Colloids and Surfaces B: Biointerfaces 102 (2013) 687–693

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Colloids and Surfaces B: Biointerfaces

journal homepage: www.elsevier.com/locate/colsurfb

Multiwall carbon nanotubes decorated with NiFe2 O4 magnetic nanoparticles, a

new catalyst for voltammetric determination of cefixime
Ali A. Ensafi ∗ , Ali R. Allafchian
Department of Chemistry, Isfahan University of Technology, Isfahan 84156-83111, Iran

a r t i c l e i n f o a b s t r a c t

Article history: Multiwall carbon nanotubes were decorated with synthesized NiFe2 O4 magnetic nanoparticles. The new
Received 17 March 2012 materials were characterized with different techniques such as transform infrared spectroscopy, trans-
Received in revised form mission electron microscopy, atomic force microscopy and electrochemical impedance spectroscopy. The
17 September 2012
multiwall carbon nanotubes decorated with NiFe2 O4 magnetic nanoparticles was used as a new mediator
Accepted 18 September 2012
for the voltammetric determination of cefixime. Under the optimum conditions at pH 8.0, the oxidation
Available online 29 September 2012
of cefixime was occurred at 850 mV at the surface of the modified electrode. Linear sweep voltammetry
exhibited two wide linear dynamic ranges of 0.1–100 and 100–600 ␮mol L−1 cefixime. The detection
Keywords:
NiFe2 O4 nanoparticles
limit was found to be 0.02 ␮mol L−1 cefixime. Finally, the modified electrode showed good sensitivity,
Modified multiwall carbon nanotubes selectivity and stability for the determination of cefixime in real samples.
Electrocatalytic effect © 2012 Elsevier B.V. All rights reserved.
Cefixime
Voltammetry

1. Introduction and biotechnology, and industrial process control [23]. Modified

electrodes are very important tools for the analysis of several com-
Preparation, investigation, and application of nanomaterials are pounds at trace and ultra trace levels. The sensitivity and selectivity
very important in chemical science. Nanoparticles of a variety of of the voltammetric methods depend on the characteristics of the
shapes, sizes and compositions are changing the bioanalytical mea- modifier.
surement nowadays [1]. Carbon nanotubes (CNTs) is one of the Cefixime [6R-[6a,7b(Z)]]-7-[[(2-amino-4-thiazoyl)[(carboxy-
best candidates for the preparation of the electrocatalytic nano- methoxy)imino]acetyl]amino]-3- ethenyl-8-oxo -5 - thia-1-azabi-
composite materials. CNTs have attracted considerable attention cyclo[4.2.0]oct-2-ne-2-carboxylic acid, is an oral third generation
due to their fascinating physical, optical, chemical, mechanical, cephalosporin antibiotic. Cefixime is a cephalosporin antibiotic
and electrical properties [2–5]. The nanostructures with large used to treat infections caused by bacteria such as pneumonia,
specific surface area could provide an important and feasible plat- bronchitis, gonorrhea, and ear, lung, throat and urinary tract
form for catalysis [6], separation [7], sensing [8–10] and fuel cells infections. Cefixime is available as the trihydrate [24] (Scheme 1A).
[11]. Modification of the surface of CNTs with different materials Forty to fifty percent of the oral dose of cefixime is adsorbed from
such as metals, metal oxides, complex metal oxides and poly- the gastrointestinal tract. The plasma half-life is usually about
mers [12–14] can improve CNTs characteristics [15,16]. Decoration 3–4 h and may be prolonged when there is renal impairment.
of CNTs by spinel ferrites nanoparticles with chemical formula There is no evidence of metabolism of cefixime in vivo [24]. To
MFe2 O4 (M = Mn, Co, Ni, Mg, or Zn), which are very important mag- date, numerous methods have been proposed for the analysis of
netic materials, can improve optical, magnetic and electrochemical cefixime using different analytical techniques such as fluorimetry
properties of CNTs [17–19]. The magnetic CNTs have applications [25,26], high performance liquid chromatographic-electrospray
as magnetic data storage [20], microwave absorbing materials [21] ionization mass spectrometric [27–29], high performance liquid
and magnetic composites for drug delivery [22]. chromatography [30], high performance thin layer chromatogra-
Electrochemical methods of analysis have become one of phy [31], liquid chromatography (LC)–tandem mass spectrometry
the important methods in medicine, environmental monitoring, [32], and voltammetry [33–35].
This work describes the synthesis and study of a magnetic nano-
composite of MWCNTs decorated with spinel ferrite NiFe2 O4 using
∗ Corresponding author. Tel.: +98 311 3912351; fax: +98 311 3912350. citrate sol–gel method. The multiwall carbon nanotubes decorated
E-mail addresses: Ensafi@cc.iut.ac.ir, ensafi@yahoo.com, ensafi[email protected] with NiFe2 O4 nanoparticles (NiFe2 O4 -MWCNTs) was characterized
(A.A. Ensafi). with different methods such as transform infrared spectroscopy

0927-7765/$ – see front matter © 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.colsurfb.2012.09.037
688 A.A. Ensafi, A.R. Allafchian / Colloids and Surfaces B: Biointerfaces 102 (2013) 687–693

Scheme 1. (A) Structure of cefixime; (B) fitted circuit for electrochemical impedance spectroscopic data.

Table 1
Comparison of the proposed electrochemical sensor with the reported voltammetric method for the determination of cefixime.

Technique Type of electrode Limit of detection (␮mol L−1 ) Linear range (␮mol L−1 ) Reference

Differential pulse polarography Hanning mercury electrode 0.046 0.06–12.0 33

Square wave polarography Hanning mercury electrode 0.064 6.0–200.0 34
Square-wave cathodic Hanning mercury electrode 0.008 0.056–0.110 35
adsorptive stripping
Polarography
Cyclic voltammetry NiFe2 O4 -MWCNTs 0.09 0.1–600 This method
modified glassy carbon
electrode

(FT-IR), transmission electron microscopy (TEM), atomic force The AC voltage amplitude used was 5 mV, and the equilibrium
microscopy (AFM), vibrating sample magnetometer (VSM) and time was 15 s. NiFe2 O4 -MWCNTs modified glassy carbon electrode
electrochemical impedance spectroscopy (EIS). This method is (NiFe2 O4 -MWCNTs-GCE), a Pt-electrode and an Ag/AgCl (KClsat )
based on the different properties of the mediators plus nanoparti- were employed as a working, auxiliary and reference electrodes,
cles such as strong adsorptive ability, huge specific area and subtle respectively.
electronic properties. The suitability of NiFe2 O4 -MWCNT as a work- Fourier transform IR spectra were recorded using a JASCO
ing electrode in electrochemical methods was checked for cefixime FT-IR (680 plus) spectrometer using KBr pellets. The vibrational
determination using voltammetry. This method was convenient transition frequencies are reported in wave numbers (cm−1 ).
and useful because it has good sensitivity and low detection limit. Transmission electron microscopy was carried out on the powder
Table 1 shows the figures of merit of the proposed method relative samples with a Tecnai-F30-TEM operating at an accelerating volt-
to published voltammetric method for cefixime analysis. Finally, age of 300 kV. In addition, energy dispersive X-ray analysis was
the ability of this methodology for the determination of cefixime used. Scanning electron microscope (SEM) was performed with a
in pharmaceutical and urines has been discussed with satisfactory Philips XLC.
results. Magnetic properties of the samples were measured by vibrating
sample magnetometers with a maximal applied field of 10 kOe.
Atomic force microscopy was performed in ambient conditions
2. Experimental
using Bruker Nanosinstrument (Germany), operating in contact
mode.
2.1. Chemicals
2.3. Preparation of MWCNTs modified electrode
All chemicals were of analytical reagent grade purchased from
Merck (Darmstadt, Germany) unless otherwise stated. Deionized
To activate MWCNTs and remove any residual metals in the
water of resistivity less than 18.0 m at 25 ◦ C was used throughout.
nano-structure, 1.00 g of MWCNTs plus 20 mL of 3.0 mol L−1 HNO3
Cefixime was purchased from Aldrich. Cefixime tablet (200 and
were mixed in a 25-mL flux and then the mixture was refluxed
400 mg per tablet) was prepared as a real sample from Loghman
for 15 h. Then, the MWCNTs were separated from the mixture and
Pharmaceutical & Hygienic Company (Tehran, Iran). Cefixime stock
washed with 50 mL doubly distilled water, centrifuged (3500 rpm)
solution, 0.010 mol L−1 , was prepared in methanol. Working solu-
and dried at room temperature. The stable suspension of the acti-
tions under voltammetric investigation were prepared by dilution
vated MWCNTs was obtained by ultrasonicating of MWCNTs in
of the stock solution with methanol/water (20/80, v/v) solution.
dimethyl formamide (0.10 mg MWCNTs per 5 mL). A glassy car-
Phosphate buffer solutions (0.10 mol L−1 ) with different pH val-
bon (GC) disk electrode supplied by Metrohm was further polished
ues were used to study the pH influence.
with 0.05 mm alumina powder on a polishing micro-cloth for 3 min.
MWCNTs was prepared from Aldrich with a diameter of
Then, it was cleaned in an ethanol/water solution (50%, v/v) in the
10–30 nm, a length of 5–15 ␮m and the purity of >90%.
ultrasonic bath and rinsed thoroughly with doubly distilled water
prior to modification. Finally, 10 ␮L of the stable MWCNTs suspen-
2.2. Apparatus sion was dropped onto the surface of the glassy carbon electrode
and it was dried in a hot air flow at 50 ◦ C.
Electrochemical studies were carried out in a conventional
three-electrode cell powered by an electrochemical system com- 2.4. Preparation of NiFe2 O4 -MWCNTs modified electrode
prising of Autolab system (PGSTAT 12 and FRA2 boards, Eco
Chemie B.V., Utrecht, Netherlands). The system was run on a An in situ chemical citrate gel method was developed to
PC using GPES and FRA 4.9 software. For impedance measure- obtain the NiFe2 O4 -MWCNTs precursor. First, 0.75 g of the acti-
ments, a frequency range of 100 kHz to 1.0 Hz was employed. vated MWCNTs was added into 10 mL of 1.0 mol L−1 citric acid.
 A.A. Ensafi, A.R. Allafchian / Colloids and Surfaces B: Biointerfaces 102 (2013) 687–693 689

Then, it was ultrasonicated for 10 min. Afterward, the suspension absorption band at 1730 cm−1 corresponds to stretching vibration
was mixed with 10 mL solution of analytical grade of 0.5 mol L−1 of carbonyl group (C O). The stretching vibration of the carbox-
Ni(NO3 )2 ·6H2 O and 1.0 mol L−1 Fe(NO3 )3 ·9H2 O (in which the Ni:Fe ylate group (C O) is observed around 1383 cm−1 . The stretching
molar ratio was maintained at 1:2) and was dissolved in distilled vibration of C C group also localized at 1622 cm−1 . The absorp-
water. Then, the pH value reached to 9.0 using 0.10 mol L−1 ammo- tion band around 1100 cm−1 is assigned the stretching vibration of
nium hydroxide solution. The mixture was also stirred at 30 ◦ C for C C C group. Also two absorption bands at 578 cm−1 and 453 cm−1
48 h to complete the reaction. The produced mixture was dried in are corresponding to the vibration of tetrahedral and octahedral
an oven at 100 ◦ C for 12 h. The produced substance was calcinated complexes respectively, which are indicative of formation of spinel
at 620 ◦ C for 2 h in argon atmosphere. The resulted powder was ferrite structure [36–38]. As can be seen from the spectra, the nor-
denoted as NiFe2 O4 -MWCNTs. The structural, morphological and mal mode of vibration of tetrahedral cluster (578 cm−1 ) is higher
magnetic properties of the nano-composite were characterized by than that of octahedral cluster (453 cm−1 ). This can be due to the
XRD, FT-IR, TEM, AFM and VSM. After this, preparation of a sta- shorter bond length of tetrahedral cluster than the octahedral clus-
ble suspension of NiFe2 O4 -MWCNTs and modification of the glassy ter.
carbon electrode was repeated as described in Section 2.3. The magnetic properties of the decorated MWCNTs were mea-
sured in fields of ±10 kOe at room temperature. The values of the
saturation magnetization (MS ), coercivity (HC ), and retentivity (MR )
2.5. Preparation of real samples
of MWCNT-NiFe2 O4 obtained from the VSM data were obtained as
67.05 emu g−1 , 164.2 Oe, and 14.99 emu g−1 , respectively.
Urine and blood plasma samples were centrifuged (3000 rpm)
AFM was also used to obtain further details of the surface
for 3 min to remove any solid particles. Then, 1.0 mL of the sam-
structure such as roughness and thickness. Fig. 1B shows an
ple solution plus 9.0 mL of 0.10 mol L−1 buffer (pH 8.0, containing
AFM topology of the surface of NiFe2 O4 -MWCNTs modified elec-
20% (v/v) methanol) were transferred into the cell to measure the
trode corresponding to 2D (Fig. 1C, a) and 3D (Fig. 1C, b) images
cefixime contents using standard addition method.
recorded over an area of 20 ␮m × 20 ␮m. The 2D image of NiFe2 O4 -
For tablet analysis, 5 tablets of cefixime containing 200 and/or
MWCNTs modified electrode surface consists of continuous small
400 mg each were completely ground and homogenized. Then,
clusters smoothly grown on the entire surface containing spheri-
an enough weight of the homogenized powder was accurately
cal granules. The existence of particles with less than 50 nm size at
weighed and transferred into a 150 mL beaker containing 50 mL
NiFe2 O4 -MWCNTs modified electrode surface is clearly reflected in
methanol. The content was sonicated for 4 min to complete dis-
3D AFM image, which is characterized by nearly knoll-type projec-
solution of the sample. The solution was transferred into a 50-mL
tion in the z direction.
volumetric flask and diluted to the mark with methanol (equal to
Fig. 2A displays a typical morphology of NiFe2 O4 -MWCNTs
0.0025 mol L−1 cefixime). Finally, 10 ␮L of the solution plus 5 mL
modified electrode characterized by SEM. This figure shows that
of the buffer solution (0.10 mol L−1 , pH 8.0) were transferred into
NiFe2 O4 well distributed on the surface of MWCNTs and it did not
the electrochemical cell. The analysis was carried out using the
change the morphology of MWCNTs, but made it more compact.
standard addition method.
However, it can be clearly seen that MWCNTs dispersed homoge-
neously.
3. Results and discussion
3.2. Study of electrochemical behavior of cefixime at
3.1. Morphology and structure NiFe2 O4 -MWCNTs film-GCE

The structures of NiFe2 O4 -MWCNTs was studied by AFM, VSM, Cefixime has NH groups those make cefixime as an oxidizable
FT-IR spectroscopy, TEM, cyclic voltammetry (CV) and electro- compound and can be detected by electrochemical methods based
chemical impedance spectroscopy (EIS). on anodic oxidation [35]. Voltammetric responses of 300 ␮mol L−1
XRD spectra of NiFe2 O4 -MWCNTs magnetic nano-composite cefixime on the surface of the GCE, MWCNTs and NiFe2 O4 -MWCNTs
shows eleven characteristic peaks occur at 2 of 30.42◦ , 35.77◦ , modified electrode at pH 8.0 were recorded. Fig. 2B (curves
37.37◦ , 44.22◦ , 51.47◦ , 57.32◦ , 63.07◦ , 71.52◦ , 74.42◦ , 75.57◦ and a–c) shows the voltammograms of GCE, MWCNTs and NiFe2 O4 -
79.72◦ which are marked by their corresponding index (2 2 0), MWCNTs modified electrodes, respectively in the presence of
(3 1 1), (2 2 2), (4 0 0), (4 2 2), (5 1 1), (4 4 0), (6 2 0), (5 3 3), (6 2 2) and cefixime. The results confirm that the oxidation of cefixime at the
(4 4 4), respectively. The diffraction peaks at 2 of 26.27◦ , 43.42◦ surface of the bare GCE and at MWCNTs (Fig. 2B, curves a and
and 53.92◦ are the typical Bragg peaks of pristine CNTs and can b) has a weak peak current, whereas on the surface of NiFe2 O4 -
be indexed to (0 0 2), (1 0 1) and (0 0 4) reflection of MWCNTs. This MWCNTs modified electrode (Fig. 2B, curves c), an increase in the
reveals that the magnetic particles are pure NiFe2 O4 -MWCNTs with peak current could be observed.
a spinel structure. No diffraction peaks of the other compounds To compare the surface areas of the GCE, MWCNTs and
such as ␣-Fe2 O3 or NiO were observed. The sizes of the nanopar- NiFe2 O4 -MWCNTs-GCE, microscopic areas of the same size of
ticles ranges were from 30 to 40 nm, which is consistent with the the electrodes were measured by cyclic voltammetry using
result, is calculated using the Scherer equation. 1.0 mmol L−1 K3 Fe(CN)6 as a probe at different scan rates. For a
Fig. 1A shows TEM image (sample morphology) of NiFe2 O4 - reversible process, the Randles–Sevcik formula was used:
MWCNTs-GCE. This figure confirms that MWCNTs and NiFe2 O4
I pa = 2.69n3/2 AC 0 D1/2 1/2 (1)
were distributed on the surface of GCE. The spaghetti-like NiFe2 O4 -
MWCNTs and MWCNTs formed a porous structure. The entangled where Ipa (A) refers to the anodic peak current, n is the electron
cross linked fibrils offered a highly accessible surface area. In addi- transfer number, A (cm2 ) is the surface area of the electrode, D
tion, Fig. 1A shows that the surface morphology of MWCNTs is (cm2 s−1 ) is the diffusion coefficient, C0 (mol cm−3 ) is the con-
different when MWCNTs decorated with NiFe2 O4 . centration of K3 Fe(CN)6 , and  (V s−1 ) is the scan rate. Using
FT-IR spectra (Fig. 1B) of MWCNTs decorated with NiFe2 O4 1.0 mmol L−1 K3 Fe(CN)6 in the presence of 0.10 mol L−1 KCl with
clearly shows an absorption bands around 3436 cm−1 , which are n = 1 and D = 7.6 × 10−6 cm2 s−1 , the microscopic areas of the elec-
characteristic stretching vibration of hydroxyl functional group trodes can be calculated from the slope of the Ipa vs. 1/2 . The
(O H) on the surface of CNTs or adsorbed water in the sample. The results showed that for the bare GCE, the electrode surface area
690 A.A. Ensafi, A.R. Allafchian / Colloids and Surfaces B: Biointerfaces 102 (2013) 687–693

Fig. 1. (A) TEM image of the MWCNTs decorated by NiFe2 O4 nanoparticles; (B) FT-IR spectra of MWCNTs decorated with NiFe2 O4 ; (C) 2D (a), and 3D (b) AFM topology of the
surface of NiFe2 O4 -MWCNTs modified electrode.

was 0.0391 cm2 whereas for MWCNTs-modified electrode the sur- cefixime in 0.1 mol L−1 phosphate solutions with different pH val-
face area was 0.1564 cm2 . In addition, the calculated surface area for ues (3.0 < pH < 11.0) using cyclic voltammetry. The results showed
NiFe2 O4 -MWCNTs modified electrode was about 0.2340 cm2 . This that by increasing the solution pH from 2.0 to 8.0, the anodic peaks
means that the surfaces area for MWCNTs-modified electrode and current of cefixime increased and reached to its maximum value at
NiFe2 O4 -MWCNTs modified electrode is four and six times greater pH 8.0. Therefore, pH 8.0 was chosen as the optimum pH for the
than that for the bare GCE, respectively. determination of cefixime.
The effects of scan rate on the CV peak current and peak potential
3.3. Influence of variables of 300 ␮mol L−1 cefixime at NiFe2 O4 -MWCNTs-GCE were investi-
gated at pH 8.0. The results showed that the anodic peak current
The electrochemical behavior of cefixime depends on the pH increased linearly by increasing the scan rate according to the equa-
of the sample solution. Therefore, in order to obtain the oxidation tion of I(␮A) = 1.0031/2 (mV s−1 ) − 1.014 (r2 = 0.998). These results
peak current of cefixime, optimization of the solution pH seems indicate that the oxidation of cefixime on the surface of the modi-
to be necessary. Thus, we studied the electrochemical behavior of fied electrode is diffusion controlled.

Fig. 2. (A) SEM image of the MWCNTs decorated by NiFe2 O4 nanoparticles; (B) Voltammetric response of 300.0 ␮mol L−1 cefixime: (a) at a bare GCE; (b) at MWCNTs-GCE;
and (c) at NiFe2 O4 -MWCNTs modified electrode. Conditions: pH 8.0; scan rate, 200 mV s−1 .
 A.A. Ensafi, A.R. Allafchian / Colloids and Surfaces B: Biointerfaces 102 (2013) 687–693 691

Fig. 3. Nyquist plot of 2.5 mmol L−1 Fe(CN)6 3/4− in 0.10 mol L−1 KNO3 with (a) an
unmodified GCE; (b) MWCNTs; (c) NiFe2 O4 -MWCNTs modified electrode. Inset:
cyclic voltammograms of the above solution (d) at unmodified GCE; (e) at MWCNTs;
and (f) at NiFe2 O4 -MWCNTs modified electrode.

3.4. Electrochemical impedance spectroscopy Fig. 4. Calibration plot of (A) 100–0.1 ␮mol L−1 ; (B) 600–100 ␮mol L−1 cefixime; and
(C) voltammograms of cefixime at various concentration; (a) 600; (b) 550; (c) 450;
The mediator ability of NiFe2 O4 -MWCNTs was investigated (d) 350 and (e) 300 ␮mol L−1 . Conditions: pH 8.0; scan rate, 200 mV s−1 .

using electrochemical impedance spectroscopy. Fig. 3 shows

Nyquist diagrams of the imaginary impedance (Zim ) vs. the real obtain the construct of the calibration curve. The results showed
impedance (Zre ) of the EIS obtained at unmodified GCE (a), at two linear segments with different slopes for cefixime concentra-
MWCNT (b), and at NiFe2 O4 -MWCNTs modified electrode (c) in a tion; namely, for 0.1–100 ␮mol L−1 the regression equation was
solution containing 2.5 mmol L−1 of Fe(CN)6 4−/3− in 0.10 mol L−1 I(␮A) = (0.029 ± 0.002)CCefixime + (0.929 ± 0.030) (r2 = 0.993, n = 13),
KNO3 . The electrochemical impedance spectroscopic data of the while for 100–600 ␮mol L−1 cefixime, the regression equation was
three electrodes were fitted on a simple equal circuit, which is Ip (␮A) = (0.007 ± 0.001)CCefixime + (3.205 ± 0.050) (r2 = 0.994, n = 7),
shown in Scheme 1B. In this circuit, Rs , C and Rct represent solution where CCefixime is ␮mol L−1 concentration of cefixime. The detection
resistance; the double-layer capacitance, and the charge transfer limit was determined at 0.02 ␮mol L−1 cefixime (S/N = 3) using the
resistance associated with the oxidation of low-valence mediator peak current.
species. The increasing in the amount of charge transfer resistance
is in line with the coating of the surface of GCE and creates a new 5. Interferences study
layer on the surface of the electrode (Table 2).
Cyclic voltammetry was also performed to characterize the The influence of various substances as potential interfering
modified electrode. Fig. 3 (inset) shows cyclic voltammograms of compounds on the determination of 100.0 ␮mol L−1 cefixime was
2.5 mmol L−1 of Fe(CN)6 4−/3− in 0.10 mol L−1 KNO3 at unmodified studied. The tolerance limit was defined as the maximum concen-
GCE (d), at MWCNT (e), and at NiFe2 O4 -MWCNTs modified elec- tration of the interfering substance that caused an error less than
trode (f) with a scan rate of 100 mV s−1 . The nanoporous coating ±5% for the determination of cefixime. The results showed that nor
of the modified electrode surface causes increasing the oxidation 1000-fold of Ca2+ , NH4 + , SO4 2− , CO3 2− , tartaric acid, and nor 100-
current of Fe(CN)6 4−/3− clearly. fold of glucose, leucine, tryptophan, glycine, glucose, starch, citric
acid, uric acid, ascorbic acid, captopril, cysteine, sodium sesqui-
3.5. Stability and reproducibility hydrate and pantoprazole affect the current response of cefixime.
These results indicated that all conventional cations, anions, and
The repeatability and stability of the modified electrode was organic substances do not affect the peak current of cefixime. On
investigated by cyclic voltammetry. The relative standard devia- the other hand ranitidine, arginine, valine, cephalexin, and histidine
tion (RSD%) for ten successive assays of 30.0 ␮mol L−1 cefixime could be interfere at more than 10-fold.
was 3.1%. When using five different electrodes, the RSD% for five
measurements of 30.0 ␮mol L−1 cefixime was 3.6%. These results 6. Real sample analysis
indicate that the modified electrode has good stability and repro-
ducibility, and could be used for cefixime determination with a Because of high selectivity of the electrochemical sensor,
reasonable precision. cefixime could be determined in real samples. To evaluate the appli-
cability of the proposed sensor, cefixime was determined in tablet,
4. Analytical features of the sensor blood plasma, and urine samples using standard addition method.
The results are given in Table 3. Comparison of the results of the
Linear sweep voltammetry was used to make the calibration proposed method with spectrophotometric method (288 nm) [34]
graph. Fig. 4 shows linear sweep voltammetry of the modified elec- also confirmed the accuracy of the results obtained by the modified
trode in different concentrations of cefixime. Under the optimized electrode. The results confirm that there are not significant differ-
conditions, the oxidation peak current of cefixime was used to ences between the results of the proposed sensor and the standard
692 A.A. Ensafi, A.R. Allafchian / Colloids and Surfaces B: Biointerfaces 102 (2013) 687–693

Table 2
Electrochemical impedance spectroscopy data of 2.5 mmol L−1 [Fe(CN)6 ]3/4− in 0.10 mol L−1 KNO3 at the surface of a bare GCE, MWCNTs, and NiFe2 O4 -MWCNTs modified
electrode.

R1 (C[R2 W]) GCE MWCNTs-GCE NiFe2 O4 -MWCNTs-GCE

Value Error% Value Error% Value Error%

R1 0.199 k 2.969 0.205 k 3.115 0.207 k 2.339

C 0.498 ␮F 3.501 0.526 ␮F 1.250 0.581 ␮F 2.408
R2 0.793 k 3.617 0.943 k 2.411 0.995 k 5.307
W 0.173 × 10−3 3.041 0.175 × 10−3 3.073 0.134 × 10−3 4. 021

Table 3
Determination of cefixime in real sample at pH 7.0 (± indicates the standard deviation for n = 3).

Sample Cefixime added Cefixime found Recovery Spectrophotometric method

(␮mol L−1 ) (␮mol L−1 ) (%) (␮mol L−1 )

Tableta – 4.87 ± 0.30 97.4 –

Tableta 15.00 19.62 ± 0.30 98.1 19.81 ± 0.90
Tabletb – 4.72 ± 0.20 94.4 –
Tabletb 20.00 24.68 ± 0.40 98.7 24.78 ± 0.95
Urine – <Limit of detection – <Limit of detection
Urine 15.00 15.78 ± 0.70 105.2 14.87 ± 0.50
Urine 30.00 29.18 ± 0.90 97.3 29.17 ± 0.60
Plasma – <Limit of detection – <Limit of detection
Plasma 10.00 9.52 ± 0.50 95.2 9.94 ± 0.60
Plasma 25.00 24.74 ± 0.30 98.96 24.61 ± 0.70
a
Tablet content of 20 mg of cefixime diluted to sufficient concentration, Loghman Pharmaceutical & Hygienic Company, Tehran, Iran.
b
Tablet content of 40 mg of cefixime diluted to sufficient concentration, Loghman Pharmaceutical & Hygienic Company, Tehran, Iran.

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