Sci. Bull.
com
DOI 10.1007/s11434-016-1151-6
Review
Recent advances in ionic liquid-based electrochemical biosensors
Xiaolin Wang • Jingcheng Hao
Received: 17 May 2016 / Revised: 2 July 2016 / Accepted: 7 July 2016
Ó Science China Press and Springer-Verlag Berlin Heidelberg 2016
Abstract Ionic liquids (ILs) have been generally described
as molten salts which are composed of asymmetric cations
and anions. They exist in liquid state below 100 °C. Both
ILs and their composite materials have been widely used in
various fields. Attributed to the outstanding properties
including the thermal and chemical stabilities, the negli-
gible volatility, the high ionic conductivity, the wide
electrochemical window, and the easy design in the con-
struction, ILs have been applied in electrochemical appli-
cations including the electrocatalysis, the electrosynthesis,
the electrodeposition, the electrochamical devices and
sensors. In addition to the application in electrochemical
sensors, ILs have also been used in biosensors because of
their biocompatibiciy. Here, we review the recent devel-
opments for the applicaitons of ILs in electrochemical
sensors and biosensors, including the corresponding prop-
erties of ILs suitable for electrochemical sensors. Electro-
chemical biosensors constructed by numorous composites
are the emphasis in the review.
Keywords Ionic liquids  Electrochemical sensors 
Biosensors
1 Introduction
As ideal candidates in wide applications of electrochemical
sensors and biosensors, many significant advances in
electrochemical sensing systems fabricated based on ionic
X. Wang  J. Hao (&)
Key Laboratory of Colloid and Interface Chemistry and Key
Laboratory of Special Aggregated Materials, Ministry of
Education, Shandong University, Jinan 250100, China
e-mail: jhao@sdu.edu.cn
www.scibull.
www.springer.com/scp
Chemistry
liquids (ILs) have been reported. Though the precise defi-
nition for ILs is still controversial, traditionally, ILs are
believed to be molten salts with the melting points lower
than 100 °C. They are constituted by organic cations and
inorganic or organic anions, and it is flexibile for the
molecular structure design by easily varying the cations
and anions. Figure 1 shows the most common cations and
anions for ILs. Generally, the reported cations include
tetraalkylammonium, tetraalkylphosphonium, trialkylsul-
fonium, imdazolium, pyridinium, pyrrolidinium and
piperidinium. While the common anions contain halide
ions, tetrafluoroborate, hexafluorophosphate, dicyanamide,
bis(trifluoromethylsulfony)amide, thiocyanate and thifluo-
romethane-sulfonate triflate, etc. Attributed to the almost
unlimited structural tunability, ILs can be applied to vari-
uos application fields including the preparations of func-
tional materials, catalysis, organic synthesis, the fabrication
of electrochemical devices and analysis and so on.
The fist reported ionic liquid can be traced back to 1888
[1]. Gabiel discovered the ionic liquid ethanolammonium
nitrate which has a melting point of 52–55 °C. Subse-
quently, another protic ionic liquid ethylammonium nitrate
(EAN) was reported by Walden [2] and it is a room-tem-
perature IL with a melting point of 12 °C. EAN is the most
widely investigated protic ionic liquid so far [3], which
may be attributed to their easy preparation process [4] and
the water-like properties such as the existence of hydrogen-
bonded network [5, 6]. Although they were discovered so
early, ILs could not catch the attention of researchers. Until
1975, the electrochemistry of ILs with chloroaluminate
anions was investigated [7, 8]. However, they tend to
hydrolyze because they are very reactive to the atmo-
spherimoisture. Then, with the advances in imidazolium
ILs were obtained in the 1990s [9, 10], numerous ILs have
been continuously explored.
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Fig. 1 Typical structures and nomenclatures of cations and anions
used for ILs
The most attractive properties of ILs may be the out-
standing electrochemical properties. Therefore, they have
been widely applied in electrochemical device fabrications.
Here, we focus on their applications in electrochemical
sensors and electrochemical biosensors. Two aspects can
be roughly incorporated for the electroanalytical applica-
tions of ILs. On the one hand, ILs can be used as elec-
trolytes. On the other hand, the composite materials
containing ILs can be used to modify the electrodes. In
present review, starting from the fundamental information
of ILs, we summarized the properties of ILs which are
suitable for the fabrications of electrochemical sensors and
their applications in electrochemical sensors. We made
effort to describe the recent advances in the IL-based
electrochemical biosensors. Finally, advantages and future
perspectives for applications of ILs in electrochemical
biosensors were also presented.
2 Properties of ILs suitable for electrochemical sensors
ILs have many intrinsic properties that are really inspiring.
Actually, the properties of ILs can be easily adjusted for
specific applications by changing the diverse cations and
anions. Furthermore, more functional ILs have been syn-
thesized to meet different needs. It is believed that the
liquid state may be attributed to the huge difference in the
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Sci. Bull.
sizes of cations and anions, which leading to the loose
coordination between cationic and anionic parts and the
difficulty of the packing for them.
Many properties of ILs are suitable for them to elec-
trochemical applications. Attributed to the high viscosity,
ILs can be used as the binder on the electrode, and may
effectively immobilize the sensitive biomolecules onto the
surface of the electrode. While the influence of the vis-
cosity on the rate of mass transport in the solutions should
be taken into account [11]. The most attractive advantages
for their applications in electrochemical sensors are their
excellent electrochemical properties including both the
wide electrochemical window [12] and the good electrical
conductivity [13]. Therefore, ILs can be used as elec-
trolytes in electrochemical devices [14, 15], or they can be
used with other composites to modify the electrode. Their
non-flammability, negligible volatility as well as the elec-
trochemical and thermal stabilities make them especially
safe and suitable in electrochemical sensor fabrications.
The negligible volatility makes it possible for them to be
applied under high vacuum conditions.
For the application of the electrolyte in the biosensor,
water has been used as the media for a long time. However,
its volatility and the narrow temperature range all restrict
the development of the biosensor. ILs can avoid these
troubles. For the fabrication of the electrochemical
biosensors, the biocompatibility of ILs and their effect on
the natural activity of biomolecules such as the enzymes
should be seriously considered. Satisfyingly, ILs exhibit
good biocompatibility with biomolecules [11, 16–23]. ILs
could also enhance the activity of some biomolecules,
leading to the more sensitive and more satisfactory detec-
tion results.
3 IL-based electrochemical sensors
Various electrochemical sensors based on ILs have been
successfully fabricated, where ILs are used as electrolytes
[24, 25] or modified materials on electrodes [26–29].
Rehman and Zeng [15] have summarized the applications
of ILs acting as electrolytes in chemical sensors. In addi-
tion, ILs have been used to modify the electrodes with
other materials in many different sensing systems. Com-
mon electrochemical sensors reported include gas sensors,
voltammetric sensors and ion selective electrodes (ISE)
based on ILs.
Attributed to their negligible vapor pressure, ILs are
usually used in gas sensors for detections of numerous
gases such as NO2 [30, 31], CO2 [32–34], O2 [35–37], SO2
[38, 39], HCl [40] and so on. Recently, Rehman and Zeng
[41] have reviewed relevant contents concerning the gas
detection devices employing ILs as participant materials.
Sci. Bull.
Gebicki et al. [42] reported another review for applications
of IL in amperometric gas sensors. Willa et al. [32]
reported the CO2 sensing system based on the electrodes
modified by the composite of poly(ionic liquids)s (PILs)
and La2O2CO3 nanoparticles. The PILs contain tetraalky-
lammonium and hexafluorophosphate ðPF 6 Þ; and the
authors found that different contents of La2O2CO3 have
different influence on the interfacial effect of the elec-
trodes. The negative charges on the surface of nanoparti-
cles could interact with tetraalkylammonium through
electrostatic interaction, which leading to the increasing
amount of PF 6 which could move freely. When exposed to
different pulses of CO2, the CO2 detection performance of
the modified electrode was measured through the direct
current (DC) resistance changes as shown in Fig. 2. The
decrease of resistance could be attributed to the increased
conductivity of the composite film. The authors believed
that the increased conductivity may be explained by the
further interaction between the CO2 and tetraalkylammo-
nium which causing the increased mobility of PF 6.
Voltammetric sensors based on ILs have been largely
reported [43–50]. Chen et al. [46] reported the voltam-
metric sensor for the bisphenol A (BPA) detection based on
the electrode modified by a composite film. First, the
authors synthesized a nanocomposite constructed by the
carboxylic acid-functionalized single walled carbon nan-
otubes (SWCNTs-COO-) and 3-butyl-1-[3-(N-pyrrolyl)-
propyl] imidazolium. Then the composite was modified
onto the glassy carbon electrode (GCE) followed by the
Fig. 2 Sensing performance of films composed of 70 wt%
La2O2CO3 at 50 % rh in air and at RT. a DC resistance changes
during exposure to CO2 pulses between 150 and 2,400 ppm
(1 ppm = 1 mg/L). b Corresponding sensor signal, calculated as
resistance in air divided by resistance under CO2. c Nyquist plots with
(circles) and without (squares) 2,400 ppm CO2. Measured data
(symbols), fitted curve (solid line). Reproduced with permission from
[32]. Copyright 2015 Wiley-Blackwell
cyclic voltammetric scanning to obtain the final composite
film, SWCNTs/poly{3-butyl-1-[3-(N-pyrrolyl)propyl] imi-
dazolium ionic liquid}. The BPA was effectively detected
in the concentration range from 5.0 9 10-9 to 3.0 9 10-5
mol/L with a detection limit of 1.0 9 10-9 mol/L (S/
N = 3). Yu et al. [47] also fabricated a novel voltammetric
sensor for the BPA detection. The b-cyclodextrin and IL
were employed to modify the carbon paste electrode (CPE)
and the voltammetry and electrochemical impedance
spectroscopy (EIS) measurements were performed to
measure the electrochemical properties of the modified
electrode. The electrode displayed the enhanced sensitivity
to BPA detection with the concentration ranging from
1.0 9 10-7 to 1.1 9 10-5 mol/L with a detection limit of
8.3 9 10-8 mol/L (S/N = 3). A voltammetric sensor for
the detection of nicotinamide adenine dinucleotide
(NADH) was fabricated by Karimi-Maleh et al. [49]. The
CPE was modified with IL/NiO nanoparticles. The pro-
posed CPE exhibited enhanced detectability than CPE with
a linear range of 0.03–900 lmol/L and a detection limit of
0.009 lmol/L.
ISE based on ILs are also very popular electrochemical
sensing systems [51–55]. The Cu(II) ion-selective elec-
trode based on 1-ethyl-3-methyl imidazolium chloride was
reported by Wardak and Lenik [53]. The results revealed
that the incorporation of the IL improved the analytical
performance of the electrode which displayed a Nernstian
response to the Cu(II) ions with the concentration ranging
from 1 9 10-7 to 1 9 10-1 mol/L. The detection limit for
copper ions was 3.2 9 10-8 mol/L.
4 IL-based electrochemical biosensors
The electrochemical biosensor is an analytical device used
for the detection of a variety of molecules. Roughly, a
biosensor system contains three parts. One is the analyte
recognition constructed by the sensitive biological ele-
ments such as enzymes, nucleic acids, antibodies, cell
receptors, microorganisms, etc. The second part is the
signal transducer which can transform the interaction sig-
nal between the target analytes and the biological materials
modified on the electrode into the electrical signal. The
third part of the electrochemical biosensor device is the
electronic reader. ILs as an ideal materials used in the
electrochemical biosensors have broad application pro-
spects. The most advantage of ILs is the good biocom-
patibility with biomolecules as has been described in
previous reports. In the report, a cholesterol biosensor has
been fabricated by immobilizing the cholesterol oxidase
(ChOx) in the hydrophobic 1-otctyl-3-methylimidazolium
trifluoromethylsulfonate thin film on the GCE. The result
revealed that the IL provides a biocompatible environment
123

for the ChOx and an enhanced signal of the fabricated
electrochemical biosensor [11]. In addition, the stability
over the wide electrochemical window, the high ionic
conductivity and the enhanced sensitivity and activity all
contribute to the growing applications of ILs in electro-
chemical biosensors. IL-based electrochemical biosensors
have been uesd to detect a variety of molecules such as
glucose, pesticides, NaNO2, cholesterol, adenine, dopa-
mine, choline, antigen, catechol, etc. ILs can be used as
electrolyte or modified on various electrodes in the elec-
trochemical biosensing systems. Here, we focus on the
electrochemical biosensors based on the composites con-
taing ILs and the corresponding gels.
4.1 Carbon nanomaterial/IL-based biosensors
Due to the distinctive features including both the structural
characteristics and physicochemical properties, the carbon
nanomaterials (CNMs) have been highly utilized in the
electrochemical detection. The reported CNMs used in the
electrochemical biosensors include the fullerene (C60),
graphene (GN), single wall carbon nanotube (SWCNT),
multi wall carbon nanotube (MWCNT), carbon fiber and
carbon dots, etc. [56]. All materials can be used to design
electrodes of sensors and biosensors [57]. The outstanding
advantages such as low background current and low cost
and so on attribute to the increasing their applications in
electrochemical sensors. The applications of CNMs in
sensors [57] and electrochemical biosensors have been
summarized in many reviews, for example, interested
readers are directed to the GN-based electrochemical
biosensors in a recent review [58]. IL-CNM hybrids com-
bine the advantages of both materials and promote signif-
icantly the development of the electrochemical sensors and
biosensors. Abo-Hamad et al. [59] have provide an over-
view of IL-CNM hybrids in electrochemical sensor appli-
cations, the fabrication procedures both of electrochemical
sensors and biosensors are shown below (Fig. 3). There-
fore, we emphasize the electrochemical biosensors based
on these composites.
Carbon nanodots (CDs) are discrete nanoparticles with
sizes \10 nm, and they have low toxicity and high bio-
compability [60, 61]. Li et al. [62] fabricated an effective
glucose biosensor by using IL-functionalized CDs where
the combination of ILs and CDs is via covalent or non-
covalent interactions. The glucose oxidase (GOx) is
immobilized on an IL-CD-modified GCE. The cyclic
voltammogram (CV) results show that the IL-CDs
improved the electron transport between GOx and the
electrode substrate, and the limit of detection (LOD) of the
glucose is 7 lmol/L.
The macro-/meso-/porous carbon materials with high
surface area and large pore volume possess numerous
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Sci. Bull.
applications in sensor systems [19, 63]. Recently, an
acetylcholinesterase (AChE) biosensor was constructed by
immobilizing AChE on the boron-doped diamond elec-
trode which was modified by 1-(4-sulfonic acid) butyl-3-
methylimidazolium hydrogensulfate [(BSmim)HSO4]–
AuNPs–porous carbon composite [19]. The CV and EIS
were applied and the biosensor showed high sensitivity and
stability for detecting organophosphate pesticides. As for
the dichlorvos, the detection range is 4.5 9 10-13–
4.5 9 10-9 mol/L, and the detection limit is 2.99 9 10-13
mol/L.
As the basic building block for graphitic materials, GN
has attracted considerable attention in electrochemical
sensors since discovered in 2004 [64]. Many electro-
chemical biosensors based on IL-GN multicomponent
including hemoglobin (Hb) have been reported
[20, 21, 65]. Sun et al. [20] investigated the direct elec-
trocatalysis of Hb immobilized on the GCE by 1-butyl-3-
methylimidazolium hexafluorophosphate [(Bmim)PF6]–
chitosan–TiO2–GN composite. They found that the bioac-
tivity of Hb could be maintained and the well-defined
redox peaks corresponding to the Fe(III)/Fe(II) couple
could be observed. The reduction of hydrogen peroxide
(H2O2) in the range of 1–1,170 lmol/L could be detected
by this biosensor and the detection limit concentration is
0.3 lmol/L. Sun et al. [21] fabricated a Hb bioelectrode by
modifying the carbon ionic liquid electrode (CILE) with
GN oxide (GO), 1-ethyl-3-methylimidazolium tetrafluo-
roborate [(Emim)BF4] and Nafion composite. The Nafion/
Hb-GO-IL/CILE displayed good electrocatalytic activity to
the reduction of different substrates including the tri-
chloroacetic acid (TCA), H2O2 and NaNO2. As for H2O2,
the linear range was from 0.08 to 635.0 lmol/L and the
detection limit was 0.0137 lmol/L. Li el al. [65] synthe-
sized an ionic liquid 1,3-di(4-amino-1-pyridinium)propane
tetrafluoroborate (DAPPT). The Hb was immobilized on
the DAPPT-GN by a cross-linking step with chitosan and
glutaraldehyde. The constructed biocompatible platform
was used to bioelectrocatalyze the reduction of H2O2. The
linear range of the modified GCE to H2O2 concentration
was from 4.5 9 10-7 mol/L to 7.6 9 10-4 mol/L and the
detection limit was 0.08 lmol/L. Sun et al. [66] con-
structed another similar bioelectrode for the electrocataly-
sis of the TCA, and the detection limit is 0.133 mmol/L.
Similarly, myoglobin (Mb) biosensors were also con-
structed [22, 67, 68]. In the report, the Mb was immobi-
lized in the composite film including the GN, IL 1-ethyl-3-
methylimidazolium tetrafluoroborate [(Emim)BF4] and
chitosan [22]. The native structure of Mb could not be
destroyed in the film. The well and quasi-reversible redox
peaks could be observed from the CV results and the
detection limit of 0.03 lmol/L for TCA, which indicating
that the composite is very suitable for the immobilization
Sci. Bull.
Fig. 3 (Color online) Available procedures to fabricate IL-CNM based electrochemical sensors. Reproduced with permission from [59].
Copyright 2015 Elsevier Science Publishing
of the protein. In another report, Mb was immobilized on
the CILE modified by the GN and gold nanoparticles
(GNPs) [67]. The modified bioelectrode exhibited excellent
electrocatalytic activity to the reduction of both the TCA
and H2O2. Electrochemical DNA biosensors with GN
modified CILE have been designed [69, 70]. A CILE where
IL 1-butylpyridinium hexafluorophosphate (BPPF6) was
used as the binder was modified by dendritic GNPs and the
reduced GN composite and was used as the platform for the
DNA biosensor [69]. The schematic representation of the
fabrication process for the DNA biosensor is shown in
Fig. 4. Briefly, after the modification of reduced GN and
the Au nanoparticles, the amino modified ssDNA was
linked to the electrode by the covalent interaction between
the amino and the mercaptoacetic acid. The commonly
used electrochemical indicator in DNA biosensor, methy-
lene blue (MB) was used here. By the measurement of MB
with the differential pulse voltammetric (DPV) reduction
peak currents, the Listeria monocytogenes hly ssDNA
sequences could be detected. The linear range was
1.0 9 10-12 to 1.0 9 10-6 mol/L and the detection limit
was 2.9 9 10-13 mol/L (3r). In addition, this DNA
biosensor could identify the one-base and three-base mis-
matched ssDNA sequences.
Many other molecules could also be sensitively detected
by IL-GN based biosensors, such as the glucose, nitric
oxide (NO), adenine, cholesterol, dopamine, uric acid, and
catechol, etc. [71–76]. Ping et al. [71] proposed a
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Fig. 4 (Color online) A schematic representation of this electrochemical DNA biosensor. Reproduced with permission from [69]. Copyright
2012 Elsevier Science Publishing
bioelectrode by one-step electrodeposition of the electro-
chemically reduced GO (ER-GNO) on the IL doped screen-
printed electrode (IL-SPE). The biosensor could selectively
detect the NADH and H2O2 in the presence of potential
interferences. Compared to the IL-SPE without the ER-
GNO, the modified bioelectrode displayed the more
favorable electron transfer kinetics, which may be attrib-
uted to the high density of the edge-plane-like defective
sites on ER-GNO. Then the GOx and the ER-GNO com-
posite were modified on the different electrodes for the
amperometric biosensing of glucose. The results showed
that the GOx/ER-GNO/IL-SPE exhibited good detection
sensitivity to glucose and the detection limit was
10 lmol/L. Finally, the reproducibility, the operational and
storage stability and the feasibility for the routine analysis
for the bioelectrode were all investigated. This work
proved the importance of the GN in the application of
bioelectrochemistry. In another report, the authors fabri-
cated an amperometric cholesterol biosensor by immobi-
lizing both ChOx and catalase on the GN/IL modified GCE
[74]. CV was used to study the electron transfer between
enzymes and the electrode. The constructed biosensor
could effectively detect the cholesterol in human serum
samples.
Carbon nanotubes (CNTs) are another very important
carbon material in sensor applications [77–82]. On the one
hand, CNTs can accelerate the electron transfer kinetic. On
the other hand, CNTs can immobilize the sensitive bio-
molecules through interactions such as the covalent inter-
action. However, as we all know, CNTs tend to entangle
with each other. The agglomerate restricted the applica-
tions. Fukushima et al. [83] found that SWCNTs could
untangle to finer bundles when they were dispersed in
imidazolium ILs. Gel formed when grounding the
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Sci. Bull.
SWCNT-IL mixture. Attributed to the cation–p interaction
between the imidazole of ILs and CNT, the CNT/IL
composites play an important role in applications of elec-
trochemical biosensors. A highly sensitive choline
biosensor was constructed by the modified GCE based on
MWCNT/IL/Plussian blue (PB) nanocomposite [84]. The
Ni2? ions were used to improve the stability of PB in the
alkaline media. By using the cross-linking method, the
choline oxidase was modified on the GCE. The incorpo-
ration of the PB is to lower the over potential required for
H2O2 oxidation when detecting the choline. In the linear
concentration range from 4.5 9 10-7 to 1.0 9 10-4 mol/L,
the modified bioelectrode exhibited high sensitivity. The
detection limit for choline was 4.5 9 10-7 mol/L. Khez-
rian et al. [85] developed a simple and sensitive electro-
chemical aptamer-based biosensor. The fabrication process
is shown in Fig. 5. The GCE was modified by MWCNT/
IL/chitosan nanocomposite, which is used to improve the
conductivity and increase the loading amount of aptamer
DNA sequence at the same time. The 50 -amino-terminated
aptamer was modified onto the nanocomposite through the
covalent bond with the amine groups of chitosan, and the
glutaraldehyde acted as the linker. Before the adding of the
human immunoglobulin E (IgE), the MB could be inter-
calated into the aptamer by their interaction with DNA
sequence and they could produce a strong DPV signal.
Once the IgE was added, the decreasing DPV signal would
be obtained for the release of MB from the aptamer.
Therefore, the biosensor could be used to detect the human
lgE. The linear detection IgE concentration ranges from 0.5
to 30 nmol/L and the detection limit is 37 pmol/L. The
result was very inspiring and the biosensor was also
investigated for the IgE detection in human serum sample.
By using CNT materials in the electrochemical biosensors,
Sci. Bull.
Fig. 5 (Color online) Schematic outline of the principle for label-free electrochemical IgE biosensing. Reproduced with permission from [85].
Copyright 2013 Elsevier Science Publishing
various molecules have been detected, such as the prostate-
specific antigen (PSA), and rosterone, catechol, H2O2,
NADH and hydrazine, etc. [86–91].
4.2 Metal nanomaterials/IL-based biosensors
Due to their unique physical and chemical properties, metal
nanomaterials have attracted increasing attention in the
sensor applications. Briefly, the properties including the
high surface area, the electrical conductivity and the elec-
trocatalytic activity and so on are all beneficial to the
improvement of the sensitivity when they are used as
biosensors. At the same time, they are very stable and
biocompatible with the biomaterials. Common metal
nanomaterials applied in electrochemical biosensor contain
noble metals, metal oxides, metal sulfides, metal nitrides
and bimetal composites. Recently, review articles con-
cerning the applications of metal nanomaterials and CNMs
in electrochemical biosensors have been published
[92–96], helping readers who are interested in the area to
obtain the sufficient information.
GNPs may be the most studied metal nanomaterials in
the biosensors. The most attractive features for their
applications are the high surface free energy, the simple
and mature preparation, and the perfect biocompatibility
[93]. Putzbach and Robkainen [93] have summarized the
immobilization of enzymes onto GNPs, including the
physical adsorption, chemisorption, self-assembling
monolayers, and the co-immobilization of GNPs with other
composites onto the electrode. Here, we place the emphasis
on recent advances in the applications of GNP/IL com-
posites in the electrochemical biosensing. In a report,
the authors prepared an ionic liquid of a quantum-sized
Au25 nanocluster by the ion-pairing of (3-mercapto-
propyl)sulfonate stabilizing Au25 cluster anions and 1-de-
cyl-3-methylimidazolium (DMIm) cations [97]. They
demonstrated that this ionic liquid (DMIm-Au25) could
easily form a film on the electrode and the film is electri-
cally conductive. Then the GOx was incorporated into
DMIm-Au25 film and the electrode modified with this
composite is shown in Fig. 6. When detecting the glucose,
the linear concentration range was 0.028–2.0 mmol/L and
the sensitivity was 0.76 lA L/mmol. Combining both the
properties of IL and the Au nanocluster, the authors
believed that the multifunctional DMIm-Au25 could be
used both in electrochemical biosensors and numerous
other electrochemical devices. An effective human IgG
immunosensor was fabricated based on the IL-modified
nanogold [98]. In the work, the authors synthesized the IL
4-amino-1-(3-mercapto-propyl)-pyridine hexafluorophos-
phate (AMPPH) and fabricated AMPPH-modified GNPs.
The anti-human IgG (anti-HIgG) was immobilized onto the
GCE by a cross-linking step with glutaraldehyde. Then the
bovine serum albumin (BSA) was used to fill the unspecific
sites on the electrode to obtain the final BSA/anti-HIgG-
AMPPH-AuNPs/GCE biosensor. The results in Fig. 7
display that the linear detection of the IgG concentration
range is 0.1–5.0 and 5.0–100.0 ng/mL, and the detection
limit is 0.08 ng/mL. The constructed immunosensor was
used to detect human IgG immunoglobulin in human
serum.
Liu et al. [99] reported a very sensitive electrochemical
immunosensor by modifying the antibodies into the IL-
functionalized GN/GNP composite. The modified electrode
exhibited very good sensitivity when detecting the carci-
noembryonic antigen with a linear detection range from
123

Fig. 6 (Color online) Schematic illustration of processes occurring in
a GOx-DMIm-Au25 composite electrode. Au25-mediated electro-
oxidation of glucose-reduced GOx and ensuing electron hopping
transport through Au25 sites in a GOx–DMIm–Au25 composite
electrode. The anodic current is proportional to the concentration of
glucose, which forms the basis for amperometric detection of glucose.
Reproduced with permission from [97]. Copyright 2014 American
Chemical Society
1 fg/mL to 100 ng/mL. The detection limit was found to as
low as 0.1 fg/mL (S/N = 3). In another report, the authors
fabricated a PSA immunosensor based on a multicompo-
nent including GNPs, polyamidoamine dendrimer
(PAMAM), MWCNTs, IL and chitosan [100]. The detec-
tion limit for PSA was 1 pg/mL, and the detection limit for
the PSA in human serum samples was 0.5 ng/mL. In
addition, the fabricated immunosensor displayed good
stability and reproducibility. They believed that the incor-
poration of GNPs accelerated the electron transfer process.
Electrochemical biosensor based on GNPs can also be used
to detect other materials such as the superoxide anion
[101], the cholesterol [102], hydrogen peroxide [103] and
carcinoembryonic antigen [104], etc. In addition to GNP
Fig. 7 (Color online) Differential pulse voltammograms of the immunosensing system incubated in human IgG solution with different
concentrations (a) and calibration curves for human IgG determination (b). Error bars represent standard deviation, n = 3. Reproduced with
permission from [98]. Copyright 2014 American Chemical Society
123
Sci. Bull.
noble metal, Pt nanoparticles (PtNPs) could also be applied
to construct the immunosensor. Recently, a novel human
chorionic gonadotropin (hCG) immunosensor was fabri-
cation based on PtNPs and the GN/IL/chitosan nanocom-
posite [105]. Besides, rutin was used for the first time as the
redox probe in the electrochemical immunosensor. The
GCE was first modified with the GN/IL/chitosan
nanocomposite, and then PtNPs were attached onto the
nanocomposite. The anti-hCG molecules were immobi-
lized onto the PtNPs because of the chemisorption between
PtNPs and amine groups of the anti-hCG. Finally, to
eliminate the nonspecific adsorptions, the BSA was used to
block the residual active sites of the electrode surface.
Three measurements containing the CV, DPV and EIS
were performed to investigate the detection activity of the
modified electrode. Once the antibody interacted with
hCG, the peak current of rutin decreased. According to the
DVP results, for the detection of the hCG, one can see that
the linear concentration ranges were 0.00106–2.12 and
2.12–350 mIU/mL. The detection limit was 0.00035 mIU/
mL. The results demonstrated that the PtNP-based elec-
trode was very sensitive and highly specific for hCG
detection.
In addition to noble metals, metal oxides [106], metal
sulfides [107] and metal nitrides [108] are all frequently
used to modify the biosensors. Zhu et al. [107] reported an
impedimetric DNA biosensor based on the rod-like bis-
muth sulfide (rBi2S3) nanoparticles. First, the rBi2S3
nanoparticles were modified onto the ionic liquid-carbon
paste electrode (IL-CPE), then polyaniline was modified
outside the nanoparticles. Both EIS and CV were carried
out to investigate the DNA detection activity. When the
probe DNA hybridized with the target DNA, the elec-
trochemical impedance would increase with the
Sci. Bull.
increasing DNA concentration. The target DNA detection
concentration ranged from 1.0 9 10-15 to 1.0 9 10-11
mol/L and the detection limit was 4.37 9 10-16 mol/L.
The constructed electrode exhibited good biocompatibil-
ity with the immobilized probe DNA. Saadati el al. [108]
reported an electrochemical biosensor based on the IL/
titanium-nitride nanoparticles (TiNNPs). By electrooxi-
dation of the amine group in the terminal of the IL, IL
could be attached to TiNNPs on the electrode through the
covalent interaction. Then the Hb could be adsorbed onto
the electrode through the electrostatic interactions
between IL and it. The electrochemical biosensor exhib-
ited good detection activity to the nitrite with a detection
limit of (0.10 ± 0.010) lmol/L, and it was also found
useful for the nitrite detection of real samples. Reports
concerning metal oxide-based electrochemical biosensors
are relatively more than other metal compounds. Metal
oxide nanoparticles that have been reported include CeO2
[109], NiO [49, 110], Fe3O4 [111], CdO [112], ZnO [113]
and ZrO2 [114, 115], etc. Karimi-Maleh el al. [49] mod-
ified the CPE with IL and NiO nanoparticles and used it to
detect the NADH. The results revealed that the linear
concentration range was from 0.03 to 900 lmol/L and the
detection limit was 0.009 lmol/L. In a previous report
concerning the application of ZrO2 nanoparticles, the GN/
ZrO2NP composite was modified onto the CILE [115].
The fabricated bioelectrode was applied to simultaneously
determine the adenosine and the guanosine. Electro-
chemical parameters were calculated and they found that
the GN/ZrO2NP composite could enhance the electrocat-
alytic activity of the CILE. Finally, satisfactory results
were also obtained when the modified bioelectrode was
used for the detection of adenosine and guanosine in
human urine samples. Bimetal composites could also be
applied to fabricate the surface of the electrode. Lou and
coworkers [116] fabricated an effective electrochemical
Mb biosensor by using the IL-functionalized Mg2Al lay-
ered double hydroxide (LDH). They found that Mb could
maintain their native activity which demonstrating the
good biocompatibility of the composites. CV results
revealed that the fabricated CILE possessed good detec-
tion activity for the TCA with the concentration ranging
from 1.0 to 17.0 mmol/L, and the detection limit was
0.344 mmol/L.
In summary, the advantages of the combination of ILs
and metal nanomaterials can be described as follows.
Firstly, they can improve the capability of the electron
transfer and enhance the electronic conductivity. Secondly,
their good biocompatibility can also improve the biocom-
patibility and the bioactivity of the immobilized bio
materials. Thirdly, they provide diverse immobilization
approaches for biomolecules onto the electrode and open
effective ways for the biosensor fabrication.
4.3 Gel-based biosensors
Gels formed by ILs are generally called ionogels. ILs can
be solidified by various components including organic
materials, inorganic materials and the hybrid materials
[117]. Ionogels combine both properties of ILs and the
additions, and exhibit great prospect in many application
fields, such as lubricating materials [118, 119], drug release
[120], dye absorption [121] and membrane materials [122].
The most applications of them are electrochemical fields
including the solid electrolyte [123], electrochemilumi-
nescent materials [124], the electrochemical transducer
[125], electrochemical sensors [126–128], and electro-
chemical biosensors [18]. Lately, an electrochemical sen-
sor for the blood glucose detection was fabricated based on
the GN/CNT/IL gel [128]. The preparation process was
shown in Fig. 8. The reduced GO (rGO)-CNT-IL gel was
prepared first, and then the biosensor was fabricated based
on the gel. The IL acted as the binder when printing the
hybrid ionogel on the free-standing GN paper. Nguyen
et al. [129] reported that the ionogel formed by liquid
crystalline block copolymers and GNPs exhibited excellent
properties such as high ionic conductivity and long-term
electrochemical stability over a large potential range. The
ionogel can be applied in electrochemical devices.
As shown in Fig. 9, an AChE biosensor was fabricated
based on the IL-functionalized GN and gelation (IL-GN-
Gel) composite [23]. First, by epoxide ring-opening reac-
tion, the IL-functionalized GN was prepared. Then the
AChE was immobilized onto the IL-GN-Gel modified GCE
by using glutaraldehyde as the cross-linker. The results
displayed that the composite provided good biocompati-
bility to the AChE. The biosensor was applied to detect two
pesticides, and the detection concentration ranges were
1.0 9 10-14–1.0 9 10-8 mol/L for the carbaryl and
1.0 9 10-13–5.0 9 10-8 mol/L for the monocrotophos.
The detection limits were 5.3 9 10-15 and
-14
4.6 9 10 mol/L for the carbaryl and monocrotophos,
respectively.
AChE biosensor was fabricated by Zamfir et al. [130]
based on tetrathiafulvalene–tetracyanoquinodimethane
(TTF–TCNQ)/IL gels. The preparation of the ionogel was
similar to the process for preparing the CNT/IL gels. Two
ionogels are formed through the cation–p interaction
between the additions and ILs. As for the amperometric
detection of thiocholine, the detection limit was 7.6 lmol/
L. Then the AChE biosensor was used to detect two ther-
apeutic drugs including the eserine and the neostigmine
with the detection limits of 26 and 0.3 nmol/L, respec-
tively. Chen et al. [131] reported a glucose biosensor based
on a novel three dimensional macroporous (3DM) IL doped
poly [N(3-(trimethoxysilyl)propylaniline)] (PTMSPA) sol–
gel composite. Both horseradish peroxidase (HRP) and
123
 Sci. Bull.

Fig. 8 (Color online) Preparation process of PtAu alloy nanoparticles decorated graphene-CNT-IL/GP. Step I: grinding 3D graphene-CNT
assembly with IL to form printable graphene-CNT-IL gel. Step II: printing graphene-CNT-IL gel on GP. Step III: ultrasonic-electrodepositing
PtAu alloy nanoparticles on graphene-CNT-IL-GP electrode. Reproduced with permission from [128]. Copyright 2016 Elsevier Science
Publishing

Fig. 9 (Color online) The schematic diagram of the fabrication of the AChE biosensor. Reproduced with permission from [23]. Copyright 2015
Elsevier Science Publishing

GOx were immobilized onto the modified electrode. The
bioelectrode exhibited electrochemical detection for the
glucose with a linear response from 0.05 to 1.0 and 1.0 to
8.0 mmol/L. The detection limit of the glucose was
0.01 mmol/L. A gel was prepared by the polymerization of
the toluidine blue O (TBO) functionalized ordered meso-
porous carbon (OMC) and IL [132]. The authors believed
that the interaction between the TBP-OMC and the IL was
p–p stacking interaction. The composite was applied to
modify the GCE which showed high electroactivity for the
oxidation of NADH at a low applied potential of
-0.034 V. The linear response range was from 1.0 to
6.0 mmol/L with a detection limit of 0.4 lmol/L for the
NADH detection. By an electrochemical etching approach,
Valentini el al. [133] prepared the GN/IL nanocomposite
gels and modified the paste electrodes with the nanocom-
posite-gel. The modified electrode displayed a selective
and specific detection for the caffeic acid. The linear
concentration range was from 0.025 to 2.00 mol/L and the
detection limit was 0.005 mmol/L. The reproducibility, the
sensitivity and the fast response time were obtained. They
believed that the nanocomposite-gel could provide a new
strategy to construct biosensors for the detection of
numerous materials. In a report, the IL was applied with
GNP-carbon aerogel to fabricate an amperometric biosen-
sor [134]. By using the ethylene glycol reducing method,
the GNP-carbon aerogel (Au-CA) was prepared. Then the
bioelectrode was modified with the Au-CA and IL com-
posite, and it provided enough sites and channels for the Hb
immobilization. The biosensor was applied to detect H2O2
and nitrite (NO2-) with the detection limit of 2.0 and
1.3 lmol/L, respectively.
5 Conclusions
In this article, we summarized the essential information for
ILs including the history, the structures as well as the

123
Sci. Bull.
outstanding properties for their applications in electro-
chemical sensors. The electrochemical sensors based on
ILs such as the gas sensor, the voltammetric sensors and
the ISEs have been described to provide the latest progress
in this filed. We highlighted the recent advances in appli-
cations of ILs in electrochemical biosensors. Common
electrochemical methods used to measure the detection
capability and the electrochemical properties include the
amperometric measurements, the potentiometric measure-
ments and the conductometric measurements. Detailed
information has been shown in the review by the specific
measurement results. From the numerous reported results,
we could draw the conclusion that the importance of the
applications of ILs in both electrochemical sensors and
electrochemical biosensors. The reasons could be
explained by the greatly enhanced electrochemical cat-
alytic activity and the relatively simple preparations. For
the flexible tunability of the structures, ILs can be applied
to a variety of electrochemical sensors and biosensors for
particular applications. The advances in recent years
described in the review have promoted the development for
employing ILs in electrochemical biosensors.
Nonetheless, there are still many challenges for
applying ILs in the electrochemical sensors and biosen-
sors. The aspects that need urgent investigation involve
the electrochemistry, the biochemistry and the surface
chemistry and so on. For example, when used as elec-
trolyte, the intrinsic disadvantages of ILs such as the
existence of the impurities and water in them may have a
negative effect on the electrochemical results. Impurities
in ILs may have complicated interactions with the target
molecules, and the negative results are really not easy to
be detected. Also, the water caused by the hygroscopicity
of ILs may lead to a lower electrochemical response rate.
It is well known that the ion transfer rate is important in
the electrode reaction. However, the high viscosity of ILs
may restrict the transport rate of molecules to the elec-
troactive surface, leading to poorer response. From
physical chemistry aspects, the surface chemistry and
uncertain aggregation behaviors between the ILs and
other solutes such as the biomolecules remain to be
thoroughly explained. Actually, few reports about the
fundamental information could be obtained. These phys-
ical chemistry problems may hinder the fabrication of the
stable and multifunctional electrodes. For example, when
IL molecules react with the water, the stability of the
electrode surface will be destroyed for the collapse of
electrode materials. Also, the problem gives rise to an
adverse consequence, that is, the poor selectivity to the
target molecule. To obtain the highly stable electrochem-
ical sensors based on ILs which possess high and con-
tinuous selectivity, both the biochemistry and the surface
chemistry should be further explored. Once more
breakthroughs are made in these fundamental aspects, it
will provide significant guides for further developments
and commercial applications of IL-based electrochemical
sensors and biosensors.
Acknowledgments This work was supported by the National Natural
Science Foundation of China (21420102006, 21273134).
Conflict of interest The authors declare that they have no conflict of
interest.
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