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A Review of Glucose Biosensors Based on

Graphene/Metal Oxide Nanomaterials
a a b a b
Siti Nur Akmar Mohd Yazid , Illyas Md Isa , Suriani Abu Bakar ,
a b c
Norhayati Hashim & Sazeli Ab Ghani
a
Department of Chemistry, Faculty of Science and Mathematics ,
University Pendidikan Sultan Idris , Perak , Malaysia
b
Nanotechnology Research Center, Faculty of Science and
Mathemathics , University Pendidikan Sultan Idris , Perak , Malaysia
c
Department of Mathematics, Faculty of Science and Mathematics ,
University Pendidikan Sultan Idris , Perak , Malaysia
Accepted author version posted online: 17 Mar 2014.Published
online: 26 Jun 2014.

To cite this article: Siti Nur Akmar Mohd Yazid , Illyas Md Isa , Suriani Abu Bakar , Norhayati
Hashim & Sazeli Ab Ghani (2014) A Review of Glucose Biosensors Based on Graphene/Metal Oxide
Nanomaterials, Analytical Letters, 47:11, 1821-1834, DOI: 10.1080/00032719.2014.888731

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 Analytical Letters, 47: 1821–1834, 2014
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ISSN: 0003-2719 print=1532-236X online
DOI: 10.1080/00032719.2014.888731

Electrochemistry

A REVIEW OF GLUCOSE BIOSENSORS BASED ON

GRAPHENE/METAL OXIDE NANOMATERIALS
Downloaded by [University of Newcastle (Australia)] at 07:37 12 September 2014

Siti Nur Akmar Mohd Yazid,1 Illyas Md Isa,1,2 Suriani

Abu Bakar,1,2 Norhayati Hashim,1,2 and Sazeli Ab Ghani3
1
Department of Chemistry, Faculty of Science and Mathematics, University
Pendidikan Sultan Idris, Perak, Malaysia
2
Nanotechnology Research Center, Faculty of Science and Mathemathics,
University Pendidikan Sultan Idris, Perak, Malaysia
3
Department of Mathematics, Faculty of Science and Mathematics,
University Pendidikan Sultan Idris, Perak, Malaysia

In recent years, considerable attention has been paid to developing economical yet rapid
glucose sensors using graphene and its composites. Recently, the excellent properties of
graphene and metal oxide nanoparticles have been combined to provide a new approach
for highly sensitive glucose sensors. This review focuses on the development of graphene
functionalized with different nanostructured metal oxides (such as copper oxide, zinc oxide,
nickel oxide, titanium dioxide, iron oxide, cobalt oxide, and manganese dioxide) for use as
glucose biosensors. Additionally, a brief introduction of the electrochemical principles of
glucose biosensors (including amperometric, potentiometric, and conductometric) is
presented. Finally, the current status and future prospects are outlined for graphene/metal
oxide nanomaterials in glucose sensing.

Keywords: Enzymatic sensor; Glucose biosensor; Graphene; Metal oxide; Nonenzymatic sensor

INTRODUCTION
Diabetes mellitus is a group of endocrine disorders marked by an elevated
level of sugar in the blood. It is a leading cause of major health problems such as
blindness and kidney failure (Bastaki 2005). The World Health Organization
(WHO) estimated that 366 million people with diabetes in 2011 represented a 30%
increase from the estimated 285 million in 2010 (Whiting et al. 2011), and this total
will increase to 439 million by 2030. The worldwide increase in the number of
diabetic patients has been troubling most developed societies and has encouraged
the development of glucose biosensors.

Received 1 November 2013; accepted 22 January 2014.

Address correspondence to Illyas Md Isa, Department of Chemistry, Faculty of Science and
Mathematics, Universiti Pendidikan Sultan Idris, 35900 Tanjung Malim, Perak, Malaysia. E-mail:
illyas@fsmt.upsi.edu.my

1821
 1822 S. N. A. MOHD YAZID ET AL.

Historically, the idea of glucose enzyme electrode was proposed by Clark and
Lyons in 1962 (Clark and Lyons 1962). During the 1980s, self-monitoring of blood
glucose had been introduced to check the level of glucose in blood at a given point
in time. The first electrochemical glucose meter was a pen-sized electrode strip and
was launched in 1987s as ExacTech by Medisense Inc. It used an enzyme electrode strip
contained glucose oxidase and ferrocene (an electron transfer mediator). The reduction
process of the mediator produced a current which was then detected by an ampero-
metric sensor (Matthews et al. 1987). More recently, there is increasing interest in
nanostructured materials with grain sizes less than 100 nm because of the expectation
of their unique properties, reflecting the growing emphasis on nanotechnology.
Graphene, a single atomic layer of graphite, is the building block of all sp2
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bonded carbon materials including graphite and carbon nanotubes. The explosion
of recent interest in graphene is in large part due to its exceptional electronic proper-
ties and its potential applications, such as for nanoelectronic devices and chemical=
bio-sensors (Schedin et al. 2007; Ohno et al. 2009). Unlike carbon nanotubes, with
a two-dimensional structure, the monolayer graphene has its whole volume exposed
to the environment, which can maximize the sensing effect. Graphene-based
electrochemical sensors and biosensors have recently received increasing attention
in the field of electroanalysis (D. Chen, Tang, and Li 2010; Pumera 2010;
Pumera et al. 2010; Shao et al. 2010), such as direct electrochemistry of enzymes
(Lu et al. 2007; Shan et al. 2009; K. Liu et al. 2010; G. H. Wu et al. 2013), and small
biomolecule detection (Shang et al. 2008; M. Zhou, Zhai, and Dong 2009; Alwarap-
pan et al. 2010).
Being an unrolled carbon nanotube, graphene has a high specific area
(2630 m2 g
1) that can serve as a superior platform for building nanocomposites. Fur-
thermore, its unique two-dimensional crystal structure makes it extremely attractive
as a support material for metal oxide nanoparticles due to its photophysical and
electrochemical properties. Deposition of nanoparticles, such as zinc oxide, titanium
dioxide, copper oxide, and nickel oxide, on graphene sheets reveals special features in
new hybrids that can be widely utilized in chemical=bio-sensors. These graphene-
based hybrid materials have shown greater versatility as enhanced electrode materials
for electrochemical sensors and biosensor applications. Graphene=metal oxide
biosensors exhibit good direct electrochemistry without any electron mediator, as well
as good sensitivity and fast response time towards molecule detection (S. Chen, Zhu,
and Wang 2010).
This review particularly focuses on the development of graphene functionalized
with different nanostructured metal oxide [such as copper oxide, zinc oxide, nickel
oxide, titanium dioxide, iron oxide, cobalt oxide, and manganese dioxide] based
glucose biosensors. Additionally, a brief introduction of electrochemical principles
of glucose biosensors (including amperometric, potentiometric, and conductometric)
is presented. Finally, the current status and future prospects are outlined for
graphene=metal oxide nanomaterials in glucose sensing.

GRAPHENE/METAL OXIDE NANOCOMPOSITES

Graphene offers a unique two-dimensional environment for fast electron
transport and has potential applications in the field of electrochemical sensors and
 GLUCOSE BIOSENSORS BASED ON GRAPHENE 1823

biosensors (Rao et al. 2009; Choi et al. 2010; Kuila et al. 2011). It exhibits a
theoretical surface area of 2630 m2 g
1, which is approximately 260 times greater
than graphite and twice that of carbon nanotubes. Thus, graphene enhances the
electrochemical catalytic activity of materials by greatly increasing the surface area
(X. M. Chen et al. 2011). Besides, the four edges of a graphene sheet offer significant
number of centers for fast heterogeneous electrons (F. Chen and Tao 2009), as com-
pared to single-walled carbon nanotubes for which heterogeneous electron transfer
occurs only at the two ends of the nanotube (Pumera 2009). Therefore, graphene
may have good potential in electrochemistry sensing (Shao et al. 2009; Brownson
and Banks 2010).
With a large surface area and the unique properties, graphene is an attractive
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choice as the matrix material for metal oxide catalyst nanoparticles. Functionaliza-
tion of graphene with various metal oxide nanoparticles can further enhance the
properties of graphene for glucose detection as metal oxide nanoparticles make excel-
lent catalysts, due to their high ratio of surface atoms with free valences to the cluster
of total atoms and may even provide electrochemical reversibility for redox reactions
(Hrapovic et al. 2006; Katz, Willner, and Wang 2004; Rahman et al. 2010). In other
words, the combination of graphene with metal oxide nanoparticles provides a new
solution for highly sensitive graphene-based glucose sensors for which metal oxide
nanoparticles can act as the active site to enhance the specificity and sensitivity,
whereas graphene offers fast electron transfer in the electrochemical reaction (Solanki
et al. 2011; Z. Zhu et al. 2012).
There are various growth processes to produce metal oxide nanostructures on
graphene sheets such as in situ chemical synthesis (S. Chen, Zhu, and Wang 2011;
L. Zhu et al. 2013; Teymourin, Salimi, and Khezrian 2013), hydrothermal processes
(Pan and Liu 2012; Qin, Luo, and Chang 2012; Golsheikh et al. 2013), microwave
heating (S. Wang, Jiang, and Wang 2011), and electrodeposition (J. Luo et al. 2012;
L. Luo, Zhu, and Wang 2012; Y. Zhu et al. 2010). The growth mechanism of metal
oxide nanostructures on graphene is due to the attraction of positively-charged
metal=metal-oxide ions by the polarized bonds of the functional groups on the gra-
phene (such as –OH, C=O of carboxylic, O=C-O of carboxylate, C-O and O-C-O)
(Y. Zhu et al. 2010; Sheshmani and Amini 2013). For example, tin oxide
nanoparticle=graphene nanocomposites have been developed by a facile microwave
method (Zhao et al. 2011). When graphene oxide was mixed with Sn2þ ions in the
presence of sodium hydroxide, a platform was provided for electrostatic interaction
between the negatively charged oxide functional group of graphene oxide and the
positively charged Sn2þ ions. Nucleation process occurred at the sites, resulting in
the growth of tin oxide nanoparticles on the graphene nanosheets during the micro-
wave process. Graphene oxide was reduced to graphene due to the simultaneous pres-
ence of Sn2þ, sodium hydroxide, and microwave treatment (Lim et al. 2012).

GLUCOSE BIOSENSORS BASED ON GRAPHENE/METAL OXIDE

NANOCOMPOSITES
Generally, there are two derivatives of graphene: graphene oxide and reduced
graphene oxide. Graphene oxide is functionalized graphene with various oxygen-
bearing groups (such as C=O, C
O, and
OH), while reduced graphene oxide is
 Downloaded by [University of Newcastle (Australia)] at 07:37 12 September 2014

Table 1. Graphene=metal oxide nanocomposites available for glucose biosensors and their functional properties

Enzymatic= Sensitivity=detection Response time (s)=

Electrode matrix nonenzymatic limit (mM) applied potential (V) Ref.

CuO=graphene nonenzymatic 1065 mA mmol
1 L cm
2=1
=þ0.60 Hsu et al. 2012

Cu2O=graphene nanosheet nonenzymatic
=1.2 <3=þ0.45 Qian et al. 2012
CuO nanocubes=graphene nonenzymatic 1360 mA mM
1 cm
2=0.7 <5=þ0.55 L. Luo, Zhu, and Wang 2012
CuO=graphene nanosheets nonenzymatic 1480 mA mM
1 cm
2=0.29 3=þ0.40 Li et al. 2013
CuO=graphene nonenzymatic
=6.7  1 3=þ0.55 Yu et al. 2013
CuO=rGO=CNF nonenzymatic 912.7 mA=0.1 <2=þ0.60 Ye et al. 2013
CuOG-SPCE nonenzymatic 2367 mA mM
1=34.3  10
3
=
C. L. Sun et al. 2013
Cu2O=GNS nonenzymatic
=3.3 <9=
0.4 M. Liu, Liu, and Chen 2013
Cu2O=rGO nonenzymatic 19.5 mA=mM
1=

=
F. Xu et al. 2013
RGOs-Cu2O nonenzymatic 185 mA mM
1=0.05 mM 3 s=0.60 D. L. Zhou et al. 2014
ZnO=nanographene sheets enzymatic 2.5 mL=min=0.02
=
Norouzi et al. 2011
rGO=ZnO enzymatic 18.97 mAmM
1=0.02 mM
=0.40 Palanisamy, Vilian, and Chen 2012
Graphene-ZnO nonenzymatic
=

=
Kavitha et al. 2012
Graphene-Ni=NiO nonenzymatic 3410.3 mA=mM=0.28 =0.2 and 0.8 Kumary et al. 2013

1824
NiO-graphene nonenzymatic
=5.0 <3=þ0.35 V L. Zhu et al. 2013
NiONPs=GO nonenzymatic 1087 mA mM
1 cm
2=1.00
=þ0.6 Yuan, Xu, Liu, et al. 2013
GNS=NiO hybrids nonenzymatic
=2.5 <8=þ0.6 Lv et al. 2012
NiONFs=GO nonenzymatic 1100 mA mM
1 cm
2=0.77 <5=þ0.6 Y. Zhang et al. 2012
RGO-TDN nonenzymatic 35.8 mA mM
1 cm
2=4.80 10=
0.7 Z. Luo et al. 2013
Ti2O-graphene nonenzymatic 6.2 mA=mM cm2= =
0.6 Jang et al. 2012
Fe3O4=GRO nonenzymatic
=3.2 <5=
Kong et al. 2012
Nafion=EGO=Co3O4 nonenzymatic 560 mA mmol
1 L cm
2=0.30
=þ0.76 Ensafi, Asl, and Rezaei 2013
PtAu-MnO2=graphene nonenzymatic 58.54 mA cm
2 mM
1=0.02 mM
=
Xiao et al. 2013
Cu2O=NiOx=GO enzymatic
=

=
Yuan et al. 2013

CuO: copper oxide; Cu2O: cuprous oxide; CuO=rGO=CNF: CuO nanoneedle=graphene=carbon nanofiber; CuOG-SPCE: CuO=graphene-modified screen-printed
carbon electrode; Cu2O=GNS: Cu2O nanocubes graphene nanosheets; Cu2O=rGO: cuprous oxide-reduced graphene oxide; ZnO: zinc oxide; rGO=ZnO: reduced gra-
phene oxide=zinc oxide; Ni=NiO: nickel=nickel oxide; NiONPs=GO: nickel oxide nanoparticles=graphene oxide; GNS=NiO: graphene nanosheet=nickel oxide;
NiONFs=GO: nickel oxide nanofibers=graphene oxide; RGO-TDN: reduced graphene oxide- highly dispersed titanium oxide nanoclusters; Ti2O: titanium dioxide;
Fe3O4=GRO: reduced graphene oxide=ferroferric oxide nanocomposites; Nafion=EGO=Co3O4: Nafion=exfoliated graphene oxide-cobalt oxide; PtAu-MnO2:
platinum-gold alloy and manganese dioxide.
 GLUCOSE BIOSENSORS BASED ON GRAPHENE 1825

normally obtained through chemical reduction of graphene oxide (Y. Sun, Wu, and
Shi 2011; Singh et al. 2011). Recently, nanocomposites of graphene and metal oxides
have been successfully prepared on the basis of either graphene oxide or reduced
graphene oxide. An electrochemical technique has attracted tremendous attention
for producing glucose biosensors due to their sensitivity and selectivity, lower
detection limits, faster response times, better long term stability, and low cost
(Jetkins, Heinemen, and Halsall 1988; Kvist et al. 2006; Park, Boo, and Chung
2006; Heller and Feldman 2008; Toghill and Compton 2010). Sensing materials
without damaging the system (Arora et al. 2011) and the possibility to use samples
with small volumes (Ronkainen-Matsuno et al. 2002) are some other advantages of
electrochemical biosensors. In this section, the application of graphene=metal oxide
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nanocomposites for electrochemical glucose sensor is reviewed. Table 1 shows

graphene=metal oxide nanocomposites applicable to glucose biosensors reported thus
far and give brief descriptions in terms of the availability of enzymatic or nonenzy-
matic operations, sensitivity, detection limit, response time, and applied potential.

COPPER OXIDE GRAPHENE BASED GLUCOSE SENSORS

Recent advances in nanotechnology have revealed the potential of copper oxide
nanoparticles with application to glucose oxidation and hydrogen peroxide detection
with good stability (McAuley et al. 2008; X. Wang et al. 2010). As a p-type semicon-
ductor with a narrow band gap of 1.2 eV, copper oxide nanomaterials are promising
in the development of glucose sensors because of highly specific surface area, good
electrochemical activity, and the possibility of promoting electron transfer reactions
at a lower overpotential (Reitz et al. 2008; Zhuang et al. 2008). The incorporation of
graphene with copper oxide nanoparticles produces synergistic effects leading to
improved glucose detection. For example, a graphene=copper oxide glucose sensor
has been developed by electrodepositing copper oxide nanocubes on graphene sheets
(L. Luo, Zhu, and Wang 2012). The effects of copper electrodeposition time, pH, and
applied potential have been studied for optimization of the sensing conditions. An
optimized copper electrodeposition time (120 s), 0.1 M of sodium hydroxide solution,
and þ0.55 V of applied potentials were selected for further investigation. Under the
physiological condition, a linear range up to 4 mM with a sensitivity of 1360 mA
mM
1 cm
2 at a positive potential (i.e., þ0.55 V) was obtained.
The particle sizes of copper oxide nanoparticles can affect the sensitivity of
glucose detection. In a related study by Hsu et al. (2012), graphene=copper oxide
nanocomposites were prepared via electrodeposition on a glassy carbon electrode
for electrochemical detection of glucose. A larger capacitance of cyclic voltammo-
gram was shown by the graphene=copper oxide electrode compared to the graphene
and copper oxide nanoparticle modified electrodes, respectively. A linear range up to
8 mmol L
1 glucose was achieved by this sensor, with a detection limit of 1 mmol L
1
(signal=noise ¼ 3) at a detection potential of þ0.60 V. The authors proposed that
the particle sizes of copper oxide nanoparticles were influenced by pH values in the
solution. However, it might have been helpful to provide more details on the size-
dependent sensitivity of graphene=copper oxide nanocomposites towards glucose in
real samples. In addition, the growth processes of copper oxides on graphene, the
probability of toxicity, the reproducibility, and stability still requires attention.
 1826 S. N. A. MOHD YAZID ET AL.

In recent years, various approaches have been performed to reduce graphene=

metal oxide nanocomposites via a green chemical route which does not involve any
hazardous chemicals. Qian et al. (2012) have decorated copper oxide on the surface
of graphene nanosheets at a low temperature using sodium citrate as the reductant
and stabilizer in alkaline medium. Higher sensitivity and selectivity towards glucose
was shown by graphene=copper oxide nanosheets with a good linear dependence on
glucose concentration and a detection limit of 1.2 mM (at signal=noise ¼ 3). High
catalytic active sites for the glucose oxidation were provided by the decoration of
copper oxide nanoparticles on the surface of graphene nanosheets, which may be
attributed to the involvement of Cu(II) and Cu(III) surface species in the oxidation
of glucose in alkaline medium (Wei et al. 2009; H. X. Wu et al. 2010).
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In addition to the graphene=copper oxide glucose sensor, recently Li et al. (2013)

synthesized a nonenzymatic glucose sensor by immobilizing nanocomposites on glassy
carbon electrode with Nafion. A remarkable electrocatalytic activity towards the oxi-
dation of glucose has been shown by the graphene=copper oxide nanocomposites
glassy carbon electrode and led to an enzymeless glucose sensor with a wide linear
range between 2.0 mM to 0.06 mM, and a lower detection limit of 0.29 mM (signal=
noise ¼ 3). A much larger peak current was displayed by the graphene=copper oxide=
Nafion=glassy carbon electrode compared to bare glassy carbon electrode and copper
oxide=Nafion=glassy carbon electrode. This demonstrated that graphene=copper
oxide nanocomposites have a larger electroactive surface than the copper oxide nano-
particles and can thus act as a promoter to enhance the electrochemical reaction for
glucose detection. The findings are clearly presented as they also examined the poison-
ing possibility of chloride to the activity of graphene=copper oxide nanocomposites
and also anti-interference property toward dopamine, uric acid, and ascorbic acid.

ZINC OXIDE GRAPHENE GLUCOSE SENSOR

Zinc oxide nanomaterial is a wide band gap (3.37 eV) semiconductor having a
large excitation binding energy of 60 meV at room temperature, high specific surface
area, nontoxicity, chemical stability, and high electrical conductivity (Nakahara et al.
2001; Lu, Ng, and Yang 2008). A high isoelectric point (IEP) of about 9.5 and the
positively charged of zinc oxide are helpful to immobilize the negatively charged
glucose oxidase (IEP ¼ 4.2) at the reduced graphene oxide=zinc oxide composite in
the physiological pH (7 to 7.4) (F. F. Zhang et al. 2004; Zang et al. 2007).
Several investigations have been performed to produce graphene=zinc oxide
nanocomposites for glucose detection. In the work by Norouzi et al. (2011), an
enzymatic glucose biosensor was synthesized based on zinc oxide nanoparticles doped
in nanographene sheets. Nafion was used in the construction of the biosensor to
prevent loss of the enzyme molecules. The authors claimed that the large quantity
of well-dispersed zinc oxide nanoparticles on the graphene sheet were suitable for
the immobilization of the glucose oxidase enzyme and thus led to a sensitive glucose
sensor with a linear response range between 0.1 to 20 mM and lower detection limit of
0.02 mM at a signal-to-noise ratio of 3. However, the authors offered no information
on the size distribution of the zinc oxide nanoparticles.
A similar approach has been reported by Palanisamy, Villian, and Chen (2012).
An enzymatic glucose sensor was prepared using reduced graphene oxide=zinc oxide
 GLUCOSE BIOSENSORS BASED ON GRAPHENE 1827

nanocomposites on a glassy carbon electrode by electrochemical approach at room

temperature. Good electrocatalysis toward the reduction of oxygen and oxidation of
glucose was exhibited by the as-fabricated reduced graphene oxide=zinc oxide=
glucose oxidase composite with a linear range from 0.02 to 6.24 mM and a detection
limit of 0.02 mM. The authors found that the reduction current decreased linearly
with the addition of glucose indicating excellent catalytic activity for glucose.
However, this study offered no explanation on the effect of different concentration
of glucose toward the sensitivity of glucose detection using graphene=zinc oxide=
glucose oxidase composite film modified glassy carbon electrode.
In other work, Kavitha et al. (2012) introduced a glucose oxidase biosensor
using graphene nanosheets decorated with zinc oxide nanoparticles through the in
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situ thermal decomposition at a moderate temperature. The sensitivity toward

glucose was improved using graphene=zinc oxide nanocomposites compared to bare
graphene. The enhanced performance of the graphene=zinc oxide biosensor was
attributed to the synergistic influence of graphene (large surface area-to-volume
ration and the high conductivity) and zinc oxide nanoparticles (good biocompatibil-
ity), thus provided good enzyme activity, which eventually resulted in direct electron
transfer between the redox sites of the enzyme and electrode’s surface (Kavitha et al.
2012). Nevertheless, the evidence cited in this article does not support the overall con-
clusion as this research did not take into account the toxicity test, anti-interference
test, and stability test of the graphene-nickel=nickel oxide composite towards glucose.
It has to be admitted that the current study is still far from being conclusive and
further studies must be undertaken.

NICKEL OXIDE GRAPHENE GLUCOSE SENSOR

Various metal=metal oxide nanoparticles and graphene have been prepared so
far due to the special properties of these materials. In practice, the high cost of the
electrode using metal materials may limit their commercial application (Cao et al.
2011; Mu et al. 2011). Thus, some researchers have concentrated on the use of
low-cost metal oxide materials such as nickel oxide nanomaterials. Nickel oxide based
graphene nanocomposites have received considerable attention in electrochemical
sensors, especially in glucose sensor due to its excellent electrocatalytic, inexpensive
properties, and absence of interferences by other elecroactive species, such as ascorbic
acid, dopamine and uric acid (Lv et al. 2012; Y. Zhang et al. 2012; Kumary et al. 2013;
Zhu et al. 2013; Yuan et al. 2013).
Zhu et al. (2013) developed a nonenzymatic glucose sensor by directly electro-
depositing nickel on a glassy carbon electrode with a graphene modifier. Then, the
nickel was oxidized to nickel(II) oxides by potential cycling (Zhu et al. 2013). A high
electrocatalytic activity for the oxidation of glucose was shown by the graphene=
nickel oxide=glassy carbon electrode as there was a great enhancement of the anodic
peak current while the cathodic peak current obviously decreased. A linear range up
to 4.5 mm glucose level was achieved by this electrode sensor with a detection limit of
5 mM (at a signal=noise ¼ 3) and the response time was very short (<3 s). These results
are consistent with the goal of this research to prepare nickel (II) oxides and graphene
nanocomposites modified glassy carbon electrode for the amperometric determi-
nation of the glucose concentration with high sensitivity and stability.
 1828 S. N. A. MOHD YAZID ET AL.

Recently, solving the problem of irreversible agglomeration of graphene sheets

using solution based techniques has received considerable attention to synthesize
graphene=metal oxide nanocomposites. Kumary et al. (2013) prepared a graphene-
nickel=nickel oxide composite via solar exfoliation of graphite oxide=nickel acetate
precursor for glucose sensor application. An alkaline medium (0.1 M of sodium
hydroxide solution) was chosen as the supporting electrolyte because it provided
the best peak current response to glucose (Qiao and Zheng 2012). A linear range
up to 5 mM with a sensitivity of 3.410.3 mA=mM and a detection limit of 0.28 mM
was obtained at a substantially positive potential (0.2 and 0.8 V). The discussion
consistently relates the key findings in this research.
In other work, the graphene=metal oxide hybrids showed a poor water-dispersing
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ability which caused obstacles for the fabrication of the sensing electrodes and thus,
appropriate dispersants (such as DNA, alcohol, sulfonated poly(ether-ether-ketone)
were required (Lv et al. 2010). Lv et al. (2012) introduced a nonenzymatic glucose
sensor through a self-assembly process of powdered graphene nanosheets=nickel oxide.
Then, ss-DNA (single-strand DNA) was employed to disperse the powdered graphene
nanosheets=nickel oxide hybrid in aqueous solution. Electrocatalytic activity toward the
oxidation of glucose with a linear range between 1 mM to 200 mM and a detection limit of
2.5 mM at a detection potential of 0.6 V has been reported when using the obtained
graphene nanosheets=nickel oxide=DNA hybrids for glucose sensing. The findings are
clearly presented using schematic diagrams and a graph of electrochemical performance
of the graphene nanosheets=nickel oxide glassy carbon electrode toward glucose.

OTHER METAL OXIDE-GRAPHENE GLUCOSE SENSORS

Other graphene=metal oxide nanomaterials such as graphene=titanium dioxide,
graphene=iron oxide, graphene=cobalt oxide, and graphene=manganese dioxide have
been reported for glucose sensing application (Z. Luo et al. 2013; Jang et al. 2012;
Kong et al. 2012; Ensafi, Asl, and Rezaei 2013; Teymourin, Salimi, and Khezrian
2013; Xiao et al. 2013). Titanium dioxide nanomaterials are biocompatible,
environmentally-friendly, and have been shown to have promising applications
[130]. Z. Luo et al. (2013) developed a highly dispersed titanium dioxide nanocluster
on reduced graphene oxide under microwave irradiation. The reduced graphene oxi-
de=titanium dioxide nanocluster is responsible for the high loading of glucose oxidase
and a short response time (10 s) with sensitivity 35.8 mA mM
1 cm
2. In addition, a
detection limit of 4.8 mM has also been reported.
Functionalization of iron oxide nanomaterials on graphene has been explored for
glucose sensing as the magnetic properties of these nanocomposites promise a greatly
improved delivery and recovery of biomolecules (Rossi, Quach, and Rosenzweig 2004;
Ma et al. 2012). However, there are only a few biosensor applications. Kong et al.
(2012) introduced the application of graphene=iron oxide nanocomposites as an
electrode material for glucose sensing. The nanocomposites were synthesized by a
coprecipitation method. A low response time of less than 5 seconds with a detection
limit of 3.2 mM (S=N ¼ 3) was shown using the graphene=iron oxide electrode for
glucose detection.
Ensafi et al. (2013) reported an amperometric glucose sensor based on a
Nafion=exfoliated graphene oxide=cobalt oxide nanocomposite coated glassy carbon
 GLUCOSE BIOSENSORS BASED ON GRAPHENE 1829

electrode. A remarkable electrocatalytic activity towards the oxidation of glucose

was shown by the Nafion=exfoliated graphene oxide=cobalt oxide coated glassy
carbon electrode with a detection limit of 0.3 mmol L
1 at a detection potential of
0.76 V. Experimental data for the glucose detection was in good agreement with
results from the method performed in milk.
The growing attention for compact point-of-care medical devices and portable
instruments for glucose sensing application has encouraged Xiao et al. (2013) to pro-
duce electrochemical biosensors based on free-standing graphene paper carrying
binary nanocomposites of platinum-gold alloy and manganese. The coral-like
platinum-gold=manganese dioxide nanocomposites were grown on the substrate
through one-step template-free electrodeposition, leading to intimate contact between
Downloaded by [University of Newcastle (Australia)] at 07:37 12 September 2014

the platinum-gold alloy and manganese dioxide matrix. A greatly enhanced sensing
performance such as wide linear range (0.1 mM to 30.0 mM), high sensitivity
(58.54 mA cm
2 mM
1), and a low detection limit (0.02 mM, S=N ¼ 3) were reported
using the platinum-gold=manganese dioxide manganese dioxide binary nanostructure-
decorated graphene paper for glucose.

CONCLUSIONS: FUTURE PROSPECTS AND CHALLENGES

With the advent of nanotechnology, various materials have been investigated as
biosensors for monitoring glucose without interference from other electroactive
species. Metal oxide nanoparticles have large surface-to-volume ratios and can act
as the active site to immobilize glucose oxidase and high isoelectric point (IEP). This
review briefly summarized the most frequently-used electrochemical methods and
metal oxides to functionalize graphene including copper oxide (IEP ¼ 6.5), zinc oxide
(IEP ¼ 9.5), nickel oxide (IEP ¼ 9.9–11), titanium dioxides (IEP ¼ 3.9–8.2), iron
oxide (IEP ¼ 6.5–6.6), and manganese dioxide (IEP ¼ 4–5) in glucose biosensors. Zinc
oxide and nickel oxide which have high IEPs might be the most suitable graphene
electrode materials for glucose biosensors. Additionally, the high IEP of zinc oxide
and nickel oxide provide a better surface for glucose oxidase immobilization which
further improves the sensitivity and selectivity during glucose monitoring.
Despite the impressive advances in glucose biosensor technology, there are still
several challenges related to the achievement of stable and reliable glucose sensing
based on graphene=metal oxide nanocomposites. The challenges include determining
the toxicity and biocompatibility of graphene=metal oxide nanocomposites. The
increases use of graphene=metal oxide nanocomposites in a variety of biomedical
applications will require stringent toxicological assessment in vitro and in vivo. It is
a challenge as there are a limited number of studies that have looked into the toxicity
profile of graphene=metal oxide nanocomposites. Meanwhile, under biocompatibil-
ity, it is important to consider the effect of sensor upon the in vivo environment
for a prolonged operation in the blood. It is a major challenge and significant progress
must be made towards the continuous monitoring of glucose using graphene=metal
oxide sensors.
Amperometric electrochemical biosensors for glucose play a leading role in this
sensing area. Besides, the development of a cheap, sensitive and interference free sen-
sor for nonenzymatic glucose detection is still greatly in demand. Indeed, research
interest in glucose sensors will grow with increasing numbers of diabetic patients.
 1830 S. N. A. MOHD YAZID ET AL.

Taking into account the excellent individual properties of graphene and metal oxide
nanomaterials, the combination of graphene with metal oxide nanomaterials
provides a new solution for highly sensitive graphene-based glucose sensors.

FUNDING
Financial support by Ministry of Higher Education Malaysia through
Exploratory Research Grant Scheme (ERGS), grant number: 2013-0082-102-22
and MyPhD scholarship are gratefully acknowledged.
Downloaded by [University of Newcastle (Australia)] at 07:37 12 September 2014

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