NJC

PAPER

Synergic effect of plasmonic gold nanoparticles

and graphene oxide on the performance of
Cite this: New J. Chem., 2019,
43, 18925 glucose sensing†
Sadia Tabassum,‡ab Saira Naz,†ac Amjad Nisar, a Hongyu Sun,d Shafqat Karim, a

Maaz Khan,a Shiasta Shahzada,b Ata ur Rahmanc and Mashkoor Ahmad *a

Received 2nd September 2019,
Accepted 26th October 2019
DOI: 10.1039/c9nj04532e
rsc.li/njc
In this study hybrid nanostructures of Au–graphene oxide (Au–GO) were synthesized via a two-step
process and used to modify the glassy carbon electrode (GCE) for electrochemical measurements of
glucose. The modified electrode exhibits a fast response less than 4 s, a low detection limit of 0.025 mM
and a high signal-to-noise ratio (S/N) of 3.5. The fabricated sensor shows a linear response in a large
2
concentration range from 0.0025 mM to 15 mM with a reproducible sensitivity of 84.53 mA cm mM 1,
which is much higher than that of the individual Au, GO and previously reported GO/rGO based sensors.
In addition, the biosensor shows excellent results for human serum which agree well with those
obtained using a laboratory glucometer. Moreover, the glucose amount in selective commercially
available food samples and fresh juices was also successfully measured. The biosensor exhibits excellent
selectivity, thermal stability and reproducibility. The enhanced and efficient sensitivity of the developed
Au–GO based biosensor may be due to the synergic effects of the plasmonic Au-nanoparticles and GO.
The performance of the biosensor suggests that the reported Au–GO hybrid nanostructures can provide
a novel platform for developing non-enzymatic biosensors for biomedical and industrial applications.

1. Introduction involved in the fast, accurate and selective detection of target

The fast and accurate measurement of glucose is crucial for
saving precious lives because it can cause many diseases such
as diabetes and endocrine and metabolic disorders. According
to the World International Diabetes Federation (WIDF),
425 million people across the world are suffering from diabetes
and the figure is expected to reach 629 million by the year 2045
with an increase of nearly 54 per cent.1 Glucose sensors based
on electrochemical signal transduction have become an active
research area since the first publication in 1962.2 In the last few
decades, enzyme based glucose sensors have been extensively
studied and were found to address some common drawbacks
including high cost, low stability and large operational potential
as well as low efficiency under harsh conditions.3,4 Therefore,
researchers are interested in developing non-enzymatic sensors
a
Nanomaterials Research Group, Physics Division PINSTECH, Islamabad 44000,
Pakistan. E-mail: mashkoorahmad2003@yahoo.com
b
Department of Physics, Faculty of Basic and Applied Sciences, International
Islamic University, Islamabad 44000, Pakistan
c
Institute of Chemical Sciences, University of Peshawar, Peshawar, Pakistan
d
Department of Micro- and Nanotechnology, Technical University of Denmark,
2800 Kongens Lyngby, Denmark
† Electronic supplementary information (ESI) available. See DOI: 10.1039/c9nj04532e
‡ These two authors contributed equally.
molecules. Oxidative detection of glucose using different modified
glassy carbon electrodes (GCE) in the absence of enzymes has been
reported in the literature.5–7 Generally, noble metal nanoparticles
such as Pt, Au and Ag have been increasingly considered as electro-
active materials for the anodic electro-oxidation of glucose mole-
cules at high potential.7–9 Unfortunately, these electrodes suffer
from different problems such as poisoning/fouling of electrode
surfaces, etc. Additionally, these metal NPs tend to agglomerate
and are not cost effective when used alone in the fabrication of the
working electrode. As a consequence, a modified electrode with a
low operating potential and enhanced electron transfer kinetics is
highly desired.
From this perspective, various combinations of metal, metal
oxides, polymers and graphene and its derivatives have been
extensively investigated for the development of reliable electro-
chemical glucose biosensors.10–15 Among these materials graphene
oxide (GO) due to its unique optical, electrical and surface charge
properties is one of the most promising candidates for application
not only in biological/chemical sensing but also in other areas such
as energy conversion/storage and catalysis.16,17 However, the use
of GO alone has certain limitations, such as irreversible self-
agglomeration, low colloidal stability, and poor compatibility.
The intrinsic properties of GO can be tuned by incorporating
noble metal NPs having a surface plasmon resonance effect

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which may tailor the surface properties of the hybrid material at
the nanoscale.18 The integration of Au NPs into GO not only
overcomes existing problems but also provides additional synergetic
properties such as enhancement of the effective surface area,
catalytic efficiency, electronic conductivity and biocompatibility.19,20
The hybrid structure offers a unique synergy for bio-applications
in comparison to the individual materials. The potential implemen-
tation of such hybrid systems in sensing, and Raman imaging and
as transparent conductive materials has recently been envisioned in
Au–GO based hybrid devices.21–23 In the last two decades, a lot of
effort has been devoted to the development of noble metal–GO
hybrid structures with tuned properties, however, these structures
have been less considered and are explored for electrochemical
applications.24,25 In this work, we report a facile synthesis of the
Au–GO hybrid structure and a systematic investigation of its
electrochemical properties for glucose sensing. A detailed study
is conducted to explain the electrochemical performance of
Au–GO based glucose biosensors in comparison to individual
Au NPs and the GO structure. It is expected that the Au–GO
based biosensor can reduce the sample analysis cost, and
enhance accuracy, stability and reproducibility.
2. Experimental
2.1 Reagents and materials
Graphite, L-cysteine and Nafion solution were purchased from
Sigma Aldrich. Chloroauric acid, dodecanthiol, sodium boro-
hydrate, tetrabutylammonium bromide and chloroform were
obtained from Alfa Aesar. NaCl, NaOH, NaH2PO4 and Na2HPO4
were supplied by MERCK (E. Merck, Darmstadt, F. R. Germany).
HNO3, ethanol (99.8%) and glucose were purchased from
Scharlau (Spain). Cholesterol, ascorbic acid (AA), urea, and
citric acid were received from Sinopharm Chemical Regent
Co., Ltd. Phosphate buffer saline (PBS, 0.1 M) was prepared
by mixing stock solutions of NaH2PO4 (0.2 M) and Na2HPO4
(0.2 M). Deionized water was used throughout the synthesis and
measurements. For electrochemical measurements of glucose in
human blood serum, fresh blood samples were collected from
the PAEC hospital, Nilore, Islamabad in blood collection tubes
and used within 2 h.
2.2 Synthesis of GO
The synthesis of GO was carried out using a modified Hummers
method.26 Graphite flake (2 g) and sodium nitrate were mixed in
90 ml of sulphuric acid (H2SO4). The whole mixture was stirred
in an ice bath at a temperature below 5 1C. The mixture was
stirred for 4 h and then 12 g of potassium permanganate was
added very slowly to maintain the temperature below 15 1C. The
mixture was diluted with 184 ml of water and the rate of
addition was controlled very carefully due to the exothermic
nature of the reaction. The solution was kept on stirring for two
hours. The ice bath was then removed and the mixture was
stirred for 2 h at 35 1C. Furthermore, the above mixture was kept
in a reflux system at 98 1C for 10–15 min. After 10 min the
temperature was reduced to 30 1C which provided a brown
coloured solution. After another 10 min, the temperature was
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reduced to 25 1C and the solution was allowed to stir for 2 h.
40 ml of H2O2 and 160 ml of hot water were added into the
solution and kept for stirring for 1 h. The mixture was left for 6 h
without stirring which allowed the GO particles to settle down at the
bottom. The solution was placed in a sonication bath for 35 min
and finally washed with 10% of HCl and de-ionized water several
times to remove impurities. The gel like product of GO was collected
by centrifugation and was dried at 60 1C in an oven for 24 h.
2.3 Synthesis of the Au–GO hybrid structure
For the synthesis of the Au–GO composite, tetrabutylammonium
bromide solution (50 mg in 15 ml of chloroform) was slowly added
in chloroauric acid solution (0.0151 g in 15 ml of water) under
continuous stirring. The stirring was continued for 1 h and the
organic layer was collected for further use. 250 mg of the
as-prepared GO was dispersed in 15 ml of ethanol by sonication.
After this, 8 ml of the as-prepared chloroauric acid solution was
slowly added to the above GO dispersion under continuous
stirring. After 10 min, 200 ml of dodecanthiol was added and
after further 5 min 1 ml of the freshly prepared solution of
sodium borohydride (0.05 g of sodium borohydride in 1 ml of
H2O) was added under continuous stirring. The whole mixture was
kept under stirring for 30 min. Finally, the mixture was washed
three times with water and two times with ethanol. The obtained
product of the Au–GO composite was dried at 60 1C for 10 h.
2.4 Characterization
The Raman spectrum was recorded by using an SPEX 1877
spectrometer. Crystallographic investigation was carried out using
a Bruker Model D8 Advance X-ray powder diffractometer (XRD)
with Cu-Ka radiation (l = 1.5418 Å). Fourier transform infrared
spectroscopy (FTIR) was performed using a Nicolett iS50 FTIR
Spectrometer. The morphological and microstructural analyses
were conducted by field-emission scanning electron microscopy
(FESEM; FESEM; MIRA3, 30 keV) and transmission electron
microscopy (TEM; JEOL, JEM-ARM200F, 200 keV).
2.5 Fabrication of the working electrode
To fabricate the working electrode, a conventional GCE was
rinsed with PBS to generate a hydrophilic surface. Then 1.0 mg of
the Au–GO composite was dispersed in 5 ml poly(vinyl alcohol) (PVA)
by ultrasonication. 5 ml of the above solution was deposited on a
GCE having a diameter of 3 mm. To ensure the binding of Au–GO
on the electrode surface 5 ml of Nafions 117 solution was dropped
and allowed to form a film upon drying. For comparison purposes,
two more electrodes modified with Au NPs and GO separately were
also prepared by following the above procedure. The electrochemical
measurements of the biosensor were carried out at room
temperature using an electrochemical work station (CHI660E).
3. Results and discussion
3.1. Structure and morphology analysis
Raman spectrum analysis was used to characterize the electronic
and structural properties of the synthesized material. Fig. 1 shows
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are mainly due to the uniform distribution of Au NPs on the GO

surface.19,29 The peaks at 381, 441, 641 and 781 indexed to the
(111), (200), (220) and (311) planes in Au–GO agree well with the
standard diffraction data of the face-centered cubic structure of
gold.30 The XRD pattern of Au–GO shows that hybrid structures
are formed which are further confirmed by SEM and EDX results.
Fig. 3 displays the FTIR spectra of GO and the Au–GO
composite recorded at the same frequencies. The broad peak
in the range 3000–3650 cm 1 corresponds to the bending and
stretching vibration of the O–H group of water molecules
absorbed on GO.31 While in Au–GO two absorption peaks at
2914 cm 1 and 2845 cm 1 correspond to the symmetric and
anti-symmetric stretching of CH2, the peak at 1337 cm 1
corresponds to the C–N stretching vibration.32 The bands at
Fig. 1 Raman spectra of the synthesized GO and Au–GO composite. 1750 cm 1 and 1590 cm 1 are attributed to the stretching
vibration of CQO and CQC.33 The peak at 932 cm 1 shows the
out of plane C–H bending. The presence of the oxygen containing
the Raman spectra of the synthesized GO and Au–GO hybrid
group shows that graphite has been oxidized. In particular the
nanostructure. The D and G bands in the spectrum located at
B1350 cm 1 and 1580 cm 1 and the 2D band at the position of
B2735 cm 1 respectively are characteristic graphene oxide peaks.
The position and the shape of the G peak confirm the formation of
graphene oxide. The D band is related to the presence of defects in
graphene and also to the degree of edge chirality. Defects arise due
to composite formation with Au NPs attached to the graphene
oxide surface as reported.27,28 The 2D band at B2735 cm 1 is
related to the number of layers of graphene oxide.
The XRD patterns of the GO and Au–GO hybrid nanostructure
are shown in Fig. 2. The diffraction patterns show a sharp and
intense peak at 2y = 111 which corresponds to the interplanar
distance of 0.82 nm in the GO sample. A little broad peak present
in GO at 2y = 261 with an interplanar distance of 0.334 nm shows
the presence of small graphite flakes which are not oxidized
during the chemical reduction process. The intense sharp peak of
GO and the increase in the interplanar spacing confirm the
presence of oxygen functional groups and also show that the
material is oxidized after chemical oxidation and exfoliation.
Fig. 3 FTIR spectra of the synthesized GO and the Au–GO composite.
The GO pattern shows a small reflection peak at 2y = 421 because
of the turbostratic band of the disordered carbon material. The
slight shift and the reduced intensity of the GO peak in Au–GO

Fig. 4 (a and b) Low and high resolution SEM images of GO, (c) SEM
image of Au–GO hybrid structures, (d and e) TEM images of Au–GO hybrid
structures and (f) high resolution TEM image of Au–GO hybrid structures
Fig. 2 XRD spectra of GO and the Au–GO composite. and the corresponding fast Fourier transform (FFT) pattern (inset).

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hydroxyl group is due to the formation of hydrogen bonds between
graphite and water molecules indicating the hydrophilic nature of
the GO structure.
Fig. 4(a and b) show the low and high magnification FESEM
images of the synthesized GO. It can be seen that a large
number of flakes are formed. The high magnification FESEM
image Fig. 4(b) shows that the flakes are composed of a large
number of interconnected nanosheets. The sheets are continuous
and connected to each other. The edges and wrinkled area of the
GO sheet can be easily distinguished. Fig. 4(c) displays a typical
image of the Au–GO hybrid structure. It can be clearly observed
that the thin layered GO surfaces are decorated with small Au
NPs. The diameter of the Au NPs is B5–10 nm. The detailed
morphology of the hybrid product is characterized by using TEM.
Fig. 4(d and e) show the low magnification TEM images of the
Au–GO hybrid structure. It can be clearly seen that the Au NPs are
anchored on the thin GO layer, which is in good agreement with
the FESEM observations. Fig. 4(f) shows the magnified TEM
images of Au NPs anchored on the GO surface which reveals
the single crystal nature of the particles. The inter-planar distance
of the fringes is measured to be 0.24 nm, which corresponds to
the spacing of the (111) plane of fcc Au NPs. The corresponding
fast Fourier transform (FFT) pattern (the inset in Fig. 4(f)) con-
firms the spacing and demonstrates the crystalline nature of the
Au NP in the nanohybrids.
The compositional analysis of the hybrid structure is per-
formed by XPS. Fig. 5(a) shows the high resolution scan of Au 4f
which consists of two binding energy peaks located at 83.91 eV

Fig. 5 (a) High resolution spectra of Au 4f (b) C 1s and (c) O 1s peaks at room temperature.

Fig. 6 (a) Nitrogen adsorption–desorption isotherm of the GO, Au NPs and Au–GO hybrid structure and (b) pore size distribution curve of the Au–GO
composite.

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and 87.54 eV corresponding to the electronic state of Au 4f7/2
and Au 4f5/2. The energy separation between these two peaks is
3.63 eV, which is the characteristic of the Au metallic form and
agrees well with the literature.7,34 Fig. 5(b) shows the core-level
C 1s peak located at 284.45 eV corresponding to C–C/CQC,
C–O, CQO and O–CQO bonds in GO sheets. The high resolution
peak in Fig. 5(c) located at 531.56 eV corresponding to the
electronic state of O 1s is attributed to the remaining hydroxyl
groups and adsorbed water on the surface of the Au–GO struc-
ture. From the close observation, it was observed that the binding
energy spectra of Au4f show a negative shift of about 0.55 eV in
comparison to those of bulk Au, which is probably caused by
electron transfer from the plasmonic Au NPs to GO sheets due to
the electronic interaction between the Au NPs and the oxide
support. The high resolution spectra of C 1s show a similar
nature to those of Au 4f. However, the high resolution spectra of
O 1s can be best fitted by three components located at 533, 532
and 531 eV. These peaks are attributed to the oxygen atoms in the
lattice (OL), OH group related species and oxygen atoms in water
molecules absorbed on the surface (Ow). These oxygen containing
groups are strongly bonded with carbon atoms in GO.
The nitrogen adsorption–desorption isotherms of the Au,
GO and Au–GO composite are shown in Fig. 6(a). By comparing
the isotherms, it is found that the isotherm of the Au–GO
composite shows a wide hysteresis loop in the relative pressure
range of 0.29–1.0 P/P0 and the corresponding BET specific
surface area is ca. 80.4 m2 g 1 which is larger than those of
Au NPs (52.3 m2 g 1) and GO (29.2 m2 g 1). The higher surface
area of the hybrid structure can be attributed to the presence of
Au NPs on the GO surface. The mesoporous size distribution is

Fig. 7 (a) Cyclic voltammograms of the bare GCE, GO–GCE, Au–GCE and Au–GO–GCE in the presence of 100 mM glucose in pH 7.0 PB solution, (b) CV
response of Au–GO–GCE with the addition of glucose concentration from 0–10 mM at a scan rate of 50 mV s 1, (c) corresponding calibration curve,
(d) CV response of Au–GO–GCE at scan rates of 10, 20, 50, 80 and 100 mV s 1 in the presence of 100 mM glucose and (e) corresponding calibration curve
at different scan rates.

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confirmed by the corresponding pore size distribution curve as
shown in Fig. 6(b). The BJH pore size distribution curve shows
the mesoporous nature of the hybrid structure. The high surface
area and mesoporous nature of the Au–GO hybrid are promising
for the efficient electrochemical reaction and very beneficial for
the electrochemical detection of biomolecules.
3.2. Electrochemical measurements
3.2.1. Cyclic voltammetry (CV). The electrocatalytic activities
of the GO, Au NPs and Au–GO hybrid structure for glucose
oxidation were evaluated by performing cyclic voltammetry (CV)
measurements in PB buffer solution. Fig. 7(a) shows the CV
curves for GO, Au NPs and Au–GO in 100 mM glucose solution at a
scan rate of 50 mV s 1. To note the background response, CV
curves of the bare GCE were also collected. It can be seen that the
oxidation current of the Au–GO electrode is much stronger than
those of the bare GCE, Au and GO electrodes. This enhanced
oxidation current indicates that the electrochemical activity of the
hybrid structure is higher than those of the GO and Au NPs. In
the CV scan, glucose is oxidized to dehydrogenated glucose by the

Fig. 8 (a) Comparative amperometric response of Au–GO–GCE, Au–GCE and GO–GCE based biosensors with successive addition of 100 mM glucose,
(b) amperometric response of the Au–GO–GCE biosensor in the presence of different concentrations of glucose at 0.6 V in a pH 7.0 PB solution under
stirring, (c) amperometric response of the Au–GO–GCE biosensor in the presence of low concentrations of glucose in PB solution under stirring,
(d) corresponding calibration curve of the biosensor, and (e) amperometric response of the Au–GO–GCE in the presence of the same amount of
different fresh juices (apple, mango, red grapes and guava).

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conversion of the hybrid structure and the dehydrogenated
glucose is further oxidized to gluconolactone due to the oxygen-
containing functional groups of GO. The activity of the glucose
oxidation on the hybrid structure surface is attributed to the large
surface area and the high edge-plane-like defective sites existing
on GO, which provide abundant active sites for electron transfer
to biological species.35 Thus the presence of more Au NPs on the
GO surface with a large surface area enhances the catalytic
activity for the electrochemical oxidation of glucose. Fig. 7(b)
shows the CV curves of the Au–GO in 0.1 M PBS with varying
concentrations of glucose from 0 to 10 mM. The results show that
the oxidation current increases gradually with the increase of
glucose concentration. Fig. 7(c) exhibits a linear relation between
the oxidation current and glucose concentration ranging from
0 to 10 mM (R2 = 0.966). The electrokinetics of glucose oxidation
was also analyzed by performing CV measurements at various
scan rates from 10 to 100 mV s 1 in the presence of 100 mM
glucose as shown in Fig. 7(d). It can be observed that the
oxidation peak current increases linearly with the increase in
the scan rate. The square root of the scan rates is proportional to
the oxidation current with a correlation coefficient of R2 = 0.999,
suggesting a surface controlled electrochemical process and
demonstrating a diffusion-controlled behavior. This shows that
the electrochemical reaction with the Au–GO electrode is faster
than that of diffusion, which is very useful for the electro-
chemical application.
3.3 Performance of the biosensor
3.3.1 Amperometric response. The efficiency of the biosensor
was also studied by measuring the amperometric response. The
amperometric response of the three modified electrodes i.e.
GO–GCE, Au–GCE and Au–GO–GCE with the successive addition
of 100 mM glucose into 0.1 M PB solution under continuous
stirring is shown in Fig. 8a. It is clearly seen that the GO–Au–
GCE biosensor exhibits a fast response for the detection of
glucose molecules. The sensitivity of the Au–GO is obviously
higher than that of the Au and GO due to synergetic effects.
Au–GO–GCE exhibited about 96% steady-state current within
less than 4 s. The observation shows that Au–GO–GCE has
good electrochemical catalytic oxidation as well as an efficient
electron exchange ability. Fig. 8b shows the amperometric
response of the Au–GO biosensor with different glucose con-
centrations. It is clear that the biosensor is highly efficient
for glucose sensing and delivers significant enhancement in
current upon the addition of glucose. For comparison, the
response of the Au–GCE biosensor with different glucose
concentrations was also monitored as shown in ESI,† S1. The
corresponding calibration curve shows that the sensitivity of
Au–GO is rather low when compared with that of the Au–GO–
GCE biosensor. The amperometric response of the Au–GO–GCE
biosensor in the presence of glucose at low concentrations is
shown in Fig. 8c. It can be seen that the lowest concentration
detected by the Au–GO–GCE is 0.025 mM with S/N = 3.5. This low
limit of detection is better that that of many other carbon based
nanomaterials as shown in Table 1. The corresponding calibration
curve of the Au–GO–GCE biosensor is shown in Fig. 8d. This
reveals that the current response increases linearly with the
increase in the glucose concentration with a correlation coefficient
R2 = 0.9998. The linear range of the calibration curve is from
0.0025 mM to 15 mM. The sensitivity of the biosensor is
calculated to be 84.53 mA mM 1 cm 2 which is much higher than
the already reported nanomaterial based biosensors (Table 1).
This enhanced sensitivity can be attributed to the large specific
surface area and enhanced electrical conduction of the Au–GO
system. These results prove that the Au–GO hybrid structure is a
suitable material for glucose detection as compared to the pure
GO and Au NPs due to the synergic effect. Fig. 8e shows the
amperometric response of the Au–GO biosensor upon the
addition of different fresh juices in PB solution. It can be clearly
seen that the biosensor exhibits a very good response for glucose
detection in the fresh juices.
3.3.2 Selectivity. The electro-active species present in serum
can affect biosensor efficiency; therefore, the selectivity of the
biosensor is studied with the addition of various electro-active
species such as fructose, lactose, cholesterol, ascorbic acid,
L-Cys and urea. Fig. 9a shows the amperometric response of

Table 1 Comparison of the performance parameters of the Au–GO glucose biosensor with other graphene/GO/rGO based hybrid nanostructures

Sensitivity Linear Applied Detection Response

S. no. Electrode material (mA mM 1 cm 2) range (mM) potential (V) limit (mM) time (s) Ref.
1 AuNPs/Graphene/MWCNTs 29.72 — 0.45 4.8 5 36
2 RGO/GODx 1.85 0.1–27 0.44 — 5 37
3 Graphene/nanoAu/GOD/GCE 56.93 — 0.39 17 5 38
4 Pd/RGO/GCE 14.1 — 0.5 0.034 3 39
5 CS-Fc/GO/GOx 10 0.02–6.78 — 7.6 5 40
6 AuNBP/MWCNTs 101.2 0.01–36.7 0.15 3.0 — 41
7 Graphene–Au NPs 0.195 6–28.5 0.0 1.0 — 42
8 AuNPs/Ni(OH)2 NS 82.71 0.002–6 — 0.66 — 43
9 AuNP/GONR/CS 59.1 0.005–4.92 0.2 5 44
10 Porous Co NBs/rGO 39.32 0.15-6.25 — 47.5 45
11 Co/graphene 4700 0.0017–0.47 — 0.68 46
12 DVD-laser scribed graphene 1518 1–4.54 — 1.00 47
13 Substrate CuS/GO 53.5 0.001–2 o6 0.19 48
14 NiO/GO 1100 5 0.77 49
15 Go-GO/ITO 32.32 0.05–10 — — 50
16 Au–GO/GCE 84.53 0.0025–15 0.6 0.025 4 Present work

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Fig. 9 (a and b) Selectivity of the biosensor in PB solution with 100 mM glucose.

Fig. 10 (a) Thermal stability and (b) pH response of the biosensor in the presence of 100 mM glucose.

the Au–GO–GCE biosensor in the presence of cholesterol,

ascorbic acid, L-Cys and urea. These species were consecutively
added in 0.1 M PB solution under stirring. It can be observed
that cholesterol and L-Cys have no influence on the performance
of the biosensor but ascorbic acid shows a small increase in
current about 10% as compared to 0.1 mM glucose. Similarly,
the addition of 0.5 M urea shows only 3% increment in current.
But as the glucose is added the biosensor shows a significant
response. Furthermore, the selectivity of the biosensor was also
investigated with the addition of common interferents such as
fructose and lactose. Fig. 9b shows the amperometric response
of the Au–GO sensor for 0.1 mM glucose, 0.25 mM fructose and
0.25 mM lactose samples.
It can be observed that the biosensor shows a good response Fig. 11 Stability and repeatability of the biosensor.
for glucose and a negligible response for interfering species.
The obtained results demonstrate that the biosensor has the
ability to resist the interference from foreign molecules and
thus exhibit excellent selectivity towards glucose.
Table 2 Measurement of glucose concentration in human blood serum
3.3.3 Thermal stability. The thermal stability of the biosensor samples using a commercial glucometer and the Au–GO based biosensor
was also examined in the presence of 10 mM glucose by observing
the current response at different temperatures between 30 and Human blood Measurement by commercial Measurement by Au–GO
serum samples glucometer (mM) based biosensor (mM)
60 1C as shown in Fig. 10(a). It is observed that the biosensor
response increases with the increase of temperature. The biosensor Sample # 1 4.5  0.5 3.9  0.9
Sample # 2 10  0.8 11.2  1.2
exhibits an optimum value at around 60 1C suggesting enhanced Sample # 3 5.6  0.3 6.5  0.7
electrocatalytic activity at elevated temperatures. This excellent Sample # 4 8.5  0.9 7.8  1.3

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Table 3 Measurement and recovery of glucose in commercial food samples using the Au–GO biosensor
Concentration of
S. no. Food samples glucose (mM)
1 Nescafe 38.5
2 Chocolate 71.8
3 Vita lemon tea 45.4
4 Fresh orange juice 86
5 Nutritional drink 29.8
thermal stability of the Au–GO–GCE biosensor is ascribed to the
hydrophobic nature of the Au–GO structure which provides
suitable conditions for the electrocatalytic reaction. The results
show that the biosensor could be used safely in an environment
with a temperature range of 30–60 1C.
3.3.4 pH effect. The pH of the reaction medium has a
strong influence on the activity of the redox reaction. The pH
effect on biosensor performance is investigated by measuring
the current response for 2 to 8 pH. As clearly seen in Fig. 10(b),
the biosensor shows an optimal sensitivity between pH 6.5 and
7. Considering that the pH of human blood is about 7.4, all the
amperometric experiments have been carried out at pH 7.
3.3.5 Stability and repeatability. The stability and repeat-
ability of the sensor were evaluated by analyzing its performance
after every three days. It can be observed from Fig. 11 that the
biosensor shows good stability and repeatability for glucose
detection. The biosensor retains 95% of its initial performance
after 21 days.
3.3.6 Human blood sample analysis. The feasibility of the
biosensor for practical applications was also tested by measuring
glucose in human blood serum. Quantitative measurement of
glucose concentration was done by a standard method. It was
observed that the glucose concentration in blood serum samples
measured by our biosensor agrees well with the laboratory gluco-
meter values along with the error shown in Table 2. These results
demonstrate that the proposed biosensor may be used in measur-
ing glucose concentration in real samples.
3.3.7 Food sample analysis. The proposed biosensor was
also applied to measure the glucose concentration in real food
samples such as Nescafe, chocolate, vita Lemon tea, fresh
orange juice and nutritional drink collected from the market.
All the samples contain different glucose amounts. Among
these samples, the nutritional drink contains the lowest con-
tent while Nescafe contains the highest glucose content as
shown in Table 3. In order to determine the recovery, a known
amount of standard glucose is added to the real sample and
then the concentration is determined by the Au–GO based
biosensor. It can be seen that the recovery range is 90.3–
97.4% which demonstrates that the Au–GO based biosensor
shows excellent accurate and precise concentrations of glucose
in real samples.
Conclusions
In summary, a highly sensitive Au–GO nanostructure based
non-enzyme glucose biosensor was fabricated. The synergy of
This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2019 New J. Chem., 2019, 43, 18925--18934 | 18933
Paper
Concentration of Concentration of
glucose added (mM) glucose observed (mM) Recovery (%)
20 57 97.4
10 75 91.6
100 138 94.9
50 130 95.5
20 45 90.3
Au NPs and GO enhances the sensing capabilities of the bio-
sensor for the detection of glucose. The Au–GO nanostructures
exhibit an enhanced sensitivity of 84.53 mA mM 1 cm 2,
selectivity, thermal stability and reproducibility. The developed
sensor is equally applicable for real time applications such as
measurement of the glucose concentration in human blood
serum and commercially available food samples such as coffee,
tea and fresh juices. The abundant active sites of the Au–GO
hybrid structure and the excellent electron transport properties
result in a high electrochemical current response for glucose
sensing making it a promising candidate for fabricating cost-
effective electrochemical biosensors. We expect that the reported
hybrid nanostructure based concept can be extended for sensing
bio-molecules at the industrial level.
Conflicts of interest
There are no conflicts to declare.
Acknowledgements
The authors are thankful to the Pakistan Science Foundation and
TWAS for financial support through projects (PSF/Res/C-PINSTECH/
Phys (172)) and (13-319RG/MSN/AS-C-UNESCO FR:3240279202)
respectively. The authors also acknowledge the contribution of
Dr Corneliu Ghica and Dr Valentin-Adrian MARALOIU, the
National Institute of Material Physics (NIMP), Bucharest, Romania
for structural analysis. The authors are also very grateful to
materials science beam scientists for helping in XPS analysis at
Elettra – Synchrotron Trieste, Italy.
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