Sensors and Actuators B 177 (2013) 634–642
Contents lists available at SciVerse ScienceDirect
Sensors and Actuators B: Chemical
journa l h o me pa ge: www.elsevier.com/locate/snb
Simultaneous determination of guanine and adenine in DNA based on NiFe
2
O
4
magnetic nanoparticles decorated MWCNTs as a novel electrochemical sensor
using adsorptive stripping voltammetry
Ali A. Ensafi
∗
, M. Jafari-Asl, B. Rezaei, A.R. Allafchian
Department of Chemistry, Isfahan University of Technology, Isfahan 84156–83111, Iran
a r t i c l e i n f o
Article history:
Received 13 August 2012
Received in revised form 31 October 2012
Accepted 11 November 2012
Available online 22 November 2012
Keywords:
Magnetic nanoparticles decorated MWCNTs
Hydrodynamic amperometry
Guanine and adenine
a b s t r a c t
An electrochemical sensor was developed for guanine and adenine detection using multiwall carbon
nanotubes (MWCNTs) decorated with NiFe
2
O
4
magnetic nanoparticles on a glassy carbon electrode.
Incorporation of MWCNT/NiFe
2
O
4
nanohybrid on the surface of the electrode significantly increases oxi-
dation the peaks currents but reduces the peaks potential of guanine and adenine. The modified electrode
was employed for detecting purine bases using linear sweep voltammetry and hydrodynamic amperom-
etry. With hydrodynamic amperometry, the peaks current of both guanine and adenine showed linear
dependence on their concentrations in the range of 3.0–45.0 mol L
–1
for guanine and 3.0–40.0 mol L
–1
for adenine. When linear sweep voltammetry was used, the peak currents exhibited linear dependence
on guanine in the concentration range of 0.05–3.0 mol L
–1
and on adenine in the concentration range
of 0.1–4.0 mol L
–1
. The limit of detection (S/N = 3) was found to be 0.006 and 0.01 mol L
–1
for guanine
and adenine, respectively. Linear sweep voltammetry was also used for simultaneous determination of
adenine and guanine. Finally, the proposed electrochemical sensor was employed to determine guanine
and adenine in single-strand deoxyribonucleic acid (ssDNA) samples with satisfactory results.
© 2012 Elsevier B.V. All rights reserved.
1. Introduction
Nucleosides and their metabolic products, such as guanine and
adenine, play fundamental roles in life processes [1,2]. Guanine
and adenine bases are the building blocks in both DNA and RNA
[3]. They have widespread effects on coronary and cerebral circu-
lation, control of blood flow, inhibition of neurotransmitter release,
and modulation of adenylatecyclase activity [4]. Their concentra-
tion levels are considered to be important indicators of cancers,
AIDS, and myocardial cellular energy status [5]. Therefore, selec-
tive and sensitive detection methods are required for the analysis
of these compounds. Different analytical methods such as liquid
chromatography or electrophoresis combined with different detec-
tion techniques have been developed for the analysis of purine
bases in nucleic acids [6–11]. Although these methods are sensitive,
they are disadvantageous due to their complicated instrument and
time-consuming sample pretreatment requirements.
Simplicity, rapidity, high sensitivity, and low cost are the main
advantages of electrochemical techniques for the analysis of biolog-
ical compounds [12]. Several electrochemical detection methods
∗
Corresponding author. Tel.: +98 311 3913269; fax: +98 311 3912350.
E-mail addresses: Ensafi@cc.iut.ac.ir, ensafi@yahoo.com, ensafi2009@gmail.com
(A.A. Ensafi).
mostly based on either reduction of purine bases on a hanging
mercury drop electrode [13] or oxidation of both guanine and ade-
nine on unmodified carbon electrode [14–16] have been reported.
However, the electrochemical responses of most electrodes toward
oxidation of purine bases are poor with high oxidative potential.
Furthermore, direct oxidation of guanine and adenine reportedly
pronounces the fouling effect that results in poor reproducibility.
High overpotential and/or poor reproducibility usually limit the use
of bare electrodes for direct detection of purine bases in biological
substances.
Modification of different electrode surfaces with various elec-
tron transfer mediators is used to improve the sensitivity and selec-
tivity of electroanaytical methods for guanine and adenine detec-
tion. For example, Sun et al. studied the electrochemistry of adenine
and guanine on a carbon ionic liquid electrode, which was useful for
the simultaneous analysis of adenine and guanine from denatured
DNA [17]. Abbaspour and Ghaffarinejad demonstrated that adenine
sand guanine yielded a well-defined and very sensitive oxidation
peak at the carbon nanotube ceramic electrode [18]. Tang et al. used
multiwall carbon nanotubes incorporated with poly (new fuchsin)
composite film modified glassy carbon electrode for the simulta-
neous determination of adenine, guanine, and thymine by cyclic
voltammetry [19]. Liu et al. investigated the direct electrochemistry
of guanine and adenine at a PbO
2
–carbon nanotube–ionic liquid
composite and developed a sensitive electrochemical technique for
0925-4005/$ – see front matter © 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.snb.2012.11.028