DOI: 10.1002/elan.201900036
Differential Pulse Voltammetry Determination of
OfloxacininHumanSerumandUrineBasedonaNovel
Tryptophan-graphene Oxide-Carbon Nanotube
Electrochemical Sensor
Yuqiu Zhu,
[a]
Chengkun Li,
[a]
Lumin Wang,
[a]
Miao Chen,
[a]
Jingang Yu,
[a]
Qi Liu,*
[a]
and Xiaoqing Chen*
[a, b]
Abstract: The highly sensitive determination of ofloxacin
(OFL) in human serum and urine was achieved on a novel
tryptophan-graphene oxide-carbon nanotube (Trp-GO-
CNT) composite modified glassy carbon electrode (Trp-
GO-CNT/GCE). The Trp-GO-CNT composite was fab-
ricated, and its morphologies and surface functional
groups were characterized by field emission scanning
electron microscopy (FE-SEM) and Fourier transform
infrared (FT-IR) spectroscopy. The electrochemical prop-
erties of Trp-GO-CNT/GCE were investigated by cyclic
voltammetry (CV) and electrochemical impedance spec-
troscopy (EIS). The superior electrochemical behaviors of
Trp-GO-CNT/GCE toward OFL can be mainly assigned
to the excellent electrocatalytic activity of Trp, the great
conductivity and high surface area of GO and CNT, and
the synergistic effect between Trp, GO and CNT. Under
optimum conditions, a wide and valuable linear range
(0.01–100 μM), a low detection limit (0.001 μM, S/N = 3),
a good linear relationship (R2 > 0.999), good stability and
repeatability were obtained for the quantitative determi-
nation of OFL. Furthermore, the Trp-GO-CNT electro-
chemical sensor was successfully applied to the determi-
nation of OFL in human serum and urine samples, and
satisfactory accuracy and recovery could be obtained.
Keywords: Electrochemical detection · Ofloxacin · Tryptophan-graphene oxide-carbon nanotube composite · Differential pulse
voltammetry · Quantitative determination
1 Introduction
Ofloxacin (OFL), one of the synthetic fluoroquinolones,
has been widely used against many pathogenic gram-
negative and gram-positive bacteria through inhibition of
their DNA gyrase [1]. Especially, OFL is widely used for
bactericide due to its low cost, wide bactericidal spectrum
and rapid absorption [2]. Therefore, fast and accurate
analysis of OFL is very important for understanding the
patient‘s medical process in clinical treatment. Further-
more, OFL is not only applied in human medicine but
also widely used in the veterinary industry to prevent and
treat various infectious diseases, and even used as growth-
promoting reagents. However, drug residues which enter
the food chain have caused some potential hazards such
as bacterial resistance, hypersensitivity reaction and toxic
effect [3]. Especially, synthetic fluoroquinolones are
usually overused in long-term care, which is harmful to
the pregnancy and breastfeeding mothers, and the grow-
ing children and adolescents [4]. Therefore, the maximum
residue levels (MRLs) for fluoroquinolones and with-
drawal periods have been enacted in more and more
countries. Developing a reliable and simple method to
detect the trace amount of OFL in the environment or
human serum is impending.
Up to now, various techniques such as fluorimetric
detection [5], UV visible spectrophotometry [6], high
performance liquid chromatography (HPLC) [7], liquid
chromatography-mass spectrometry (LC-MS) [8], capil-
lary electrophoresis [9] and microbiological assay [10]
have been developed for the determination of OFL.
However, these methods have exhibited some drawbacks
such as time-consuming in sample detection, complex and
expensive instruments required, and complicated sample
pretreatments needed. Recently, electrochemical detec-
tion methods have attracted considerable interest because
they are relatively more facile and stable, less time-
consuming, more environment-friendly and less costly
besides the excellent detection limits [11,12]. Previously
reported studies have indicated that the fabrication of
modified electrodes is essential for electrochemical analy-
sis [13]. Therefore, it is highly desirable to develop novel
electrodes for the precise detection of OFL.
[a] Y. Zhu, C. Li, L. Wang, M. Chen, J. Yu, Q. Liu, X. Chen
College of Chemistry and Chemical Engineering, Central
South University, Changsha 410083, Hunan, China
E-mail: iliuqi@csu.edu.cn
xqchen@csu.edu.cn
[b] X. Chen
Key Laboratory of Hunan Province for Water Environment
and Agriculture Product Safety, Central South University,
Changsha 410083, Hunan, China
Supporting information for this article is available on the
WWW under https://doi.org/10.1002/elan.201900036
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