhian et al., 2016).

In order to obtain the optimum conditions for determination of different compounds, various methodologies can be applied such as statistical multivariate techniques. One of these techniques is response surface methodology (RSM) that can investigate the effects of the variables on the response and also the interaction between them, with a minimum number of experiments. As initially a screening operation selects important variables and then optimization was performed using RSM for selected variables (Box et al., 1978; Urkut et al., 2011). Central composite design (CCD) is frequently used in RSM performing. CCD is a fractional factorial design with center points and axial points equidistant to the center point (Myers, 1976). Some researchers applied CCD for optimization of conditions in construction of sensors and biosensors (Alizadeh and Zare, 2009; Shekarchizadeh et al., 2013).

Pencil graphite electrode (PGE) is the new kind of carbon electrode. It has been applied to the cathodic and anodic voltammetry by virtue of its high electrochemical reactivity, good mechanical resistance, low expense and ease of modification (Gao et al., 2005; Karadeniz et al., 2003; Demetriades et al., 2004 ).

Reduced graphene oxide (rGO) is one of the derivatives of graphene oxide (GO) that can be produced using chemical or electrochemical reduction of GO. The rGO has surprising properties such as excellent conductivity, large surface area and high stability (Pang et al., 2016). These properties help to design of new high-quality sensors for determination of different analytes (Zarei and Khodadadi, 2017; Ensafi et al., 2014). It has also been applied as reduced graphene oxide nanowall (rGONW) for the very sensitive determination of leukemia (Akhavan et al., 2014a,b, 2012 ).

Newly, hollow metallic nanoparticles such as hollow gold and hollow platinum have fabricated (Kim et al., 2002; Schmidt and Ostafin, 2002; Wong et al., 2002; Sun and Xia, 2002; Lu et al., 2007 ) via different templates such as nanoparticles (Liu et al., 2010). Hollow gold nanoparticles (HGNPs) are known as materials with advantages such as low density and high specific surface area and also low cost. Previously, for the preparation of HGNPs, cobalt nanoparticles were first produced using a chemical reaction and then replaced with gold nanoparticles using a displacement reaction (Liu et al., 2010). Finally, the Au nanoparticles were attached to the gold electrode via thiol linkages to fabricate a DNA biosensor with improved electrocatalytic properties (Liu et al., 2010). In this work, cobalt nanoparticles were simply produced using electrochemical deposition and then displacement reaction was applied to produce HGNPs on the electrode surface.

In this study, initially, rGO was electrodeposited on the electrode surface. After this stage, HGNPs were produced on the rGO/PGE via displacement reaction with cobalt nanoparticles (CoNPs) and eventually, the adsorption differential pulse stripping voltammetry (AdDPV) was used for measuring of oxidation current of the CFX. Optimization of instrumental and concentration parameters was achieved using CCD. The sensor showed excellent sensitivity and good selectivity toward determination of CFX. To the best of our knowledge, there is no report on the construction of HGNPs/rGO/PGE and also on the determination CFX using this sensor.

2 Experimental

2.1

2.1 Apparatus and reagents

An Autolab electrochemical system with PGSTAT 12 together with GPES and FRA 4.9 softwares were applied for voltammetric experiments and electrochemical impedance spectroscopy (EIS), respectively. The electrochemical system comprises a HGNPs/rGO/PGE as the working electrode (the PGE was 20 mm of the Owner pencil with 0.5 mm diameter and surface area of 0.316 cm² which was placed vertically in the solution via A Noki pencil that holds pencil), Ag/AgCl/KCl (saturated) as the reference electrode and a platinum wire as counter electrode. For impedance experiments, a frequency range of 0.10 Hz to 100 kHz and an AC voltage amplitude of 5 mV was used. Field emission scanning electron microscopy (FESEM) and transmission emission microscopy (TEM) were conducted with MIRA3TESCAN-XMU and Zeiss-EM10c-80KV microscopes, respectively. To obtain the FESEM images, the surfaces of modified electrodes were coated with a thin layer of gold. To prepare of TEM image, the scratched powder from the electrode surface was dissolved in ethanol solution and then a drop of this colloidal solution was placed onto a carbon-coated Cu grid under ambient conditions.

CFX was generously taken from Jaber Ebne Hayyan Pharmaceutical Co. (Iran). CoCl₂ and HAuCl₄ were bought from Merck and Sigma–Aldrich, respectively. Graphite oxides were prepared from graphite powder by Hummers method (Hummers and Offeman, 1958).

2.2

2.2 Fabrication of HGNPs/rGO/PGE

Initially, PGE was placed in the 120 mg L⁻¹ of GO suspension and potential of −1 V was applied to it during 260 s and in this way, the electrode was changed to rGO/PGE. After that to display CoNPs on the electrode surface, the rGO/PGE was transported to 20 mM of the CoCl₂ solution and −0.5 V potential was applied to the electrode for 200 s and consequently, the electrode was converted to CoNPs/rGO/PGE. Finally, to construct of HGNPs/rGO/PGE, CoNPs/rGO/PGE was transported to 600 µM HAuCl₄ for 600 s. With attention to the reduction potential of the AuCl₄⁻/Au redox couple (0.935 V vs SHE) is much higher than that of the Co²⁺/Co redox couple (−0.277 V vs SHE), the galvanic replacement reaction occurs when CoNPs/rGO/PGE was contacted with Au³⁺ ions and HGNPs/rGO/PGE was formed and hollow gold nanoparticles were formed. To compare rGO and HGNPs effects on the current response, one electrode was also constructed (HGNPs/PGE) which its construction was similar to HGNPs/rGO/PGE only without deposition of rGO.

2.3

2.3 Procedure of CFX determination

The optimum parameters for CFX determination by DPV such as acid concentration, adsorption potential, adsorption time and scan rate were obtained by applying a CCD.

However, for determination of CFX, specified amounts of CFX in the range of $1.0 \times 10^{- 12} M$ to $1.0 \times 10^{- 9} M$ , in 0.35 M HClO₄ were placed into the voltammetric cell. The accumulation was performed at 0.3 V during 190 s while the solution was stirred. Then potential was scanned from 0.6 to 1.1 V with a scan rate of 55 mV s⁻¹, interval time of 0.2 s and step potential of 10 mV using differential pulse voltammetry method. A blank solution without CFX was used to get the blank peak current.

3 Results and discussion

3.1

3.1 Characterization of modified electrode

3.1.1

3.1.1 Characterization of modified electrode using FESEM and TEM

The morphology of bare PGE, rGO/PGE, and HGNPs/rGO/PGE was studied using FE-SEM. Fig. 2 shows the topographies of the modified PGEs at different steps. Fig. 2a shows bare PGE surface. It was found that the applied potentials and the types of materials are effective on the formation of rGO and HGNPs on the surface of PGE. As rGO planes are clearly seen in Fig. 2b and GNPs in Fig. 2c. TEM in Fig. 2d is related to HGNPs/rGO/PGE which rGO planes and hollow nanoparticles are recognized very well in that. Moreover, energy dispersive X-ray analysis (EDX) was performed for surface characterization of modified PGEs and the results are shown in Table 1 and Fig. S1. The results given in Table 1 confirm that after displacement reaction of Au instead of Co, cobalt percent was highly decreased and gold percent was increased. In other words, it seems that Co was practically completely replaced by Au.

SEM image of bare PGE (a); rGO/PGE (b); HGNPs/rGO/PGE (c); and TEM image of HGNPs/rGO/PGE (d).

Table 1 EDX results for CoNPs/rGO/PGE and HGNPs/rGO/PGE.

	Element	Weight percentage	Atomic percentage
rGo/PGE	C	88.77	91.33
	O	11.23	8.67
		100.00	100.00

	C	87.40	90.98
CoNPs/rGO/PGE	O	11.14	8.71
	Co	1.46	0.31
		100.00	100.00

	C	87.26	94.78
HGNPs/rGO/PGE	O	5.83	4.75
	Co	0.05	0.01
	Au	6.87	0.45
		100.00	100.00

3.1.2

3.1.2 Characterization of rGO/PGE using Raman spectroscopy

Raman spectroscopy can be used as an essential tool to characterize the electronic structure of carbon materials such as graphene. Raman spectrum of rGO/PGE is shown in Fig. S2. Although, the high I_D/I_G ratios (with values higher than 1) have been usually reported for rGO, Fig. S2 shows I_D intensity is lower than I_G, which it can be assigned to the graphitic structure of the substrate. In Raman spectroscopy, the position and shape of 2D band and intensity of I_2D/I_G ratio have been applied to the characterization of stacking of the sheets. Fig. S2 shows the position of the 2D band at nearly 2684 cm⁻¹. In addition, the I_2D/I_G ratio was found nearly equal to 0.36. Since, some of the intensity of the G band was originated from the substrate; these results indicated the formation of the rGO by graphene sheets substantially having structures with lower than 3-layers (Akhavan et al., 2014b).

3.1.3

3.1.3 Characterization of modified electrode using EIS

The EIS was frequently used for investigation of variations in the electrode surface during modification stages. Fig. 3 shows Nyquist diagrams of bare PGE and also rGO/PGE and HGNPs/rGO/PGE in 0.5 mM [Fe(CN)₆]^−3/−4 containing 0.1 M KCl. All Nyquist plots displayed a low-frequency diffusion tail characteristic for the [Fe(CN)₆]^−3/−4 system. Among the investigated samples bare PGE showed a semicircle with the largest diameter indicating relatively slow charge transfer. However, the resistance was decreased with progress in modification from bare PGE (3527 Ω) to rGO/PGE (1290 Ω) and finally, it reached the minimum at the HGNPs/rGO/PGE (896 Ω) due to the high conductivity of nanoparticles and also increasing of the electrode surface.

EIS of bare PGE (a); rGO/PGE (b); and HGNPs/rGO/PGE (c) in 5.0 mM [Fe(CN)6]3−/4− containing 0.1 M KCl at the potential 0.1.

3.2

3.2 Optimization of experimental parameters using CCD

In order to achieve optimization of variables using central composite design (CCD), initially we have to select the more important parameters that can affect on the sensor performance. These parameters can be related to construction of electrode such as: GO, Co(II) and Au(III) concentrations and also deposition times of each of them or to the acid concentration or even to the instrumental parameters such as adsorption potential and time and also potential scan rate. To this purpose, the Plackett–Burman design was used. For experimental design 10 variables were selected and twelve experiments were performed in triplicate and the mean resulted currents are shown in Table S1. The effects of 10 variables on the DPV current response and their statistical significance at 95% confidence level are shown in Fig. 4. As can be seen in Fig. 4, scan rate, the adsorption potential and time, Co(II), GO and Au(III) concentrations, GO deposition time and acid concentration are factors that were selected and then CCD were applied for the optimization of 8 selected factors. For optimization, 8 factors were divided into two sets, as effective factors on the electrode modification stage, such as Co(II), GO and Au(III) concentrations and also GO deposition time were placed in the first set and the other four selected factors, scan rate, the adsorption potential and time and acid concentration were put in the second set. A three level CCD and 27 experiments were designed for each of two sets and the currents values for each experiment were obtained. Then regression analysis was performed on the experimental data using Minitab 16 software and the following equations were obtained for each of the sets:

The evaluated effects from the Plackett-Burman design for 10 variables and their statistical significance at 95% confidence level.

For the first set:

(1)

I = - 0.8556 + 2779.5 (C_{GO}) + 0.0778 (C_{Co}) + 0.0082 (C_{Au}) + 0.0064 (t_{dep (GO)}) - 2, 832, 755 {(C_{GO})}^{2} - 5.4 \times 10^{- 5} {(C_{Au})}^{2} + 16.6667 (C_{GO} C_{Au})

where C_GO, C_Co, C_Au, and t_{dep (GO)} are Go, Co(II) and Au (III) concentrations and deposition time of GO, respectively.

And for the second set:

(2)

I = - 8.4236 + 8.5926 (C_{acid}) + 4.0741 (E_{ads .}) + 0.0457 (t_{ads .}) + 0.1812 (Scan rate) - 3.1482 {(C_{acid})}^{2} - 7.0370 {(E_{ads .})}^{2} - 1.1831 \times 10^{- 4} {(t_{ads .})}^{2} - 0.0016 {(Scan rate)}^{2}

where C_acid, E_ads, and t_ads refer to the acid concentration, adsorption potential and adsorption time, respectively.

Then, an analysis of variance (ANOVA) was performed to verify that selected variables are significant. The results are shown in Tables S2 and S3 for the first and second sets, respectively. Small p–value (<0.05) shows significant of selected variables at 95% confidence limit. Also large p–value for lack of fit shows that model has been fitted very well. The calculated R² and R²_adj. were obtained as 93.22% and 90.72% for the first set (Eq. (1)) and 93.86% and 91.13% for the second set (Eq. (2)), respectively. Finally, to get the optimum values, graphical analysis of surface Figs. 5 and 6) related to equations of (1) and (2) were obtained using Minitab 16 software. The results of Figs. 5 and 6 show that the optimum values for C_Go, C_Co, C_Au and t_{dep. (GO)} are 120 mg L⁻¹, 20 mM, 600 µM and 260 s, respectively. The optimum amounts were considered in maximum sensitivity and less variations of current signal. Also, the optimum values for C_acid, E_ads., t_ads. and scan rate can be concluded as 0.35 M, 0.3 V, 190 s and 55 mV s⁻¹, respectively.

The optimum values for CGo, CCo, CAu and tdep. (GO).

The optimum values for Cacid, Eads., tads. and scan rate.

3.3

3.3 Electrochemical behavior of CFX at various electrodes

The electrochemical oxidation current of CFX was studied at different electrodes using the AdDPV method and the results are shown in Fig. 7. It can be seen that very low current was registered for the bare PGE, but after modification of the electrode surface with rGO the current increased and a peak at about 0.9 V appeared. To compare the effects of rGO and HGNPs on the oxidation current of CFX, the current response for HGNPs/PGE was also obtained. As it is seen in Fig. 7, its current response is more than rGO/PGE electrode which can be attributed to the formation of HGNPs that improved the surface area and conductivity of HGNPs/PGE compared to rGO/PGE and bare PGE. Therefore, it can be concluded that HGNPs exhibit much higher electrocatalytical activity for CFX oxidation rather than rGO. However, the peak current significantly increased for HGNPs/rGO/PGE due to synergistic effect of HGNPs and rGO that could be led to higher surface electrode, electrocatalytical activity and conductivity for HGNPs/rGO/PGE rather than bare PGE, rGO/PGE and HGNPs/rGO/PGE.

Differential pulse voltammograms of 1.0 nM CFX at bare PGE (a); RGO/PGE (b); HGNPs/PGE (c) and HGNPs/rGO/PGE (d); in 0.35 M HClO4 at scan rate of 55 mV s−1 and 190 s accumulation time.

3.4

3.4 The pH effect

The pH effect was investigated at phosphate buffers with pH in the range of 2.0–5.5 using AdDPV (Fig. S3(a)). The experiments showed that currents were decreased with increasing of pH, therefore different acidic media were examined and the best response was obtained in the HClO₄ medium. After that, different concentrations of HClO₄ were investigated to reach the best responses which with CCD optimization in the previous section, the optimum acid concentration was obtained as 0.35 M HClO₄.

Peak potential variations with pH were also studied in the range 2.0–5.5. The results showed that there is a linear dependence between peak potential and pH with linear regression (Fig. S3(b)):

(3)

Ep (mV) = - 59.1 pH + 1003 (R^{2} = 0.990)

The slope 59.1 shows the protons are involved in the oxidation reaction and also shows the protons and electrons number are equal. During the oxidation of CFX, the amino group at aminothiazole substituent is oxidized to imino radical and during this process it lost one electron and one proton. Then two radicals are coupled and a dimer is produced (Shahrokhian et al., 2016). Therefore the changes of E_p and pH are in accordance with the suggested mechanism Scheme 1).

The proposed electrochemical oxidation mechanism of CFX at HGNPs/rGO/PGE.

3.5

3.5 Scan rate effect

The cyclic voltammetry was used to study the scan rate effect on the oxidation of CFX. Fig. 8a shows cyclic voltammograms of CFX in different scan rates from 20 to 120 mV s⁻¹ and the anodic peak current variation versus scan rate is seen in Fig. 8b. The figure shows as scan rate increased, the anodic peak current was linearly increased with the equation of I_pa(μA) = 0.137υ (mV s⁻¹) + 1.333 (R² = 0.995) that it confirms adsorptive property of CFX on the modified electrode and also the irreversibility of the adsorption process. The variations of E_p against log (scan rate) in Fig. 8c is exhibited with equation E_p (mV) = 69.40 (logυ) + 868.8. The slope of this equation is equal with 69.4 which with attention to Laviron equation (Laviron, 1979):

(4)

Ep = E^{0} + (\frac{2.303 RT}{α nF}) \log \frac{α nF}{{RTk}_{s}} + (\frac{2.303 RT}{α nF}) \log (ν)

CVs of the CFX at the HGNPs/rGO/PGE at various scan rate (20–120) mV s−1 (a); plot of ΔI versus scan rate (υ, mV s−1) (b); plot of Ep versus log(υ) (c).

And with considering of the assumed mechanism that considers n = 1, and with using above equation, the electron transfer coefficient (α) can be calculated as 0.86.

3.6

3.6 Chronocoulometric experiments

Chronocoulometry was applied to compute the effective surface area of bare PGE and HGNPs/rGO/PGE electrodes. K₃[Fe(CN)₆] was used as a model compound and the slope of the plot of Q vs. $t^{1 / 2}$ was derived using chronocoulometry. Finally, the effective surface area was calculated based on the following equation (Li et al., 2012):

(5)

Q (t) = \frac{2 {nFAcD}^{1 / 2} t^{1 / 2}}{π^{1 / 2}} + Q_{dl} + Q_{ads}

where n is the number of transferred electron (for K₃[Fe(CN)₆] n is 1), F is Faraday constant, A is effective surface area of working electrode, c is concentration of (K₃[Fe(CN)₆]), D is diffusion coefficient (D of K₃[Fe(CN)₆] is 7.6 × 10⁻⁶ cm² s⁻¹ (Li et al., 2012), Q_dl is double layer charge, Q_ads is produced charge from adsorption. Fig. 9(A) shows the variations of Q versus time for bare PGE and HGNPs/rGO/PGE electrodes. Based on the slope of the equation Q and

t^{1 / 2}

, in Fig. 9(B), the effective surface area A can be calculated as 0.185 and 0.962 cm² for bare PGE and HGNPs/rGO/PGE electrodes, respectively. The results showed that the electrode effective surface area was increased 5.2 times after the electrode was modified with HGNPs/rGO/PGE.

(A) Plot of Q–t for the HGNPs/rGO/PGE (a); and bare PGE (b) in 1 mM K3[Fe(CN)6]; (B) plot of Q–t1/2 curves for the HGNPs/rGO/PGE (a); and bare PGE (b) in 1 mM K3[Fe(CN)6], and potential −0.3 V. (C) Plot of Q–t for HGNPs/rGO/PGE in 0.35 M HClO4 in the presence of 0.1 µM CFX and potential 1.0 V (a); and in absence of CFX (b) and (D) Plot of Q–t1/2 for the HGNPs/rGO/PGE in 0.35 M HClO4 in the presence of 0.1 µM CFX (background subtracted).

The chronocoulometry experiments were also performed in 0.35 M HClO₄ in the absence and presence of CFX in order to calculate the adsorption capacity of CFX for HGNPs/rGO/PGE Fig. 9C). In this way, the adsorption capacity of CFX was calculated from the intercept of blank subtracted plot of Q versus t1/2 for CFX Fig. 9D) with attention to the below equation:

(6)

Q_{ads} = nFA Γ_{s}

where Γ_s is the adsorption capacity. To this way, the adsorption capacity can be calculated as 8.07 × 10⁻⁹ mol cm⁻².

3.7

3.7 Calibration curve, detection limit, reproducibility, stability and selectivity

The constructed modified electrode HGNPs/rGO/PGE was employed for the measurement of CFX using AdDPV under the optimized experimental positions. Fig. 10(A) shows obtained voltammograms for different concentrations of CFX. The relationship between peak currents and CFX concentration were linear in the range of $1.0 \times 10^{- 12} M$ to $1.0 \times 10^{- 11} M$ Fig. 10(B)) and $1.0 \times 10^{- 11} M$ to $1.0 \times 10^{- 9} M$ Fig. 10(C). The existence of two linear ranges proposes occurrence of adsorption. In the lower concentrations, charge transfer kinetic did not change, but in higher concentrations the peak current was decreased due to partial saturation of electrode surface by CFX (Hummers and Offeman, 1958).

(A) Stripping differential pulse voltammograms of 0.35 M HClO4 containing different concentrations of CFX from zero to 1 × 10−9 M and (B) plot of the peak currents as a function of CFX concentrations in the range of 1.0 × 10−12 to 1 × 10−11 M and (C) in the range of 1.0 × 10−11 to 1 × 10−9 M.

The detection limit was estimated as 3.5 × 10⁻¹³ M utilizing the equation of 3S_b/m where S_b is the standard deviation of 10 repetitive of the blank solution and m is the slope of the regression equation. In the other report that we could find about the electrochemical determination of CFX (Shahrokhian et al., 2016), the linear dynamic range and detection limit were reported as 0.02–7.0 µM and 6 nM, respectively. Comparison of this work results with the other reported results, for determination of CFX, shows that the linear dynamic range of our sensor is wider and its detection limit is lower than those from the previously reported works Table 2).

Table 2 Detection limit and linear dynamic range of various methods for determination of CFX.

Method	Linear range (µM)	Detection limit (µM)	Ref.
RP-HPLC	0.13–260	0.26	Arayne et al. (2007)
Ag nanoparticles decorated nano diamond‐graphite	0.02–7	0.006	Shahrokhian et al. (2016)
Capillary zone electrophoresis	26–2600	2.6	Solangi et al. (2010)
Poly(o-anisidine)/SDS/Ni/CPE	100–2000	80	Ojani et al. (2010)
Fulleren/GCE	3.1–26	0.0007	Jain et al. (2010)
HGNPs/rGO/PGE	1 × 10⁻⁶–0.001	3.5 × 10⁻⁷	This work

The reproducibility of the sensor was investigated by the determination of 0.1 nM of CFX for ten replica determinations (using ten different HGNPs/rGO/PGEs prepared under the same conditions), and the relative standard deviation of the peak currents was attained as 3.0%. The intraday precision was calculated by determination of CFX on 7 different days, as 4.9%.

The sensor current was decreased to the 96% of initial response after two days and to 80% after 7 days, which represents acceptable stability for the modified sensor.

The effect of some other species which possibly can trouble the determination of CFX was studied using oxidation peak of 0.1 nM of CFX. The disturbance limit is defined as the foreign-ion concentration causing an error smaller than 2.5% for the determination of CFX. The results showed that cationic and anionic species such as Al³⁺, Ba²⁺, Ca²⁺, Cd²⁺, Mg²⁺, ${CO}_{3}^{2 -}$ , F⁻, Cl⁻, Ni²⁺ and Zn²⁺ and also pharmaceutical compounds such as cefazoline, chloramphenicol, streptomycin, ascorbic acid and uric acid have no interference on the determination of CFX using constructed electrode.

3.8

3.8 Determination of CFX in biological and pharmaceutical samples

The utility of proposed sensor was assessed via determination of spiked CFX in blood serum. The results are shown in Table 3. The statistical t–test introduced absence of systematic error in the determination of CFX. The recoveries of this method were obtained in the range from 90% to 108%.

Table 3 Determination of CFX in blood serum and intramuscular injection.

Sample	Added nM)	Found^a,b (nM)	Recovery%
	0.0050	0.0054 ± 0.0004	108.0%
Plasma	0.10	0.10 ± 0.01	100%
	0.50	0.45 ± 0.03	90%

	0	0.049 ± 0.003	–
	0.01	0.058 ± 0.005	90.0%
CFX ampoule	0.05	0.104 ± 0.006	110.0%
	0.50	0.55 ± 0.04	100.0%

a Each sample was assayed in triplicate (n = 3).

b Mean ± standard deviation.

Also, CFX amount was identified in the pharmaceutical form of this drug as CFX ampoule. The specified amount of this drug was dissolved in the water and then further diluted and spiked with different amounts of CFX. After that, the content of CFX was calculated and the results are shown in Table 3.

4 Conclusion

The purpose of this work is the very easy construction of HGNPs/rGO/PGE sensor. Initially, the GO was turned to rGO using electrochemical reduction and then the HGNPs were formed via galvanic displacement reaction with electrodeposited CoNPs. FESEM indicated the electrode surface variations during modification progress and TEM showed the formation of hollow nanoparticles. EIS and CV were also applied to characterize the modified electrodes. The effective surface area for modified electrode and also adsorption capacity of CFX were determined using chronocoulometry. The fabricated sensor can be used for ultrasensitive determination of CFX in biological and pharmaceutical samples.

Acknowledgements

The authors acknowledge to the Research Council of Damghan University for the partial support of this work and also from Jaber Ebne Hayyan Pharmaceutical Co. for the preparation of CFX.

References

Akhavan O., Ghaderi E., Rahighi R., . Toward single-DNA electrochemical biosensing by graphene nanowalls. ACS Nano. 2012;6:2904-2916.
[Google Scholar]
Akhavan O., Ghaderi E., Hashemi E., Rahighi R., . Ultra sensitive detection of leukemia by graphene. Nanoscale. 2014;6 14810 11481
[Google Scholar]
Akhavan O., Ghaderi E., Hashemi E., Rahighi R., . Spongy graphene electrode in electrochemical detection of leukemia at singlecell levels. Carbon. 2014;79:654-663.
[Google Scholar]
Alizadeh T., Zare M., . Enhancement of sensitivity of molecularly imprinted polymer based parathion voltammetric sensor by using experimental design techniques. Anal. Bioanal. Electrochem.. 2009;1:169-187.
[Google Scholar]
Arayne M.S., Sultana N., Bi-Bi Z., . Simultaneous determination of cefazolin or ceftizoxime in presence of ascorbic acid from pharmaceutical formulation and human serum by RP-HPLC. Pak. J. Pharm. Sci.. 2007;20:56-61.
[Google Scholar]
Box G.E., Hunter W.G., Hunter J.S., . Statistics for Experimenters. New York: John Wiley and Sons; 1978.
Demetriades D., Economou A., Voulgaropoulos A., . A study of pencil-lead bismuth-film electrodes for the determination of trace metals by anodic stripping voltammetry. Anal. Chim. Acta. 2004;519:167-172.
[Google Scholar]
Ensafi A.A., Jafari-Asl M., Rezaei B., . A new strategy for the synthesis of 3-D Pt nanoparticles on reduced graphene oxide through surface functionalization, application for methanol oxidation and oxygen reduction. Electrochim. Acta. 2014;130:397-405.
[Google Scholar]
Gao W., Song J., Wu N., . Voltammetric behavior and square-wave voltammetric determination of trepibutone at a pencil graphite electrode. J. Electroanal. Chem.. 2005;576:1-7.
[Google Scholar]
Hummers W.S., Offeman R.E., . Preparation of graphitic oxide. J. Am. Chem. Soc.. 1958;80:1339.
[Google Scholar]
Jain R., Rather J.A., Dwivedi A., . Highly sensitive and selective voltammetric sensor fullerene modified glassy carbon electrode for determination of cefitizoxime in solubilized system. Electroanalysis. 2010;22:2600-2606.
[Google Scholar]
Karadeniz H., Gulmez B., Sahinci F., Erdem A., Kaya G.I., Unver N., Kivcak B., Ozsoz M., . Disposable electrochemical biosensor for the detection of the interaction between DNA and lycorine based on guanine and adenine signals. J. Pharm. Biomed. Anal.. 2003;33:295-302.
[Google Scholar]
Kim S., Kim M., Lee W.Y., Hyeon T., . Fabrication of hollow palladium spheres and their successful application to the recyclable heterogeneous catalyst for suzuki coupling reactions. J. Am. Chem. Soc.. 2002;124:7642-7643.
[Google Scholar]
Laviron E., . General expression of the linear potential sweep voltammogram in the case of diffusionless electrochemical systems. J. Electroanal. Chem.. 1979;101:19-28.
[Google Scholar]
Li J., Kuang D., Feng Y., Zhang F., Xu Z., Liu M., . A graphene oxide-based electrochemical sensor for sensitive determination of 4-nitrophenol. J. Hazard. Mater.. 2012;201–202:250-259.
[Google Scholar]
Liu S., Liu J., Han X., Cui Y., Wang W., . Electrochemical DNA biosensor fabrication with hollow gold nanospheres modified electrode and its enhancement in DNA immobilization and hybridization. Biosens. Bioelectron.. 2010;25:1640-1645.
[Google Scholar]
Lu W., Lin L., Jiang L., . Nanogold hollow balls with dendritic surface for hybridization of DNA. Biosens. Bioelectron.. 2007;22:1101-1105.
[Google Scholar]
Myers R., . Response Surface Methodology. Ann Arbor, MI: Edwards Brothers; 1976.
Ojani R., Raoof J.-B., Zamani S., . A novel sensor for cephalosporins based on electrocatalytic oxidation by poly (o-anisidine)/SDS/Ni modified carbon paste electrode. Talanta. 2010;81:1522-1528.
[Google Scholar]
Pang Y., Zhang Y., Li W., Ding H., Shen X., . Synergetic accumulation and simultaneous determination of naphthol isomers on electrochemically reduced graphene oxide modified electrode. J. Electroanal. Chem.. 2016;769:89-96.
[Google Scholar]
Sanli S., Sanli N., Gumustas M., Ozkan S.A., Karadas N., Aboul-Enein H.Y., . Simultaneous estimation of ceftazidime and ceftizoxime in pharmaceutical formulations by HPLC method. Chromatographia. 2011;74:549-558.
[Google Scholar]
Schmidt H.T., Ostafin A.E., . Liposome directed growth of calcium phosphate nanoshells. Adv. Mater.. 2002;14:532-535.
[Google Scholar]
Sengun F.I., Fedai I., . Analytical investigations on cephalosporins—IV: Application of Ellman's reagent. Talanta. 1986;33:366-369.
[Google Scholar]
Shahrokhian S., Ranjbar S., Ghalkhani M., . Modification of the electrode surface by Ag nanoparticles decorated nano diamond-graphite for voltammetric determination of ceftizoxime. Electroanalysis. 2016;28:469-476.
[Google Scholar]
Shekarchizadeh H., Ensafi A.A., Kadivar M., . Selective determination of sucrose based on electropolymerized molecularly imprinted polymer modified multiwall carbon nanotubes/glassy carbon electrode. Mater. Sci. Eng. C Mater. Biol. Appl.. 2013;33:3553-3561.
[Google Scholar]
Solangi A., Memon S., Mallah A., Memon N., Khuhawar M.Y., Bhanger M.I., . Determination of ceftriaxone, ceftizoxime, paracetamol, and diclofenac sodium by capillary zone electrophoresis in pharmaceutical formulations and in human blood serum. Turk. J. Chem.. 2010;34:921-934.
[Google Scholar]
Sun Y., Xia Y., . Increased sensitivity of surface plasmon resonance of gold nanoshells compared to that of gold solid colloids in response to environmental changes. Anal. Chem.. 2002;74:5297-5305.
[Google Scholar]
Suzuki A., Noda K., Noguchi H., . High-performance liquid chromatographic determination of ceftizoxime, a new cephalosporin antibiotic, in rat serum, bile and urine. J. Chromatogr. B. Biomed. Sci. Appl.. 1980;182:448-453.
[Google Scholar]
Urkut Z., Kara P., Goksungur Y., Ozsoz M., . Response surface methodology for optimization of food borne pathogen detection in real samples based on label free electrochemical nucleic acid Biosensors. Electroanalysis. 2011;23:2668-2675.
[Google Scholar]
Wong M.S., Cha J.N., Choi K., Deming T.J., Stucky G.D., . Assembly of nanoparticles into hollow spheres using block copolypeptides. Nano Lett.. 2002;2:583-587.
[Google Scholar]
Zarei K., Khodadadi A., . Very sensitive electrochemical determination of diuron on glassy carbon electrode modified with reduced graphene oxide–gold nanoparticle–Nafion composite film. Ecotoxicol. Environ. Saf.. 2017;144:171-177.
[Google Scholar]
Zhang X., Feng Y., Hu Q., . Feasibility and extension of universal quantitative models for moisture content determination in beta-lactam powder injections by near-infrared spectroscopy and chromatography. Anal. Chim. Acta. 2008;630:131-140.
[Google Scholar]

Appendix A

Supplementary material

Supplementary data associated with this article can be found, in the online version, at https://doi.org/10.1016/j.arabjc.2018.02.004.

Appendix A

Supplementary material

Supplementary data 1

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[1] Akhavan O., Ghaderi E., Rahighi R., . Toward single-DNA electrochemical biosensing by graphene nanowalls. ACS Nano. 2012;6:2904-2916.
[Google Scholar]

[2] Akhavan O., Ghaderi E., Hashemi E., Rahighi R., . Ultra sensitive detection of leukemia by graphene. Nanoscale. 2014;6 14810 11481
[Google Scholar]

[3] Akhavan O., Ghaderi E., Hashemi E., Rahighi R., . Spongy graphene electrode in electrochemical detection of leukemia at singlecell levels. Carbon. 2014;79:654-663.
[Google Scholar]

[4] Alizadeh T., Zare M., . Enhancement of sensitivity of molecularly imprinted polymer based parathion voltammetric sensor by using experimental design techniques. Anal. Bioanal. Electrochem.. 2009;1:169-187.
[Google Scholar]

[5] Arayne M.S., Sultana N., Bi-Bi Z., . Simultaneous determination of cefazolin or ceftizoxime in presence of ascorbic acid from pharmaceutical formulation and human serum by RP-HPLC. Pak. J. Pharm. Sci.. 2007;20:56-61.
[Google Scholar]

[6] Box G.E., Hunter W.G., Hunter J.S., . Statistics for Experimenters. New York: John Wiley and Sons; 1978.

[7] Demetriades D., Economou A., Voulgaropoulos A., . A study of pencil-lead bismuth-film electrodes for the determination of trace metals by anodic stripping voltammetry. Anal. Chim. Acta. 2004;519:167-172.
[Google Scholar]

[8] Ensafi A.A., Jafari-Asl M., Rezaei B., . A new strategy for the synthesis of 3-D Pt nanoparticles on reduced graphene oxide through surface functionalization, application for methanol oxidation and oxygen reduction. Electrochim. Acta. 2014;130:397-405.
[Google Scholar]

[9] Gao W., Song J., Wu N., . Voltammetric behavior and square-wave voltammetric determination of trepibutone at a pencil graphite electrode. J. Electroanal. Chem.. 2005;576:1-7.
[Google Scholar]

[10] Hummers W.S., Offeman R.E., . Preparation of graphitic oxide. J. Am. Chem. Soc.. 1958;80:1339.
[Google Scholar]

[11] Jain R., Rather J.A., Dwivedi A., . Highly sensitive and selective voltammetric sensor fullerene modified glassy carbon electrode for determination of cefitizoxime in solubilized system. Electroanalysis. 2010;22:2600-2606.
[Google Scholar]

[12] Karadeniz H., Gulmez B., Sahinci F., Erdem A., Kaya G.I., Unver N., Kivcak B., Ozsoz M., . Disposable electrochemical biosensor for the detection of the interaction between DNA and lycorine based on guanine and adenine signals. J. Pharm. Biomed. Anal.. 2003;33:295-302.
[Google Scholar]

[13] Kim S., Kim M., Lee W.Y., Hyeon T., . Fabrication of hollow palladium spheres and their successful application to the recyclable heterogeneous catalyst for suzuki coupling reactions. J. Am. Chem. Soc.. 2002;124:7642-7643.
[Google Scholar]

[14] Laviron E., . General expression of the linear potential sweep voltammogram in the case of diffusionless electrochemical systems. J. Electroanal. Chem.. 1979;101:19-28.
[Google Scholar]

[15] Li J., Kuang D., Feng Y., Zhang F., Xu Z., Liu M., . A graphene oxide-based electrochemical sensor for sensitive determination of 4-nitrophenol. J. Hazard. Mater.. 2012;201–202:250-259.
[Google Scholar]

[16] Liu S., Liu J., Han X., Cui Y., Wang W., . Electrochemical DNA biosensor fabrication with hollow gold nanospheres modified electrode and its enhancement in DNA immobilization and hybridization. Biosens. Bioelectron.. 2010;25:1640-1645.
[Google Scholar]

[17] Lu W., Lin L., Jiang L., . Nanogold hollow balls with dendritic surface for hybridization of DNA. Biosens. Bioelectron.. 2007;22:1101-1105.
[Google Scholar]

[18] Myers R., . Response Surface Methodology. Ann Arbor, MI: Edwards Brothers; 1976.

[19] Ojani R., Raoof J.-B., Zamani S., . A novel sensor for cephalosporins based on electrocatalytic oxidation by poly (o-anisidine)/SDS/Ni modified carbon paste electrode. Talanta. 2010;81:1522-1528.
[Google Scholar]

[20] Pang Y., Zhang Y., Li W., Ding H., Shen X., . Synergetic accumulation and simultaneous determination of naphthol isomers on electrochemically reduced graphene oxide modified electrode. J. Electroanal. Chem.. 2016;769:89-96.
[Google Scholar]

[21] Sanli S., Sanli N., Gumustas M., Ozkan S.A., Karadas N., Aboul-Enein H.Y., . Simultaneous estimation of ceftazidime and ceftizoxime in pharmaceutical formulations by HPLC method. Chromatographia. 2011;74:549-558.
[Google Scholar]

[22] Schmidt H.T., Ostafin A.E., . Liposome directed growth of calcium phosphate nanoshells. Adv. Mater.. 2002;14:532-535.
[Google Scholar]

[23] Sengun F.I., Fedai I., . Analytical investigations on cephalosporins—IV: Application of Ellman's reagent. Talanta. 1986;33:366-369.
[Google Scholar]

[24] Shahrokhian S., Ranjbar S., Ghalkhani M., . Modification of the electrode surface by Ag nanoparticles decorated nano diamond-graphite for voltammetric determination of ceftizoxime. Electroanalysis. 2016;28:469-476.
[Google Scholar]

[25] Shekarchizadeh H., Ensafi A.A., Kadivar M., . Selective determination of sucrose based on electropolymerized molecularly imprinted polymer modified multiwall carbon nanotubes/glassy carbon electrode. Mater. Sci. Eng. C Mater. Biol. Appl.. 2013;33:3553-3561.
[Google Scholar]

[26] Solangi A., Memon S., Mallah A., Memon N., Khuhawar M.Y., Bhanger M.I., . Determination of ceftriaxone, ceftizoxime, paracetamol, and diclofenac sodium by capillary zone electrophoresis in pharmaceutical formulations and in human blood serum. Turk. J. Chem.. 2010;34:921-934.
[Google Scholar]

[27] Sun Y., Xia Y., . Increased sensitivity of surface plasmon resonance of gold nanoshells compared to that of gold solid colloids in response to environmental changes. Anal. Chem.. 2002;74:5297-5305.
[Google Scholar]

[28] Suzuki A., Noda K., Noguchi H., . High-performance liquid chromatographic determination of ceftizoxime, a new cephalosporin antibiotic, in rat serum, bile and urine. J. Chromatogr. B. Biomed. Sci. Appl.. 1980;182:448-453.
[Google Scholar]

[29] Urkut Z., Kara P., Goksungur Y., Ozsoz M., . Response surface methodology for optimization of food borne pathogen detection in real samples based on label free electrochemical nucleic acid Biosensors. Electroanalysis. 2011;23:2668-2675.
[Google Scholar]

[30] Wong M.S., Cha J.N., Choi K., Deming T.J., Stucky G.D., . Assembly of nanoparticles into hollow spheres using block copolypeptides. Nano Lett.. 2002;2:583-587.
[Google Scholar]

[31] Zarei K., Khodadadi A., . Very sensitive electrochemical determination of diuron on glassy carbon electrode modified with reduced graphene oxide–gold nanoparticle–Nafion composite film. Ecotoxicol. Environ. Saf.. 2017;144:171-177.
[Google Scholar]

[32] Zhang X., Feng Y., Hu Q., . Feasibility and extension of universal quantitative models for moisture content determination in beta-lactam powder injections by near-infrared spectroscopy and chromatography. Anal. Chim. Acta. 2008;630:131-140.
[Google Scholar]

Ultrasensitive determination of ceftizoxime using pencil graphite electrode modified by hollow gold nanoparticles/reduced graphene oxide

Abstract

Keywords

Hollow gold nanoparticles

Reduced graphene oxide

Graphite pencil electrode

Ceftizoxime

1 Introduction

2 Experimental

2.1 Apparatus and reagents

2.2 Fabrication of HGNPs/rGO/PGE

2.3 Procedure of CFX determination

3 Results and discussion

3.1 Characterization of modified electrode

3.1.1 Characterization of modified electrode using FESEM and TEM

3.1.2 Characterization of rGO/PGE using Raman spectroscopy

3.1.3 Characterization of modified electrode using EIS

3.2 Optimization of experimental parameters using CCD

3.3 Electrochemical behavior of CFX at various electrodes

3.4 The pH effect

3.5 Scan rate effect

3.6 Chronocoulometric experiments

3.7 Calibration curve, detection limit, reproducibility, stability and selectivity

3.8 Determination of CFX in biological and pharmaceutical samples

4 Conclusion

Acknowledgements

References

Appendix A

Supplementary material

Appendix A

Supplementary material

Supplementary data 1

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