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Graphene-Based Electrochemical Sensors
small 2013, 9, No. 8, 1160–1172 © 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.small-journal.com 1161
reviews S. X. Wu et al.
reduction of GO using various reducing agents, referred to of Materials Research and Engineering of
A*STAR in Singapore. Her current research
as CrGO. The most commonly used agent is hydrazine. The
interest focuses on the synthesis of graphene-
rGO-modified electrodes can be fabricated by casting suspen- based composites and their application in
sion of CrGO onto the GCE[42–45] or Au electrode.[46] Prior electrochemical sensors.
to immobilizing CrGO onto the GCE, the electrode can be
modified by electrochemical polymerization of pyrrole, which
forms a stable matrix to enhance the encapsulation of CrGO
(Figure 1).[47] Similarly, Bo et al. modified GCE by using the
oxidized CrGO, which was obtained by oxidation of CrGO
with sulphuric acid and nitric acid, and polyaniline nanow- et al. prepared the nanocomposites of CrGO and AuNPs
ires formed by the electrochemical polymerization.[48] To through the sodium borohydride (NaBH4) reduction of
improve the immobilization of the enzyme and the electro- HAuCl4 onto PVP-protected CrGO, which mixed with chi-
catalytic activity of the electrode, metal nanoparticles (NPs) tosan for the modification of Au electrode.[38] In addition,
were anchored onto the CrGO-modified GCE. For example, ionic liquids, such as polyethleneimine-functionalized ionic
Hu et al. used electrodeposition to grow gold nanoparticles liquid (PFIL)[53,54] and 1-butyl-3-methylimidazolium hexafluo-
(AuNPs) on the CrGO-modified electrode.[49] Chen et al. pre- rophosphate ([bmim][PF6]),[55,56] are widely used for better
pared the CrGO-AuNPs hybrid material through the in-situ dispersion of CrGO and immobilization of enzyme.
reduction method and then dropped its solution onto GCE.[50] Moreover, the dispersibility of CrGO can also be improved
Zheng et al. used DNA as a linker to induce the formation by functionalization of CrGO through three steps: (1) pre-
and self-assembly of AuNPs on the CrGO-modified electrode reduction of GO by NaBH4, (2) reaction with diazonium salt
in the presence of the enzyme.[51] Lu et al. used chemical to introduce sulfonic groups onto the partially reduced GO,
reduction of Pd2+ ions adsorbed on the GCE modified by the and (3) post-reduction with hydrazine.[57] GCE modified with
mixture of CrGO and nafion (i.e. CrGO-nafion).[52] the mixture of sulfonated CrGO-nafion, AuNPs and enzyme
To improve the dispersibility of CrGO in water, poly- solution showed superior electrochemical sensing perfor-
vinylpyrrolidone (PVP) was added into the solution during the mance.[57] Zhang et al. used similar procedures to produce
hydrazine reduction to protect CrGO from aggregation. Shan functionalized CrGO for GCE modification except they used
polymeric ionic liquid of poly(1-vinyl-3-butylimidazolium
bromide) (poly(ViBuIm+Br−)) in the second step.[58] Other
functionalized CrGO for electrode modifications includes the
silanized CrGO (Figure 2),[59] 3,4,9,10-perylene tetracarbox-
ylic acid (PTCA)[60] and COOH-functionalized CrGO.[61]
It is worth mentioning that the CrGO-chitosan composite
is a promising material for electrodes since chitosan is used
to produce well dispersed CrGO and provide a good bio-
compatible environment for enzyme immobilization.[62–64] In
addition, chitosan is a good reducing agent for the prepara-
Figure 1. Representation of graphene (CrGO)-glucose oxidase (GOD) tion of CrGO dispersion,[65] and it can be covalently grafted
entrapped within a porous polypyrrole (Ppy) matrix. Reproduced with to CrGO, which offers a platform to attach other nanomate-
permission.[47] Copyright 2010, American Chemical Society. rials, e.g. Pd NPs, through the in-situ decoration.[66]
1162 www.small-journal.com © 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim small 2013, 9, No. 8, 1160–1172
Graphene-Based Electrochemical Sensors
Figure 2. Schematic illustration of silanization of graphene (CrGO). Reproduced with permission.[59] Copyright 2010, American Chemical Society.
As known, the commonly adopted drop-casting method developed by Zeng et al.[67] Various intermolecular inter-
for preparation of electrodes usually produces a non- actions can be utilized during the assembly process, such
uniform coating of rGO thin film onto the electrodes and as electrostatic interactions, hydrophobic interactions and
shows the poor control over the film thickness. Hence, an hydrogen bonds. In this work, CrGO was firstly modified
unconventional layer-by-layer (LbL) assembly method to by pyrene-grafted poly(acrylic acid) (PAA) through the
fabricate multilayer CrGO film-modified electrode was π–π interaction and van der Waals force. The electrode was
then prepared by alternating immersion
of GCE in poly(ethyleneimine) (PEI)
and PAA-CrGO solution, and the multi-
layer CrGO film was formed due to the
electrostatic attraction between the posi-
tively charged PEI and the negatively
charged PAA-CrGO. In addition, the
negatively charged enzyme, e.g. glucose
oxidase and glucoamylase, can be immo-
bilized onto the PEI/PAA-CrGO modi-
fied GCE by alternating immersion of
the electrode into the positively charged
PEI and the negatively charged enzyme
solutions.
small 2013, 9, No. 8, 1160–1172 © 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.small-journal.com 1163
reviews S. X. Wu et al.
Figure 4. Schematic illustration of preparation of ErGO-modified electrode through electrochemical reduction of graphene oxide (GO) adsorbed
on the 3-aminopropyltriethoxysilane (APTES) modified glassy carbon electrode (GCE) and the subsequent modification of the electrode with
polymerization of N-succinimidyl acrylate (pNSA) and glucose oxidase (GOx). Reproduced with permission.[30a] Copyright 2009, American Chemical
Society.
Recently, our group has prepared graphene-modified PtNi NPs occurred simultaneously, referred to as ErGO-PtNi
electrode through the direct electrochemical reduction of NPs (Figure 5).[72] Moreover, Unnikrishnan et al. casted the
GO adsorbed on the 3-aminopropyltriethoxysilane (APTES)- mixture of GO and enzyme on GCE, which was then elec-
modified GCE (GCE-APTES), referred to as ErGO.[30a,71] To trochemically reduced to produce the electrode for glucose
bond the enzyme covalently and hence improve the enzyme sensing.[73] Similarly, Zhang et al.[74] and Du et al.[75] con-
immobilization, N-succinimidyl acrylate (NSA) was electro- structed the ErGO-modified electrodes by dropping GO, NiO
grafted onto the GCE-APTES-ErGO (Figure 4).[30a] Gao nanofibers (NiONFs) and nafion suspensions or dropping pol-
et al. fabricated the ErGO-modified electrode through the yaniline and GO suspensions sequentially on GCE, respec-
direct ultrasonic-electrodeposition, by which the electrochem- tively, followed by the electrochemical reduction, referred to
ical reduction of GO-modified GCE and electrodeposition of as ErGO-NiONF-nafion[74] or ErGO-polyaniline.[75]
Figure 5. Schematic illustration of formation of reduced graphene oxide (ErGO)-PtNi NPs by the direct ultrasonic-electrodeposition method.
Reproduced with permission.[72] Copyright 2011, American Chemical Society.
1164 www.small-journal.com © 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim small 2013, 9, No. 8, 1160–1172
Graphene-Based Electrochemical Sensors
Alternatively, Liu et al. prepared the ErGO-modified elec- Furthermore, graphene with alternative morpholo-
trode by electrochemical reduction of GO casted on GCE, gies has also been applied for electrochemical sensors. For
followed by drop-casting of PVP on the electrode, referred example, Zhao et al. utilized graphene quantum dots (GQD)
to as ErGO-PVP.[76] Specifically for the DNA sensor, Dong synthesized by hydrothermal cutting of thermally reduced
et al. fabricated the ErGO-based electrode by drop-casting GO sheets as a smart sensor platform for DNA and pro-
of thiol-group-DNA strand (d(GT)29SH) and probe-labeled tein detections.[82] Wu et al. prepared the sensing electrode
gold nanoparticles (AuNPs-ssDNA) after electrochemical with the composite of graphene nanoribbon (GNR) and
reduction of GO casted on GCE, referred to as ErGO- nafion for the selective detection of cysteine.[83a] GNR was
d(GT)29SH-AuNPs-ssDNA.[77] To produce amplified detec- obtained through oxidation of multiwalled carbon nanotubes
tion signal, the signal tag of streptavidin (SA)-horseradish (MWCNTs) followed by the hydrazine reduction.[83b] The
peroxidase (HRP) functionalized carbon spheres (referred as-obtained GNR contained abundant oxygen-containing
to as SA-HRP-CNS) was dropped onto the electrode after groups that were beneficial for detection of thiols based on
hydrization with biotinylated target DNA.[77] either the 1,4 Michael addition or cycling addition reaction
Different from the aforementioned methods, Shang between thiols and carbonyl groups present on GNR.[83a]
et al. fabricated multilayer graphene nanoflake films (MGNFs)
by microwave-assisted plasma chemical vapour deposition
(MPCVD) on Si substrate, which can be directly used as a 3. Graphene-Based Electrochemical Sensors
working electrode for electrochemical sensing applications.[78]
Similarly, Lim et al. used the epitaxial graphene, first grown 3.1. Enzyme Biosensors
on silicon carbide substrates and subsequently anodized by
electrochemical treatment, as the working electrode.[79] As mentioned in the Introduction part, graphene possesses
Most recent advances include using the 3D graphene outstanding physical and electrochemical properties, such as
foam fabricated on Ni foam by CVD (CVD-3D-GF) as the large surface area, high conductivity, abundant defect sites,
electrochemical electrode to increase the active surface area superior electrocatalytic activity and fast electron transfer
and create multiplexed charge transport pathways and hence rate, hence various enzyme biosensors based on this attrac-
improve the sensitivity of the electrochemical sensor.[80a] tive material have been fabricated recently. One of the
Afterwards, they integrated the 3D graphene foam with most extensively studied examples is the graphene-based
cobalt oxide (Co3O4) nanowires, which showed electrocata- glucose sensor as the determination of glucose is highly
lytic behavior towards the glucose oxidation, to obtain the important in diagnosis of diabetes.[84] To detect glucose, the
superior enzymeless glucose sensor, referred to as CVD- graphene-based electrode is usually modified by glucose oxi-
3D-GF-Co3O4.[80b] Differently, Penmatsa et al. fabricated dase (GOD) in the final step of electrode preparation, i.e.
3D graphene structure with large surface area through the casting of the solution containing GOD onto the electrode.
electrostatic spray deposition of graphene solution onto 3D The glucose sensing performances of different graphene-
carbon micropillars.[81] based materials are compared and summarized in Table 1.
Table 1. Performance of glucose sensors with graphene-based electrodes. RSD: relative standard deviation.
Graphene-based materials Linear range Detection limit Sensitivity Reproducibility: RSD for Stability,% of initial Ref.
[mM] [μM] [μA mM−1 cm−2] (No. of electrodes) response after (days)
GO-Fc-chitosan 0.02–6.78 7.6 10 4.3% (5) >90% (1 month) [39a]
GO-F-SiO2-AgNP 2–12 310 4.1% (5) 83% (4 days) [40]
CrGO 0.1–10 10 ± 2 110 ± 3 2.5% (6) No obvious decrease [43]
(2 days)
CrGO-chitosan 0.08–12 20 37.93 5.3% (6 experiments) 95% (1 week) [62]
CrGO-poly(ViBuIm+Br−) 0.8–20 267 7.67 × 105 92% (2 weeks) [58]
CrGO-chitosan-Pd NPs 0.0–011 0.2 31.2 5.1% (5) 80% (3 weeks) [66]
CrGO-nafion-Pd NPs 0.010–5 1 3.7% (10) 98% (35 days) [52]
CrGO-AuNPs 0.1–10 35 0.74% (3) 80% (4 months) [50]
CrGO-DNA-AuNPs 0.0008–0.05 0.3 2.44 × 104 2.1% (6) 95% (1 month) [51]
Sulfonated 0.015–5.8 5 5.4% (5) 90% (3 weeks) [57]
CrGO-nafion-AuNPs
SrGO-CdS 2–16 700 1.76 4.2% (5) 93% (30 days) [69]
ErGO-PtNi alloy NPs Up to 35 10 20.42 < 5.0% (10) 90.5% (50 days) [72]
ErGO-NiONFs-nafion 0.002–0.6 0.77 1100 7.7% (6) 90.0% (1 month) [74]
CrGO-Ni(II)-quercetin 0.003–0.9 0.5 187 μAmM−1 5.1% (7) 92.1% (20 days) [86a]
CVD-3D-GF-Co3O4/glass Up to 0.080 0.025 3390 [80b]
small 2013, 9, No. 8, 1160–1172 © 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.small-journal.com 1165
reviews S. X. Wu et al.
All the electrodes in Table 1 are graphene-modified GCEs among all the graphene-based electrodes. Moreover, it also
except the electrode of CVD-3D-GF-Co3O4 on glass. Similar shows a high sensitivity of 3.39 mA mM−1 cm−2. The elec-
graphene-based materials are listed in the table to give a trocatalytic activity and large electrochemical capacitance
comparison. of Co3O4 nanowires as well as the large surface area and
It can be seen from Table 1 that the rGO-based glucose high conductivity of 3D graphene foam contribute to the
biosensors are favoured over the GO-based ones in terms impressive sensing performance towards glucose detec-
of sensing performance. It is known that GO contains more tion. In addition, it is obvious that the sensor prepared with
oxygen-containing groups than does rGO, while the con- ErGO-NiONFs-nafion shows a much lower detection limit
ductivity of rGO is much higher than that of GO due to the and higher sensitivity than those with ErGO-PtNi alloy NPs,
recovery of conjugated graphitic network after the reduc- which could be attributed to the large microscopic surface
tion process. Therefore, GO-based electrodes exhibit a lower area and good catalytic activity of NiONFs as well as to the
sensitivity than do most of rGO-based ones. Casero et al. superior electrochemical properties of ErGO.[74] Interest-
studied the electrochemical impedance spectra of GO and ingly, the sensor constructed with CrGO-Ni(II)-quercetin
rGO, showing that the charge transfer resistance of GO is exhibits similar sensing performance to that with ErGO-
much higher than that of rGO.[85] In their study, it was dem- NiONFs-nafion. It is believed that the quercetin, which can
onstrated that the presence of abundant oxygen-containing form stable complexes with various metal cations,[88] such as
groups would contribute to the finite-length Warburg element Ni(II), may contribute to the steady and strong electrocata-
in the impedance spectra, hence the GO-based electrode lytic activity of Ni(II) for glucose detection.
showed the finite-length diffusion, while the rGO-modified In addition to GOD, other enzymes may be immobilized
one showed the semi-infinite diffusion.[85] onto graphene-based electrodes for construction of various
Among the rGO-based electrodes, the electrode modified enzyme biosensors, such as horseradish peroxidase (HRP),[89]
with CrGO-chitosan-Pd NPs shows the lowest detection limit, alcohol dehydrogenase (ADH),[90] catalase[91] and urease.[92]
0.2 μM.[66] The superior performance can be attributed to the For example, very recently, Prasannakumar et al. fabricated an
covalent functionalization of CrGO with chitosan, which alcohol biosensor using graphene-carbon nanotubes (CNTs)
improves the hydrophilicity and biocompatibility of CrGO; modified graphite electrode immobilized with ADH.[90a] The
and the well dispersed, high loading of Pd NPs with small size as-fabricated electrode showed a linear range of 25–200 μM, a
(∼4–5 nm) and its high electrocatalytic activity.[66] Compared sensitivity of 82.5 nA μM−1 cm−2 (i.e. 82.5 μA mM−1 cm−2) and
to the CrGO-chitosan-Pd NPs, the CrGO functionalized with a detection limit of 10 μM.[90a] The sensitivity is a bit higher
nafion and decorated with Pd NPs (CrGO-nafion-Pd NPs) than that using the ionic liquid-functionalized graphene-based
shows a higher detection limit but much better reproduc- electrode fabricated by Shan et al. (37.43 μA mM−1 cm−2).[90b]
ibility and long-term stability. It is known that nafion has a The higher sensitivity of graphene-CNT modified electrode
hydrophobic backbone while chitosan is hydrophilic. Such a could be attributed to the high conductivity of graphene-
difference would result in different interactions with CrGO CNT composite resulted from the interconnections between
and produce Pd NPs with different morphologies. Obviously, graphene and CNTs which bridge the gaps among graphene
the resulted Pd NPs (size of 30–40 nm) in CrGO-nafion-Pd sheets.[93]
NPs is larger than those in CrGO-chitosan-Pd NPs, which
may explain the different sensing behaviors of these two
electrodes. 3.2. Nonenzymatic Sensors for Small Biomolecules
In addition, the sensor made by CrGO-DNA-AuNPs
showed a much lower detection limit and much higher sensi- Electrochemical sensing of small biomolecules, such as dopa-
tivity compared to other CrGO-based electrodes containing mine, ascorbic acid and uric acid, is another important appli-
AuNPs.[50,57] It was ascribed to the robust self-assembly of cation of graphene-based electrodes in electrochemistry due
SH and NH2 of the DNA strand with AuNPs.[51] Moreover, to the fast electron transfer kinetics and superior electro-
it could be explained by the synergistic effects from the catalytic activity of graphene-based materials. Dopamine is
DNA functionalized CrGO and AuNPs in terms of electron one of the most studied small biomolucules using graphene-
transfer ability and signal amplification from materials in based biosensors. Dopamine measurement is crucial since
nanoscale.[51] its change in the concentration is closely linked to one's
Furthermore, CrGO-poly(ViBuIm+Br−) shows the highest health status.[78] However, it is difficult to be detected selec-
sensitivity in glucose detection compared to other CrGO- tively and sensitively in the presence of its coexisting species,
based electrodes since CrGO modified with the specific ionic ascorbic acid (AA) and uric acid (UA), due to their overlap-
liquid exhibits the improved conductivity and gives the direct ping voltammetric response.[78] Recently, graphene-based
electron transfer between the immobilized GOD and the electrodes have shown great performance as electrochemical
CrGO-modified electrode surface.[58] sensors towards dopamine[94–100] even in the presence of AA
Recently, several nonenzymatic glucose biosensors based or/and UA due to its excellent physical and electrochemical
on graphene-modified GCE have been developed[72,74,86,87] properties and the feasible electron transfer between gra-
such as ErGO-PtNi alloy NPs,[72] ErGO-NiONFs,[74] CrGO- phene and dopamine through the π–π interaction.[45a,64,94,95]
Ni(II)-quercetin[86a] and CVD-3D-GF-Co3O4.[80b] Surpris- Table 2 summarizes the dopamine sensing performances
ingly, the glucose sensor based on 3D graphene-Co3O4 from different graphene-based electrodes. All the electrodes
composite shows the lowest detection limit of 25 nM[80b] in Table 2 are graphene-modified GCE except the electrodes
1166 www.small-journal.com © 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim small 2013, 9, No. 8, 1160–1172
Graphene-Based Electrochemical Sensors
Table 2. Performance of dopamine sensors with graphene-based electrodes. RSD: relative standard deviation.
Graphene-based Linear range Detection limit Reproducibility: RSD Stability,% of initial Detection limit Ref.
materials [μM] [μM] for (No. of electrodes) response after (times obtained in the pres-
of experiments (days) ence of interfering
compounds
MPCVD-MGNFs/Si 1–100 (two ranges) 0.17 80% (300 scans) 1 mM AA, 0.1 mM UA [78]
CVD-3D-GF/glass Up to 25 0.025 [80a]
CrGO 4–100 2.64 2.1% (4) 90% (5 measurements) 1 mM AA [45a]
CrGO-β-cyclodextrin 0.009–12.7 (two 0.005 [96]
ranges)
CrGO-chitosan 1.0–24 1.0 0.1 mM AA, 0.02 mM [64]
UA
Silanized CrGO-nafion 0.20–25 0.01 1 mM AA [59]
CrGO-poly (p-amin- 0.03–1.16 or 0.05–10 0.01 or 0.02 4.2% (5) 98.5% (14 days) Without AA or With 0.1 [97]
obenzoic acid) (two ranges) mM AA
CrGO-Congo red- 0.1–830 0.1 3.77% (6 detections) 95.3% (3 weeks) [100]
molecular imprinted
polymers
CrGO-Pt NPs 0.03–8.13 0.03 [98]
CrGO-Zn/Al layered 1.019–9 0.3 5.4% (8 88.4% (5 weeks) 0.1 mM AA [99]
double hydroxide films measurements)
SrGO-Cu2O NPs 0.11–0 0.01 or 0.2 3.5% (10) Without UA or With 0.5 [70]
mM UA
ErGO-PVP 0.0005–1130 0.0002 2.16% (5) 90.1% (10 days) 1 mM AA [76]
of MPCVD-MGNFs on Si and CVD-3D-GF on glass. Sim- in the absence of AA and UA. The silanized CrGO-nafion
ilar graphene-based materials are listed in the table to give a combined the advantages from both nafion and silanized
comparison. CrGO.[59] Nafion can improve the selectivity of the electrode
From Table 2, it can be seen that MGNFs grown on Si towards dopamine due to its sulphuric groups that act as an
by MPCVD showed a lower detection limit compared to anion barrier.[59] The silanized CrGO has the large active
the CrGO-modified GCE. The superior sensing perfor- electrode surface area and more active functional groups due
mance from MGNFs could be explained by its abundant to the chemical modification of CrGO.[59] Both can accelerate
edge defects that have different electrochemical interaction the electron transfer, catalyze the dopamine oxidation and
potential with dopamine and its negative charge from struc- concentrate dopamine from solutions containing anionic spe-
tural motifs, which repels anionic AA and UA but favourably cies.[59] The excellent sensing performance from CrGO-poly
interacts with cationic dopamine.[78] It is emphasized that the (p-aminobenzoic acid)-modified GCE can be attributed to
oxygen-containing groups on MGNFs are not the reason for the good conductivity and high catalytic ability of CrGO-poly
distinguishing dopamine from AA and UA.[78] (p-aminobenzoic acid).[97] More importantly, the negatively
Moreover, the sensor based on ErGO-PVP shows the charged p-aminobenzoic acid, which contains high density of
lowest detection limit of 0.2 nM and largest linear range from carboxyl groups, could enhance its electrostatic interaction
0.0005 to 1130 μM in the presence of 1 mM AA. The impres- with dopamine.[97] From the study of SrGO-Cu2O NPs in the
sive sensing performance from ErGO-PVP is obtained by dopamine detection, it is found that the superior sensitivity
optimizing the concentration of GO and PVP and the pH.[76] of the electrode is mainly because of the highly dispersed
In addition, the high selectivity towards DA in the presence Cu2O NPs on SrGO, that lead to the improved electron
of AA from ErGO-PVP could be explained by the strong transfer rate of SrGO and increased electrocatalytic ability
adsorption property of PVP to phenolic compounds in DA towards dopamine.[70] It is worthy to mention that the sensor
but week interaction with AA as well as the particular elec- made by CVD-3D-GF with macroporous structure and high
trode preparation method.[76] Besides, CrGO-β-cyclodextrin conductivity shows a low detection limit of 25 nM based
shows the second lowest detection limit of 0.005 μM in the on the signal to noise ratio of 5.6 and a high sensitivity of
absence of interfering compounds. One reason for its supe- 619.6 μA mM−1 cm−2.[80a] The superior sensing performance
rior performance is that the addition of β-cyclodextrin could could be attributed to the novel architecture of CVD-3D-GF,
improve the dispersion of CrGO, which results in more acces- which could provide large surface area for interaction with
sible active sites and enhanced catalytic activity.[96] dopamine and multiplexed conductive pathways for the elec-
In addition to the CrGO-β-cyclodextrin, the silanized tron transport between graphene and dopamine.[80a]
CrGO-nafion, CrGO-poly (p-aminobenzoic acid) and SrGO- In addition to dopamine, graphene-based electrodes have
Cu2O NPs also show very low detection limit of 0.01 μM been fabricated as nonenzymatic sensors to detect other
small 2013, 9, No. 8, 1160–1172 © 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.small-journal.com 1167
reviews S. X. Wu et al.
small biomolecules, such as hydrogen peroxide (H2O2).[101] Table 3. DNA sensing performance from different graphene-based
For example, the Sun group has recently studied the nonen- electrodes. RSD: relative standard deviation; IL: amine-terminated
ionic liquid, 1-(2-aminoethyl)-3-methylimidazolium bromide.
zymatic detection of H2O2 using AgNPs and rGO compos-
ites (AgNPs/rGO).[101] The AgNPs/rGO synthesized with
Graphene-based Dynamic range Detection Reproducibility: RSD for Ref.
a reducing agent of diethylenetriamine (AgNPs/rGO-1) materials [nM] limit [pM] (No. of experiments)
showed a linear detection range from 0.1 to 100 mM and a
ErGO-polyaniline 0.0001–100 0.032 5.4% (10) [75]
detection limit of 3.6 μM.[101a] Comparatively, AgNPs/rGO
Oxidized 0.00212–2120 0.325 1.15% (7) [48]
synthesized under alkaline condition without any reducing
CrGO-polyaniline
agent (AgNPs/rGO-2) showed a linear range from 0.1 to
60 mM and a detection limit of 1.8 μM.[101b] Their electro- CrGO-DNA-AuNPs- 0.2–500 72 [105]
Ag
chemical sensing performances are quite similar since both
used the composite of AgNPs and rGO. The slight differ- PTCA functionalized 0.001–1000 0.5 [60]
CrGO
ence could be attributed to the different morphologies of
AgNPs formed under different synthesis conditions. AgNPs PTCA functionalized 0.0001–1000 0.034 6.04% (4) [106]
CrGO-IL-AuNPs
in AgNPs/rGO-1 had sizes ranging from 10 to 150 nm while
those in AgNPs/rGO-2 had a bimodal size distribution ErGO-d(GT)29SH- 1E-8–1E-4 5E-6 [77]
at 5 nm and 40 nm, respectively.[101] The smaller AgNPs in AuNPs-ssDNA
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Graphene-Based Electrochemical Sensors
sensitivity can be further improved by using nanomaterials hydrazine oxidation.[115a] Li et al. realized the determination
entrapped with antibodies to amplify the electrochemical of p-aminophenol based on the ErGO-modified electrode,
signals of the immunological reactions, such as quantum dot, which showed a linear range of 0.01–10 μM and a detection
CNTs and metal NPs. For example, Yang et al. constructed limit of 2.9 nM based on the signal to noise ratio of 3.[116a]
a sandwich-type immunosensor using graphene sheets (GS) Such a sensing electrode takes the advantages of ErGO in
and quantum dot functionalized graphene (QD-GS) to terms of large surface area, fast electronic transport kinetics
immobilize primary antibody (Ab1) and secondary antibody and good π–π interaction with p-aminophenol.[116a]
(Ab2), respectively. The as-constructed immunosensor was
applied for the detection of PSA and showed a linear range
of 0.005-10 ng/mL and a detection limit of 3 pg/mL.[108] Lu 4. Summary
et al. built a sandwich-type immunosensor with AuNPs
dotted CNTs-graphene composite to detect the human chori- This review presents a brief introduction on the advanta-
onic gonadotrophin (hCG).[109] They particularly emphasized geous properties of graphene and briefly summarizes various
the fixation of AuNPs onto the composite of thionine and graphene preparation methods. The superior electrochemical
mesoporous nanoparticles MCM-41, in which thionine could sensing performances of graphene-based electrodes towards
provide a strong linkage between MCM-41 and AuNPs and the detection of various biomolecules and chemicals have
enhance the loading of the secondary antibody.[109] In addi- been demonstrated in this review, especially the recent pro-
tion, MCM-41 with a high surface-to-volume ratio could also gress of applications of graphene in electrochemical sensors
improve the conjugation of biomolecules.[109] In the AuNPs has been addressed. Nonetheless, there is still much room
dotted CNTs-graphene composite, AuNPs were used to pro- for the exploration of graphene-based electrodes in electro-
vide effective electron transport and ideal microenvironment chemical sensors and challenges remain in the understanding
for the attachment of biomolecules. The coupling between and developing of graphene in the area of electrochemistry.
CNTs and graphene was used to improve the electron transfer For example, methods to obtain graphene with the desired
efficiency and immobilization of primary antibody.[109] The as- morphology (e.g. graphene nanoribbon, quantum dot, 3D
built sensor showed a linear range from 0.005 to 500 mIU/mL network), structure (e.g. amount of oxygen functional groups,
(about 0.0003–30 ng/mL) and a detection limit of 0.0026 mIU/mL presence of other specific functional groups), and properties
(about 0.000156 ng/mL).[109] The sensing performance is (e.g. catalysis, conductivity) should be developed. Further-
much superior to the immunosensor fabricated by Li et al. more, the interactions between graphene and analyte mol-
using nanoporous Au foil and graphene for the detection of ecules, such as the absorption mechanism of molecules on
hCG with a linear range of 0.5–40.0 ng/mL and a detection graphene and the charge transport kinetics at the graphene
limit of 0.034 ng/mL.[110] interface, should be explored. In addition, the construction
of electrochemical sensors with different graphene-based
materials, different sensor structures and different sensing
3.5. Other Sensors mechanisms is also a great challenge. In addition to graphene,
other 2D nanomateirals, such as transition metal dichalco-
In addition to biomolecules, graphene-based electrodes have genides,[117] can also be applied for electrochemical sensing
been applied for the detection of chemicals.[111–113] Due to the applications as well. Recently, our group has synthesized
large surface area and high conductivity of graphene, it can single-layer MoS2 through an electrochemical lithiation pro-
sensitively detect heavy metal ions,[114] toxic chemicals,[115] cess[118] and applied it for glucose and biomolecules detec-
organic molecules[116] and so on. For example, Gao et al. syn- tions.[119] The electrochemically reduced MoS2 demonstrates
thesized the AlOOH-rGO nanocomposites for the electro- the high electrochemical activity and good sensing perfor-
chemical analysis of Cd(II) and Pb(II) simultaneously in one mance, which offers an alternative platform for the electro-
solution.[114a] Since AlOOH shows a strong adsorption and chemical sensor.
accumulation capacity toward the heavy metal ions, and rGO
possesses the excellent conductivity for efficient charge trans-
port between electrode surface and metal ions, the nanocom-
posites combine the advantages of the two materials and show
a detection limit of 352 nM for Cd(II) and 932 nM for Pb(II) Acknowledgements
during the detection of two metal ions in one solution.[114a]
Moreover, the detection of other meal ions simultaneously This work was supported by MOE under AcRF Tier 2 (ARC 10/10,
can be achieved by the composite, such as Zn(II), Cu(II), and No. MOE2010-T2-1-060), Singapore National Research Foun-
Hg(II), based on different detection potentials for different dation under CREATE programme: Nanomaterials for Energy
metal ions.[114a] Lei et al. used the MnO2/GO composite for and Water Management, and NTU under the Start-Up Grant
hydrazine detection, which showed a linear range of 3 μM to (M4080865.070.706022) in Singapore.
1.12 mM, with a detection limit of 0.16 μM and a sensitivity of
1.007 mA mM−1 cm−2.[115a] The high electrochemical sensing
performance can be attributed to the abundant oxygen- [1] a) N. O. Weiss, H. L. Zhou, L. Liao, Y. Liu, S. Jiang, Y. Huang,
containing groups and large surface area of GO for the MnO2 X. F. Duan, Adv. Mater. 2012, 24, 5782; b) X. Huang, X. Y. Qi,
absorption, and the superior catalytic properties of MnO2 for F. Boey, H. Zhang, Chem. Soc. Rev. 2012, 41, 666.
small 2013, 9, No. 8, 1160–1172 © 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.small-journal.com 1169
reviews S. X. Wu et al.
[2] D. Chen, L. H. Tang, J. H. Li, Chem. Soc. Rev. 2010, 39, 3157. [28] a) S. Yang, W. Yue, D. Huang, C. Chen, H. Lin, X. Yang, RSC Adv.
[3] X. Huang, Z. Y. Yin, S. X. Wu, X. Y. Qi, Q. Y. He, Q. C. Zhang, 2012, 2, 8827; b) X. B. Fan, W. C. Peng, Y. Li, X. Y. Li, S. L. Wang,
Q. Y. Yan, F. Boey, H. Zhang, Small 2011, 7, 1876. G. L. Zhang, F. B. Zhang, Adv. Mater. 2008, 20, 4490.
[4] a) J. F. Tian, L. A. Jauregui, G. Lopez, H. Cao, Y. P. Chen, Appl. [29] J. B. Liu, S. H. Fu, B. Yuan, Y. L. Li, Z. X. Deng, J. Am. Chem. Soc.
Phys. Lett. 2010, 96, 263110; b) K. S. Novoselov, A. K. Geim, 2010, 132, 7279.
S. V. Morozov, D. Jiang, Y. Zhang, S. V. Dubonos, I. V. Grigorieva, [30] a) Z. Wang, X. Zhou, J. Zhang, F. Boey, H. Zhang, J. Phys.
A. A. Firsov, Science 2004, 306, 666. Chem. C 2009, 113, 14071; b) Y. Harima, S. Setodoi, I. Imae,
[5] K. S. Novoselov, A. K. Geim, S. V. Morozov, D. Jiang, K. Komaguchi, Y. Ooyama, J. Ohshita, H. Mizota, J. Yano, Electro-
M. I. Katsnelson, I. V. Grigorieva, S. V. Dubonos, A. A. Firsov, chim. Acta 2011, 56, 5363.
Nature 2005, 438, 197. [31] a) M. Zhou, Y. L. Wang, Y. M. Zhai, J. F. Zhai, W. Ren, F. A. Wang,
[6] A. K. Geim, Science 2009, 324, 1530. S. J. Dong, Chem. Eur. J. 2009, 15, 6116; b) Z. J. Wang, S. X. Wu,
[7] X. Huang, Z. Y. Zeng, Z. X. Fan, J. Q. Liu, H. Zhang, Adv. Mater. J. Zhang, P. Chen, G. C. Yang, X. Z. Zhou, Q. C. Zhang, Q. Y. Yan,
2012, 24, 5979. H. Zhang, Nanoscale Res. Lett. 2012, 7, 161.
[8] a) M. D. Stoller, S. J. Park, Y. W. Zhu, J. H. An, R. S. Ruoff, Nano [32] X. Huang, X. Zhou, S. Wu, Y. Wei, X. Qi, J. Zhang, F. Boey,
Lett. 2008, 8, 3498; b) C. Liu, S. Alwarappan, Z. F. Chen, H. Zhang, Small 2010, 6, 513.
X. X. Kong, C. Z. Li, Biosens. Bioelectron. 2010, 25, 1829. [33] G. Williams, B. Seger, P. V. Kamat, ACS Nano 2008, 2, 1487.
[9] M. Pumera, A. Ambrosi, A. Bonanni, E. L. K. Chng, H. L. Poh, [34] H. A. Becerril, J. Mao, Z. Liu, R. M. Stoltenberg, Z. Bao, Y. Chen,
Trends Anal. Chem. 2010, 29, 954. ACS Nano 2008, 2, 463.
[10] a) D. A. C. Brownson, C. E. Banks, Analyst 2010, 135, 2768; [35] Y. Zhou, Q. Bao, L. A. L. Tang, Y. Zhong, K. P. Loh, Chem. Mater.
b) Y. Y. Shao, J. Wang, H. Wu, J. Liu, I. A. Aksay, Y. H. Lin, Electro- 2009, 21, 2950.
anal. 2010, 22, 1027. [36] a) A. Lerf, H. He, M. Forster, J. Klinowski, J. Phys. Chem. B 1998,
[11] a) B. Pérez-López, A. Merkoçi, Anal. Bioanal. Chem. 2011, 399, 102, 4477; b) W. Gao, L. B. Alemany, L. Ci, P. M. Ajayan, Nat.
1577; b) D. Chen, H. Feng, J. Li, Chem. Rev. 2012, 112, 6027. Chem. 2009, 1, 403.
[12] B. C. Brodie, Philos. Trans. R. Soc. London 1859, 149, 249. [37] Y. Liu, D. S. Yu, C. Zeng, Z. C. Miao, L. M. Dai, Langmuir 2010,
[13] R. Zacharia, H. Ulbricht, T. Hertel, Phys. Rev. B 2004, 69, 26, 6158.
155406. [38] C. S. Shan, H. F. Yang, D. X. Han, Q. X. Zhang, A. Ivaska, L. Niu,
[14] M. J. Allen, V. C. Tung, R. B. Kaner, Chem. Rev. 2010, 110, 132. Biosens. Bioelectron. 2010, 25, 1070.
[15] R. Zhang, Y. L. Dong, W. J. Kong, W. P. Han, P. H. Tan, Z. M. Liao, [39] a) J.-D. Qiu, J. Huang, R.-P. Liang, Sens. Actuators B 2011,
X. S. Wu, D. P. Yu, J. Appl. Phys. 2012, 112, 104307. 160, 287; b) Z. J. Wang, J. Zhang, Z. Yin, S. X. Wu, D. Mandler,
[16] a) R. S. Weatherup, B. C. Bayer, R. Blume, C. Baehtz, H. Zhang, Nanoscale 2012, 4, 2728.
P. R. Kidambi, M. Fouquet, C. T. Wirth, R. Schlogl, S. Hofmann, [40] W. B. Lu, Y. L. Luo, G. H. Chang, X. P. Sun, Biosens. Bioelectron.
ChemPhysChem 2012, 13, 2544; b) D. Nezich, A. Reina, 2011, 26, 4791.
J. Kong, Nanotechnol. 2012, 23, 015701; c) X. H. Cao, Y. M. Shi, [41] X. M. Sun, Z. Liu, K. Welsher, J. T. Robinson, A. Goodwin, S. Zaric,
W. H. Shi, G. Lu, X. Huang, Q. Y. Yan, Q. C. Zhang, H. Zhang, H. J. Dai, Nano Res. 2008, 1, 203.
Small 2011, 7, 3163; d) X. H. Cao, Z. Y. Zeng, W. H. Shi, [42] a) B. Ntsendwana, B. B. Mamba, S. Sampath, O. A. Arotiba, Int.
P. R. Yep, Q. Y. Yan, H. Zhang, Small 2013, DOI: 10.1002/ J. Electrochem. Sci. 2012, 7, 3501; b) M. Zhou, Y. Zhai, S. Dong,
smll.201200683. Anal. Chem. 2009, 81, 5603.
[17] a) L. Tao, J. Lee, M. Holt, H. Chou, S. J. McDonnell, D. A. Ferrer, [43] P. Wu, Q. A. Shao, Y. J. Hu, J. A. Jin, Y. J. Yin, H. Zhang, C. X. Cai,
M. G. Babenco, R. M. Wallace, S. K. Banerjee, R. S. Ruoff, Electrochim. Acta 2010, 55, 8606.
D. Akinwande, J. Phys. Chem. C 2012, 116, 24068; [44] S. Alwarappan, A. Erdem, C. Liu, C. Z. Li, J. Phys. Chem. C 2009,
b) T. Terasawa, K. Saiki, Carbon 2012, 50, 869. 113, 8853.
[18] P. W. Sutter, J.-I. Flege, E. A. Sutter, Nat. Mater. 2008, 7, 406. [45] a) Y. R. Kim, S. Bong, Y. J. Kang, Y. Yang, R. K. Mahajan, J. S. Kim,
[19] X. Yang, X. Dou, A. Rouhanipour, L. Zhi, H. J. Rader, K. Mullen, H. Kim, Biosens. Bioelectron. 2010, 25, 2366; b) Q. X. Wang,
J. Am. Chem. Soc. 2008, 130, 4216. M. X. Zheng, J. L. Shi, F. Gao, Electroanal. 2011, 23, 915.
[20] T. Kuila, S. Bose, A. K. Mishra, P. Khanra, N. H. Kim, J. H. Lee, [46] S. L. Yang, B. F. Xu, J. Q. Zhang, X. D. Huang, J. Ye, C. Z. Yu,
Prog. Mater Sci. 2012, 57, 1061. J. Phys. Chem. C 2010, 114, 4389.
[21] W. S. Hummers, R. E. Offeman, J. Am. Chem. Soc. 1958, 80, [47] S. Alwarappan, C. Liu, A. Kumar, C. Z. Li, J. Phys. Chem. C 2010,
1339. 114, 12920.
[22] a) D. Li, M. B. Muller, S. Gilje, R. B. Kaner, G. G. Wallace, Nat. [48] Y. Bo, H. Y. Yang, Y. Hu, T. M. Yao, S. S. Huang, Electrochim. Acta
Nanotechnol. 2008, 3, 101; b) J. T. Han, J. I. Jang, B. H. Jeong, 2011, 56, 2676.
B. J. Kim, S. Y. Jeong, H. J. Jeong, J. H. Cho, G.-W. Lee, J. Mater. [49] Y. J. Hu, J. A. Jin, P. Wu, H. Zhang, C. X. Cai, Electrochim. Acta
Chem. 2012, 22, 20477. 2010, 56, 491.
[23] X. Y. Qi, K. Y. Pu, H. Li, X. Z. Zhou, S. X. Wu, Q. L. Fan, B. Liu, [50] Y. Chen, Y. Li, D. Sun, D. B. Tian, J. R. Zhang, J. J. Zhu, J. Mater.
F. Boey, W. Huang, H. Zhang, Angew. Chem. Int. Ed. 2010, 49, Chem. 2011, 21, 7604.
9426. [51] J. B. Zheng, Y. P. He, Q. L. Sheng, H. F. Zhang, J. Mater. Chem.
[24] X. Z. Zhou, X. Huang, X. Y. Qi, S. X. Wu, C. Xue, F. Y. C. Boey, 2011, 21, 12873.
Q. Y. Yan, P. Chen, H. Zhang, J. Phys. Chem. C 2009, 113, [52] L. M. Lu, H. B. Li, F. L. Qu, X. B. Zhang, G. L. Shen, R. Q. Yu, Bio-
10842. sens. Bioelectron. 2011, 26, 3500.
[25] S. Stankovich, D. A. Dikin, G. H. B. Dommett, K. M. Kohlhaas, [53] C. S. Shan, H. F. Yang, J. F. Song, D. X. Han, A. Ivaska, L. Niu,
E. J. Zimney, E. A. Stach, R. D. Piner, S. T. Nguyen, R. S. Ruoff, Anal. Chem. 2009, 81, 2378.
Nature 2006, 442, 282. [54] F. H. Li, J. Chai, H. F. Yang, D. X. Han, L. Niu, Talanta 2010, 81,
[26] a) W. Chen, L. Yan, Nanoscale 2011, 3, 3132; b) G. Wang, 1063.
J. Yang, J. Park, X. Gou, B. Wang, H. Liu, J. Yao, J. Phys. Chem. C [55] C.-H. Wang, C.-H. Wu, J.-W. Wu, M.-T. Lee, J.-K. Chang, M.-D. Ger,
2008, 112, 8192. C.-L. Sun, Analyst 2013, 138, 576.
[27] V. Dua, S. P. Surwade, S. Ammu, S. R. Agnihotra, S. Jain, [56] M. H. Yang, B. G. Choi, H. Park, W. H. Hong, S. Y. Lee, T. J. Park,
K. E. Roberts, S. Park, R. S. Ruoff, S. K. Manohar, Angew. Chem. Electroanal. 2010, 22, 1223.
Int. Ed. 2010, 49, 2154. [57] K. F. Zhou, Y. H. Zhu, X. L. Yang, C. Z. Li, Electroanal. 2010, 22, 259.
1170 www.small-journal.com © 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim small 2013, 9, No. 8, 1160–1172
Graphene-Based Electrochemical Sensors
[58] Q. Zhang, S. Y. Wu, L. Zhang, J. Lu, F. Verproot, Y. Liu, Z. Q. Xing, [87] a) J. Luo, S. S. Jiang, H. Y. Zhang, J. Q. Jiang, X. Y. Liu, Anal. Chim.
J. H. Li, X. M. Song, Biosens. Bioelectron. 2011, 26, 2632. Acta 2012, 709, 47; b) J. Luo, H. Y. Zhang, S. S. Jiang, J. Q. Jiang,
[59] S. F. Hou, M. L. Kasner, S. J. Su, K. Patel, R. Cuellari, J. Phys. X. Y. Liu, Microchim. Acta 2012, 177, 485; c) M. Mallesha,
Chem. C 2010, 114, 14915. R. Manjunatha, G. S. Suresh, J. S. Melo, S. F. D’Souza,
[60] Y. W. Hu, F. H. Li, X. X. Bai, D. Li, S. C. Hua, K. K. Wang, L. Niu, T. V. Venkatesha, J. Solid State Electrochem. 2012, 16, 2675.
Chem. Commun. 2011, 47, 1743. [88] a) P.-G. Pietta, J. Nat. Prod. 2000, 63, 1035; b) L. Zheng,
[61] K. J. Huang, D. J. Niu, J. Y. Sun, C. H. Han, Z. W. Wu, Y. L. Li, J. F. Song, J. Solid State Electrochem. 2010, 14, 43.
X. Q. Xiong, Colloids Surf. B 2011, 82, 543. [89] a) L. L. Zhang, H. H. Cheng, H. M. Zhang, L. G. Qu, Electrochim.
[62] X. H. Kang, J. Wang, H. Wu, I. A. Aksay, J. Liu, Y. H. Lin, Biosens. Acta 2012, 65, 122; b) Q. Zhang, Y. Qiao, L. Zhang, S. Y. Wu,
Bioelectron. 2009, 25, 901. H. Zhou, J. W. Xu, X. M. Song, Electroanal. 2011, 23, 900.
[63] a) S. Yang, S. Luo, C. Liu, W. Wei, Colloids Surf. B 2012, 96, [90] a) S. Prasannakumar, R. Manjunatha, C. Nethravathi, G. S. Suresh,
75; b) Y. Wang, Y. M. Li, L. H. Tang, J. Lu, J. H. Li, Electrochem. M. Rajamathi, T. V. Venkatesha, J. Solid State Electrochem. 2012,
Commun. 2009, 11, 889. 16, 3189; b) C. S. Shan, H. F. Yang, D. X. Han, Q. X. Zhang,
[64] D. X. Han, T. T. Han, C. S. Shan, A. Ivaska, L. Niu, Electroanal. A. Ivaska, L. Niu, Biosens. Bioelectron. 2010, 25, 1504.
2010, 22, 2001. [91] a) K. J. Huang, D. J. Niu, X. Liu, Z. W. Wu, Y. Fan, Y. F. Chang,
[65] S. Liu, J. Q. Tian, L. Wang, Y. L. Luo, W. B. Lu, X. P. Sun, Biosens. Y. Y. Wu, Electrochim. Acta 2011, 56, 2947; b) S. W. Ting,
Bioelectron. 2011, 26, 4491. A. P. Periasamy, S. M. Chen, R. Saraswathi, Int. J. Electrochem.
[66] Q. Zeng, J. S. Cheng, X. F. Liu, H. T. Bai, J. H. Jiang, Biosens. Bio- Sci. 2011, 6, 4438.
electron. 2011, 26, 3456. [92] a) R. K. Srivastava, S. Srivastava, T. N. Narayanan, B. D. Mahlotra,
[67] G. H. Zeng, Y. B. Xing, J. A. Gao, Z. Q. Wang, X. Zhang, Langmuir R. Vajtai, P. M. Ajayan, A. Srivastava, ACS Nano 2011, 6,
2010, 26, 15022. 168; b) G.-P. Nikoleli, M. Q. Israr, N. Tzamtzis, D. P. Nikolelis,
[68] A. N. Cao, Z. Liu, S. S. Chu, M. H. Wu, Z. M. Ye, Z. W. Cai, M. Willander, N. Psaroudakis, Electroanal. 2012, 24, 1285.
Y. L. Chang, S. F. Wang, Q. H. Gong, Y. F. Liu, Adv. Mater. 2010, [93] V. C. Tung, L. M. Chen, M. J. Allen, J. K. Wassei, K. Nelson,
22, 103. R. B. Kaner, Y. Yang, Nano Lett. 2009, 9, 1949.
[69] K. Wang, Q. A. Liu, Q. M. Guan, J. Wu, H. N. Li, J. J. Yan, Biosens. [94] a) X. Y. Ma, M. Y. Chao, Z. X. Wang, Anal. Methods 2012, 4,
Bioelectron. 2011, 26, 2252. 1687; b) X. Liu, L. L. Xie, H. L. Li, J. Electroanal. Chem. 2012,
[70] F. Y. Zhang, Y. J. Li, Y. E. Gu, Z. H. Wang, C. M. Wang, Microchim. 682, 158.
Acta 2011, 173, 103. [95] a) Z. H. Sheng, X. Q. Zheng, J. Y. Xu, W. J. Bao, F. B. Wang,
[71] Z. Wang, J. Zhang, P. Chen, X. Zhou, Y. Yang, S. Wu, L. Niu, Y. Han, X. H. Xia, Biosens. Bioelectron. 2012, 34, 125; b) S. J. Li,
L. Wang, P. Chen, F. Boey, Q. Zhang, B. Liedberg, H. Zhang, Bio- D. H. Deng, Q. Shi, S. R. Liu, Microchim. Acta 2012, 177, 325.
sens. Bioelectron. 2011, 26, 3881. [96] L. Tan, K. G. Zhou, Y. H. Zhang, H. X. Wang, X. D. Wang, Y. F. Guo,
[72] H. C. Gao, F. Xiao, C. B. Ching, H. W. Duan, ACS Appl. Mater. H. L. Zhang, Electrochem. Commun. 2010, 12, 557.
Interfaces 2011, 3, 3049. [97] K. J. Huang, Q. S. Jing, Z. W. Wu, L. Wang, C. Y. Wei, Colloids Surf.
[73] B. Unnikrishnan, S. Palanisamy, S. M. Chen, Biosens. Bioelec- B 2011, 88, 310.
tron. 2013, 39, 70. [98] C. L. Sun, H. H. Lee, J. M. Yang, C. C. Wu, Biosens. Bioelectron.
[74] Y. Q. Zhang, Y. Z. Wang, J. B. Jia, J. G. Wang, Sens. Actuators B 2011, 26, 3450.
2012, 171, 580. [99] Y. L. Wang, W. Peng, L. Liu, M. Tang, F. Gao, M. G. Li, Microchim.
[75] M. Du, T. Yang, X. Li, K. Jiao, Talanta 2012, 88, 439. Acta 2011, 174, 41.
[76] Q. Liu, X. Zhu, Z. H. Huo, X. L. He, Y. Liang, M. T. Xu, Talanta [100] Y. Mao, Y. Bao, S. Y. Gan, F. H. Li, L. Niu, Biosens. Bioelectron.
2012, 97, 557. 2011, 28, 291.
[77] H. F. Dong, Z. Zhu, H. X. Ju, F. Yan, Biosens. Bioelectron. 2012, [101] a) Q. Z. Li, X. Y. Qin, Y. L. Luo, W. B. Lu, G. H. Chang, A. M. Asiri,
33, 228. A. O. Al-Youbi, X. P. Sun, Electrochim. Acta 2012, 83, 283;
[78] N. G. Shang, P. Papakonstantinou, M. McMullan, M. Chu, b) X. Y. Qin, Y. L. Luo, W. B. Lu, G. H. Chang, A. M. Asiri,
A. Stamboulis, A. Potenza, S. S. Dhesi, H. Marchetto, Adv. Funct. A. O. Al-Youbi, X. P. Sun, Electrochim. Acta 2012, 79, 46.
Mater. 2008, 18, 3506. [102] Y. Umasankar, B. Unnikrishnan, S.-M. Chen, T.-W. Ting, Anal.
[79] C. X. Lim, H. Y. Hoh, P. K. Ang, K. P. Loh, Anal. Chem. 2010, 82, Methods 2012, 4, 3653.
7387. [103] a) L. Y. Feng, Y. Chen, J. S. Ren, X. G. Qu, Biomater. 2011, 32,
[80] a) X. C. Dong, X. W. Wang, L. H. Wang, H. Song, H. Zhang, 2930; b) O. Akhavan, E. Ghaderi, R. Rahighi, ACS Nano 2012, 6,
W. Huang, P. Chen, ACS Appl. Mater. Interfaces 2012, 4, 3129; 2904; c) L. M. Zhu, L. Q. Luo, Z. X. Wang, Biosens. Bioelectron.
b) X. C. Dong, H. Xu, X. W. Wang, Y. X. Huang, M. B. Chan-Park, 2012, 35, 507.
H. Zhang, L. H. Wang, W. Huang, P. Chen, ACS Nano 2012, 6, [104] M. Giovanni, A. Bonanni, M. Pumera, Analyst 2012, 137, 580.
3206. [105] L. Lin, Y. Liu, L. H. Tang, J. H. Li, Analyst 2011, 136, 4732.
[81] V. Penmatsa, T. Kim, M. Beidaghi, H. Kawarada, L. Gu, Z. F. Wang, [106] Y. W. Hu, S. C. Hua, F. H. Li, Y. Y. Jiang, X. X. Bai, D. Li, L. Niu,
C. L. Wang, Nanoscale 2012, 4, 3673. Biosens. Bioelectron. 2011, 26, 4355.
[82] J. Zhao, G. F. Chen, L. Zhu, G. X. Li, Electrochem. Commun. 2011, [107] K. X. Mao, D. Wu, Y. Li, H. M. Ma, Z. Z. Ni, H. Q. Yu, C. N. Luo,
13, 31. Q. Wei, B. Du, Anal. Biochem. 2012, 422, 22.
[83] a) S. Wu, X. Lan, F. Huang, Z. Luo, H. Ju, C. Meng, C. Duan, Bio- [108] M. H. Yang, A. Javadi, S. Q. Gong, Sens. Actuators B 2011, 155,
sens. Bioelectron. 2012, 32, 293; b) A. Sinitskii, A. Dimiev, 357.
D. V. Kosynkin, J. M. Tour, ACS Nano 2010, 4, 5405. [109] J. J. Lu, S. Q. Liu, S. G. Ge, M. Yan, J. H. Yu, X. T. Hu, Biosens.
[84] H. D. Jang, S. K. Kim, H. Chang, K. M. Roh, J. W. Choi, J. Huang, Bioelectron. 2012, 33, 29.
Biosens. Bioelectron. 2012, 38, 184. [110] R. Li, D. Wu, H. Li, C. X. Xu, H. Wang, Y. F. Zhao, Y. Y. Cai, Q. Wei,
[85] E. Casero, A. M. Parra-Alfambra, M. D. Petit-Domínguez, B. Du, Anal. Biochem. 2011, 414, 196.
F. Pariente, E. Lorenzo, C. Alonso, Electrochem. Commun. 2012, [111] a) T. Gan, S. S. Hu, Microchim. Acta 2011, 175, 1; b) A. Prakash,
20, 63. S. Chandra, D. Bahadur, Carbon 2012, 50, 4209.
[86] a) J. Y. Sun, K. J. Huang, Y. Fan, Z. W. Wu, D. D. Li, Microchim. [112] W. M. Si, W. Lei, Y. H. Zhang, M. Z. Xia, F. Y. Wang, Q. L. Hao,
Acta 2011, 174, 289; b) N. Q. Qiao, J. B. Zheng, Microchim. Electrochim. Acta 2012, 85, 295.
Acta 2012, 177, 103; c) W. Lv, F. M. Jin, Q. G. Guo, Q. H. Yang, [113] Z. J. Li, X. L. Sun, Q. F. Xia, R. Y. Li, Y. J. Fang, S. P. Yang, J. K. Liu,
F. Y. Kang, Electrochim. Acta 2012, 73, 129. Electrochim. Acta 2012, 85, 42.
small 2013, 9, No. 8, 1160–1172 © 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.small-journal.com 1171
reviews S. X. Wu et al.
[114] a) C. Gao, X. Y. Yu, R. X. Xu, J. H. Liu, X. J. Huang, ACS Appl. Mater. T. Liang, M. M. Shi, H. Z. Chen, Chem. Rev. 2013, DOI: 10.1021/
Interfaces 2012, 4, 4672; b) B. Wang, Y. H. Chang, L. J. Zhi, New cr300263a; d) M. Chhowalla, H. S. Shin, G. Eda, L. J. Li, K. Loh,
Carbon Mater. 2011, 26, 31. H. Zhang, Nat. Chem. 2013, DOI: 10.1038/nchem.1589.
[115] a) J. Y. Lei, X. F. Lu, W. Wang, X. J. Bian, Y. P. Xue, C. Wang, L. J. Li, [118] Z. Y. Zeng, Z. Y. Yin, X. Huang, H. Li, Q. Y. He, G. Lu, F. Boey,
RSC Adv. 2012, 2, 2541; b) Y. P. He, J. B. Zheng, S. Y. Dong, Ana- H. Zhang, Angew. Chem. Int. Ed. 2011, 50, 11093.
lyst 2012, 137, 4841. [119] S. X. Wu, Z. Y. Zeng, Q. Y. He, Z. J. Wang, S. J. Wang, Y. P. Du,
[116] a) S. J. Li, D. H. Deng, H. Pang, L. Liu, Y. Xing, S. R. Liu, J. Solid Z. Y. Yin, X. P. Sun, W. Chen, H. Zhang, Small 2012, 8,
State Electrochem. 2012, 16, 2883; b) Y. Fan, J. H. Liu, C. P. Yang, 2264.
M. Yu, P. Liu, Sens. Actuators, B 2011, 157, 669.
[117] a) X. Huang, Z. Y. Zeng, H. Zhang, Chem. Soc. Rev. 2013, Received: November 21, 2012
42, 1934; b) Q. H. Wang, K. K. Zadeh, A. Kis, J. N. Coleman, Revised: January 8, 2013
M. S. Strano, Nat. Nanotechnol. 2012, 7, 699; c) M. S. Xu, Published online: March 13, 2013
1172 www.small-journal.com © 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim small 2013, 9, No. 8, 1160–1172