Microchimica Acta (2018) 185: 453

https://doi.org/10.1007/s00604-018-2970-8

ORIGINAL PAPER

Tungsten disulfide (WS2) nanosheet-based

photoelectrochemical aptasensing of chloramphenicol
Yunlei Zhou 1 & Chengji Sui 1 & Huanshun Yin 1 & Yue Wang 1 & Minghui Wang 1 & Shiyun Ai 1

Received: 20 June 2018 / Accepted: 18 August 2018 / Published online: 12 September 2018
# Springer-Verlag GmbH Austria, part of Springer Nature 2018

Abstract
A method is described for photoelectrochemical determination of chloramphenicol (CLOA). It is based on the use of (a) aptamers
protected with photoactive WS2 nanosheets, and (b) DNase I-assisted target recycling. The DNA aptamer without label was
employed for recognition of CLOA. In the absence of CLOA, the aptamer is adsorbed on the surface of WS2. This leads to a
decrease of photocurrent due to the steric-hindrance effect of aptamer DNA. The adsorption of WS2 also protects the aptamer
from digestion by DNase. In the presence of CLOA, the aptamer will be desorbed from the WS2 surface due to formation of an
aptamer/CLOA conjugate. This results in an increased photocurrent due to a decreased amount of aptamer DNA on the electrode
surface. The increase of photocurrent can be further improved by applying DNase triggered catalytic recycling of CLOA. Under
optimal experimental conditions, the response is linear 10 pM – 10 nM CLOA concentration range, with a 3.6 pM lower detection
limit (at 3σ). This method is acceptably selective, accurate and stable. It was applied to the determination of CLOA in spiked milk
samples and gave satisfactory results.

Keywords Photoelectrochemistry . Amperometry . Transition metal dichalcogenide . Tungsten disulfide . Antibiotic detection .
DNA aptamer . Food sample . Signal amplification

Introduction Among these methods, PEC-based detection is a new plat-

form for bioassay, in which the light is employed to excite the
Chloramphenicol (CLOA) has been widely used to cure bac- photoactive material to generate electron, then the electron can
terial infections. The overdose intake of CLOA can result in be transferred to electrode to produce photocurrent as detec-
serious side effects, such as bone marrow suppression, kidney tion signal [7]. Due to the advantages of fast response, simple
damage and allergic reactions [1]. Thus it is crucial to develop operation, inexpensive instrument, low background current
various methods for simple, rapid and sensitive detection of and low consumption, PEC technique has attracted increasing
CLOA. Up to now, various methods have been employed to attentions, and various target can be detected by this tech-
detect CLOA, including fluorescence [2], high-performance nique, such as organic small molecules [8, 9], heavy metal
liquid chromatography with tandem mass spectrometry ions [10, 11], nucleic acids and their derivatives [12, 13],
(HPLC-MS/MS) [3], electrochemistry [4], proteins [14–16] and cell [17]. In PEC bioassay, photoactive
electrochemiluminescence (ECL) [5] and materials are usually designed as the matrix to immobilize or
photoelectrochemical (PEC) method [6]. capture the subsequent biological recognition unit. As a kind
of two-dimensional inorganic semiconductor nanomaterials
with some unusual physical, chemical or electronic properties
Electronic supplementary material The online version of this article
(https://doi.org/10.1007/s00604-018-2970-8) contains supplementary [18], transition metal dichalcogenides (TMDs) receive more
material, which is available to authorized users. attentions on the field of opto-electronic/electronic devices,
electrocatalysis, sensors and energy storage. Among them,
* Huanshun Yin WS2 is promising photoactive nanomaterial in the construc-
yinhs@sdau.edu.cn tion of PEC biosensors [19]. More importantly, WS2 presents
excellent adsorption ability for single-stranded DNA (ssDNA)
1
College of Chemistry and Material Science, Shandong Agricultural and fluorescence quenching ability for the labeled dye at the
University, 271018 Taian, Shandong, People’s Republic of China terminal of ssDNA. When ssDNA hybridizes with its
453 Page 2 of 8 Microchim Acta (2018) 185: 453

complementary DNA to form double-stranded DNA, or Experimental section

ssDNA interacts with its target molecule to form aptamer-
target conjugate, the adsorbed ssDNA can be released from Reagents and instruments
WS 2 surface [20]. Based on this property, WS 2 -based
nanomaterials have been widely applied in biosensors using CLOA, florfenicol, thiamphenicol, tobramycin, streptomycin,
fluorescence and electrochemical techniques [21, 22]. tetracycline, kanamycin, oxytetracycline, ampicillin, amoxi-
Inspired by the excellent properties of WS2 nanomaterial, a cillin, penicillin, lincomycin, melamine,
sensitive PEC method was designed with combining the ad- tris(hydroxymethyl)aminomethane (Tris), EDTA, MgCl2,,
sorption property and photoactivity of WS2. As shown in CaCl2 and KCl were provided by Aladdin (Shanghai, China,
Scheme 1, DNA aptamer was used as CLOA recognition el- http://www.aladdin-e.com/). DNase I was provided by New
ement. After DNA was adsorbed on WS2 modified ITO elec- England Biolab (USA, http://www.neb-china.com/). WS2 was
trode (WS2/ITO) surface, the PEC response of WS2 was de- purchased Sigma (USA, https://www.sigmaaldrich.com).
creased greatly due to hindrance effect of the aptamer DNA, DNA was offered by Sangon Biotech. (Shanghai, China,
which blocked the transfer of the photogenerated electron of https://www.sangon.com/). The sequences were as follows.
WS2, and promoted the recombination of photogenerated DNA aptamer, 5′-AGC AGC ACA GAG GTC AGA TGC
electron and hole. Moreover, when DNA aptamer was ACT CGG ACC CCA TTC TCC TTC CAT CCC TCA
adsorbed on the WS2 surface, it can protect DNA aptamer to TCC GTC CAC CCT ATG CGT GCT ACC GTG AA-3′.
avoid the digestion of DNase I. However, When CLOA was ITO conductive glass was purchased from Zhuhai Kaivo
further introduced on electrode surface, CLOA-DNA com- Electronic Components Co., Ltd. (Zhuhai, China, ITO
plex was formed and then released from WS2 surface, which coating 180 ± 25 nm, sheet resistance <15 Ω/cm2, http://
would lead to the increase of the PEC response due to the www.zh-kv.com).
decreased hindrance effect. Afterwards, the released DNA The buffers used in this work were as follows. DNA dis-
was further digested by DNase I, and the CLOA-DNA struc- solution buffer, 10 mM Tris-HCl and 1 mM EDTA, pH 8.0.
ture was destroyed, which made the regeneration of CLOA DNase I buffer, 10 mM Tris-HCl (pH 7.6), 2.5 mM MgCl2,
target. The released CLOA then binds to another aptamer, and 0.5 mM CaCl2. Washing buffer, 10 mM Tris-HCl and 50 mM
starts a new cycle. This results in the successive release of KCl, pH 7.4. Detection buffer, 10 mM Tris-HCl, pH 7.4.
aptamer from WS2 surface. As a result, a small amount of The X-ray diffraction patterns were recorded using a D8
target CLOA can effectively induce the release of lots of advance (Bruker-AXS, Germany) diffractometer with Cu Ka
DNA aptamer form WS2/ITO electrode surface, which can radiation (λ = 0.1546 nm). The morphologies and structures
lead to the greatly increase the photocurrent. By monitoring of WS2 were characterized by scanning electron microscopy
the change of photocurrent, the quantitative determination of (SEM, FEI-QUANTA400, USA) and transmission electron
CLOA can be achieved. microscopy (TEM, Tecnai G2 F20 S-TWIN, FEI, USA).
The Raman spectroscopy was performed using a Raman

Scheme 1 Schematic representation of the PEC assay strategy and CLOA detection
Microchim Acta (2018) 185: 453 Page 3 of 8 453

spectrometer (Horiba XploRA™ PLUS, France) with laser 0.22 μm filter membrane. Finally, the filtrate was diluted with
excitation at 638 nm. Tris-HCl (pH 7.4) to prepare the sample for measurement.
The milk powder sample was purchased from a local su-
Electrode fabrication permarket. The sample was treated with previous report with
minor revision [24]. In brief, 1.0 g milk powder was added
Firstly, the ITO conductive glass was first cut into 5.0 × into 10.0 mL 10 mM Tris-HCl (pH 7.4) and stirred for 15 min.
1.0 cm 2 pieces and sonicated respectively in ethanol/ Then, the pH of the solution was adjusted to 4.6 by 20% acetic
NaOH mixed solution (v/v, 1:1), acetone and double dis- acid. After incubating for 30 min, the sample was centrifuged
tilled deionized water for 30 min, followed by drying at to remove the coagulation of proteins and fats. Subsequently,
60 °C for 2 h. Then, 12 mg WS2 was dispersed into 4 mL the collected solution was filtered with 0.22 μm filter mem-
water and sonicated for 30 min to obtain a well dispersion brane. Finally, the pH solution was adjusted to 7.4 for
solution with the concentration of 3 mg mL−1. After that, measurement.
40 μL WS2 dispersion solution was dropped on ITO elec-
trode surface and dried under infrared lamp irradiation.
The prepared electrode was noted as WS2/ITO. After the
electrode was rinsed with washing buffer and dried under Results and discussion
N2 blowing, 20 μL of 5 μM aptamer DNA was dripped
onto the electrode surface and incubated for 60 min at Choice of materials
room temperature in a humid cell. The electrode was then
washed with washing buffer and dried under N2 blowing. Recently, transition metal dichalcogenides (TMDs) receive
The electrode was marked as DNA/WS2/ITO. Afterwards, more and more attentions in many fields due to the advantages
the electrode was further incubated with 20 μL of mixed of unusual physical, chemical or electronic properties.
solution containing various concentrations of target Especially, TMDs also present the PEC property with
CLOA and 50 unit mL−1 DNase I for 105 min at 37 °C visible-light activity, which make them alternative material
under humid conditions. Finally, the electrode was for PEC assay. In addition, TMDs can adsorb ssDNA, and
washed with washing buffer and dried under N2 blowing. the adsorbed ssDNA can be released from TMDs surface after
hybridization or formation DNA-target conjugate. Based on it,
TMDs materials have been widely applied in the field of bio-
Photoelectrochemical (PEC) detection sensing. Among various TMDs materials, WS2 attracts our
attentions due to its good visible-light activity, strong PEC
PEC experiments were performed on a home-built PEC sys- response (higher than MoS2 [25]), low cytotoxicity (lower
tem. A 500 W Xe lamp equipped with optical filter is used as than MoS2 and WSe2, graphene and its analogues [26]), thus
the irradiation source to produce the visible-light (Light inten- WS2 was employed as photoactive material in this work.
sity is 20 mW/cm2). The photocurrent is recorded on a
CHI832A electrochemical workstation (CH instruments,
Austin, USA) with a three-electrode system in detection buff- Characterization of WS2
er. A modified ITO electrode with an area of 0.195 cm2 is used
as the working electrode, a Pt wire as the counter electrode and WS2 was characterized by SEM, TEM, XRD and Raman
an SCE as the reference electrode. The working potential is spectroscopy. The results are shown in Fig. 1. SEM image
−0.3 V. In addition, the photocurrent was denoted as I (I = Ilight indicates that WS2 contains many WS2 layers in its structure
on – Ilight off), where Ilight on was the photocurrent with light (Fig. 1a). As shown in Fig. 1b, transport sheets are observed
irradiation, and Ilight off was the photocurrent without light by TEM image. It also illustrates that WS2 contains layer
irradiation. structure. The XRD pattern of WS2 was investigated. As il-
lustrated in Fig. 1c, all peaks of pure WS2 show the character-
Pretreatment of chicken feed and milk powder istics of the hexagonal WS2 (JCPDS card No. 08–0237). The
samples diffraction peaks at 2θ values of 14.6°, 29.08°, 32.84°, 33.84°,
39.72°, 44.16°, 49.8°, 58.44°, 60.8°, 69.4°, 76.08° and 88.6°
The chicken feed sample was purchased from a local market, are corresponding to (002), (004), (100), (101), (103), (006),
which was pretreated according to previous report with some (105), (110), (112), (201), (116) and (118) planes of WS2. As
revision [23]. In brief, 1.0 g chicken feed was grinded using illustrated in Fig. 1d, the Raman spectra exhibited the charac-
agate mortar. Then, the powder was added into 10 mL Tris- teristic bands at 351 and 422 cm−1, corresponding to in plane
HCl (pH 7.4) and sonicated for 30 min. The dispersion was vibration E12g mode and out of plane vibration mode (A1g) of
centrifuged at 12000 rpm for 30 min and filtrated with WS2, respectively.
453 Page 4 of 8 Microchim Acta (2018) 185: 453

Fig. 1 SEM (a) and TEM (b)

images of WS2. (c) XRD pattern
of WS2. (d) Raman spectrum of
WS2

Detection feasibility assay level was lower than that the electrode was incubated with
CLOA and DNase I together, which powerfully demon-
The detection feasibility of this PEC method was investi- strated the important signal amplification effect of DNase
gated by monitoring the photocurrent change of the ITO I. The above results also prove that this method can be used
electrode with different modification processes. As shown to detect CLOA.
in Fig. 2, the bare ITO electrode presents no PEC response
due to the absence of the photoactive material (curve a).
Then, a PEC response is observed after WS2 was modified
on ITO electrode surface (curve b), indicating the PEC
activity of WS 2 . Afterwards, the PEC response is de-
creased when DNA was adsorbed on electrode surface
(curve c), which can be ascribed to the modified aptamer
DNA, blocking the transfer of the photogenerated electron
and improving the recombination of hole and electron.
However, after DNA/WS2/ITO electrode was incubated
with CLOA and DNase I, the photocurrent increased great-
ly (curve d), which can be explained as the fact that the
DNA aptamer was released from electrode surface due to
the formation of aptamer-CLOA complex, which further
induced DNase I mediated target CLOA recycling. For
testifying the signal amplification effect of DNase I, con-
Fig. 2 The PEC response of different electrodes in 10 mM Tris-HCl
trol experiment was performed. As seen in curve e, when (pH 7.4). (a) ITO, (b) WS2/ITO, (c) DNA/WS2/ITO, (d) DNA/WS2/
the DNA/WS2 /ITO electrode was only incubated with ITO after incubated with the complex of 1 nM CLOA and 50 unit
CLOA, the photocurrent still increased, but the increase mL−1 DNase I, (e) DNA/WS2/ITO after incubated with 1 nM CLOA
Microchim Acta (2018) 185: 453 Page 5 of 8 453

Fig. 3 a The PEC response of this

method with different
concentrations of CLOA under
optimal conditions. a-g: 10, 50,
100, 500, 1000, 5000, 10,000 pM.
b The linear relationship between
the photocurrent and the
logarithm value of CLOA
concentration. c The histogram of
the photocurrent with different
antibiotics. Antibiotic
concentration was 1 nM. (D) The
histogram of the
photoelectrochemical response of
seven electrodes with 1 nM
CLOA. The photocurrent was
recorded in in 10 mM Tris-HCl
(pH 7.4)

Optimization of experimental conditions time; (d) CLOA incubation time. Respective data and
Figures are given in the Electronic Supporting Material. In
The following parameters were optimized: (a) WS2 concen- short, the following experimental conditions were found to
tration; (b) aptamer DNA concentration; (c) DNA incubation give best results: (a) Optimal WS 2 concentration:

Table 1 The comparison of the

detection performances of the Methods Linear range Detection limit Refs.
PEC method with other reports on
CLOA detection Fluorescence 0.003–10 nM 1 pM [2]
Fluorescence 0.10–70.00 μM 33 nM [27]
Colorimetric immunoassay 0.03–12.53 nM 0.03 nM [28]
Piezoelectric immunosensor 1.55–310 nM 0.62 nM [29]
Electrochemistry 0.01–1 μM 2.9 nM [4]
1–400 μM
Electrochemistry 40 pM– 1 μM 17 pM [30]
Electrochemistry 0.01–35 μM 2 nM [24]
Capillary zone electrophoresis – 1.55 μM [31]
HPLC-MS/MS 0.15 nM – 0.31 μM – [3]
Electrochemistry 1.6–420 nM 1.6 nM [32]
Electrochemiluminescence 0.2–150 nM 70 pM [5]
Chemiluminescent immunoassay 0.6–10 μM 0.16 μM [33]
Electrochemistry 1–1000 nM 0.29 nM [34]
Photoelectrochemistry 10–250 nM 3.1 nM [6]
Photoelectrochemistry 1.0 pM – .0 nM 0.36 pM [35]
Photoelectrochemistry 10 pM – 0 nM 3.6 pM This work
453 Page 6 of 8 Microchim Acta (2018) 185: 453

Table 2 Detection CLOA in chicken feed and milk powder samples was further incubated with 1 nM CLOA and 50 unit mL−1
using the PEC method
DNase I as described in BElectrode fabrication^ section.
Samples Added Detected RSD (%)a Recovery (%) Finally, the PEC response was recorded and compared. After
storage for 5 and 10 days, the PEC method can remain its
Chicken feed 10 nM 9.68 nM 4.12 96.8 original photocurrent of 95.15 and 90.34%, indicating accept-
1 nM 1.06 nM 4.89 106 able storage stability.
0.1 nM 0.108 nM 7.57 108
Milk powder 10 nM 9.48 nM 3.58 94.8
1 nM 1.08 nM 5.24 108 Sample detection
0.1 nM 0.11 nM 8.27 110
To verify the feasibility and application potential of this PEC
a
The RSD value is calculated for the detected chloramphenicol content method, it was applied to detect CLOA in chicken feed and
for 7 times milk powder samples. After pretreatment, the solution was
measured by this PEC method. Because no CLOA was detect-
3 mg mL−1 (b) Optimal aptamer DNA concentration: 5 μΜ; ed in these samples, CLOA standard solutions with different
(c) Optimal DNA incubation time: 60 min; (d) Optimal CLOA concentrations were added into these samples and the recov-
incubation time: 105 min. ery experiments were performed. As shown in Table 2, the
recoveries of CLOA from the spiked milk powder samples are
ranged from 94.8 to 110%, and the RSDs are ranged from 3.58
Detection performances
to 8.27%.These results also confirm the feasibility of this
method for CLOA detection in real samples.
The detection sensitivity was estimated by detecting different
concentrations of CLOA. As shown in Fig. 3a, under optimal
experiment conditions, the photocurrent increases gradually
with changing CLOA concentration from 10 pM to 10 nM. Conclusions
In the range form 10 pM to 10 nM, the linear relationship
between the photocurrent and the logarithm value of CLOA In summary, a selective PEC method was investigated for
concentration can be achieved The linear regression equation CLOA detection based on the specific interaction between
can be expressed as I (nA) = 68.26logc (nM) + 136.9 (R = DNA aptamer and WS2, and DNase I. Due to the specific
0.9914, Fig. 3b). The detection limit was estimated to be 3.6 recognition of DNA aptamer to CLOA and enzymatic signal
pM (3σ). The detection performances of this work are com- amplification, this PEC method showed high detection selec-
pared with other work and the comparison results are listed in tivity and sensitivity. This PEC method was also proved to
Table 1. It indicates that the detection performances of this possess the applicability for detecting CLOA in milk powder
work are comparable to some of previous work. samples. More importantly, if only the aptamer was replaced
The detection specificity of this method was investigated by other antibiotic’s aptamer, this method can also be applied
by detecting different antibiotics, such as CLOA, florfenicol, to detect other antibiotics. Though this method exist the short-
thiamphenicol, tobramycin, streptomycin, tetracycline, kana- coming of time-consuming, it still possesses some merits, in-
mycin, oxytetracycline, ampicillin, amoxicillin, penicillin, lin- cluding simple operation, inexpensive instrument, high sensi-
comycin and melamine. The photocurrent change (ΔI = I1 – tivity and high selectivity, which make it attractive method for
I2) is compared, where I1 is the photocurrent of DNA/WS2/ antibiotic detection.
ITO after incubated with antibiotics and DNase I, and I2 is the
photocurrent of DNA/WS2/ITO,. As shown in Fig. 3c, the ΔI Acknowledgements This work was supported by the National Natural
for CLOA (1 nM) is greatly higher than that for other antibi- Science Foundation of China (No.21775090), the Natural Science
Foundation of Shandong province, China (No. ZR2016BM10,
otics (1 nM), indicating good detection selectivity. ZR2018MB028).
Detection reproducibility is also a crucial parameter for
analysis method. To investigate it, DNA/WS2/ITO was incu- Compliance with ethical standards The author(s) declare
bated with 1 nM CLOA and 50 unit mL−1 DNase I. Seven that they have no competing interests.
electrodes were fabricated with this process independently.
The relative standard deviation of the photocurrent is 4.42%,
indicating good detection reproducibility (Fig. 3d).
Stability is an important parameter for analytical method,
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